CN112225374A - Nanofiltration preposed low-chloride mine water treatment system and process thereof - Google Patents

Nanofiltration preposed low-chloride mine water treatment system and process thereof Download PDF

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Publication number
CN112225374A
CN112225374A CN202011015782.8A CN202011015782A CN112225374A CN 112225374 A CN112225374 A CN 112225374A CN 202011015782 A CN202011015782 A CN 202011015782A CN 112225374 A CN112225374 A CN 112225374A
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nanofiltration
mine water
sodium sulfate
water
chloride
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李买军
赵婷
赛世杰
党平
余占军
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Inner Mongolia Jiuke Kangrui Environmental Technology Co ltd
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Inner Mongolia Jiuke Kangrui Environmental Technology Co ltd
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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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a nanofiltration preposed low-chloride mine water treatment system and a nanofiltration preposed low-chloride mine water treatment process. The system comprises a pretreatment device, a nanofiltration device, a concentration device and a sodium sulfate crystallization device, wherein the pretreatment device, the nanofiltration device, the concentration device and the sodium sulfate crystallization device are sequentially connected. The process comprises the following steps: the mine water is pretreated by a pretreatment device to remove suspended matters, scaling ions, fluorides and COD in the mine water, the pretreated mine water enters a nanofiltration device for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device is directly recycled or discharged up to standard, nanofiltration concentrated water of the nanofiltration device enters a concentration device for concentration treatment, and the concentrated water of the concentration device enters a sodium sulfate crystallization device for crystallization treatment to produce sodium sulfate. The system of the invention has the advantages of low water consumption, greatly reduced investment and operation cost for mine water treatment and good treatment effect.

Description

Nanofiltration preposed low-chloride mine water treatment system and process thereof
Technical Field
The invention relates to the field of water treatment, in particular to a nanofiltration pre-positioned low-chloride mine water treatment system and a nanofiltration pre-positioned low-chloride mine water treatment process.
Background
The development and utilization of mine water as a water resource in China have been about 40 years old, and the treatment process of mine water containing suspended matters, high-salinity mine water and acidic mine water is basically mature. The process flow of the mine water containing suspended matters is generally as follows: suspended matter mine water → water quantity regulating tank → lift pump → sedimentation tank (or clarification tank) → filtration → disinfection → recycling. The pretreatment process of the high-salinity mine water is the same as that of the conventional mine water, the desalting process is added in the subsequent process, and the desalting process commonly used in China at present is a reverse osmosis technology. In the prior art, the coal mine wastewater treatment usually adopts a pretreatment-membrane separation concentration treatment process, the treated fresh water is recycled, and the strong brine is directly discharged. With the improvement of social development and environmental protection consciousness, the national environmental protection 'thirteen-five' plan clearly requires the promotion of wastewater recycling in key industries such as steel, electric power, chemical industry, coal and the like, and strives to realize zero discharge of wastewater. Realizing zero discharge of waste water becomes the self requirement and external requirement of the development of the chemical industry.
The method for realizing zero emission is an environment-friendly method for dealing with mine water with high mineralization degree, namely: the method comprises the steps of removing scaling ions and the like in wastewater through front-end pretreatment, concentrating mine water by using a reverse osmosis system and a high-pressure reverse osmosis system, completely treating the wastewater by using an evaporative crystallization system, recycling condensed water after treatment, separating salt according to different solubilities of various compounds in water along with temperature, and generally producing sodium chloride, sodium sulfate and miscellaneous salts.
The zero-emission desalination technology generally uses a reverse osmosis system, which is a relatively aggressive technology, and the reverse osmosis system selectively intercepts all salt in wastewater, thereby increasing energy consumption and excessively treating product water, and the like, for example: the mine water is derived from underground water, so that the exceeding of pollutants is not much, and in general, in order to reduce certain pollutants in the mine water, most pollutants in the product water of the zero-discharge system are far lower than recycling and discharge indexes, the mine water is subjected to over-treatment; in addition, the zero-emission technology has high requirements on the water quality entering evaporative crystallization, and can finally enter an evaporative crystallization system only through a series of pretreatment, thereby causing the defects of long process flow, large treatment difficulty, high investment cost and the like.
Disclosure of Invention
Based on the above, a nanofiltration pre-positioned low-chloride mine water treatment system and a nanofiltration pre-positioned low-chloride mine water treatment process are needed to be provided, wherein the amount of water used in the treatment process is small, the investment and operation cost of mine water treatment is greatly reduced, and the treatment effect is good.
A nanofiltration pre-positioned low-chloride mine water treatment system comprises a pretreatment device, a nanofiltration device, a concentration device and a sodium sulfate crystallization device, wherein the pretreatment device, the nanofiltration device, the concentration device and the sodium sulfate crystallization device are sequentially connected.
In one embodiment, the pretreatment device comprises a first-stage pretreatment unit, the first-stage pretreatment unit is connected to the front end of the nanofiltration device, and the first-stage pretreatment unit is used for removing suspended matters, scaling ions and fluoride in mine water.
In one embodiment, the first stage pretreatment unit comprises one or more of a high-density sedimentation tank, a V-shaped filter tank, a D-shaped filter tank, a tubular microfiltration membrane and an ultrafiltration device.
In one embodiment, the pretreatment device comprises a second stage pretreatment unit which is connected in series between the nanofiltration device and the concentration device and is used for removing scaling ions and COD in the nanofiltration concentrated water of the nanofiltration device.
In one embodiment, the second stage pretreatment unit comprises one or more of a high-density sedimentation tank, a filtering device, an ion exchange device and an advanced oxidation device, wherein the high-density sedimentation tank, the filtering device and the ion exchange device are used for removing scaling ions in the nanofiltration concentrated water, and the advanced oxidation device is used for removing COD in the nanofiltration concentrated water.
In one embodiment, the nanofiltration pre-positioned low-chloride mine water treatment system further comprises an adjusting tank, wherein the adjusting tank is connected to the front end of the first-stage pretreatment unit and is used for buffering and adjusting mine water.
In one embodiment, the nanofiltration front-end mode low-chloride mine water treatment system further comprises a mixed salt crystallization device, wherein the mixed salt crystallization device is connected with the sodium sulfate crystallization device and is used for processing the sodium sulfate crystallization mother liquor from the sodium sulfate crystallization device to produce mixed salt;
the miscellaneous salt crystallization device is one or more of a multi-effect evaporation crystallization device, MVR and TVR.
In one embodiment, the nanofiltration device comprises three or more sections of nanofiltration units connected in series.
In one embodiment, the concentration device is one or more of reverse osmosis, a high pressure reverse osmosis system, electrodialysis, an evaporative concentration system, and a DTRO system.
In one embodiment, the sodium sulfate evaporation crystallization device is one or more of a multi-effect evaporation crystallization device, MVR and TVR.
The invention also provides a nanofiltration preposed low-chloride mine water treatment process.
A nanofiltration pre-positioned low-chloride mine water treatment process comprises the following steps:
the mine water is pretreated by a pretreatment device to remove suspended matters, scaling ions and fluoride in the mine water, the pretreated mine water enters a nanofiltration device for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device is directly recycled or discharged up to standard, nanofiltration concentrated water of the nanofiltration device enters a concentration device for concentration treatment, and the concentrated water of the concentration device enters a sodium sulfate crystallization device for crystallization treatment to produce sodium sulfate.
In one embodiment, the method further comprises the following steps:
the mine water is subjected to primary pretreatment through a primary pretreatment unit to remove suspended matters, scaling ions and fluorides in the mine water, the pretreated mine water enters a nanofiltration device for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device is directly recycled or discharged up to the standard, nanofiltration concentrated water of the nanofiltration device enters a secondary pretreatment unit for secondary pretreatment to remove scaling ions, COD (chemical oxygen demand) and fluorides in the nanofiltration concentrated water, and the nanofiltration concentrated water subjected to secondary pretreatment enters a concentration device for concentration treatment.
In one embodiment, the method further comprises the following steps: and (4) allowing the sodium sulfate crystallization mother liquor of the sodium sulfate crystallization device to enter a mixed salt crystallization device for crystallization treatment to produce mixed salt.
In one embodiment, the method further comprises the following steps: the mine water enters the first-stage pretreatment unit after being buffered and regulated by the regulating reservoir.
The nanofiltration pre-positioned low-chloride mine water treatment system has the advantages that the nanofiltration device is pre-positioned, mine water is subjected to primary pretreatment and directly enters the nanofiltration device, nanofiltration produced water is recycled or discharged after reaching standards, nanofiltration concentrated water is subjected to further pretreatment and then enters sodium sulfate to be evaporated and crystallized to produce sodium sulfate, the whole nanofiltration pre-positioned low-chloride mine water treatment system is low in investment cost, low in operation cost, low in technical requirements, short in process flow, small in treatment difficulty and good in treatment effect, and the miscellaneous salt rate is reduced by 8.4% compared with that of the traditional zero-emission project.
Drawings
Fig. 1 is a schematic diagram of a nanofiltration pre-positioned low-chloride mine water treatment system according to an embodiment of the invention.
Description of the reference numerals
10. A nanofiltration pre-positioned low-chloride mine water treatment system; 100. a nanofiltration device; 200. a concentration device; 300. a sodium sulfate crystallization device; 400. a first stage preprocessing unit; 500. a second stage pre-processing unit; 600. a regulating tank; 700. miscellaneous salt crystallization device.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
In the description of the present invention, it should be understood that the terms used in the present invention are used in the description of the present invention, and it should be understood that the directions or positional relationships indicated by the terms "center", "upper", "lower", "bottom", "inner", "outer", etc. in the present invention are based on the directions or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
It should be understood that the terms "first", "second", etc. are used herein to describe various information, but the information should not be limited to these terms, which are only used to distinguish one type of information from another. For example, "first" information may also be referred to as "second" information, and similarly, "second" information may also be referred to as "first" information, without departing from the scope of the present invention.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being fixed or detachable or integrally connected; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening elements, or they may be in communication within two elements, i.e., when an element is referred to as being "secured to" another element, it may be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the invention provides a nanofiltration pre-positioned low chloride mine water treatment system 10.
A nanofiltration pre-positioned low-chloride mine water treatment system 10 comprises a pretreatment device, a nanofiltration device 100, a concentration device 200 and a sodium sulfate crystallization device 300. The pretreatment apparatus, the nanofiltration apparatus 100, the concentration apparatus 200, and the sodium sulfate crystallization apparatus 300 are sequentially connected.
The pretreatment device carries out pretreatment to remove suspended matters, scaling ions, fluoride and COD in the mine water.
The nanofiltration device 100 performs nanofiltration to intercept divalent ions in the mine water. The nanofiltration water produced by the nanofiltration device 100 is directly recycled or discharged after reaching the standard. The nanofiltration concentrated water of the nanofiltration device 100 enters a concentration device 200 for concentration treatment.
The concentrated water of the concentration device 200 enters a sodium sulfate crystallization device 300 for crystallization treatment to produce sodium sulfate crystals. The concentrated produced water of the concentration device 200 can be recycled or discharged after reaching the standard after being mixed with the nanofiltration produced water.
Referring to fig. 1, in one specific example, the preprocessing apparatus includes a first stage preprocessing unit 400. The first stage pretreatment unit 400 is connected to the front end of the nanofiltration device 100, and the first stage pretreatment unit 400 is used for removing suspended matters, scaling ions and fluorides in mine water. Specifically, the first stage pretreatment unit 400 includes one or more of a chemical softening device, a fluorine removal device, and a silicon removal device.
In one specific example, the first stage pretreatment unit 400 includes one or more of a high density sedimentation tank, a V-type filter, a D-type filter, a tubular microfiltration membrane, and an ultrafiltration device. The high-density sedimentation tank is used for reducing calcium ions in mine water to be below 20.0mg/L, and the V-shaped filter tank and the ultrafiltration device are used for reducing the SDI of the mine water to be below 3 and the turbidity to be below 1 NTU.
Referring to fig. 1, in one embodiment, the preprocessing apparatus includes a second stage preprocessing unit 500. The second stage pretreatment unit 500 is connected in series between the nanofiltration device 100 and the concentration device 200, and the second stage pretreatment unit 500 is used for removing scaling ions and COD in the nanofiltration concentrated water of the nanofiltration device 100. Preferably, the second stage pretreatment unit 500 includes one or more of a chemical softening device, a COD removal device, and an ion exchange resin device.
In one specific example, the second stage pretreatment unit 500 includes one or both of a high density settling tank, a filtration device, an ion exchange device, and an advanced oxidation device. The high-density sedimentation tank, the filtering device and the ion exchange device are used for removing scaling ions in the nanofiltration concentrated water, and the advanced oxidation device is used for removing COD in the nanofiltration concentrated water.
Referring to fig. 1, in one embodiment, the nanofiltration pre-positioned low chloride mine water treatment system 10 further comprises a conditioning tank 600. The adjusting tank 600 is connected to the front end of the first-stage pretreatment unit 400, and the adjusting tank 600 is used for buffering and adjusting mine water
Referring to fig. 1, in one embodiment, the nanofiltration pre-positioned low chloride mine water treatment system 10 further comprises a miscellaneous salt crystallization device 700. The mixed salt crystallizing device 700 is connected with the sodium sulfate crystallizing device 300, and the mixed salt crystallizing device 700 is used for processing the sodium sulfate crystallizing mother liquor from the sodium sulfate crystallizing device 300 to produce mixed salt.
In one specific example, the mixed salt crystallization device 700 is one or more of a multi-effect evaporative crystallization device, MVR, and TVR.
In one specific example, nanofiltration device 100 comprises three sections of nanofiltration units connected in series. Specifically, three sections of nanofiltration units connected in series are respectively a first section of nanofiltration unit, a second section of nanofiltration unit and a third section of nanofiltration unit, and one section of nanofiltration concentrated water of the first section of nanofiltration unit is used as second section of nanofiltration inlet water of the second section of nanofiltration unit; the two-section nanofiltration concentrated water of the second-section nanofiltration unit is used as three-section nanofiltration inlet water of the third-section nanofiltration unit, through reasonable membrane flux design, the single-section nanofiltration device 100 is reasonably arranged, so that the recovery rate is maximized, the total recovery rate of the nanofiltration device 100 is finally over 98 percent, the water amount of the nanofiltration concentrated water is greatly reduced, and the investment and the operation cost of mine water treatment are greatly reduced.
In one specific example, the concentration device 200 is one or more of a reverse osmosis, a high pressure reverse osmosis system, an evaporative concentration system, and a DTRO system.
In one specific example, the sodium sulfate evaporative crystallization device is one or more of a multi-effect evaporative crystallization device, MVR and TVR.
According to the nanofiltration front-end low-chloride mine water treatment system 10, the nanofiltration device 100 is arranged in front, mine water is subjected to primary pretreatment and then directly enters the nanofiltration device 100, nanofiltration produced water is recycled or discharged after reaching standards, nanofiltration concentrated water is subjected to further pretreatment and then enters sodium sulfate to be evaporated and crystallized to produce sodium sulfate, the whole nanofiltration front-end low-chloride mine water treatment system 10 is low in investment cost, low in operation cost, low in technical requirements, short in process flow, small in treatment difficulty and good in treatment effect, and the impurity salt rate is reduced by 8.4% compared with that of a traditional zero-emission project.
The embodiment of the invention also provides a nanofiltration preposed low-chloride mine water treatment process.
A nanofiltration pre-positioned low-chloride mine water treatment process comprises the following steps:
referring to fig. 1, mine water is pretreated by a pretreatment device to remove suspended matters, scaling ions, fluorides and COD in the mine water, the pretreated mine water enters a nanofiltration device 100 for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration product water of the nanofiltration device 100 is directly recycled or discharged after reaching standards, nanofiltration concentrated water of the nanofiltration device 100 enters a concentration device 200 for concentration treatment, and concentrated water of the concentration device 200 enters a sodium sulfate crystallization device 300 for crystallization treatment to produce sodium sulfate.
In one specific example, the nanofiltration pre-mode low-chloride mine water treatment process further comprises the following steps:
referring to fig. 1, mine water is subjected to a first pretreatment by a first-stage pretreatment unit 400 to remove suspended matters, scaling ions and fluorides in the mine water, the pretreated mine water enters a nanofiltration device 100 to be subjected to nanofiltration treatment so as to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device 100 is directly recycled or discharged after reaching standards, nanofiltration concentrated water of the nanofiltration device 100 enters a second-stage pretreatment unit 500 to be subjected to a second pretreatment so as to remove scaling ions and COD in the nanofiltration concentrated water, and the nanofiltration concentrated water subjected to the second pretreatment enters a concentration device 200 to be subjected to concentration treatment.
In one specific example, the nanofiltration pre-mode low-chloride mine water treatment process further comprises the following steps: the sodium sulfate crystallization mother liquor of the sodium sulfate crystallization device 300 enters the mixed salt crystallization device 700 for crystallization treatment to produce mixed salt.
In one specific example, the nanofiltration pre-mode low-chloride mine water treatment process further comprises the following steps: the mine water enters the first-stage pretreatment unit 400 after being buffered and regulated by the regulating reservoir 600.
Example 1
The embodiment provides a nanofiltration pre-positioned low-chloride mine water treatment process.
A nanofiltration pre-positioned low-chloride mine water treatment process is used for treating coal mine wastewater.
The coal mine wastewater is detected to have the following water quality conditions: pH: 7.1; ca2+：40.90mg/L；Mg2+：8.95mg/L；Na+：585.52mg/L；K+：3.52mg/L；Cl-：92.11mg/L；SO4 2-：1098.51mg/L；NO3 -：5.98mg/L；F-：1.2mg/L；SiO2：10.24mg/L；TDS：1847.43mg/L。
The treatment process comprises the following steps:
referring to FIG. 1, (1) the waste water from coal mine enters into the adjusting tank 600 for buffering and adjusting treatment, the inflow rate is 1000m3And/h, the retention time of the coal mine wastewater in the regulating reservoir 600 is 4 h.
(2) Coal mine waste water gets into preprocessing device after the equalizing basin 600 is handled, carry out the preliminary treatment through first order preprocessing unit 400 earlier, in this embodiment, first order preprocessing unit 400 includes high density sedimentation tank, V type filtering pond and ultrafiltration device, through throwing sodium hydroxide and sodium carbonate to high density sedimentation tank for the calcium ion in the coal mine waste water falls to below 20.0mg/L, then filter the coal mine waste water through V type filtering pond and ultrafiltration device, make coal mine waste water SDI fall to below 3, the turbidity falls to below 1NTU, in order to ensure follow-up membrane system steady operation, first order preprocessing unit 400 product water quality in this embodiment is as follows: pH: 7.5; ca2+：18.30mg/L；Mg2+：8.95mg/L；Na+：692.34mg/L；K+：3.52mg/L；Cl-：92.11mg/L；SO4 2-：1269.33mg/L；NO3 -：5.98mg/L；F-：1.2mg/L；SiO2：10.24mg/L；COD：23.5mg/L；
(3) The water produced by the first-stage pretreatment unit 400 enters a nanofiltration system, the nanofiltration device 100 in this embodiment is designed according to three stages, the first-stage recovery rate is 80%, the second-stage recovery rate is 75%, the third-stage recovery rate is 66%, and the nanofiltration water quality of the nanofiltration device 100 is as follows in table 1:
table 1 nanofiltration water production quality meter of nanofiltration device 100
Figure BDA0002699018550000081
Figure BDA0002699018550000091
As can be seen from the above table 1, TDS (total dissolved solids) of the nanofiltration produced water is 499.65mg/L, which is superior to the requirement of the quality of the make-up water of the open circulating cooling water system in GB/T19923-1996 municipal wastewater recycling industrial water quality and the requirement of the relevant standard of unit discharge constructed in 1 month 1 after 1998 of GB 499.65-1996 integrated wastewater discharge standard. The three-stage nanofiltration concentrated water is used as the final nanofiltration concentrated water of the nanofiltration device 100, and as can be seen from the above table, due to the negative interception effect of the three-stage nanofiltration system, the chloride ions of the three-stage nanofiltration produced water are higher than those of the three-stage nanofiltration inlet water (the two-stage nanofiltration concentrated water), and the final concentrated water Cl is nanofiltration-/SO4 2-92.82/60701.68, saltpeter ratio (NaCl/Na)2SO4) 1/654.0, the proportion of sodium sulfate in nanofiltration concentrated water is greatly improved, and the amount of wastewater in coal mines is 1000m from the inlet water3The/h is reduced to the present 17m3The treatment scale is greatly reduced. The nanofiltration concentrated water enters a second-stage pretreatment unit 500 to ensure the stable operation of the subsequent concentration device 200 and the sodium sulfate evaporation crystallization device.
(4) The second stage pretreatment unit 500 of the present embodiment comprises an ion exchange device, an advanced oxidation device. The ion exchange device and the advanced oxidation device respectively remove scaling ions (containing calcium ions and magnesium ions) and COD in the nanofiltration concentrated water; after passing through the second stage pretreatment unit 500, the quality of the water produced by the second stage pretreatment unit 500 is as follows: pH: 7.6; ca2+：0.5mg/L；Mg2+：0.2mg/L；Na+：29119.81mg/L；K+：5.33mg/L；Cl-：51.06mg/L；SO4 2-：60701.68mg/L；NO3 -：20.57mg/L；F-：3.46mg/L；SiO2：57.50mg/L；COD：198.39mg/L。
(5) The water produced by the second stage pretreatment unit 500 enters the concentration device 200, in this embodiment, the concentration device 200 is a high pressure reverse osmosis system, in other embodiments, an evaporation concentration system or a DTRO system or other systems with similar functions can be used, in this embodiment, the water produced by the second stage pretreatment unit 500 enters the concentration device 200In the middle, the designed recovery rate of the concentration device 200 is 42%, and the concentration water produced by the concentration device 200 is mixed with the nanofiltration water produced and recycled or discharged after reaching the standard. The concentrated water of the concentration device 200 enters a sodium sulfate evaporation crystallization device, and the quality of the concentrated water of the embodiment is as follows: pH: 7.8 of; ca2+：0.85mg/L；Mg2+：0.34mg/L；Na+：49784.83mg/L；K+：9.11mg/L；Cl-：87.29mg/L；SO4 2-：103778.95mg/L；NO3 -：35.16mg/L；F-：5.91mg/L；SiO2：98.31mg/L；COD：339.17mg/L。
(6) Concentrated water enters a sodium sulfate evaporation crystallization device, the sodium sulfate evaporation crystallization device used in the embodiment is a triple-effect evaporation crystallization device, and other items can also use a single-effect evaporation crystallization device, MVR, TVR or other devices with similar functions. This example yielded sodium sulfate 1.41t/h, purity: 99.26%, water-insoluble matter: 0.01%, calcium and magnesium: 0.11%, chloride: 0.14%, iron: 0.0008%, moisture: 0.17%, whiteness: 88%, TOC: 42mg/kg, reaches the first-class product standard of GB/T6009-2014 industrial anhydrous sodium sulfate class I, and simultaneously meets the first-class product standard of T/CCT 001-2019 coal chemical industry byproduct industrial sodium sulfate class II. The sodium sulfate evaporative crystallization device of this embodiment produces a mother liquor of sodium sulfate crystals of 0.33m3The water quality of the sodium sulfate crystallization mother liquor is as follows: pH: 7.9; ca2+：25.64mg/L；Mg2+：10.26mg/L；Na+：98905.60mg/L；K+：273.33mg/L；Cl-：2618.67mg/L；SO4 2-：202816.90mg/L；NO3 -：1054.80mg/L；F-：177.26mg/L；SiO2：178.32mg/L；COD：10175.20mg/L。
(7) The sodium sulfate crystallization mother liquor enters a mixed salt crystallization device 700, in the embodiment, the mixed salt crystallization device 700 uses a single-effect evaporation crystallization system, and other items can also use a multi-effect evaporation crystallization system, MVR, TVR or other devices with similar functions, so that the mixed salt is finally produced at 0.1 t/h. The whole miscellaneous salt rate of this embodiment is 6.6%, very big reduction the useless treatment cost of danger.
The embodiment finally produces sodium sulfate crystal salt of 1.41t/h and miscellaneous salt of 0.10t/h, and the miscellaneous salt rate is reduced by 8.4 percent compared with the common zero-emission project.
In conclusion, the nanofiltration device 100 is arranged in front of the nanofiltration pre-positioned low-chloride mine water treatment system 10, mine water is subjected to primary pretreatment and then directly enters the nanofiltration device 100, nanofiltration produced water is recycled or discharged after reaching standards, nanofiltration concentrated water is subjected to further pretreatment and then enters sodium sulfate to be evaporated and crystallized to produce sodium sulfate, and the whole nanofiltration pre-positioned low-chloride mine water treatment system 10 is low in investment cost, low in operation cost, low in technical requirement, short in process flow, small in treatment difficulty and good in treatment effect, and the impurity salt rate is greatly reduced compared with that of the traditional zero-discharge project.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (14)

1. The nanofiltration pre-positioned low-chloride mine water treatment system is characterized by comprising a pretreatment device, a nanofiltration device, a concentration device and a sodium sulfate crystallization device, wherein the pretreatment device, the nanofiltration device, the concentration device and the sodium sulfate crystallization device are sequentially connected.
2. The nanofiltration front-end low-chloride mine water treatment system according to claim 1, wherein the pretreatment device comprises a first-stage pretreatment unit, the first-stage pretreatment unit is connected to the front end of the nanofiltration device, and the first-stage pretreatment unit is used for removing suspended matters, scaling ions and fluorides in mine water.
3. The nanofiltration front-end type low-chloride mine water treatment system according to claim 2, wherein the first-stage pretreatment unit comprises one or more of a high-density sedimentation tank, a V-shaped filter tank, a D-shaped filter tank, a tubular microfiltration membrane and an ultrafiltration device.
4. The nanofiltration front-end type low-chloride mine water treatment system according to claim 2, wherein the pretreatment device comprises a second-stage pretreatment unit, the second-stage pretreatment unit is connected in series between the nanofiltration device and the concentration device, and the second-stage pretreatment unit is used for removing scaling ions and COD in the nanofiltration concentrated water of the nanofiltration device.
5. The nanofiltration front-end type low-chloride mine water treatment system according to claim 4, wherein the second-stage pretreatment unit comprises one or more of a high-density sedimentation tank, a filtration device, an ion exchange device and an advanced oxidation device, the high-density sedimentation tank, the filtration device and the ion exchange device are used for removing scaling ions in the nanofiltration concentrated water, and the advanced oxidation device is used for removing COD in the nanofiltration concentrated water.
6. The nanofiltration front-end type low chloride mine water treatment system according to any one of claims 2 to 5, further comprising an adjusting tank, wherein the adjusting tank is connected to the front end of the first-stage pretreatment unit, and the adjusting tank is used for buffering and adjusting mine water.
7. The nanofiltration front-end low chloride mine water treatment system according to any one of claims 1 to 5, further comprising a mixed salt crystallization device connected to the sodium sulfate crystallization device, wherein the mixed salt crystallization device is configured to treat a sodium sulfate crystallization mother liquor from the sodium sulfate crystallization device to produce mixed salt;
the miscellaneous salt crystallization device is one or more of a multi-effect evaporation crystallization device, MVR and TVR.
8. The nanofiltration front-end type low-chloride mine water treatment system according to any one of claims 1 to 5, wherein the nanofiltration device comprises three or more sections of nanofiltration units connected in series.
9. The nanofiltration pre-positioned low chloride mine water treatment system according to any one of claims 1 to 5, wherein the concentration device is one or more of a reverse osmosis system, a high pressure reverse osmosis system, an electrodialysis system, an evaporative concentration system and a DTRO system.
10. The nanofiltration front-end low chloride mine water treatment system according to any one of claims 1 to 5, wherein the sodium sulfate evaporative crystallization device is one or more of a multi-effect evaporative crystallization device, MVR and TVR.
11. A nanofiltration pre-positioned low-chloride mine water treatment process is characterized by comprising the following steps:
the mine water is pretreated by a pretreatment device to remove suspended matters, scaling ions, fluorides and COD in the mine water, the pretreated mine water enters a nanofiltration device for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device is directly recycled or discharged up to standard, nanofiltration concentrated water of the nanofiltration device enters a concentration device for concentration treatment, and the concentrated water of the concentration device enters a sodium sulfate crystallization device for crystallization treatment to produce sodium sulfate.
12. The nanofiltration front-end low-chloride mine water treatment process according to claim 11, further comprising the steps of:
the mine water is subjected to primary pretreatment through a first-stage pretreatment unit to remove suspended matters, scaling ions and fluorides in the mine water, the pretreated mine water enters a nanofiltration device for nanofiltration treatment to intercept divalent ions in the mine water, nanofiltration produced water of the nanofiltration device is directly recycled or discharged up to standard, nanofiltration concentrated water of the nanofiltration device enters a second-stage pretreatment unit for secondary pretreatment to remove scaling ions and COD in the nanofiltration concentrated water, and the nanofiltration concentrated water subjected to secondary pretreatment enters a concentration device for concentration treatment.
13. The nanofiltration front-end low-chloride mine water treatment process according to claim 11, further comprising the steps of: and the sodium sulfate crystallization mother liquor of the sodium sulfate crystallization device enters a mixed salt crystallization device for crystallization treatment to produce mixed salt.
14. The nanofiltration pre-positioned low chloride mine water treatment process according to any one of claims 12 to 13, further comprising the steps of: the mine water enters the first-stage pretreatment unit after being buffered and regulated by the regulating reservoir.
CN202011015782.8A 2020-09-24 2020-09-24 Nanofiltration preposed low-chloride mine water treatment system and process thereof Pending CN112225374A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173671A (en) * 2021-04-28 2021-07-27 四川美富特环境治理有限责任公司 Full-quantitative treatment system and treatment method for mine wastewater

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173671A (en) * 2021-04-28 2021-07-27 四川美富特环境治理有限责任公司 Full-quantitative treatment system and treatment method for mine wastewater

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