CN105502782B - A kind of coal chemical industry coking wastewater water resource and salt recovery process - Google Patents

A kind of coal chemical industry coking wastewater water resource and salt recovery process Download PDF

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CN105502782B
CN105502782B CN201510881304.8A CN201510881304A CN105502782B CN 105502782 B CN105502782 B CN 105502782B CN 201510881304 A CN201510881304 A CN 201510881304A CN 105502782 B CN105502782 B CN 105502782B
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strong brine
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CN105502782A (en
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肖国军
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HUNAN XIANGNIU ENVIRONMENT PROTECTING INDUSTRY Co Ltd
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    • 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
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • C01D3/06Preparation by working up brines; seawater or spent lyes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • 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
    • 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
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • 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
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • 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
    • C02F2101/12Halogens or halogen-containing compounds
    • C02F2101/14Fluorine or fluorine-containing compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • 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
    • C02F5/02Softening water by precipitation of the hardness
    • C02F5/06Softening water by precipitation of the hardness using calcium compounds

Abstract

A kind of coal chemical industry coking wastewater water resource and salt recovery process, include the following steps: to be chemically treated FLUORIDE REMOVAL IN WASTEWATER, sodium carbonate softening precipitation process is carried out simultaneously, TOC degradation is carried out using advanced oxidation processes, multimedium is carried out and active carbon filter is separated by filtration, carry out ultrafiltration, carry out nanofiltration UF membrane, calcium ions and magnesium ions are separated, nanofiltration produces water calcium ions and magnesium ions lower than 2mg/L hereinafter, being hardly formed CaF2Fouling is crystallized, nanofiltration is obtained by liquid and nanofiltration strong brine, then nanofiltration is respectively processed by liquid and nanofiltration strong brine.The present invention is by fluorinion in waste water, hardness, organic carbon removal, by the separation of multivalent salts and monovalent salt, the concentration of salt and evaporative crystallization, recycle 98% or more water resource, the salt resource of 95% or more recycling, secondary dangerous waste is not generated, system operation cost is reduced, it is final to solve resource reclaim and environmental problem.

Description

A kind of coal chemical industry coking wastewater water resource and salt recovery process
Technical field
The present invention relates to field of environment engineering technology, specially a kind of coal chemical industry coking wastewater water resource and salt recycle work Skill.
Background technique
Publication in Environmental Protection Department on April 21st, 2014 " reinforces environmental protection about during dissolving production capacity seriously superfluous contradiction The notice of management " it is distinctly claimed " coking wastewater use pretreatment (gravity oil-removing method, coagulant sedimentation, oil removal by air bubbling method)+nitre Change, denitrification biochemical processing, wastewater containing phenol and cyanide reuse after processing must not outlet ".Coal chemical industry coking wastewater bio-chemical effluent zero-emission It puts very difficult, is world-class technical problem, Major Difficulties are that TOC content is higher in coking wastewater bio-chemical effluent, salt content Height, hardness is higher, and fluoride is high, and such waste component is complicated, it is necessary to which real zero-emission can just be accomplished by capturing several technical problems And resource reclaim.Domestic typical case is made a living using technique dissolves water using lime softening+filtering+film concentration+evaporation, last work Sequence, which evaporates kettle base solution, can not crystallize, be formed due to containing TOC, calcium, magnesium, fluorine ion and a large amount of sulfate ions, evaporation kettle base solution Strong brine slurries are adhered to, dangerous waste processing can only be finally done.The rate of recovery of water can not be recycled in 92%-95% or so, salt.Therefore, mesh Preceding country's prevailing technology does not accomplish zero-emission and the resource reclaim of complete meaning.
Summary of the invention
Technical problem solved by the invention is to provide a kind of coal chemical industry coking wastewater water resource and salt recovery process, from The problems in and solve above-mentioned background technique.
Technical problem solved by the invention is realized using following technical scheme:
A kind of coal chemical industry coking wastewater water resource and salt recovery process, include the following steps:
(1) FLUORIDE REMOVAL IN WASTEWATER is chemically treated, fluorine ion is reduced to 0.5mg/L or less;
(2) sodium carbonate is carried out to the waste water of step (1) simultaneously and softens precipitation process, by total hardness be reduced to 150mg/L with Under;
(3) TOC degradation is carried out to the waste water that step (2) obtains using advanced oxidation processes;
(4) multimedium is carried out to suspended matter in the waste water of step (3) processing and active carbon filter is separated by filtration, will suspended Object partial size is greater than 5um substance and is retained;
(5) waste water that step (4) obtains is retained using ultrafiltration, 0.05um substance is greater than to partial size and is retained;
(6) nanofiltration UF membrane is carried out to the waste water that step (5) obtains, calcium ions and magnesium ions is separated, nanofiltration produces water calcium ions and magnesium ions Lower than 2mg/L hereinafter, being hardly formed CaF2Fouling is crystallized, nanofiltration is obtained and passes through liquid and nanofiltration strong brine;
(7) reverse osmosis salt water separation is carried out by liquid to the nanofiltration of step (6), 70% or more waste water water resource recycling obtains Monovalent salt strong brine carry out reverse osmosis concentration, monovalent salt is concentrated, sodium chloride is concentrated to 12000~15000mg/L or more, Obtained strong brine is concentrated into using ED electrodialysis, sodium chloride is concentrated to 120000~150000mg/L, obtained strong brine It is evaporated crystallization, obtains crystallization sodium chloride salt;
(8) the nanofiltration strong brine obtained to step (6) carries out fluorine removal chemical treatment, by fluorine ion be reduced to 0.5mg/L with Under, and sodium carbonate softening precipitation process is carried out, total hardness is reduced to 80mg/L hereinafter, suspended matter in water is carried out multimedium again It is separated by filtration with active carbon filter, and fluorine removal chemical treatment is carried out to strong brine, water outlet fluorine ion is less than 0.5mg/L, then It is retained using ultrafiltration, colloid, microorganism, fine particulate matter is retained;Obtained ultrafiltrate is inhaled using resin Attached organic matter is removed strong brine TOC, and is softened using resin, is removed strong brine hardness, nanofiltration UF membrane is finally carried out, into one Step is by sodium sulphate and sodium chloride separation and concentrated vitriol sodium, and sodium sulfate concentration is 10000~15000mg/L after concentration, and nanofiltration is saturating It crosses liquid to enter step (7), and nanofiltration strong brine is concentrated using ED electrodialysis, sodium sulphate is concentrated to 120000~ 150000mg/L, and crystallization is evaporated to strong brine, obtain five aqueous sodium persulfate salt of crystallization.
In the present invention, as a kind of perferred technical scheme, fluorine removal chemical treatment using calcium chloride, lime chemical technology into Row, and using aluminum oxide as adsorbing medium, so that fluorine ion goes out water content less than 0.5mg/L.
In the present invention, as a kind of perferred technical scheme, FLUORIDE REMOVAL IN WASTEWATER chemical treatment, sodium carbonate soften precipitation process packet Include following steps:
Firstly, feeding lime and calcium chloride in first order reaction pond, utilize Ca therein2++ OH-With the F in waste water-+ Mg2+Reaction generates CaF2+Mg (OH) 2 floccule body, removes the fluorine ion in water body while magnesium ion of having gone out, heavy using coagulation Shallow lake device or air-floating apparatus, solid-liquid is separated, and reduces hardness concentration;
Then, the water outlet of first order reaction pond, which enters, removes fluorine ion device, and calcirm-fluoride and magnesium hydrate precipitate are separated, dropped Low fluorine ion and magnesium hardness concentration, water outlet enter in second order reaction pond, sodium carbonate are added in second order reaction pond, utilization is therein CO32-With the Ca in waste water2+Reaction generates CaCO3 floccule body, removes the calcium ion in water body;Utilize coagulative precipitation device or gas Floating device, solid-liquid is separated, and reduces hardness concentration;
Finally, the water outlet of second order reaction pond enters in coagulative precipitation tank, mud-water separation is carried out;
Coagulant is added simultaneously in first order reaction pond and second order reaction pond, the coagulant is chloride containing aluminium 10wt%, yin The aqueous solution of cationic polyacrylamide 0.1wt%.
In the present invention, in step (3), advanced oxidation processes use ozone+hydrogen peroxide, ozone dosage 50mg/L, dioxygen Water dosage is 30mg/L, both oxidants degrade TOC, and TOC is reduced to 50mg/L or less.
In the present invention, step (7) and step (8) are evaporated crystallization treatment using MVR evaporator.
In the present invention, it includes following aspect that sodium carbonate, which softens precipitation process:
Firstly, feeding lime and calcium chloride in reaction tank in step (1), utilize Ca therein2++ OH-In waste water F-+ Mg2+Reaction generates CaF2+Mg (OH) 2 floccule body, removes the fluorine ion in water body while magnesium ion of having gone out;Reaction tank Water outlet, which enters, removes coagulative precipitation device or air-floating apparatus, and solid-liquid is separated, hardness concentration is reduced;
Second, reaction tank adds sodium carbonate in step (2), CO3 therein is utilized2-With the Ca in waste water2+Reaction generates Ca CO3 floccule body removes the calcium ion in water body;Reaction tank water outlet, which enters, removes coagulative precipitation device or air-floating apparatus, by solid-liquid It is separated, reduces hardness concentration;
Third, calcium ions and magnesium ions are carried out separation concentration using nanofiltration in step (6);
Fourth, by, using sodium carbonate is added, CO3 therein is utilized in nanofiltration strong brine that step (6) obtains2-And waste water In Ca2+Reaction generates Ca CO3 precipitating, removes the calcium ion in water body;Reaction tank water outlet, which enters, removes coagulative precipitation device, Gu Liquid separation, reduces hardness concentration;
Fifth, strong brine hardness is removed using softening resin in step (8).
In the present invention, TOC removal uses following aspect:
First, advanced oxidation processes use ozone+hydrogen peroxide, ozone dosage 50mg/L in step (3), hydrogen peroxide is thrown Dosage is 30mg/L, both oxidants degrade TOC, and TOC is reduced to 50mg/L or less;
Second, using activated carbon adsorption TOC in step (4), TOC is reduced to 30mg/L or less;
Third, TOC is separated and be concentrated by nanofiltration in step (6), TOC is concentrated 4 times, nanofiltration concentrated water TOC exists 120mg/L or so;
Fourth, nanofiltration strong brine uses activated carbon adsorption TOC in step (8), TOC is reduced to 80mg/L or less;
Fifth, the ultrafiltrate obtained in step (8) use resin adsorption organic matter, by TOC be reduced to 10mg/L with Under.
In the present invention, monovalent salt and multivalent salts carry out separation and use step (6) nanofiltration technique, sodium sulphate in nanofiltration strong brine Content is greater than 80%, and sodium chloride content is less than 20%;By sodium sulphate content in liquid less than 5%, sodium chloride content is greater than for nanofiltration 95%.
In the present invention, sodium sulfate salt purifying uses step (8), respectively reduces strong brine total hardness, and content is less than 1mg/ L, content of fluoride ion are less than 1mg/L;TOC content is less than 10mg/L.
In the present invention, the crystallization of sodium chloride salt concentration and evaporation uses step (7), by sodium chloride strong brine TDS from 2500~ 4000mg/L is increased to 8000~10000mg/L, and sodium chloride strong brine is increased to 12000~15000mg/L, and sodium chloride is dense Degree is increased to 100000~150000mg/L, and sodium chloride strong brine is evaporated crystallization, obtains 95% sodium chloride.
In the present invention, the crystallization of sodium sulfate salt concentration and evaporation uses step (8), by strong brine TDS from 3000~4000mg/L It is increased to 8000~10000mg/L, strong brine TDS is increased to 120000~150000mg/L, sodium sulphate strong brine is carried out Evaporative crystallization obtains five aqueous sodium persulfates of 94% or so purity.
Due to using above technical scheme, the invention has the following advantages:
Present invention process uses isolation and purification technique, by fluorinion in waste water, hardness, organic carbon removal, by multivalent salts The concentration of separation, salt with monovalent salt and evaporative crystallization recycle 98% or more water resource (micro-moisture is taken away with solidification sludge), The salt resource of 95% or more recycling does not generate secondary dangerous waste, reduces system operation cost, final to solve resource reclaim and environment Problem.
Relative to domestic mainstream technique of zero discharge waste water water resource recycling 92 ~ 95%, salt can not be recycled, a small amount of solid waste rubbish Landfill, for having a large amount of dangerous wastes to dispose, there are significant beneficial effects and inventive features outstanding by the present invention.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below Specific embodiment is closed, the present invention is further explained.
Embodiment
A kind of coal chemical industry coking wastewater water resource and salt recovery process, include the following steps:
(1) FLUORIDE REMOVAL IN WASTEWATER is chemically treated, fluorine ion is reduced to 0.5mg/L or less;
(2) sodium carbonate is carried out to the waste water of step (1) simultaneously and softens precipitation process, by total hardness be reduced to 150mg/L with Under;
(3) waste water obtained using advanced oxidation processes to step (2) carries out TOC degradation, advanced oxidation processes using ozone+ Hydrogen peroxide, ozone dosage 50mg/L, hydrogen peroxide dosage are 30mg/L, and TOC is degraded, TOC is dropped by both oxidants As low as 50mg/L hereinafter, containing macromolecule chemical combination since pollutant kind is various in coking wastewater bio-chemical effluent, complicated component Object and nitrogenous, oxygen, sulphur heterocyclic organic compounds difficult to degrade, softening sedimentation basin water outlet contain micro zoogloea Extracellular enzyme Equal substances, it is easy to reclaiming system organic film be generated organic dirty stifled, it is necessary to reduce organic dirty stifled factor.Waste water organic contamination because Son has been subjected to biochemical degradation, and by chemical degradation, pollution factor substance chemistry can only occur for the pollution factor for being difficult biochemical degradation The premise of reaction is that polluter molecule must must have foot with chemical molecule generation effective collision and reactant molecule Enough big energy.Molecule activation decomposition apparatus is by the more oxidized molecules of dissolved under pressure, effectively the molecule valence mutually collided The electrostatic repulsion forces of electron cloud are reduced, to overcome the repulsive force between valence electron cloud, make the fracture of original chemical bond and new The formation of chemical bond plays the role of powerful outer energy, and more molecules become anakmetomeres, increase the hundred of anakmetomeres Score can be improved the probability of molecular collision, increase touching for molecule so that effective collision number in the unit time be made to dramatically increase The collision time hit energy, extend reaction molecular, to accelerate chemical reaction velocity;
(4) multimedium is carried out to suspended matter in the waste water of step (3) processing and active carbon filter is separated by filtration, will suspended Object partial size is greater than 5um substance and is retained;
(5) waste water that step (4) obtains is retained using ultrafiltration, 0.05um substance is greater than to partial size and is retained;
(6) nanofiltration UF membrane is carried out to the waste water that step (5) obtains, calcium ions and magnesium ions is separated, nanofiltration produces water calcium ions and magnesium ions Lower than 2mg/L hereinafter, being hardly formed CaF2 crystallization fouling, obtains nanofiltration and pass through liquid and nanofiltration strong brine;
(7) reverse osmosis salt water separation is carried out by liquid to the nanofiltration of step (6), 70% or more waste water water resource recycling obtains Monovalent salt strong brine carry out reverse osmosis concentration, monovalent salt is concentrated, sodium chloride is concentrated to 12000~15000mg/L or more, Obtained strong brine is concentrated into using ED electrodialysis, sodium chloride is concentrated to 120000~150000mg/L, obtained strong brine It is evaporated crystallization, obtains crystallization sodium chloride salt;
(8) the nanofiltration strong brine obtained to step (6) carries out fluorine removal chemical treatment, by fluorine ion be reduced to 0.5mg/L with Under, and sodium carbonate softening precipitation process is carried out, total hardness is reduced to 80mg/L hereinafter, suspended matter in water is carried out multimedium again It is separated by filtration with active carbon filter, and fluorine removal chemical treatment is carried out to strong brine, water outlet fluorine ion is less than 0.5mg/L, then It is retained using ultrafiltration, colloid, microorganism, fine particulate matter is retained;Obtained ultrafiltrate is inhaled using resin Attached organic matter is removed strong brine TOC, and is softened using resin, is removed strong brine hardness, nanofiltration UF membrane is finally carried out, into one Step is by sodium sulphate and sodium chloride separation and concentrated vitriol sodium, and sodium sulfate concentration is 10000~15000mg/L after concentration, and nanofiltration is saturating It crosses liquid to enter step (7), and nanofiltration strong brine is concentrated using ED electrodialysis, sodium sulphate is concentrated to 120000~ 150000mg/L, and crystallization is evaporated to strong brine, obtain five aqueous sodium persulfate salt of crystallization.
The fluorine removal chemical treatment of above-mentioned step (1) and step (8) is carried out using calcium chloride, lime chemical technology, and is adopted Use aluminum oxide as adsorbing medium, so that fluorine ion goes out water content less than 0.5mg/L.
FLUORIDE REMOVAL IN WASTEWATER chemical treatment, sodium carbonate softening precipitation process include the following steps:
Firstly, feeding lime and calcium chloride in first order reaction pond, utilize Ca therein2++ OH-With the F in waste water-+ Mg2+Reaction generates CaF2+Mg (OH) 2 floccule body, removes the fluorine ion in water body while magnesium ion of having gone out, heavy using coagulation Shallow lake device or air-floating apparatus, solid-liquid is separated, and reduces hardness concentration,
Its chemical equation is as follows:
Mg2++2OH-→Mg(OH)2
2F-+Ca2+→CaF2
Ca2++SO42-=CaSO4↓;
Then, the water outlet of first order reaction pond, which enters, removes fluorine ion device, and calcirm-fluoride and magnesium hydrate precipitate are separated, dropped Low fluorine ion and magnesium hardness concentration, water outlet enter in second order reaction pond, sodium carbonate are added in second order reaction pond, utilization is therein CO32-With the Ca in waste water2+Reaction generates CaCO3 floccule body, removes the calcium ion in water body;Utilize coagulative precipitation device or gas Floating device, solid-liquid is separated, and reduces hardness concentration, and chemical equation is as follows:
CaSO4+Na2CO3→CaCO3↓+Na2SO4
CaCl2+Na2CO3→CaCO3↓+2NaCl
MgSO4+Na2CO3→MgCO3↓+Na2 SO4
Finally, the water outlet of second order reaction pond enters in coagulative precipitation tank, mud-water separation is carried out;
Coagulant is added simultaneously in first order reaction pond and second order reaction pond, the coagulant is chloride containing aluminium 10wt%, yin The aqueous solution of cationic polyacrylamide 0.1wt% can generate CaCO after calcium chloride sofening treatment in water3、CaF2And Mg (OH) 2Etc. the substance for being insoluble in water, Cong Shuizhong is precipitated out.These sediments cannot usually form large particle, some are then in Colloidal state suspends in water.In the presence of Organic substance in water, organic matter particle can be then adsorbed on these colloidal solids, be formed " electric double layer ", so that sediment colloid be prevented to precipitate from aggregating into large particle.Therefore, calcium chloride sofening treatment and coagulation It handles while carrying out, coagulant can remove the harmful organic matter of certain pairs of precipitation processes from water, be conducive to the analysis of sediment Out.Coagulating treatment is formed by the colloid co-precipitation that flocks can also be formed with adsorbing chlorinated calcium simultaneously.
Consider in NF concentrated water or RO concentrated water, moisture content is also relatively high, and it is higher to be directly evaporated meeting energy consumption.To reduce evaporation Water is handled, in step (7) and step (8), vaporising device front end is concentrated concentrated water using ED electrodialysis process again, subtracts Few evaporation process water.Electroosmose process (electrodialysis(ED)) it is the effect for utilizing amberplex and electric field, by force By ion to attraction at electrode, the ion concentration at position among electrode is caused greatly to decline, so that a kind of method of fresh water be made. Ordinary circumstance, which is lauched intermediate ion, can pass freely through amberplex.Amberplex is a kind of functional membrane, be divided into yin from Proton exchange and cation-exchange membrane, (abbreviation cavity block and anode membrane).Anode membrane only allows cation only to allow anion by cavity block Pass through, here it is the selective penetrated properties of amberplex.Extra electric field under the action of, yin in aqueous solution, cationic meeting Respectively to anode and movable cathode, if intermediate add a kind of exchange membrane, it is possible to achieve the purpose that separation concentration.
In the present invention, step (7) and step (8) are evaporated crystallization treatment using MVR evaporator.Wherein, MVR is utilized Evaporator is evaporated crystallization treatment.Waste water will generate the concentrated water of part after nanofiltration and reverse osmosis membrane processing, dense in concentrated water The pollutants such as most of organic matter and the salinity to have contracted in original waste water.Due to " about in the serious superfluous contradiction mistake of neutralizing production capacity In journey reinforce environmental protection pipe reason notice " (ring hair (2014) No. 55) require coking wastewater must not outlet, if the salinity in concentrated water It recycling in systems always, salinity will constantly be accumulated, and it will lead to the decline of counter-infiltration system water-yielding capacity and even result in equipment damage, Therefore processing appropriate must be carried out to concentrated water.The present invention is handled concentrated water by the way of evaporation.MVR evaporator utilizes The secondary steam that evaporator generates is carried out compression by compressor increases its pressure and temperature, and it is fresh then to make evaporimeter thermal source substitution Steam.The recycling for realizing thermal energy in secondary steam, makes the heat energy recycling of evaporator.As long as providing a small amount of be driven by electricity Compressor operating, which does not need fresh steam, can make evaporator heat energy recycling, continuous evaporation.The MVR evaporator in thermodynamics It can be understood as open type heat pump.The effect of compressor does not generate the heat that evaporation needs instead of, conveys the heat shape of evaporator At recycle heat.MVR evaporator is vaporizer technology of new generation, is a kind of energy-saving and environment-friendly new and high technology.MVR evaporator unit Power consumption is different according to material characteristic, one ton of water consumption 25-70 degree electricity of general every evaporation, and Conventional vaporizer consumes 1.25 tons Fresh steam, 3 effect evaporators consume about 0.4 ton of fresh steam, and to same solution, MVR energy-output ratio and production cost are significantly low It is a kind of high-new energy saving evaporation technique in Conventional vaporizer.MVR evaporator does not need recirculated cooling water, without cooling-water consumption. The coal-burning boiler or high-cost oil burning boiler of construction high pollution are not needed.MVR evaporator more ring more water-saving than Conventional vaporizer It protects.MVR evaporator application range is wide, and the field of all Conventional vaporizer applications is suitable for MVR evaporator, and MVR evaporator steams Hair temperature is low, the temperature difference is small, evaporation is mildly more suitable for thermosensitive solution.Solution process in evaporator is short, and the residence time is short molten Matter should not go bad.MVR evaporator is controlled using full-automatic computer, and system performance is more stable.It can also be continuous at low load Operation.MVR evaporator is the State Scientific and Technological Commission, National Development and Reform Committee power-saving technology promotion project, meets national energy conservation and emission reduction and environmentally friendly new and high technology There are special fund support in promoted extension, government.MVR evaporator construction cost is about 2-3 times higher than Conventional vaporizer, but due to section The about energy, operating cost is low, and the energy saving expense of general operation 2 years can offset construction investment early period.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (1)

1. a kind of coal chemical industry coking wastewater water resource and salt recovery process, characterized by the following steps:
(1) FLUORIDE REMOVAL IN WASTEWATER is chemically treated, fluorine removal chemical treatment is carried out using calcium chloride, lime chemical technology, and uses three oxygen Change two aluminium as adsorbing medium, fluorine ion is reduced to 0.5mg/L or less;
(2) sodium carbonate is carried out to the waste water of step (1) simultaneously and softens precipitation process, total hardness is reduced to 150mg/L or less;
FLUORIDE REMOVAL IN WASTEWATER chemical treatment, sodium carbonate softening precipitation process include the following steps:
Firstly, feeding lime and calcium chloride in first order reaction pond, utilize Ca therein2+And OH-With the F in waste water-And Mg2+Instead CaF should be generated2、Mg (OH)2Floccule body removes the fluorine ion in water body and eliminates magnesium ion simultaneously, utilizes coagulative precipitation device Or air-floating apparatus, solid-liquid is separated, hardness concentration is reduced;
Then, the water outlet of first order reaction pond, which enters, removes fluorine ion device, and calcirm-fluoride and magnesium hydrate precipitate are separated, fluorine is reduced Ion and magnesium hardness concentration, water outlet enter in second order reaction pond, and second order reaction adds sodium carbonate in pond, utilizes CO therein3 2-With Ca in waste water2+Reaction generates CaCO3Floccule body removes the calcium ion in water body;Using coagulative precipitation device or air-floating apparatus, Solid-liquid is separated, hardness concentration is reduced;
Finally, the water outlet of second order reaction pond enters in coagulative precipitation tank, mud-water separation is carried out;
Coagulant is added simultaneously in first order reaction pond and second order reaction pond, the coagulant is chloride containing aluminium 10wt%, anion The aqueous solution of polyacrylamide 0.1wt%;
(3) TOC degradation is carried out to the waste water that step (2) obtains using advanced oxidation processes;Advanced oxidation processes use ozone+dioxygen Water, ozone dosage 50mg/L, hydrogen peroxide dosage are 30mg/L, and TOC is degraded, TOC is reduced to by both oxidants 50mg/L or less;
(4) multimedium is carried out to suspended matter in the waste water of step (3) processing and active carbon filter is separated by filtration, by suspended matter grain Diameter is greater than 5um substance and is retained;TOC is reduced to 30mg/L or less by activated carbon adsorption TOC;
(5) waste water that step (4) obtains is retained using ultrafiltration, 0.05um substance is greater than to partial size and is retained;
(6) nanofiltration UF membrane is carried out to the waste water that step (5) obtains, calcium ions and magnesium ions is separated, nanofiltration produces water calcium ions and magnesium ions and is lower than 2mg/L is hereinafter, be hardly formed CaF2Fouling is crystallized, nanofiltration is obtained and passes through liquid and nanofiltration strong brine;Sulphur in the nanofiltration strong brine Sour sodium content is greater than 80%, and sodium chloride content is less than 20%;The nanofiltration by sodium sulphate content in liquid less than 5%, sodium chloride Content is greater than 95%;TOC is separated and is concentrated by nanofiltration, TOC is concentrated 4 times, TOC is in 120mg/L for nanofiltration concentrated water;
(7) reverse osmosis salt water separation, 70% or more waste water water resource recycling, one obtained are carried out by liquid to the nanofiltration of step (6) Valence salt strong brine carries out reverse osmosis concentration, and monovalent salt is concentrated, sodium chloride is concentrated to 12000~15000mg/L or more, is obtained Strong brine using ED electrodialysis be concentrated, sodium chloride is concentrated to 120000~150000mg/L, obtained strong brine is steamed Hair crystallization obtains crystallization sodium chloride salt;
(8) fluorine removal chemical treatment is carried out to the nanofiltration strong brine that step (6) obtains, fluorine ion is reduced to 0.5mg/L hereinafter, simultaneously It carries out sodium carbonate and softens precipitation process, total hardness is reduced to 80mg/L hereinafter, suspended matter in water is carried out multimedium and work again Property carbon filter be separated by filtration, and to strong brine carry out fluorine removal chemical treatment, water outlet fluorine ion be less than 0.5mg/L, active carbon inhale TOC is reduced to 80mg/L or less by attached TOC;Then retained using ultrafiltration, to colloid, microorganism, fine particulate matter into Row retention;Obtained ultrafiltrate uses resin adsorption organic matter, removes strong brine TOC, TOC is reduced to 10mg/L or less; And softened using resin, strong brine hardness is removed, nanofiltration UF membrane is finally carried out, further simultaneously by sodium sulphate and sodium chloride separation Concentrated vitriol sodium, sodium sulfate concentration is 10000~15000mg/L after concentration, and nanofiltration permeate liquid enters step (7), and to nanofiltration Strong brine is concentrated using ED electrodialysis, sodium sulphate is concentrated to 120000~150000mg/L, and be evaporated knot to strong brine Crystalline substance obtains five aqueous sodium persulfate salt of crystallization;
Step (7) and step (8) are evaporated crystallization treatment using MVR evaporator.
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