CN110451707A - A kind of waste water of mine Zero discharge treatment method - Google Patents

A kind of waste water of mine Zero discharge treatment method Download PDF

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Publication number
CN110451707A
CN110451707A CN201910585591.6A CN201910585591A CN110451707A CN 110451707 A CN110451707 A CN 110451707A CN 201910585591 A CN201910585591 A CN 201910585591A CN 110451707 A CN110451707 A CN 110451707A
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water
concentrated
waste water
precipitating
mine
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沈江南
唐聪
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/08Thin film evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Abstract

The invention discloses a kind of waste water of mine Zero discharge treatment methods, this method is to handle waste water of mine successively preprocessed system, film concentration systems and evaporation and crystallization system, wherein pretreatment system processing includes flocculating setting, quartz sand filtration, active carbon filtering and softening process, to remove the impurity in water quality and reduce waste water hardness;The film concentration systems processing includes reverse osmosis concentration (RO) and electrodialysis concentration (ED);The concentrated water that film concentration systems come out enters evaporation and crystallization system and makees evaporative crystallization processing, and the contamination precipitation in pretreatment is together, and solid waste can be used for construction material preparation after being evaporated, and distilled water can store recycling.Waste water of mine Zero discharge treatment method high treating effect of the invention, required low energy consumption, operating cost is low, can by waste water water and impurity component distinguish reuse, substantially increase resource utilization.

Description

A kind of waste water of mine Zero discharge treatment method
Technical field
The present invention relates to field of waste water treatment more particularly to a kind of waste water of mine Zero discharge treatment methods.
Technical background
It will use a large amount of water resource in process of coal mining, and a large amount of waste water of mine can be generated.The waste water contains High rigidity with high salt, arbitrarily discharge not only results in Heavy environmental pollution, and is also a kind of waste of resource.
Therefore a kind of waste water of mine zero-discharge treatment system is needed, to handle waste water of mine.
Summary of the invention
The object of the present invention is to provide a kind of high treating effects, the waste water of mine zero-emission that required low energy consumption, operating cost is low Put processing method, can by waste water water and impurity component distinguish reuse, substantially increase resource utilization.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of waste water of mine Zero discharge treatment method, the method are that waste water of mine successively preprocessed system, film is dense Compression system and evaporation and crystallization system are handled;
The described pretreatment system processing the following steps are included:
(1) flocculating setting: entering waste water of mine in flocculation sedimentation tank and handled, and obtains precipitating 1 and clear liquid 1, the step Suddenly it is mainly used for removing the runic particulate contaminant in waste water;
(2) valveless filtering pool: the clear liquid 1 for obtaining step (1) is handled into valveless filtering pool, obtains precipitating 2 and clear liquid 2;
(3) quartz sand filtration: the clear liquid 2 for obtaining step (2) is filtered into quartz sand filter, is precipitated 3 and filtrate 3, the purpose of the step is further to remove silt, colloid, metal ion and organic matter;
(4) active carbon filters: the filtrate 3 for obtaining step (3) is handled into active carbon filtering device, is precipitated 4 and filtrate 4;The purpose of the step is further progress decolorization adsorption, removes a small amount of organic matter, heavy metal and virus etc.;
(5) soften: the filtrate 4 for obtaining step (4) enter melded system, the melded system include 2 parts, first Part is that sodium carbonate and sodium hydroxide are sequentially added into filtrate 4, generates precipitation of calcium carbonate and magnesium hydrate precipitate, is obtained by filtration Precipitating 5 and filtrate 5;Second part is that filtrate 5 is made to enter 732 chelating resin advanced treating calcium and magnesiums, obtains precipitating 6 and filtrate 6;Filter Liquid 6 enters water tank, and adjusts pH to 6~8 with sour (such as hydrochloric acid, sulfuric acid etc.), and calcium ions and magnesium ions content is below 0.1ppm at this time;
The described film concentration systems processing the following steps are included:
(a) RO is concentrated: so that the water in water tank is entered RO system and carries out initial concentration, is concentrated into production water power and leads not higher than 1mS/ Cm obtains concentrated water 1 and produces water 1, recycle wherein producing water 1, can be used for equipment backwash and mining process, and concentrated water 1 enters ED system;
(b) ED is concentrated;The concentrated water 1 for obtaining step (a) is further concentrated into electrodialysis system, the electrodialysis The membrane stack method of system folds method using C/A/C/A, and electrodialysis process to concentrated water conductance stops when no longer rising, and obtains 2 He of concentrated water Fresh water 2, wherein fresh water 2 returns to water tank, and concentrated water 2 enters distillation crystal system;
The evaporation and crystallization system includes Distallation systm, is that will precipitate 1, precipitating 2, precipitating 3, precipitating 4, precipitating 5, precipitating 6 Distillation processing is carried out with concentrated water 2, obtain distilled water and is evaporated product, wherein distilled water recycles, and can be used for domestic water or drink With water, being evaporated product can be used for construction material processing.
Preferably, the flocculating setting specifically uses following condition: entering waste water of mine in flocculation sedimentation tank, add Enter flocculant PAC or PAM, flocculant additive amount is 1~3ppm, and the flocculating setting time is 24~36h.
The present invention has no special requirements for quartz sand filter and active carbon filtering device, and those skilled in the art can be with Commercial goods are bought according to actual needs.
In step (5) of the present invention, the additional amount of sodium carbonate and sodium hydroxide can be according to the calcium hardness and magnesium hardness in filtrate 4 It determines, makes sodium carbonate and sodium hydroxide slightly excess.
In step (a) of the present invention, commercial goods are can be used in RO system, as reverse osmosis membrane can be limited by Hangzhou Saite membrane technology Company provides, and operating pressure is controlled in 10~20MPa.Preferably, salinity in the water in water tank is concentrated by RO system 5-7 times.
The electrodialysis system that step (b) of the present invention uses uses two compartment electrodialysis plants, the two compartments electrodialysis dress It sets including DC power supply, the anode plate being connect with the DC power anode, the cathode plate being connect with the DC power cathode And the membrane stack being placed between the anode plate and the cathode plate, the membrane stack by cation-exchange membrane, anion-exchange membrane according to Minor tick arrangement assembles, and outermost film is cation-exchange membrane, is separated between adjacent two films by a partition, Adjacent one group of cation-exchange membrane, anion-exchange membrane, cation-exchange membrane constitute the electricity of two compartment (dense room/light room) Dialysis unit, the electrodialysis cell in the membrane stack are at least one;The anode plate, cathode plate respectively with adjacent sun from Pole fluid chamber is formed between proton exchange;The dense outdoor connects concentrated water tank and is formed into a loop by circulating pump;The light outdoor connects light Water pot is simultaneously formed into a loop by circulating pump;The pole fluid chamber is distinguished external pole flow container and is formed into a loop by circulating pump.
The operation of step (b) of the present invention specifically: concentrated water 1 is added in fresh water tank, pure water is added in concentrated water tank, pole Liquid is added in the flow container of pole, opens circulating pump, make the liquid in fresh water tank, concentrated water tank and pole flow container be constantly passed through corresponding light room, Dense room, anode chamber and cathode chamber are recycled, and are allowed to carry out electrodialysis process under pressure constant state to electrodialysis plant energization, most Concentrated water 2 is obtained in concentrated water tank afterwards, fresh water 2 is obtained in fresh water tank.Preferably, the pole liquid is the sodium sulphate of 3wt.% Solution.
Preferably, making the salinity of concentrated water 1 be concentrated 3-5 times by ED system in step (b).
Preferably, the cation-exchange membrane uses Germany FKB, the anion-exchange membrane uses Germany FAM. As a further preference, electrodialysis process condition setting are as follows: membrane stack is made of 5 groups of electrodialysis cells, the effective film of every film Area is 189cm2, the feed rate of each compartment is consistent and controls in 20-40L/h, controls 5~10V of voltage (preferably 10 V), control reaction temperature is 20 DEG C~40 DEG C.
According to the above aspect of the present invention, the present invention can by waste water water and impurity component distinguish reuse, have at least the following advantages:
1. the method for the present invention not only can solve the problem of contaminated wastewater, but also production water during reverse osmosis concentration can be with Recycling is re-used and is worked in coal mining, in terms of the distilled water in evaporation and crystal process can be also used for domestic water, finally Solid after waste material is dry can be used for the preparation of construction material, substantially increase resource utilization.
2. the method for the present invention high treating effect, required low energy consumption, operating cost is low.
1. softening of the invention is using the method for resins exchange after first precipitating, not only effect is aobvious in terms of deliming content of magnesium It writes, and the 732 chelating resin cost performances used are high, effect is good, renewable.And by by feed liquid softening it is possible to prevente effectively from Due to high rigidity feed liquid bring film scale problems in electrodialytic process.
2. dual concentration is concentrated by RO concentration and ED in the present invention, not only substantially increase compared with prior art dense Contracting efficiency, process flow is short, run and cost of investment is low;
3. the ED technology in present invention concentration, electrodialytic membranes long service life is low to influent quality requirement, but cycles of concentration Height keeps subsequent evaporation device operating load low, not only can effectively avoid dense water side deposition, but also can reduce the energy consumption cost of concentration systems, To reduce total system power consumption, it is total originally low to reduce operation.
Detailed description of the invention
Fig. 1 is a kind of flow chart of waste water of mine zero-discharge treatment system
Fig. 2 is RO system enriching service schematic diagram
Fig. 3 is ED enriching service schematic diagram
Specific embodiment
In order to make operating process of the invention, purpose is clearer, below with reference to specific implementation case to of the invention Particular content more clearly illustrate, it is clear that the case is not all cases of the invention.Based on implementation of the invention Example, technical essential according to the present invention, those of ordinary skill in the art implement under the premise of no creative technology innovation, all It belongs to the scope of protection of the present invention.
The process object of the present embodiment is Jining of Shandong Province waste water of mine, which is reported as follows table:
Embodiment 1
1, enter waste water of mine in flocculating setting system, be that 2ppm (can also be replaced with PAM according to flocculant PAC dosage Generation), the flocculating setting time is 36h, obtains precipitating 1 and clear liquid 1, and precipitating 1 enters Distallation systm.By flocculating setting, remove useless Runic particulate contaminant and suspended matter in water.
2, clear liquid 1 is handled into valveless filtering pool, obtains precipitating 2 and clear liquid 2, and precipitating 2 enters Distallation systm.
3, clear liquid 2 is filtered into quartz sand filter, obtains precipitating 3 and filtrate 3, and precipitating 3 enters Distallation systm. Quartz sand filtration can further remove silt, colloid, metal ion and organic matter.
4, filtrate 3 is handled into active carbon filtering device, obtains precipitating 4 and filtrate 4, and precipitating 4 enters Distallation systm. The purpose further progress decolorization adsorption of active carbon filtering, removes a small amount of organic matter, heavy metal and virus etc..
5, filtrate 4 enters melded system, and melded system includes 2 parts, and first part is to sequentially add carbon into filtrate 4 (additional amount can refer to Jining of Shandong Province waste water of mine water quality detection report, calcium hardness 344.73ppm, magnesium for sour sodium and sodium hydroxide Hardness is 129.79ppm.1L waste water of mine is then often taken, the sodium carbonate of addition is 0.913g, and addition sodium hydroxide is 0.216g.), Precipitation of calcium carbonate and magnesium hydrate precipitate are generated, precipitating 5 and filtrate 5 is obtained by filtration.Second part is that filtrate 5 is made to enter 732 chelas Resin advanced treating calcium and magnesium obtains filtrate 6 and precipitating 6, and filtrate 6 enters water tank, and precipitating 5 and 6 enters Distallation systm.Go out at this time Calcium ions and magnesium ions content is below 0.1ppm in water.
6, after filtrate 6 enters water tank, with 3% salt acid for adjusting pH to 8 or so.
7, after step 6 processing, the water in 10L water tank is taken to enter RO system initial concentration, in concentration process, operation pressure Power is 20bar, and RO film provides for Zhejiang Saite membrane technology Co., Ltd, model RO12110408, and experimental data is as follows:
RO concentration:
As the reaction time carries out, downward trend after first rising is presented in membrane flux.Mainly experiment initial stage is also unstable, produces Water, concentrated water conductance gradually rise.It obtains producing water volume 8.6L, concentrated water volume 1.4L at the end of experiment, produces the water rate of recovery 86%.It is real Test average flux 40.31L/m2H, initial concentrated water conductance 7.46mS/cm, concentrated water conductance 38.6mS/cm, dense at the end of experiment 5.17 times of contracting produces water reuse after experiment, and concentrated water enters ED system.Concentrated water salt content is about 40000mg/L, produces water salt content and is 100mg/L.Moisture film flux is produced by original 40.5 L/m2H is down to 30 L/m2H, there are fouling membrane phenomenons, then with 2% lemon For a period of time, producing moisture film flux can be obtained recovery for lemon pickling.
8, the concentrated water that step 7 obtains enters ED system and is further concentrated, and membrane stack method uses C/A/ in the electrodialysis system C/A folds method, and referring in particular to Fig. 3, membrane stack building is that Zhejiang Saite membrane technology Co., Ltd provides, and wherein film is using German yin-yang Film (FKB, FAM), method of folding be it is male/female, 5 groups, for every film having a size of 11cm*27cm, effective membrane area is 189cm2.In this step In concentration process, most start that the concentrated water that step 7 obtains all is added in concentrated water tank and fresh water tank, liquid volume and concentrated water in fresh water tank The ratio between liquid volume is 6:1 in tank, and the metabisulfite solution of 3wt.% is added in the flow container of pole, and opening circulating pump makes feed liquid start to follow Ring, controlling each compartment flow is 30L/h, and control voltage is 10V, and control reaction temperature is 25 DEG C, electrodialysis process 1h.It is last dense The concentrated water that room tank obtains rises to 110mS/cm compared to the conductance 38.6mS/cm for the concentrated water that step 7 obtains, and is concentrated nearly 4 times.It is light The fresh water that water pot obtains returns to water tank, and concentrated water enters Distallation systm.Concentrated water salt content is 150000mg/L or so.
Waste water of mine calcium and magnesium testing result after items processing is as follows:
In the present embodiment, a kind of waste water of mine zero-discharge treatment system, Distallation systm distillation, distiller are to subtract Press distiller, operating pressure be 0.1~0.3MPa, operating temperature be 180 DEG C, distilled water recycling, can be used for domestic water or Drinking water, being evaporated product can be used for construction material processing.

Claims (6)

1. a kind of waste water of mine Zero discharge treatment method, it is characterised in that: the method is that waste water of mine is successively preprocessed System, film concentration systems and evaporation and crystallization system are handled;
The described pretreatment system processing the following steps are included:
(1) flocculating setting: entering waste water of mine in flocculation sedimentation tank and handled, and obtains precipitating 1 and clear liquid 1;
(2) valveless filtering pool: the clear liquid 1 for obtaining step (1) is handled into valveless filtering pool, obtains precipitating 2 and clear liquid 2;
(3) quartz sand filtration: the clear liquid 2 for obtaining step (2) is filtered into quartz sand filter, obtains 3 Hes of precipitating Filtrate 3;
(4) active carbon filters: the filtrate 3 for obtaining step (3) is handled into active carbon filtering device, obtains 4 Hes of precipitating Filtrate 4;
(5) soften: the filtrate 4 for obtaining step (4) enters melded system, and the melded system includes 2 parts, first part It is to sequentially add sodium carbonate and sodium hydroxide into filtrate 4, generates precipitation of calcium carbonate and magnesium hydrate precipitate, precipitating is obtained by filtration 5 and filtrate 5;Second part is that filtrate 5 is made to enter 732 chelating resin advanced treating calcium and magnesiums, obtains precipitating 6 and filtrate 6;Filtrate 6 Into water tank, and pH is adjusted with acid to 6~8;
The described film concentration systems processing the following steps are included:
(a) RO is concentrated: the water in water tank for obtaining step (5) enters RO system and carries out initial concentration, is concentrated into production water power and leads Not higher than 1mS/cm, obtains concentrated water 1 and produce water 1, recycled wherein producing water 1, concentrated water 1 enters ED system;
(b) ED is concentrated;The concentrated water 1 that obtains step (a) enter be equipped with the two of cation-exchange membrane and anion-exchange membrane every Room electrodialysis system is further concentrated, and electrodialysis process to concentrated water conductance stops when no longer rising, and obtains concentrated water 2 and fresh water 2, wherein fresh water 2 returns to the water tank of step (5), and concentrated water 2 enters distillation crystal system;
The evaporation and crystallization system includes Distallation systm, be will precipitate 1, precipitating 2, precipitating 3, precipitating 4, precipitating 5, precipitating 6 and dense Water 2 carries out distillation processing, obtains distilled water and is evaporated product.
2. waste water of mine Zero discharge treatment method as described in claim 1, it is characterised in that: the flocculating setting is specifically adopted With following condition: enter waste water of mine in flocculation sedimentation tank, be added flocculant PAC or PAM, flocculant additive amount be 1~ 3ppm, flocculating setting time are 24~36h.
3. waste water of mine Zero discharge treatment method as described in claim 1, it is characterised in that: in step (a), pass through RO system Salinity in the water in water tank is set to be concentrated 5-7 times.
4. waste water of mine Zero discharge treatment method as described in claim 1, it is characterised in that: in step (b), pass through ED system The salinity of concentrated water 1 is set to be concentrated 3-5 times.
5. waste water of mine Zero discharge treatment method as described in claim 1 or 4, it is characterised in that: described in step (b) Cation-exchange membrane uses Germany FKB, and the anion-exchange membrane uses Germany FAM.
6. waste water of mine Zero discharge treatment method as claimed in claim 5, it is characterised in that: electrodialysis process condition setting Are as follows: membrane stack is made of the electrodialysis cell of 5 group of two compartment, and effective membrane area of every film is 189cm2, the charging speed of each compartment Rate is consistent and controls in 20-40L/h, controls 5~10V of voltage, and control reaction temperature is 20 DEG C~40 DEG C.
CN201910585591.6A 2019-07-01 2019-07-01 A kind of waste water of mine Zero discharge treatment method Pending CN110451707A (en)

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CN111285531A (en) * 2020-04-01 2020-06-16 煤科集团杭州环保研究院有限公司 Method and system for concentrating high-salinity mine water
CN112093966A (en) * 2020-09-29 2020-12-18 煤科集团杭州环保研究院有限公司 Energy-saving consumption-reducing method based on mine water zero-discharge full process
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