CN108328781A - The wastewater treatment method and device generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process - Google Patents
The wastewater treatment method and device generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process Download PDFInfo
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- CN108328781A CN108328781A CN201710566579.1A CN201710566579A CN108328781A CN 108328781 A CN108328781 A CN 108328781A CN 201710566579 A CN201710566579 A CN 201710566579A CN 108328781 A CN108328781 A CN 108328781A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The present invention discloses a kind of method and device of the wastewater treatment generated in production process of titanium pigment, is comprehensively utilized to post-processing waste water using membrane process and resin process.Concrete technology is as follows：Post-processing waste water is filtered using hyperfiltration membrane assembly, hyperfiltration membrane assembly aperture is 2~200nm, by titanium dioxide retention all recycling in waste water.Then pass through reverse osmosis process, sodium chloride solution content is improved to 50~130g/L, beavy metal impurity ion in chemical agent precipitation solution is added, ultrafiltration membrance filter removes sediment, by resin adsorption to reach chlor-alkali primary brine raw material standard.The invention has the advantages that：1. operating procedure is simple, recycling titanium resource；2. treatment effeciency is high, it is not necessarily to evaporative crystallization, it is energy-saving；3. post-processing waste water is become chlor-alkali primary purification brine raw material, the combination of Titanium Dioxide Produced by Chloride Procedure technique and chloralkali process is realized.
Description
Technical field
The wastewater treatment method and device generated in a kind of production process of titanium pigment produces titanium white more particularly to chloridising
Wastewater treatment method during powder and device, belong to water-treatment technology field.
Background technology
Titanium dioxide is considered as a kind of current best white pigment of performance in the world, is widely used in coating, plastics, makes
The industry such as paper, printing ink, chemical fibre, rubber, cosmetics.The production capacity of titanium dioxide indirectly implies a national GDP degree.
Production titanium dioxide mainly has two methods of sulfuric acid process and chloridising at present.Sulfuric acid process long flow path, can only with
It has a rest based on operation, wet bench, sulfuric acid, water consumption are high, and waste and by-product are more, cause serious pollution to the environment.And chloridising is both energy saving
Environmental protection again, under current Environmental Protection in China pressure, chloridising is gradually built up, and will gradually substitute sulfuric acid process becomes main technique.
Chlorination process main flow is three big processes of chlorination, oxidation and post-processing.
A, chlorination：Titanium material is reacted generation titanium tetrachloride with reducing agent mixing under chlorine high temperature to obtain through rectification and purification
To refined titanium tetrachloride；
B, it aoxidizes：Titanium tetrachloride is preheated to be evaporated to gas, and rapid oxidation produces solid two in oxidation furnace under 1800 DEG C of high temperature
Titanium oxide, rapid cooling obtain crude titanium dioxide；
C, it post-processes：Crude titanium dioxide is dispersed through mashing, classification, surface treatment, washing, spray drying, air-flow crushing is sanded
Etc. processes prepare finished product.
A certain amount of sodium chloride is mainly contained in the post-processing waste water of production water after the washing of titanium dioxide surface-coating, and is contained
The substances such as micro titanium dioxide, sodium metasilicate, sodium metaaluminate, calgon.Direct emission causes the loss of titanium dioxide product simultaneously
Pollute environment.
Domestic and international processing method mainly has following two at present.1, outdoor sedimentation basin is established, is recycled by natural subsidence low
Quality titanium dioxide, liquid are sent to Sewage Disposal or natural evaporation；2, titanium dioxide is recycled after pre-processing, it will using reverse osmosis technology
3~5 times or so of Waste water concentrating, concentrate are sent into crystallizing evaporator and are evaporated, make
Solid sodium chloride salt is used for certain fields（Such as snow melt salt）, reuse after steam condensation.But two methods exist
Many disadvantages, outdoor sedimentation basin floor space is very big in method 1 and settling efficiency is low, and the titanium dioxide of recycling is due to for a long time
Settling quality reduces, and is polluted containing discharge of poisonous waste in waste water.Solid is flashed to using crystallizing evaporator in method 2
Salt, although solving environmental problem caused by discharge, energy consumption is very big, and processing cost is excessively high.And all do not have in two methods
The realization resource of effect makes full use of.
Invention content
Prior art is mainly based on evaporative crystallization, and present invention aims at providing, a kind of chloride process titanium dioxide flour flow design is useless
Water " zero " discharges method of comprehensive utilization, and this method can effectively remove the heavy metal ion in solution, obtains refined sodium chloride
Solution meets chlor-alkali brine raw material standard.
The wastewater treatment method generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process, includes the following steps：
Waste water in chlorination legal system titanium dioxide technique is filtered, obtains the dope containing solid and filtrate by the 1st step；
The filtrate that 1st step obtains is sent into reverse osmosis membrane and is concentrated, obtains deionized water and counter-infiltration dope by the 2nd step；
3rd step is added precipitating reagent in the counter-infiltration dope that the 2nd step obtains, makes siliceous and aluminium compound（Mainly silicate ion
With meta-aluminic acid radical ion）Precipitation, and removed precipitation by solid-liquid separation method；
4th step, the filtrate that the 3rd step obtains are sent into removal aluminium ion in ion exchange resin and remove foreign ion, refined
NaCl solution.
In 1st step, waste water comes from chlorination legal system titanium dioxide technique produces water after the washing of titanium dioxide surface-coating.
In 1st step, filtering refers to passing through ultrafiltration membrance filter.
Include titanium dioxide and/or hydrated titanium dioxide in 1st step, in the dope.
In 3rd step, precipitating reagent is selected from magnesium chloride and/or calcium chloride.
In 3rd step, filtering refers to passing through ultrafiltration membrance filter.
In 4th step, ion exchange resin be selected from cation exchange resin, anion exchange resin, amphoteric resin,
Chelating resin.
In 4th step, in the 3rd step, obtained refined NaCl brine is sent into ion film caustic soda workshop section work original
Material.
In 3rd step, before precipitating reagent is added, brine is concentrated by electrodialysis, after dope enters back into
Continuous step.
In 3rd step, before carrying out precipitation reaction, pH to 1~6 is also adjusted.
The wastewater treatment equipment generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process includes：
First filter membrane, for being separated by solid-liquid separation to waste water；
Reverse osmosis membrane is connected to the first filter membrane, and concentration is carried out for the filtrate to the first filter membrane；
Reactive tank is connected to reverse osmosis membrane, and precipitation reaction is carried out for the concentrate to reverse osmosis membrane；
Slot is added in precipitating reagent, reactive tank is connected to, for precipitating reagent to be added into reactive tank；
Second filter membrane, is connected to reactive tank, the precipitation generated for filtering out reaction；
Ion exchange resin is connected to the second filter membrane, carries out removing foreign ion for the filtrate to the second filter membrane.
Further include having ion film caustic soda electrolytic cell, be connected to ion exchange resin, for the production water to ion exchange resin
It is electrolysed.
Further include having plate filter, be connected to the second filter membrane, is separated by solid-liquid separation for the concentrate to the second filter membrane；
The per-meate side of plate filter is connected to the import of the second filter membrane.
Further include having electric dialyzator, be connected to reverse osmosis membrane, is concentrated for the concentrate to reverse osmosis membrane, electrodialysis
The dope side of device is connect with reactive tank.
Further include thering is pH to adjust unit, be connected to ion exchange resin, for the feed liquid of ion exchange resin will to be entered
PH is adjusted to acidity.
First filter membrane and/or the second filter membrane is ultrafiltration membrane.
Advantageous effect
1. processing speed is fast, turns waste into wealth and avoid environmental pollution；
2. being not necessarily to evaporative crystallization, a large amount of energy consumptions are saved；
3. obtained refined sodium chloride solution is as chlor-alkali raw material.
Description of the drawings
Fig. 1 is process flow chart provided by the invention；
Fig. 2 is the device of the invention figure；
Fig. 3 is that the present invention provides another installation drawing.
Wherein, the 1, first filter membrane；2, reverse osmosis membrane；3, reactive tank；4, slot is added in precipitating reagent；5, the second filter membrane；6, sheet frame
Filter；7, ion exchange resin；8, ion film caustic soda electrolytic cell；9, electric dialyzator.
Specific implementation mode
Present invention wastewater source to be dealt with produces in chlorination legal system titanium dioxide technique after the washing of titanium dioxide surface-coating
Water, water quality situation are：PH is in 7.5~10.5, Ca2+In 10~50ppm, Na+In 500~5000ppm, Al in 230ppm, Si
In 0.5~20ppm, Cl-In 500~6000ppm, COD is in 4~50ppm, TDS in 1000~10000 ppm.
The treatment process that the present invention uses is first to be separated by solid-liquid separation waste water, by the titanium dioxide wherein contained, hydration
Titanium dioxide etc. is isolated, recycling.Due to too low using sedimentation process or coarse filtration process efficiency, and titanium dioxide can not
Recycling comprehensively, product quality reduce, and floor space is very big, is unfavorable for modernization process requirement.It is preferred that using after ultrafiltration membrance filter
Waste water is handled, titanium dioxide all recycles, and effluent quality is limpid, NTU ＜ 0.5, SS ＜ 1ppm.Instead of original sedimentation basin or slightly
Filter reduces floor space, improves efficiency, and ultrafiltration membrane can regenerate.
Due to containing a large amount of sodium chloride in waste water, but relative concentration is not high, about 15g/L or so, if directly handling water
Greatly, operating cost is excessively high.The filtrate after separation of solid and liquid is concentrated by reverse osmosis membrane, NaCl therein, siliceous can be made
Substance, aluminium-containing substance, other impurity zwitterions are trapped, and reverse osmosis membrane 2 can obtain deionized water.By sodium chloride concentration
Improve to 50-130g/L or so.Processing water substantially reduces, and energy consumption is reduced.Since sodium chloride has market value, direct emission
It causes economic loss and pollutes environment.Not only solid salt no too big economic use value but also energy are evaporated according to conventional
It consumes high, does not meet sustainable development idea.If being used as chlor-alkali raw material after refined, not only low energy consumption, has exemplary work
Cheng Xiaoying, moreover it is possible to promote the combination of domestic chloride process titanium dioxide and chlor-alkali.But in waste water containing a certain amount of heavy metal from
Son, it is therefore necessary to first remove heavy metal ion.
Precipitating reagent is added to the concentrate of reverse osmosis membrane, the impurity of non-chlorinated sodium in fact can be got rid of, here mainly
It is silicon-containing compound, such as sodium metasilicate, sodium metasilicate, can also includes sodium metaaluminate, calgon etc..Used herein of
Desiliconizing agent, aluminium removal can be calcium chloride or magnesium chloride, by taking magnesium chloride as an example, except silicon mechanism be magnesia mixture under alkaline condition,
Part aquation forms the complicated molecule structure of magnesium hydroxide in water, and part magnesium hydroxide is dissolved in solution, thus forms
Surrounding is by OH-The positively charged complicated colloidal particle surrounded, can be with oxidation with silicic acid cereal existing for different shape in water
Colloidal magnesium particle carries out ion exchange, forms the magnesium silicate cereal to find it difficult to learn, while cohesion and the silicic acid of siliceous colloid also has occurred
The generation of calcium.The mole of the addition of precipitating reagent is 1~2 times of silicate ion and metasilicic acid radical ion molar concentration.
When carrying out precipitation reaction, acid for adjusting pH is preferably added to 1~6.The reason is that calcium chloride（Magnesium）It is sent out with meta-aluminic acid root
Raw double hydrolysis, aluminium are only only ionic species presence less than 6 in pH, generate calcium hydroxide（Magnesium）And aluminum hydroxide precipitation, it adjusts
Acidity avoids calcium hydroxide（Magnesium）Scale effect resin, and resin only adsorbs aluminium ion under acid system, does not adsorb calcium ion.
After obtaining precipitation, sediment is filtered out by filter membrane, ultrafiltration membrance filter may be used.Concentrate can pass through
After plate-frame filtering, filter residue is obtained, filter residue is mixed with chloride slag and handles making cement product.
Can refer to ultrafiltration membrane used herein of seperation film.Ultrafiltration membrane for the present invention be molecular cut off be 1000 ~
200000 film, referred to as ultrafiltration membrane, UF films etc..Here, being difficult to electron microscope etc. since the aperture of ultrafiltration membrane is too small
The aperture of film surface is measured, so replacing average pore size to be used as the index of pore size with the value of referred to as molecular cut off.
About molecular cut off, as recorded in the textbook of this field：" will be by horizontal axis, prevention rate of molecular weight solute
The longitudinal axis, curve made of being drawn to data are known as molecular cut off curve.And the molecular weight that prevention rate is 90% is known as
The molecular cut off of film ", index of the molecular cut off as the film properties for indicating ultrafiltration membrane are ripe for those skilled in the art
Know.
As the material of these ultrafiltration membranes, as long as the colloid, solid suspension, sediment removed in water can be realized in this way
The object of the invention, be not particularly limited, can enumerate：Cellulose, cellulose esters, polysulfones, polyether sulfone, polyvinyl chloride,
The organic materials such as chloropropene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), or
The inorganic material such as the metals such as person's stainless steel or ceramics.The impurity in waste water can be considered in microfiltration membranes or the material of ultrafiltration membrane
Character or operating cost suitably select, and consider from durability etc., preferably ceramic film, the average pore size scope of ceramic membrane
It is preferred that 5~2000nm, more preferable 20~500nm, when ceramic membrane is run, crossflow velocity preferred scope is 1~7m/s, running temperature
5~70 DEG C, 0.01~1.0MPa of transmembrane pressure.It, can be from existing known as the material for the perforated membrane for constituting ceramic separation film
Ceramic material in suitably select.It is, for example, possible to use aluminium oxide, zirconium oxide, magnesia, silica, titanium oxide, cerium oxide,
Yttrium oxide, the oxide materials such as barium titanate；Cordierite, mullite, forsterite, steatite, sialon, zirconium
The combined oxidations species material such as stone, ferrite；Silicon nitride, aluminum nitride and other nitride class material；The carbon compounds material such as silicon carbide；
The hydroxides composition material such as hydroxyapatite；The elements class material such as carbon, silicon；Or the two or more inorganic compoundings containing them
Material etc..Natural minerals can also be used（Clay, clay mineral, grog, silica sand, pottery stone, feldspar, white sand）Or blast-furnace slag,
Flying dust etc..Wherein, be preferably selected from it is one kind or two or more in aluminium oxide, zirconium dioxide, titanium oxide, magnesia, silica, it is more excellent
Select the ceramic powders constituted using aluminium oxide, zirconium dioxide or titanium oxide as main body.Wherein, " as main body " mentioned here
Indicate the 50 mass % or more of ceramic powders totality（It is preferred that 75 mass % or more, the more preferable 80 mass mass of %~100 %）For oxidation
Aluminium or silica.For example, in the porous material, aluminium oxide is relatively inexpensive and operational excellent.Further, it is possible to be readily formed
Porous structure with the aperture for being suitable for liquid separation, therefore the pottery with excellent liquid permeability can be easily manufactured
Porcelain seperation film.Also, in above-mentioned aluminium oxide, Alpha-alumina is particularly preferably used.Alpha-alumina have in terms of chemistry stablize,
And the characteristic of fusing point and high mechanical strength.Therefore, by using Alpha-alumina, can manufacture can be in broad use（Such as work
Industry field）The middle ceramic separation film utilized.
Permeate by ion exchange resin treatment, can get rid of some of which foreign ion again, further remove
Aluminium reaches 20ppb-200ppb（Chlor-alkali requires to be that aluminium is no more than 100ppb）, the NaCl solution after being refined meets ion
The feed needs of film caustic soda.Include but not limited to cation exchange resin, anion exchange used herein of ion exchange resin
Resin, amphoteric resin, chelating resin.Aluminium ion concentration is down to 0.01-0.5ppm after ion exchange resin adsorbs.
Before precipitating reagent is added, waste water can be concentrated by electrodialysis, dope enters back into subsequent step.Useless
It after water is separated by solid-liquid separation first, is first concentrated with electrodialysis methods, the concentration of NaCl is made to improve, since NaCl can make glue
The electric double layer of body particle is compressed, and to reduce carried charge, to make the colloidal solid in water contact with each other, and is adsorbed, is bonded
It is settled at big particle.
In one embodiment, in the 2nd step, NaOH is additionally added while precipitating reagent is added.PH be 8~
Under conditions of 11, colloid can be improved and generate effect, make to be improved except silicon rate, while also a part of impurity cationic can be made to obtain
To precipitation.The electrolysis process for coming from ion film caustic soda used herein of NaOH, the NaCl used will locate from the present invention
The waste water of reason, the NaOH being prepared can also be back to waste water treatment process, realize waste water treatment process and ionic membrane
The integrated coupling of process of caustic soda.
As a further improvement on the present invention, it is characterised in that cleaning agent waste liquid and osmosis filtration when ultrafiltration membrane regenerates
Deionized water afterwards all can serve as the use of the slurrying water in chloride process titanium dioxide chloride slag processing procedure.Realize " zero " row comprehensively
It puts.
Based on above method, device of the present invention is as shown in Figures 2 and 3.
Include：
First filter membrane 1, for being separated by solid-liquid separation to waste water；
Reverse osmosis membrane 2 is connected to the first filter membrane 1, and concentration is carried out for the filtrate to the first filter membrane 2；
Reactive tank 3 is connected to reverse osmosis membrane 2, and precipitation reaction is carried out for the concentrate to reverse osmosis membrane 2；
Slot 4 is added in precipitating reagent, reactive tank 3 is connected to, for precipitating reagent to be added into reactive tank 3；
Second filter membrane 5, is connected to reactive tank 3, the precipitation generated for filtering out reaction；
Ion exchange resin 7 is connected to the second filter membrane 5, carries out removing foreign ion for the filtrate to the second filter membrane 5.
Further include having ion film caustic soda electrolytic cell 8, be connected to ion exchange resin 7, for the production to ion exchange resin 7
Water is electrolysed.
Further include having plate filter 6, be connected to the second filter membrane 5, solid-liquid point is carried out for the concentrate to the second filter membrane 5
From；The per-meate side of plate filter 6 is connected to the import of the second filter membrane 5.
Further include having electric dialyzator 9, be connected to reverse osmosis membrane 2, is concentrated for the concentrate to reverse osmosis membrane 2, electricity
The dope side of dialyzer 10 is connect with reactive tank 3.
Further include thering is pH to adjust unit, be connected to ion exchange resin 7, for the feed liquid of ion exchange resin 7 will to be entered
PH be adjusted to acidity.
First filter membrane 1 and/or the second filter membrane 5 is ultrafiltration membrane.
Waste water quality used by following embodiment is as follows：
Embodiment 1
Post-processing waste water is handled using ceramic super-filtering film, detects titanium white powder content about 0.2-0.5g/L in initial waste,
After ceramic super-filtering film filtering and concentrating, up to 150g/L, cycles of concentration 300 are carried through titanium dioxide producer detection titanium dioxide concentration
Times or so, effluent quality NTU ＜ 0.5, SS ＜ 1ppm.
Ceramic super-filtering film filtrate concentrates by reverse osmosis membrane, after osmosis filtration concentration, sodium chloride concentration highest after testing
Improve to 120g/L or so.
Suitable magnesium chloride is added in dope（It is dense with metasilicic acid root and silicate ion mole with the molar concentration meter of magnesium
It is identical to spend summation）, natural subsidence takes supernatant to detect after reaction, measures Si content 11.5ppm, Al content 9ppm, and Mg contains
3.7ppm is measured, other heavy metals are not detected.
Supernatant measures Si content 4.8ppm, Al content 0.42ppm, Mg content after ion exchange resin adsorbs
0.6ppm, other heavy metals are not detected.
Embodiment 2
Post-processing waste water is handled using ceramic super-filtering film, detects titanium white powder content about 0.4-1.2g/L in initial waste,
After ceramic super-filtering film filtering and concentrating, up to 150g/L, cycles of concentration 260 are carried through titanium dioxide producer detection titanium dioxide concentration
Times or so, effluent quality NTU ＜ 0.8, SS ＜ 2ppm.
Ceramic super-filtering film filtrate concentrates by reverse osmosis membrane, after osmosis filtration concentration, sodium chloride concentration highest after testing
Improve to 136g/L or so.
Suitable magnesium chloride is added in dope（It is dense with metasilicic acid root and silicate ion mole with the molar concentration meter of magnesium
Spend summation 1.2 times）, natural subsidence takes supernatant to detect after reaction, measures Si content 14.2ppm, Al content 5.2ppm,
Mg content 3.4ppm, other heavy metals are not detected.
Supernatant measures Si content 3.9ppm, Al content 0.34ppm, Mg content after ion exchange resin adsorbs
1.9ppm, other heavy metals are not detected.
Embodiment 3
Post-processing waste water is handled using ceramic super-filtering film, detects titanium white powder content about 0.3-0.8g/L in initial waste,
After ceramic super-filtering film filtering and concentrating, up to 140g/L, cycles of concentration 290 are carried through titanium dioxide producer detection titanium dioxide concentration
Times or so, effluent quality NTU ＜ 1.2, SS ＜ 2ppm.
Ceramic super-filtering film filtrate concentrates by reverse osmosis membrane, after osmosis filtration concentration, sodium chloride concentration highest after testing
Improve to 130g/L or so.
Suitable magnesium chloride is added in dope（It is dense with metasilicic acid root and silicate ion mole with the molar concentration meter of calcium
Spend summation 1.3 times）, natural subsidence takes supernatant to detect after reaction, measures Si content 14.2ppm, Al content 5.8ppm,
Ga content 3.2ppm, other heavy metals are not detected.
Supernatant measures Si content 3.2ppm, Al content 0.28ppm, calcium content after ion exchange resin adsorbs
1ppm, other heavy metal ion are not detected.
Embodiment 4
With embodiment 3 difference lies in：After being concentrated using electrodialysis to the dope of reverse osmosis membrane, it is re-fed into precipitation tank in term.
Post-processing waste water is handled using ceramic super-filtering film, detects titanium white powder content about 0.3- in initial waste
After ceramic super-filtering film filtering and concentrating, up to 140g/L, concentration times are proposed through titanium dioxide producer detection titanium dioxide concentration by 0.8g/L
Number is 290 times or so, effluent quality NTU ＜ 1.2, SS ＜ 2ppm.
Ceramic super-filtering film filtrate concentrates by reverse osmosis membrane, after osmosis filtration concentration, sodium chloride concentration highest after testing
Improve to 130g/L or so.
After being concentrated to counter-infiltration dope by electric dialyzator, after so that NaCl concentration is reached 240g/L, electrodialysis plant
Operation voltage is 120V, electric current 1.5A, feed pressure 0.01MPa.Suitable magnesium chloride is added in dope（With the mole dense of calcium
Degree meter, 1.3 times with metasilicic acid root and silicate ion molar concentration summation）, natural subsidence takes supernatant to examine after reaction
It surveys, measures Si content 2.9ppm, Al content 2.6ppm, Ga content 2.5ppm, other heavy metals are not detected.
Supernatant measures Si content 1.3ppm, Al content 0.03ppm, calcium content after ion exchange resin adsorbs
1ppm, other heavy metal ion are not detected.
Claims (10)
1. the wastewater treatment method generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process, which is characterized in that include the following steps：
Waste water in chlorination legal system titanium dioxide technique is filtered, obtains the dope containing solid and filtrate by the 1st step；
The filtrate that 1st step obtains is sent into reverse osmosis membrane and is concentrated, obtains deionized water and counter-infiltration dope by the 2nd step；
Precipitating reagent is added in the counter-infiltration dope that the 2nd step obtains in 3rd step, makes siliceous and aluminum contained compound precipitation, and pass through solid-liquid
Separate mode removes precipitation；
4th step, the filtrate that the 3rd step obtains are sent into ion exchange resin and remove aluminium ion, and refined NaCl solution is obtained.
2. the wastewater treatment method generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 1, which is characterized in that
In 1st step, waste water comes from chlorination legal system titanium dioxide technique produces water after the washing of titanium dioxide surface-coating；
In 1st step, filtering refers to passing through ultrafiltration membrance filter；
Include titanium dioxide and/or hydrated titanium dioxide in 1st step, in the dope；
In 3rd step, precipitating reagent is selected from magnesium chloride and/or calcium chloride；
In 3rd step, filtering refers to passing through ultrafiltration membrance filter；
In 4th step, ion exchange resin is selected from cation exchange resin, anion exchange resin, amphoteric resin, chelating
Resin；
In 4th step, in the 3rd step, obtained refined NaCl brine feeding ion film caustic soda workshop section makees raw material.
3. the wastewater treatment method generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 1, which is characterized in that
In 3rd step, before precipitating reagent is added, brine is concentrated by electrodialysis, dope enters back into subsequent step.
4. the wastewater treatment method generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 1, which is characterized in that
In 3rd step, before carrying out precipitation reaction, pH to 1~6 is also adjusted.
5. the wastewater treatment equipment generated in a kind of Titanium Dioxide Produced by Chloride Procedure production process, which is characterized in that include：
First filter membrane（1）, for being separated by solid-liquid separation to waste water；
Reverse osmosis membrane（2）, it is connected to the first filter membrane（1）, for the first filter membrane（2）Filtrate carry out concentration；
Reactive tank（3）, it is connected to reverse osmosis membrane（2）, for reverse osmosis membrane（2）Concentrate carry out precipitation reaction；
Slot is added in precipitating reagent（4）, it is connected to reactive tank（3）, it is used for reactive tank（3）Middle addition precipitating reagent；
Second filter membrane（5）, it is connected to reactive tank（3）, the precipitation for filtering out reaction generation；
Ion exchange resin（7）, it is connected to the second filter membrane（5）, for the second filter membrane（5）Filtrate carry out remove foreign ion.
6. the wastewater treatment equipment generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 5, which is characterized in that
Further include having ion film caustic soda electrolytic cell（8）, it is connected to ion exchange resin（7）, for ion exchange resin（7）Production water
It is electrolysed.
7. the wastewater treatment equipment generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 5, which is characterized in that
Further include having plate filter（6）, it is connected to the second filter membrane（5）, for the second filter membrane（5）Concentrate carry out solid-liquid point
From；Plate filter（6）Per-meate side be connected to the second filter membrane（5）Import.
8. the wastewater treatment equipment generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 5, which is characterized in that
Further include having electric dialyzator（9）, it is connected to reverse osmosis membrane（2）, for reverse osmosis membrane（2）Concentrate concentrated, electric osmose
Parser（9）Dope side and reactive tank（3）Connection.
9. the wastewater treatment equipment generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 5, which is characterized in that
First filter membrane（1）And/or second filter membrane（5）It is ultrafiltration membrane.
10. the wastewater treatment equipment generated in Titanium Dioxide Produced by Chloride Procedure production process according to claim 5, feature exist
In, further include have pH adjust unit, be connected to ion exchange resin（7）, for ion exchange resin will to be entered（7）Feed liquid
PH is adjusted to acidity.
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