CN112520912A - High-salt high-hardness mine water near-zero discharge process - Google Patents
High-salt high-hardness mine water near-zero discharge process Download PDFInfo
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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
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
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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
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—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
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- 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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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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)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Agronomy & Crop Science (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of wastewater purification treatment, in particular to a high-salinity high-hardness mine water near-zero emission process, which realizes near-zero emission of high-salinity high-hardness mine water by using a precipitation and flocculation pretreatment → ultrafiltration and reverse osmosis advanced treatment → concentration treatment of desalted tail water → wastewater treatment of sludge dehydration treatment, and processes of desalting fresh water and desalting tail water recovery treatment and coal slime and chemical sludge recovery treatment; in order to increase the stability of an SED concentration system in the system, the invention also designs a non-ionic exchange membrane which has a porous structure inside and a compact functional layer on the surface, has excellent mechanical stability on the premise of meeting the requirement of unit price selection, can well adapt to the severe working environment of mine water inlet concentration, improves the operation stability of the whole system and prolongs the service life.
Description
Technical Field
The invention relates to the technical field of wastewater purification treatment, in particular to a high-salinity high-hardness near zero-emission process for mine water.
Background
The mine water contains a large amount of suspended matters which are difficult to settle, such as coal slime, and the like, already reaches the salt content index of seawater, and has very high requirements on corrosion resistance of matched equipment and pipelines; and the hardness of the mine raw water reaches 4253mg/L, supersaturated crystal salt is easily formed in the subsequent membrane concentration process to block the membrane element, and the membrane element is not easy to clean, so that the service life of the membrane element is directly influenced.
By adopting the high-efficiency multistage softening process, the calcium ions in the raw water can be reduced to be less than 5mg/L, and the subsequent membrane treatment system and the concentration system are ensured to have no scaling risk. However, after the wastewater is concentrated by multiple times of RO, the hardness is high, and the salt content reaches 48000mg/L, so that the risk of inorganic salt scaling of a subsequent concentration system is caused.
But the RO concentrated water can be further concentrated by adding the high-efficiency SED concentration technology in the process, so that the salt content reaches 230000mg/L, the salt can be evaporated or dried by the sun, the aim of zero emission or near zero emission is fulfilled, and the membrane system and the concentration system are ensured not to generate the accumulation of COD, silicon dioxide and the like, so that the system is crashed.
The MVA of the traditional SED is compact in structure, low in permeability and small in permeation flux, which is used for ensuring the selective performance of the membrane, but in order to obtain better salt collection concentration, the permeation flux of the membrane needs to be increased, but the mechanical strength of the membrane is reduced by increasing the permeation flux, so that the relation between the performance and the MVA of the SED is a difficult problem in structure at present.
Disclosure of Invention
In order to achieve the aim, the invention provides a near zero emission process of high-salt high-hardness mine water, and the SED high-efficiency concentration system using the MVA prepared by the invention is added to the traditional mine water inlet salt collection process, so that the salt in the mine water can be concentrated efficiently, and the zero emission of mine wastewater is realized, and the specific technical scheme is as follows:
s1, performing precipitation and flocculation pretreatment by using pretreatment unit
After mine drainage containing coal dust and rock dust is lifted out of the ground, the mine drainage firstly enters a pre-settling regulating tank, and the mine drainage is balanced in water quality and water quantity in the tank body; then the mine drainage is lifted to an inclined tube sedimentation tank by a primary lift pump, a flocculating agent PAC is added into the water body before entering the tank body, the mine drainage mixed with the flocculating agent is fully mixed and reacted with the agent in a flocculation section at the front end of the flocculation inclined tube sedimentation tank, coal powder and rock powder in the water body collide with each other under the action of the flocculating agent, particles are gradually increased, and then the coal powder and the rock powder with increased particle sizes are subjected to gravity sedimentation in a rear end inclined tube sedimentation section of the flocculation inclined tube sedimentation tank, so that the effect of purifying the water quality is achieved; the settled mine drainage gravity automatically flows into a high-density sedimentation tank (belongs to an advanced treatment unit, and the high-density sedimentation tank is arranged in front in consideration of the process requirement), the outlet water of the high-density sedimentation tank automatically flows into a valveless filter, the mine drainage further reduces the content of suspended matters in the water body through the filtering action in the valveless filter, the indexes of the outlet suspended matters basically meet the requirements of the water quality indexes of related suspended matters in the discharge standard of pollutants for coal industry (GB 20426-2006), and meanwhile, conditions are created for the subsequent advanced treatment; the effluent of the valveless filter automatically flows into the intermediate water tank.
S2 ultra-filtration and reverse osmosis advanced treatment by using advanced treatment unit
Besides the coal dust-based suspension, the mineralization (TDS, total soluble solids) of mine water is about 15000-16000 mg/L, and the total soluble solids in the water mainly exist in the form of inorganic salts. Because the inorganic salt content in the water body is high, the total hardness, the contents of sulfate, chloride, fluoride and the like are relatively high, and the mine sewage can be used as coal mine domestic water and production water after being subjected to deep desalination treatment.
The effluent of the high-density sedimentation tank enters a valveless filter (a pretreatment structure which is arranged according to the process requirement), the effluent of the valveless filter enters an intermediate water tank, and the stored water of the intermediate water tank is lifted to an ultrafiltration device by an ultrafiltration water supply pump. The ultrafiltration device can completely block particles and bacteria with larger pore diameters and viruses with smaller sizes in the inlet water. If the membrane quality is not defective, ultrafiltration can achieve good filtration effect under various water inlet conditions, and thus can be used as a pre-protection for reverse osmosis devices.
The effluent of the ultrafiltration device is stored in an ultrafiltration water tank, and the water in the ultrafiltration water tank is lifted into the reverse osmosis device by a reverse osmosis water supply pump. The reverse osmosis device is used as the core of mine water desalination. The mine water enters the membrane element under the pressure of the high-pressure pump, a part of the mine water permeates the reverse osmosis membrane to form desalted fresh water under the driving of the pressure, and the other part of the mine water becomes desalted tail water to be discharged. Comprehensively considering the salt content of raw water in the mine, the power consumption, the pressure bearing capacity of the membrane elements and the combination of the membrane elements, the desalination fresh water recovery rate of the system is controlled to be about 75 percent, and the desalination tail water discharge capacity is 25 percent. The desalted fresh water enters a clean water tank and can be reused for mine production, power plants and the like after being disinfected; and discharging the desalted tail water to a concentrated water tank.
S3 concentration of desalted tail water using desalted tail water treatment unit
The yield of the concentrated water after advanced treatment is about 2400m3And d, although the fresh water recovery rate of the part of water is 75% relative to the underground drainage rate of the mine, considering that the salt content of a large amount of drainage is high (the TDS is about 67000mg/L), a large amount of land is occupied by a drainage site, and in order to reduce the amount of discharged water, an SED concentration system is additionally arranged on tail water treatment to further treat the desalted tail water after deep treatment.
Because the salt content of the tail water is about 67000mg/L, the tail water is treated by a common reverse osmosis membrane process, so that the tail water is difficult to separate, but an SED concentration system can be realized. The SED concentration technology is one of membrane separation technology, and is characterized by that it alternatively arranges anion-cation exchange membranes between positive and negative electrodes, and uses special-made partition plate to separate them to form two systems of desalination and concentration, and under the action of D.C. electric field, and uses the potential difference as power, and utilizes the selective permeability of ion exchange membrane to separate electrolyte from solution so as to implement concentration, desalination, refining and purification of solution. And the obtained fresh water flows back to the pre-settling regulating tank, and the obtained concentrated water is discharged to the comprehensive reuse water tank.
S4 sludge dewatering treatment by sludge dewatering unit
The sludge in the sludge hopper of the pre-settling regulating tank is lifted to a sludge thickener by a sludge lifting pump for gravity concentration; the settled sludge in the inclined tube settling tank flows into the sludge tank by gravity, and the sludge in the sludge tank is lifted to the sludge thickener by the sludge pump for gravity concentration. All the sludge is subjected to gravity concentration in the sludge concentration tank, so that the solid content of the sludge is improved, and the subsequent mechanical dehydration of the sludge is facilitated.
The concentrated sludge of the sludge concentrator is lifted into a plate-and-frame filter press by a sludge feeding pump for filter pressing dehydration, the water content of the original sludge is reduced to below 75% from above 95%, sludge is dehydrated to form a mud cake, and the chemical sludge is filter-pressed and then conveyed to a power plant ash field for landfill treatment.
S5, desalination fresh water and desalination tail water recovery treatment
The desalted fresh water obtained in the step S2 is mainly used for meeting the underground production water of a mine, and the surplus part of the desalted fresh water is supplied to a power plant to meet the production water and the non-drinking domestic water of the power plant.
The desalted tail water obtained in the step S2 is only used for yellow mud grouting, gangue dump dust prevention and fire prevention of a mine industrial site.
S6 coal slime and chemical sludge recovery treatment
And (S1) carrying out filter pressing on the coal slime generated by the pre-settling regulating pond, and then sending the coal slime to a power plant to be used as power generation fuel.
The dewatered sludge generated in the step S4 can be pressed into a mud cake at the early stage and transported to a power plant ash yard for landfill treatment, and sodium chloride, sodium nitrate and sodium hydroxide can be obtained by evaporation and crystallization at the later stage for sale.
Further, in step S1, the specific processing steps of each apparatus are as follows:
and S1-1, lifting the mine water in the pre-settling regulating tank to an inclined tube sedimentation tank by a lifting pump, and pumping the precipitated coal slurry to a coal slurry concentration tank.
S1-2, mixing the mine water mixed with the flocculating agent at a flocculation section at the front end of the inclined tube sedimentation tank, and automatically flowing into a high-density sedimentation tank by gravity after sedimentation; the precipitated coal slime in the inclined tube sedimentation tank automatically flows into a sludge tank by gravity and finally enters a sludge concentration tank.
S1-3, because the mine drainage hardness is high, in order to reduce the influence of subsequent membrane blocking and prolong the service life of the membrane element, the mine water needs to be subjected to pH adjustment, softening and sedimentation. The softening function is realized by arranging a high-density sedimentation tank. Adding sodium hydroxide into the mine water entering the high-density sedimentation tank to adjust the pH value of the mine drainage to 10-12, and simultaneously adding sodium carbonate and Ca in the water body into the water2+Respectively converted into CaCO3And Mg (OH)2And the insoluble substances are precipitated and removed in the water body, and finally hardness removal of the mine water is realized. In order to improve the utilization rate of the flocculating agent, part of the precipitated sludge in the high-density sedimentation tank flows back to the front end flocculation section, the concentration of suspended matters in water is improved, and the other part of the precipitated sludge is discharged to a subsequent sludge dewatering unit.
And S1-4, the valveless filter tank can perform automatic back flushing after running for a period of time, flushing water automatically flows into the water collecting tank and is lifted to a pre-settling regulating tank by a transfer pump arranged in the water collecting tank for retreatment.
Furthermore, the aperture of a filter screen of the ultrafiltration device is 0.02 mu m, the water yield of the ultrafiltration device is 3 multiplied by 150t/h, the water recovery rate is more than or equal to 90 percent (10 ℃), and the removal rate of the colloidal silica is more than or equal to 80 percent (10 ℃); the water quality characteristics of the produced water of the ultrafiltration device are as follows: SDI is 1-2, and turbidity is 0.5 FTU.
Furthermore, the water yield of the reverse osmosis device is 4 multiplied by 100t/h, and the water recovery rate is more than or equal to 75 percent (10 ℃); the water quality characteristics of the produced water of the reverse osmosis device are as follows: the turbidity is 0.2-0.5 FTU, the SS is 8-10 mg/L, the calcium hardness is 200-250 mg/L, and the alkalinity is 180-200 mg/L.
Furthermore, the recovery rate of desalted fresh water of the advanced treatment unit is controlled to be 74-76%, and the discharge capacity of desalted tail water is controlled to be 24-26%.
Further, the SED concentration system in step S3 includes MVA, which is a porous charged monovalent selective anion exchange membrane, and the preparation method thereof is as follows:
s3-1, preparing a supporting base film
The common monovalent selective anion exchange membrane is composed of an outermost functional layer and an internal supporting base membrane with a compact structure. If the internal dense base membrane is replaced by a porous structure, the monovalent selective anion exchange membrane is structurally matched with the ultrafiltration membrane. The ultrafiltration membrane adopted by the invention is a high-strength PVDF hollow fiber ultrafiltration membrane, and the preparation method is disclosed in 'review on high-strength PVDF hollow fiber ultrafiltration membrane' of 2013, and the specific preparation method is as follows:
s3-1, adopting a non-solvent induced phase separation method, and synchronously adding high-strength PVDF rib lines into the three-hole PVDF hollow fiber membrane when spinning the three-hole PVDF hollow fiber membrane to obtain the support base membrane.
S3-1-2, soaking the support base film prepared in the step S3-1-1 in distilled water for 24 hours, taking out, cleaning, drying and filling into a reactor.
S3-2, modification of charge
In order to charge the surface of the ultrafiltration membrane negatively, the invention finds a mussel-like dopamine substance disclosed by the literature, which can form a stable compact and negatively-charged adhesion layer on the surface of a plurality of substances under certain conditions and is widely applied to the surface modification of the ionic membrane. Therefore, the bionic dopamine material is an ideal material for adjusting the surface compactness and the charge property of the porous membrane, and the specific operation method is as follows:
firstly, 100mL of dopamine aqueous solution with the pH value of 8.5 is added into a reactor of the step S3-1-2, then the supported basement membrane is soaked and modified for 24 hours under the condition of stirring at room temperature, and finally the charged modified basement membrane is obtained through taking out, cleaning and drying.
S3-3, modification of outer surface layer
In order to improve the compactness and the charge property of the surface of the charge modified base film, TMC is used for crosslinking with the charge modified base film, and the specific operation method is as follows:
firstly, soaking the charge modified base film prepared in the step S3-2 into a n-hexane solution of trimesoyl chloride with the mass fraction of 0.5%, reacting for 10min, then washing with the n-hexane solution, and heating at 60 ℃ for 15min to obtain the TMC modified base film.
S3-4, modification of inner surface layer
In order to further improve the stability of the TMC modified base membrane, a small-molecule photocrosslinking agent DAS is permeated into the membrane surface layer by utilizing a membrane surface layer post-permeation method, a crosslinking reaction is generated between base materials by ultraviolet irradiation, and a modifier is crosslinked with the membrane surface through a covalent bond, so that the stability of the modified layer is improved, and the specific operation method comprises the following steps:
firstly, preparing 150mL of DAS aqueous solution with the concentration of 5mg/mL, and adjusting the pH value to 3.8 by using dilute hydrochloric acid; then soaking the TMC modified base membrane prepared in the step S3-3 in 100mL of prepared DAS solution for 1-10 min; then taking out, and crosslinking for 35min in an ultraviolet crosslinking instrument under the condition that lambda is 365 nm; and finally, soaking the prepared TMC-DAS modified membrane in pure water for storage.
Compared with the prior mine water salt concentration process, the invention has the beneficial effects that:
(1) the invention carries out advanced treatment on the mine influent wastewater, and simultaneously adds an SED concentration system to further treat the desalted tail water, thereby reducing the amount of discharged water, separating salt from COD, and realizing zero discharge of the mine influent water.
(2) The SED concentration system used by the invention is provided with the non-ion exchange membrane with the porous structure inside and the compact functional layer on the surface, has excellent mechanical stability on the premise of meeting the requirement of unit price selection, can be well adapted to the severe working environment of mine water inlet concentration, and improves the operation stability of the SED concentration system.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a highlighted view of the preprocessing unit of the present invention;
FIG. 3 is a highlighted view of the deep processing unit of the present invention;
FIG. 4 is a schematic view of a desalted tail water treatment unit according to the present invention.
Detailed Description
To further illustrate the manner in which the present invention is made and the effects achieved, the following description of the present invention will be made in detail and completely with reference to the accompanying drawings.
Example one
The main content of the first embodiment is to explain the process of concentrating salt by mineral influent water added with an SED high-efficiency concentration system, and the specific content is as follows:
s1, performing precipitation and flocculation pretreatment by using pretreatment unit
Firstly, mine water is discharged into a pre-settling regulating reservoir to balance the water quality and the water quantity; then pumping the mine water which is subjected to the pre-sedimentation treatment and added with a flocculating agent PAC into an inclined tube sedimentation tank; then discharging the deposited water into a valveless filter through a high-density sedimentation tank; and the effluent of the valveless filter tank automatically flows into the intermediate water tank.
S2 ultra-filtration and reverse osmosis advanced treatment by using advanced treatment unit
Firstly, pumping the water storage of the middle water tank in the step S1 into an ultrafiltration device; then storing the effluent of the ultrafiltration device in an ultrafiltration filter tank; and finally, lifting the stored water in the ultrafiltration water tank into a reverse osmosis device by a reverse osmosis water supply pump, treating the stored water by the reverse osmosis device, enabling part of the stored water to become desalted fresh water to enter a cleaning tank, and enabling the rest stored water to become desalted tail water to be discharged to a concentrated water tank.
S3 concentration of desalted tail water using desalted tail water treatment unit
And (4) concentrating, desalting, refining and purifying the desalted tail water in the concentrated water tank in the step S2 by using an SED concentration system, refluxing the obtained fresh water to a pre-settling regulating tank, and discharging the obtained concentrated water to a comprehensive reuse water tank.
S4 sludge dewatering treatment by sludge dewatering unit
Firstly, pumping the sludge in the pre-settling regulating tank in the step S1 into a sludge concentrator for concentration, and pumping the sludge in the inclined tube settling tank into the sludge concentrator for concentration after the sludge is collected by the sludge tank; and then, performing gravity concentration on all the sludge in a sludge concentration tank, pumping the sludge into a plate and frame filter press for filter pressing dehydration, and reducing the water content to be less than 75%.
S5, desalination fresh water and desalination tail water recovery treatment
The desalted fresh water obtained in the step S2 is mainly used for meeting the underground production water of a mine, and the surplus part of the desalted fresh water is supplied to a power plant to meet the production water and the non-drinking domestic water of the power plant.
The desalted tail water obtained in the step S2 is only used for yellow mud grouting, gangue dump dust prevention and fire prevention of a mine industrial site.
S6 coal slime and chemical sludge recovery treatment
And (S1) carrying out filter pressing on the coal slime generated by the pre-settling regulating pond, and then sending the coal slime to a power plant to be used as power generation fuel.
The dewatered sludge generated in the step S4 can be pressed into a mud cake at the early stage and transported to a power plant ash yard for landfill treatment, and sodium chloride, sodium nitrate and sodium hydroxide can be obtained by evaporation and crystallization at the later stage for sale.
Specifically, in step S1, the specific processing steps of each device are as follows:
s1-1, lifting the mine water in the pre-settling regulating tank to an inclined tube sedimentation tank by a lifting pump, and pumping the precipitated coal slurry to a coal slurry concentration tank;
s1-2, mixing the mine water mixed with the flocculating agent at a flocculation section at the front end of the inclined tube sedimentation tank, and automatically flowing into a high-density sedimentation tank by gravity after sedimentation; the precipitated coal slime in the inclined tube sedimentation tank automatically flows into a sludge tank by gravity and finally enters a sludge concentration tank;
s1-3, adding sodium hydroxide into the mine water of the high-density sedimentation tank to adjust the pH value to 11, and simultaneously adding sodium carbonate into the mine water to remove hardness of the mine water; one part of the precipitated sludge in the high-density sedimentation tank flows back to the front flocculation section, so that the concentration of suspended matters in the mine water is improved, and the other part of the precipitated sludge is discharged to a subsequent sludge dewatering unit;
and S1-4, the valveless filter tank can perform automatic back flushing after running for a period of time, flushing water automatically flows into the water collecting tank and is lifted to a pre-settling regulating tank by a transfer pump arranged in the water collecting tank for retreatment.
Specifically, the aperture of a filter screen of the ultrafiltration device is 0.02 mu m, the water yield of the ultrafiltration device is 3 multiplied by 150t/h, the water recovery rate is more than or equal to 90 percent (10 ℃), and the removal rate of colloidal silica is more than or equal to 80 percent (10 ℃); the water quality characteristics of the produced water of the ultrafiltration device are as follows: SDI was 2 and turbidity was 0.5 FTU.
Specifically, the water yield of the reverse osmosis device is 4 multiplied by 100t/h, and the water recovery rate is more than or equal to 75 percent (10 ℃); the water quality characteristics of the produced water of the reverse osmosis device are as follows: turbidity was 0.5FTU, SS was 10mg/L calcium hardness was 250mg/L, alkalinity was 200 mg/L.
Specifically, the desalination fresh water recovery rate of the advanced treatment unit is controlled to be 75%, and the desalination tail water discharge capacity is controlled to be 25%.
Example two
The second embodiment is different from the first embodiment in that: in the second embodiment, the SED high efficiency concentration system uses the porous charged monovalent selective anion exchange Membrane (MVA) prepared by the present invention, and the specific contents are as follows:
s1, performing precipitation and flocculation pretreatment by using pretreatment unit
Firstly, mine water is discharged into a pre-settling regulating reservoir to balance the water quality and the water quantity; then pumping the mine water which is subjected to the pre-sedimentation treatment and added with a flocculating agent PAC into an inclined tube sedimentation tank; then discharging the deposited water into a valveless filter through a high-density sedimentation tank; and the effluent of the valveless filter tank automatically flows into the intermediate water tank.
S2 ultra-filtration and reverse osmosis advanced treatment by using advanced treatment unit
Firstly, pumping the water storage of the middle water tank in the step S1 into an ultrafiltration device; then storing the effluent of the ultrafiltration device in an ultrafiltration filter tank; and finally, lifting the stored water in the ultrafiltration water tank into a reverse osmosis device by a reverse osmosis water supply pump, treating the stored water by the reverse osmosis device, enabling part of the stored water to become desalted fresh water to enter a cleaning tank, and enabling the rest stored water to become desalted tail water to be discharged to a concentrated water tank.
S3 concentration of desalted tail water using desalted tail water treatment unit
And (4) concentrating, desalting, refining and purifying the desalted tail water in the concentrated water tank in the step S2 by using an SED concentration system, refluxing the obtained fresh water to a pre-settling regulating tank, and discharging the obtained concentrated water to a comprehensive reuse water tank.
S4 sludge dewatering treatment by sludge dewatering unit
Firstly, pumping the sludge in the pre-settling regulating tank in the step S1 into a sludge concentrator for concentration, and pumping the sludge in the inclined tube settling tank into the sludge concentrator for concentration after the sludge is collected by the sludge tank; and then, performing gravity concentration on all the sludge in a sludge concentration tank, pumping the sludge into a plate and frame filter press for filter pressing dehydration, and reducing the water content to be less than 75%.
S5, desalination fresh water and desalination tail water recovery treatment
The desalted fresh water obtained in the step S2 is mainly used for meeting the underground production water of a mine, and the surplus part of the desalted fresh water is supplied to a power plant to meet the production water and the non-drinking domestic water of the power plant.
The desalted tail water obtained in the step S2 is only used for yellow mud grouting, gangue dump dust prevention and fire prevention of a mine industrial site.
S6 coal slime and chemical sludge recovery treatment
And (S1) carrying out filter pressing on the coal slime generated by the pre-settling regulating pond, and then sending the coal slime to a power plant to be used as power generation fuel.
The dewatered sludge generated in the step S4 can be pressed into a mud cake at the early stage and transported to a power plant ash yard for landfill treatment, and sodium chloride, sodium nitrate and sodium hydroxide can be obtained by evaporation and crystallization at the later stage for sale.
Specifically, in step S1, the specific processing steps of each device are as follows:
s1-1, pumping the precipitated coal slime in the pre-precipitation adjusting tank to a coal slime concentration tank; the settled coal slurry in the flocculation inclined tube sedimentation tank automatically flows into a sludge tank by gravity and finally enters a sludge concentration tank.
And S1-2, the valveless filter tank can perform automatic back flushing after running for a period of time, flushing water automatically flows into the water collecting tank and is lifted to a pre-settling regulating tank by a transfer pump arranged in the water collecting tank for retreatment.
And S1-3, adding sodium hydroxide into the mine water of the high-density sedimentation tank to adjust the pH value to 11, and simultaneously adding sodium carbonate serving as a flocculating agent into the mine water to remove hardness of the mine water.
Specifically, in step S1-3, in order to increase the utilization rate of the sodium carbonate flocculant, a part of the precipitated sludge in the high-density sedimentation tank flows back to the front flocculation stage, the concentration of suspended solids in the mine water is increased, and a part of the precipitated sludge is discharged to the subsequent sludge dewatering unit.
Specifically, the aperture of a filter screen of the ultrafiltration device is 0.02 mu m, the water yield of the ultrafiltration device is 3 multiplied by 150t/h, the water recovery rate is more than or equal to 90 percent (10 ℃), and the removal rate of colloidal silica is more than or equal to 80 percent (10 ℃); the water quality characteristics of the produced water of the ultrafiltration device are as follows: SDI was 2 and turbidity was 0.5 FTU.
Specifically, the water yield of the reverse osmosis device is 4 multiplied by 100t/h, and the water recovery rate is more than or equal to 75 percent (10 ℃); the water quality characteristics of the produced water of the reverse osmosis device are as follows: turbidity was 0.5FTU, SS was 10mg/L calcium hardness was 250mg/L, alkalinity was 200 mg/L.
Specifically, the desalination fresh water recovery rate of the advanced treatment unit is controlled to be 75%, and the desalination tail water discharge capacity is controlled to be 25%.
Specifically, the SED concentration system in step S3 includes MVA, which is a porous charged monovalent selective anion exchange membrane, and the preparation method thereof is as follows:
s3-1, preparing a supporting base film
S3-1, adopting a non-solvent induced phase separation method, and synchronously adding high-strength PVDF rib lines into the three-hole PVDF hollow fiber membrane when spinning the three-hole PVDF hollow fiber membrane to obtain the support base membrane.
S3-1-2, soaking the support base film prepared in the step S3-1-1 in distilled water for 24 hours, taking out, cleaning, drying and filling into a reactor.
S3-2, modification of charge
Firstly, 100mL of dopamine aqueous solution with the pH value of 8.5 is added into a reactor of the step S3-1-2, then the supported basement membrane is soaked and modified for 24 hours under the condition of stirring at room temperature, and finally the charged modified basement membrane is obtained through taking out, cleaning and drying.
S3-3, modification of outer surface layer
Firstly, soaking the charge modified base film prepared in the step S3-2 into a n-hexane solution of trimesoyl chloride with the mass fraction of 0.5%, reacting for 10min, then washing with the n-hexane solution, and heating at 60 ℃ for 15min to obtain the TMC modified base film.
S3-4, modification of inner surface layer
Firstly, preparing 150mL of DAS aqueous solution with the concentration of 5mg/mL, and adjusting the pH value to 3.8 by using dilute hydrochloric acid; then soaking the TMC modified base film prepared in the step S3-3 in 100mL of prepared DAS solution for 10 min; then taking out, and crosslinking for 35min in an ultraviolet crosslinking instrument under the condition that lambda is 365 nm; and finally, soaking the prepared TMC-DAS modified membrane in pure water for storage.
Application example
The application example is described based on the second process of the embodiment, and aims to clarify relevant measures taken to ensure stable operation of the system in the actual operation process:
1. the stability of the technological process is as follows:
(1) can cause impact on a materialized pretreatment system, mainly is valve-free filter chamber backwashing water, and the solution method when the waste water is discharged into a pretreatment facility and has the impact problem is as follows:
the valveless filter is emptied in time, backwashing discharge water of the valveless filter is staggered from peak time as much as possible, and in addition, the water outlet effect can be ensured by increasing the dosage; the water collecting tank can hold water for 24 hours, and can effectively ensure that the process is stable and the sewage is not discharged outside under the conditions of accidental discharge, water quality deterioration and main equipment maintenance.
(2) Other means for ensuring stability
The sludge discharge amount of the flocculation inclined tube sedimentation tank is properly increased; acid adding and pH adjusting facilities are arranged in the intermediate water tank, the ultrafiltration water producing tank and the RO water producing tank; the sludge discharge amount of the flocculation inclined tube sedimentation tank is properly increased; the key factors influencing the process are provided with necessary on-line monitoring instruments, and adverse factors are monitored in real time.
The impact resistance of the system is fully considered in process design, such as: the equalizing basin sets up mixing apparatus, and units such as abundant homogeneity, high density sedimentation tank set up the backward flow, increase the impact of quality of water, set up the accident catch basin, avoid the impact to the system under the accident condition.
2. The running stability of the equipment is as follows:
important equipment is set for standby, so that production is prevented from being influenced by sudden conditions; the equipment selection is realized by adopting a famous reliable brand at home and abroad; the daily maintenance and the maintenance of the equipment are enhanced.
3. Stability of the human operation:
before the device is put into production, the operator is trained on duty, and meanwhile, technical files such as emergency plans and operating rules are provided for an owner, so that the operator can control the device.
4. Assurance of operational flexibility
The type of the pump is selected according to the design scale, the pump is properly amplified during the type selection, the main equipment is provided with a standby pump, and meanwhile, the pump equipment can be adjusted between 30 percent and 110 percent according to the water volume of the incoming water;
the equipment is selected according to the design scale, the selection is carried out according to 110% of the design water quantity during the selection, and the equipment can stably run in the rated flow.
The flexibility of the process operation is ensured: the design fully considers the impact of the quality and quantity of the incoming water, and the process is provided with an accident quality and regulating tank which can fully regulate the quantity and quality of the incoming water. Meanwhile, each process section is additionally provided with large-flow backflow, so that instantaneous water quantity and water quality changes can be offset.
5. System reliability assurance
Important equipment all sets up two or more than two, when one of them breaks down, through DCS system automatic switch-over, guarantees the system and moves continuously. The other can be operated, and the capacity of the equipment is selected according to 110% of the designed water quantity, so that the yield can be improved when an accident occurs.
The ultrafiltration unit and the reverse osmosis unit produce water and are respectively provided with an online monitoring instrument and an unqualified water discharge pipeline, the online instruments are interlocked with the unqualified water discharge valve, once the quality of the produced water exceeds the standard, the discharge valve is opened immediately to close the water production valve, and the stable water quality of the water production tank is ensured to reach the standard.
And part of pumps are cold-standby in a storehouse and can be rapidly replaced when a fault occurs.
The ultrafiltration and reverse osmosis membrane component is cold-prepared in a warehouse and can be rapidly replaced when a fault occurs.
Experimental example 1
The experimental examples are described based on the processes in the first example, and are intended to illustrate the effects of the present invention.
In the experimental example, the processing object is the well water of the No. five well in the West area of the great south lake of Xu mine group Hami energy Co., Ltd, and the design processing scale is 10800m3And d. The specific design water intake index is shown in table 1. (Unit: mg/L)
TABLE 1 water intaking index of No. five well
| Item | TDS | pH | SS | Hardness of calcium |
| Mine water | ≤16252 | 7.22 | ≤600 | ≤4253 |
| Item | Ca2+ | Mg2+ | HCO3- | CODmn |
| Mine water | ≤1002 | ≤425.2 | ≤170.9 | ≤6.4 |
The specific design of the water quality index of the reuse water is as follows:
TDS: less than or equal to 1000 mg/L; pH: 6-9; and SS: less than or equal to 10 mg/L; calcium hardness: less than or equal to 250 mg/L; alkalinity: less than or equal to 200 mg/L.
The pollutant removal efficiency of the pretreatment unit and the advanced treatment unit is shown in table 2. (Unit: mg/L)
TABLE 2 pretreatment Unit and advanced treatment Unit contaminant removal efficiency
The pollutant removal efficiency of the desalted tail water treatment unit is shown in Table 3. (Unit: mg/L)
TABLE 3 contaminant removal efficiency of desalted tail water treatment unit
In conjunction with the data in tables 1 and 2, and the overall operating conditions of the treatment system, the following conclusions can be drawn:
1. the water quality removing effect of the ultrafiltration system is as follows:
the water yield of the ultrafiltration device is as follows: 3 × 150 t/h; the water recovery rate of the ultrafiltration device is more than or equal to 90 percent (10 ℃); the removal rate of the colloidal silica of the ultrafiltration device is more than or equal to 80 percent (10 ℃);
the water quality characteristics of the produced water of the ultrafiltration system are as follows: SDI is less than or equal to 2; turbidity: 0.5 FTU.
2. The water quality removing effect of the reverse osmosis system is as follows:
the water yield of the reverse osmosis device is as follows: 4 multiplied by 100 t/h; the recovery rate of the reverse osmosis system is more than or equal to 75 percent (10 ℃);
the salt rejection rate of the system: greater than or equal to 98% in one year, greater than or equal to 97% in three years, and greater than or equal to 96% in five years.
The water quality characteristics of the reverse osmosis system: turbidity <0.5 FTU; and SS: less than or equal to 10 mg/L; calcium hardness: less than or equal to 250 mg/L; alkalinity: less than or equal to 200 mg/L.
Experimental example two
The second experimental example is described based on the process in the second example, and is intended to illustrate the performance comparison between the MVA designed by the present invention and the existing commercial MVA, and the effect on the treatment effect of desalted tail water.
The commercial monovalent anion exchange Membranes (MVA) used in this experimental example were purchased from Astom, Japan, and the data for comparison with the MVA prepared according to the present invention are shown in Table 4.
TABLE 4 Main characteristics of monovalent anion exchange Membranes (MVA)
From the data in table 4, it is first noted that: the resistance of the MVA prepared by the invention is far higher than that of the traditional ion exchange membrane, because the MVA prepared by the invention is not an ion exchange membrane per se, but a porous ultrafiltration membrane is used as a support and is provided with a membrane with a compact functional layer, and therefore, an ion exchange group which is the same as that of the ion membrane is not arranged in the membrane structure. Thus, the membranes prepared according to the present invention will have a relatively high electrical resistance compared to conventional ion exchange membranes.
Secondly, it can be seen that the rupture strength of the MVA prepared by the present invention is much higher than that of the conventional ion exchange membrane because the modified membrane has an electrically wrinkled surface due to the crosslinking reaction, and the skin layer and the bottom of the surface have a finger-shaped porous support, so that the modified layer has good adhesion to the base membrane. Thus, the films prepared according to the present invention exhibit excellent mechanical stability.
To determine the monovalent selectivity of the MVA prepared according to the invention, the experimental examples were evaluated using an electrodialytically mixed sodium chloride and sodium sulfate solution system
From the results, the non-ion exchange membrane with the dense inner porous surface prepared by the invention can be used for unit price selection, and the dense and high-charge surface layer has synergistic effect with electrostatic repulsion and pore size sieving, so that the MVA prepared by the invention has good unit price selectivity.
Based on the MVA prepared by the invention, the SED concentration system has the following main performance indexes in actual operation:
and (3) TDS (total dissolved solids): not less than 20 x 105mg/L; water amount of concentrated solution: less than or equal to 45m3H; the TDS of the final product is more than 1.6 multiplied by 105mg/L。
Claims (6)
1. The near-zero emission process of the high-salt high-hardness mine water is characterized by comprising the following steps of:
s1, precipitation and flocculation pretreatment
Firstly, mine water is discharged into a pre-settling regulating reservoir to balance the water quality and the water quantity; then pumping the mine water which is subjected to the pre-sedimentation treatment and added with a flocculating agent PAC into an inclined tube sedimentation tank; then discharging the deposited water into a valveless filter through a high-density sedimentation tank; the effluent of the valveless filter tank automatically flows into an intermediate water tank finally;
s2, ultra-filtration and reverse osmosis advanced treatment
Firstly, pumping the water storage of the middle water tank in the step S1 into an ultrafiltration device; then storing the effluent of the ultrafiltration device in an ultrafiltration filter tank; finally, the stored water in the ultrafiltration water tank is lifted into a reverse osmosis device by a reverse osmosis water supply pump, after being treated by the reverse osmosis device, part of the stored water becomes desalted fresh water and enters a cleaning tank, and the rest of the stored water becomes desalted tail water and is discharged to a concentrated water tank;
s3 concentration treatment of desalted tail water
Concentrating, desalting, refining and purifying the desalted tail water in the concentrated water tank in the step S2 by using an SED concentration system, refluxing the obtained fresh water to a pre-settling regulating tank, and discharging the obtained concentrated water to a comprehensive reuse water tank;
s4 sludge dewatering treatment
Firstly, pumping the sludge in the pre-settling regulating tank in the step S1 into a sludge concentrator for concentration, and pumping the sludge in the inclined tube settling tank into the sludge concentrator for concentration after the sludge is collected by the sludge tank; then, performing gravity concentration on all the sludge in a sludge concentration tank, pumping the sludge into a plate-and-frame filter press for filter pressing dehydration, and reducing the water content to be below 75%;
s5, desalination fresh water and desalination tail water recovery treatment
The desalted fresh water obtained in the step S2 is mainly used for meeting the underground production water of a mine, and the surplus part of the desalted fresh water is supplied to a power plant to meet the production water and the non-drinking domestic water of the power plant;
the desalted tail water obtained in the step S2 is only used for yellow mud grouting, gangue dump dust prevention and fire prevention of a mine industrial site;
s6 coal slime and chemical sludge recovery treatment
The coal slime generated by the pre-precipitation regulating tank in the step S1 is subjected to filter pressing and then is sent to a power plant to be used as power generation fuel;
the dewatered sludge generated in the step S4 can be pressed into a mud cake at the early stage and transported to a power plant ash yard for landfill treatment, and sodium chloride, sodium nitrate and sodium hydroxide can be obtained by evaporation and crystallization at the later stage for sale.
2. The near-zero emission process of the high-salt and high-hardness mine water as claimed in claim 1, wherein in the step S1, the specific treatment steps of each device are as follows:
s1-1, lifting the mine water in the pre-settling regulating tank to an inclined tube sedimentation tank by a lifting pump, and pumping the precipitated coal slurry to a coal slurry concentration tank;
s1-2, mixing the mine water mixed with the flocculating agent at a flocculation section at the front end of the inclined tube sedimentation tank, and automatically flowing into a high-density sedimentation tank by gravity after sedimentation; the precipitated coal slime in the inclined tube sedimentation tank automatically flows into a sludge tank by gravity and finally enters a sludge concentration tank;
s1-3, adding sodium hydroxide into the mine water of the high-density sedimentation tank to adjust the pH value to 10-12, and adding sodium carbonate into the mine water to remove hardness of the mine water; one part of the precipitated sludge in the high-density sedimentation tank flows back to the front flocculation section, so that the concentration of suspended matters in the mine water is improved, and the other part of the precipitated sludge is discharged to a subsequent sludge dewatering unit;
and S1-4, the valveless filter tank can perform automatic back flushing after running for a period of time, flushing water automatically flows into the water collecting tank and is lifted to a pre-settling regulating tank by a transfer pump arranged in the water collecting tank for retreatment.
3. The near-zero emission process of the high-salt high-hardness mine water as claimed in claim 1, wherein the aperture of a filter screen of the ultrafiltration device is 0.02 μm, and the water yield of the ultrafiltration device is 3 x 150 t/h; under the condition of 10 ℃, the water recovery rate is more than or equal to 90 percent, and the removal rate of the colloidal silica is more than or equal to 80 percent; the water quality characteristics of the produced water of the ultrafiltration device are as follows: SDI is 1-2, and turbidity is 0.5 FTU.
4. The near-zero emission process of the high-salt high-hardness mine water as claimed in claim 1, wherein the water yield of the reverse osmosis device is 4 x 100 t/h; under the condition of 10 ℃, the water recovery rate is more than or equal to 75 percent; the water quality characteristics of the produced water of the reverse osmosis device are as follows: the turbidity is 0.2-0.5 FTU, the SS is 8-10 mg/L, the calcium hardness is 200-250 mg/L, and the alkalinity is 180-200 mg/L.
5. The near-zero emission process of the high-salinity high-hardness mine water as claimed in claim 1, wherein the desalination fresh water recovery rate of the advanced treatment unit is controlled to be 74-76%, and the desalination tail water discharge rate is controlled to be 24-26%.
6. The near-zero emission process of the high-salinity high-hardness mine water as claimed in claim 1, wherein the SED concentration system in step S3 comprises MVA, the MVA is a porous charged monovalent selective anion exchange membrane, and the preparation method thereof is as follows:
s3-1, preparing a supporting base film
S3-1-1, synchronously adding high-strength PVDF (polyvinylidene fluoride) rib yarns into the three-hole PVDF hollow fiber membrane to obtain a support base membrane by adopting a non-solvent induced phase separation method when the three-hole PVDF hollow fiber membrane is spun;
s3-1-2, soaking the support base film prepared in the step S3-1-1 in distilled water for 24 hours, taking out, cleaning, drying and loading into a reactor;
s3-2, modification of charge
Firstly, 100mL of dopamine aqueous solution with the pH value of 8.5 is added into a reactor in the step S3-1-2, then a supporting basement membrane is soaked and modified for 24 hours under the condition of stirring at room temperature, and finally the supporting basement membrane is taken out, cleaned and dried to obtain a charged modified basement membrane;
s3-3, modification of outer surface layer
Firstly, soaking the charged modified base membrane prepared in the step S3-1 into a n-hexane solution of trimesoyl chloride with the mass fraction of 0.5%, reacting for 10min, then washing with the n-hexane solution, and heating at 60 ℃ for 15min to obtain a TMC modified base membrane;
s3-4, modification of inner surface layer
Firstly, preparing 150mL of DAS aqueous solution with the concentration of 5mg/mL, and adjusting the pH value to 3.8 by using dilute hydrochloric acid; then soaking the TMC modified base membrane prepared in the step S3-3 in 100mL of prepared DAS solution for 1-10 min; then taking out, and crosslinking for 35min in an ultraviolet crosslinking instrument under the condition that lambda is 365 nm; and finally, soaking the prepared TMC-DAS modified membrane in pure water for storage.
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