CN105502756B - A kind of water-soluble liquid treating system and its processing method of the easy scale-forming ion containing concentration - Google Patents
A kind of water-soluble liquid treating system and its processing method of the easy scale-forming ion containing concentration Download PDFInfo
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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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- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- 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
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Abstract
The invention provides a kind of water-soluble liquid treating system and its processing method, the system includes hopper, pretreatment unit, nanofiltration device, analysis point permeable tank, analysis fractionation water pot and electrodialysis plant, and electrodialysis plant includes pole room tank, resets water pot, electric dialyzator and dc source.Electric dialyzator includes positive plate, minus plate, cation-exchange membrane, anion-exchange membrane, dividing plate, analysis fractionation hydroecium, the permeable room of analysis point, rearrangement hydroecium, anode chamber and cathode chamber.The present invention proposes a kind of ion analysis point and reordering technique, utilize electrodialytic transformation, anion in the permeable cationic of analysis point obtained by nanofiltration and analysis fractionation water is combined into a kind of new salt, the permeable middle anion of analysis point obtained by nanofiltration and analysis fractionation water cationic are combined into another salt, so that each ion splitting and reorganizing is into the very big salt of solubility easily in fouling salting liquid, fouling is prevented while the cycles of concentration for improving salt, increases substantially life-span of film and equipment, Water Sproading rate, concentrated water concentration.
Description
Technical field
The invention belongs to water treatment field, is related to a kind of water-soluble liquid treating system and its processing method, more particularly to a kind of
Containing the water-soluble liquid treating system and its processing method for concentrating easy scale-forming ion.
Background technology
In desalinization, bitter processing, sewage and the field such as advanced treatment of industrial waste water and power plant cycle water process,
Dissolvability solid amount is higher in generally existing dampening, and divalent ion is (representational to have the bivalent cations such as calcium and magnesium, sulfuric acid
The dianion such as root and carbonate) and some organic macromolecule ion concentrations it is also higher the problem of.Due to significant component of
Divalent salts and organic macromolecule salt solubility in water are relatively low, and the easy fouling in concentration, this seriously inhibits in above-mentioned field
The raising of Water Sproading rate.In addition, in zero-emission or near-zero release system, counter-infiltration, electrodialysis and the easy shape of distillation/vapo(u)rization system
Into the fouling of divalent salts and organic salt, the normal operation and service life of equipment are had a strong impact on.
Influence of the fouling to counter-infiltration mainly has following several respects, membrane flux can be caused to reduce after fouling, counter-infiltration energy consumption
Increase, the shortening of the Quality Down and membrane lifetime of production water.Ch.Tzotzi(Tzotzi C,et al.A study of
CaCO3scale formation and inhibition in RO and NF membrane processes Journal
of membrane science,2007,296(1):171-184.) etc. research is found, CaCO3Fouling can make different in counter-infiltration
The flux of species film reduces.Wen-Yi Shi(Shih W Y,et al.Morphometric characterization of
calcium sulfate dihydrate(gypsum)scale on reverse osmosis membranes.Journal
of Membrane Science,2005,252(1):253-263.) et al. then have studied CaSO4·2H2O is to reverse osmosis membrane flux
Reduction effect and different amounts the improvement degree that reduces to membrane flux of antisludging agent.Zaviska(Zaviska F,
et al.Using FO as pre-treatment of RO for high scaling potential brackish
water:Energy and performance optimisation.Journal of Membrane Science,2015,
492:430-438.) et al. then find in the case of without pretreatment, because fouling increases osmotic resistance, and then make energy consumption obvious
Increase.
Fouling equally can produce harm to distillation, MVR and Multi-effect Evaporation Processes.Gryta(Gryta M.Application
of membrane distillation process for tap water purification.Membrane Water
Treatment,2010,1(1):1-12.) found when studying direct contact membrane distillation, CaCO3Precipitation can increase resistance of heat transfer
Power and reduction temperature polarization coefficient, finally reduce membrane flux.He(He F,et al.Studies on scaling of
membranes in desalination by direct contact membrane distillation:CaCO3and
mixed CaCO3/CaSO4systems.Chemical Engineering Science,2009,64(8):1844-1859.) etc.
People then has found CaCO3With CaSO4The precipitation of mixing is compared to single CaCO3Easily reduce membrane flux.(Zhao Jun evaporate Zhao Jun
The harm of device fouling and Chinese oils are prevented, 2002,27 (4):94-96.) found when studying crystallizing evaporator scale problems,
When fouling of evaporator thickness is 5mm, heat transfer efficiency is about original 1/3, and steam thermal energy utilization ratio reduces.Luo Gang (Luo Gang
Deng multi-effect evaporators fouling mechanisms and precautionary measures gansu science and technologies, 2014,30 (19):50-51.) et al. think multiple-effect evaporation
The fouling of device can reduce the heat transfer property of equipment, evaporation capacity is reduced, it is necessary to shut down processing when serious.
In order to improve the Water Sproading rate of brine concentration, danger of the fouling to counter-infiltration, electrodialysis and distillation/vapo(u)rization system is prevented
Evil, the method that some need to be used to prevent such fouling.Reducing the method for fouling at present mainly has with ion exchange resin, addition
Antisludging agent or dispersant, pretreatment is added sodium carbonate or quick lime and improved the methods of acid, but these methods respectively have it to lack
Fall into and limit, it is main as follows：
(1) ion exchange resin.Water process spent ion exchange resin has that resin is broken, Organic Pollution, iron pollution, grain
The problems such as degree is uneven, resin is hardened (arrange by problem present in the operation of the water process such as Sang Junzhen spent ion exchange resin and prevention
Apply Hebei power technology, 2009 (1)).Meanwhile ion exchange resin needs to regenerate, resin regeneration is costly, not environmentally, and
Easily form secondary pollution；
(2) antisludging agent or dispersant.Antisludging agent has certain effect for delaying fouling, but many antisludging agents are phosphorous, and
It is organic polymer, easily forms secondary pollution, and the solubility that can be improved is limited.Also need to control the addition of antisludging agent
Amount, if antisludging agent is excessively added, itself easily forms dirt immune film (Antony A, et al.Scale formation
and control in high pressure membrane water treatment systems:A
review.Journal of Membrane Science,2011,383(1):1-16.).In addition, antisludging agent can also increase film quilt
The possibility of biological pollution, the speed that some antisludging agents can grow biofouling bring up to 10 times of normal value
(Vrouwenvelder J S,et al.Biofouling potential of chemicals used for scale
control in RO and NF membranes.Desalination,2000,132(1):1-10.)；
(3) pretreatment plus sodium carbonate or quick lime.This processing method not environmentally, produces more bed mud, and concentration rate
High or easy fouling；
(4) improve acid.This processing method can only reduce carbonate, and equipment is corrosive.In the higher water of alkalescence
In, it is higher to improve the cost of acidity, and as in the acid of commodity, typically by metal impurity con, the pollution of film can be accelerated
(Zeiher E H K,Ho B,Williams K D.Novel antiscalant dosing
control.Desalination,2003,157(1):209-216.)。
The content of the invention
The defects of for traditional good antiscale property method, in order to solve concentration, the mistakes such as counter-infiltration, electrodialysis and distillation/evaporation
Fouling and the low-down problem of concentration ratio during filter, the present invention propose a kind of ion weight combination technology.This technology will be received
Filter and electrodialysis combine, by the divalence anions and canons and organic macromolecule ion isolation of easy fouling in raw water, and respectively with raw water
In monovalent cation and univalent anion combine, and then realize that under conditions of fouling is prevented salt solution high power concentrates.
The present invention is allocated as using using analysis of the nanofiltration device to one, divalent ion and organic macromolecule ion, 0.5~
It is trapped the larger material of relative molecular mass or negatively charged more material under 40bar pressure, relative molecular mass
The more material transport of less material or positively charged crosses film.Then made using the fractionation of electrodialysis directional migration anions and canons
With, the easy anions and canons for forming slightly soluble even difficulty soluble salt are separated, make in raw water one, divalence anions and canons and organic big point
Daughter ion reconfigures, and the higher salt of generation solubility, so as to which the concentration of easy scale-forming ion in raw water be greatly improved, avoids
The generation of fouling.
To use following technical scheme up to this purpose, the present invention：
In a first aspect, the invention provides a kind of water-soluble liquid treating system, the system includes hopper, pretreatment dress
Put, nanofiltration device, analysis point permeable tank, analysis fractionation water pot and an electrodialysis plant, electrodialysis plant include pole room tank, reset water pot,
Electric dialyzator and dc source.
Electric dialyzator include positive plate, minus plate, cation-exchange membrane, anion-exchange membrane, dividing plate, an analysis point permeable room,
Analyse fractionation hydroecium, reset hydroecium, anode chamber and cathode chamber, the rearrangement hydroecium may include to reset hydroecium one and reset hydroecium two.
Wherein, the permeable outlet of the analysis point of nanofiltration device is connected with the entrance of the permeable tank of analysis point, the outlet and analysis of the permeable tank of analysis point
The entrance of permeable room is divided to be connected, the outlet of the permeable room of analysis point divides the entrance of permeable tank to be connected with analysis, and the analysis fractionation water of nanofiltration device goes out
Entrance of the mouth simultaneously with analysis fractionation water pot and hopper is connected, and the outlet of analysis fractionation water pot is connected with the entrance of analysis fractionation hydroecium,
The outlet of analysis fractionation hydroecium is connected with analysing the entrance of fractionation water pot, and the outlet for resetting hydroecium is connected with resetting the entrance of water pot, weight
The outlet of displacement can is connected with resetting the entrance of room, and the positive pole of dc source is connected with positive plate, negative pole and the moon of dc source
Pole plate is connected.
The connected mode of pole room tank and anode chamber and cathode chamber is conventional connected mode of the prior art in said system,
It can both take the mode of series connection, can also take the mode of parallel connection, just repeat no more herein.
Specifically, resetting hydroecium may include to reset hydroecium one and reset hydroecium two, resetting water pot may include to reset water pot one
With rearrangement water pot two, the outlet for resetting hydroecium one is connected with resetting the entrance of water pot one, resets the outlet of water pot one and resets room
One entrance is connected, and the outlet for resetting hydroecium two is connected with resetting the entrance of water pot two, resets the outlet of water pot two with resetting room
Two entrance is connected.
As the present invention preferred scheme, be additionally provided between the pretreatment unit and nanofiltration device feed pump, accumulator,
Pressure-relief valve and enter film pressure table.
Preferably, membrane pressure gauge and flow valve are provided with the analysis fractionation water outlet line of the nanofiltration device.
Preferably, the feed pump is any one in centrifugal pump, reciprocating pump, rotary pump or peripheral pump or at least two
Combination, the combination is typical but non-limiting examples have：The combination of the combination of centrifugal pump and reciprocating pump, reciprocating pump and rotary pump,
The combination of rotary pump and peripheral pump, the combination of centrifugal pump, reciprocating pump and rotary pump, the combination of reciprocating pump, rotary pump and peripheral pump
Deng.
As the preferred scheme of the present invention, the pole room tank, the permeable tank of analysis point, analysis fractionation water pot and the entrance for resetting water pot
Flowmeter and product pump are provided with pipeline.
Preferably, the product pump is any one in centrifugal pump, reciprocating pump, rotary pump or peripheral pump or at least two
Combination, the combination is typical but non-limiting examples have：The combination of the combination of centrifugal pump and reciprocating pump, reciprocating pump and rotary pump,
The combination of rotary pump and peripheral pump, the combination of centrifugal pump, reciprocating pump and rotary pump, the combination of reciprocating pump, rotary pump and peripheral pump
Deng.
As the preferred scheme of the present invention, the NF membrane in the nanofiltration device is flat film, hollow fiber form film, rolling
Any one in film or tubular membrane or at least two combination, the combination is typical but non-limiting examples have：Flat film and
The combination of hollow fiber form film, the combination of hollow fiber form film and tubular membrane, flat film, hollow fiber form film and tubular membrane
Combination, combination of hollow fiber form film, rolled film and tubular membrane etc..
The present invention utilizes the NF membrane material big to relative molecular weight and negatively charged more material in nanofiltration device
Performance is stopped, by the small material of relative molecular weight and positively charged material, or negatively charged less material and average molecular
Measure big material and negatively charged more material separation.
As the preferred scheme of the present invention, the electric dialyzator includes 1 group with upper diaphragm, and the group number of diaphragm can be 1 group, 2
Group, 3 groups, 4 groups, 6 groups, 8 groups or 10 groups or more, are not limited in above-mentioned listed group number.
Preferably, every group of diaphragm includes 2 cation-exchange membranes and 2 anion-exchange membranes.
Preferably, the current density during electric dialyzator operation is 0.1~1000A/m2, such as 0.1A/m2、10A/m2、
100A/m2、200A/m2、400A/m2、600A/m2、800A/m2Or 1000A/m2Deng.
Preferably, the electric dialyzator be common electrodialysis, bipolar membrane electrodialysis, pole-reversing electroosmosis, liquid film electrodialysis or
Any one in electrolytic electro-dialysis or at least two combination, the typical but non-limiting example of combination have：Common electric osmose
Analysis and the combination of bipolar membrane electrodialysis, pole-reversing electroosmosis and the electrodialytic combination of liquid film, liquid film electrodialysis and electrolytic electro-dialysis
Combination, the combination of common electrodialysis, bipolar membrane electrodialysis and pole-reversing electroosmosis, common electrodialysis, extremely bipolar membrane electrodialysis, electricity
Dialysis, liquid film electrodialysis and combination of electrolytic electro-dialysis etc., but be not limited to that using the species of electric dialyzator, can also be upper
State any one promoted improved electrodialysis or its combination.
Second aspect, the invention provides the processing method of above-mentioned water-soluble liquid treating system, the treating method comprises with
Lower step：
(1) accessing pending water solution carries out nanofiltration processing after pretreatment；
(2) aqueous solution after nanofiltration is handled carries out electrodialysis process.
Wherein, the pretreatment is primarily to remove the particulates such as suspension and the colloid in accessing pending water solution；It is described
Nanofiltration handles the obstruction performance of the material big to relative molecular weight and negatively charged more material, by the small thing of relative molecular weight
Matter and positively charged material, or negatively charged less material and the big material of relative molecular weight and negatively charged more thing
Matter separates；Ion recombination is made easy fouling salting liquid by nanofiltration and electrodialysis to ion analysis point by the electrodialysis process
It is reassembled into the very big salting liquid of solubility.
As the preferred scheme of the present invention, the accessing pending water solution is natural water body, running water, industrial water, industry
Any one in sewage, sanitary wastewater and bitter or at least two combination；Wherein, natural water body is primarily referred to as river, river
Water, lake water or seawater etc., industrial water refer to the condensed water or recirculated water that factory uses, and the accessing pending water solution in the present invention is simultaneously
The above-mentioned water body enumerated is not limited to, as long as the available the application of the water body containing the easy scale-forming ion of divalence or organic matter macromolecular
Described system is handled.
Preferably, CaSO is included in the accessing pending water solution4、MgSO4、CaCO3、MgCO3、CaCl2、MgCl2、Na2SO4、
Na2CO3、K2SO4、K2CO3, any one in fatty acid calcium or calcium oxalate or at least two combination, the combination it is typical but non-
Limitative examples have：CaSO4And MgSO4Combination, MgSO4、CaCO3And MgCO3Combination, CaCl2、MgCl2And Na2SO4Group
Close, Na2SO4、Na2CO3、K2SO4And K2CO3Combination, CaCO3、MgCO3, fatty acid calcium and calcium oxalate combination, CaSO4、
MgSO4、CaCO3、MgCO3, fatty acid calcium and calcium oxalate combination etc..
In the present invention, the accessing pending water solution is primarily referred to as the aqueous solution containing easy scale-forming ion, it is not limited on
State cited species, and in the aqueous solution containing easy scale-forming ion each ion institute can the ionic product of forming salt be its solubility product
0.001~99.99%.
As the preferred scheme of the present invention, pretreatment described in step (1) is flocculation, coagulation, sedimentation, filtering, husky filter, be micro-
Any one in filter, ultrasound, flotation, acidolysis, alkaline hydrolysis or pyrolysis or at least two；The combination typical case but non-limiting examples
Have：The combination of flocculation, coagulation and sedimentation, sedimentation, filtering, husky filter and the combination of micro-filtration, micro-filtration, ultrasound, flotation, acidolysis, alkaline hydrolysis
With the combination of pyrolysis, ultrasound, flotation, acidolysis and the combination of alkaline hydrolysis etc.；Above-mentioned preprocessing process is at routine of the prior art
Reason method, those skilled in the art can be selected according to being actually needed.
As the preferred scheme of the present invention, the pressure that nanofiltration is handled in step (1) is 0.5~40bar, such as 0.5bar,
1bar, 5bar, 10bar, 15bar, 20bar, 25bar, 30bar, 35bar or 40bar etc..
Preferably, the current density of electrodialysis process is 0.1~1000A/m in step (2)2, such as 0.1A/m2、10A/
m2、100A/m2、200A/m2、400A/m2、600A/m2、800A/m2Or 1000A/m2Deng.
As the preferred scheme for doing invention, pretreatment described in step (1) is carried out in pretreatment unit.
Preferably, the nanofiltration processing is carried out in nanofiltration device.
Preferably, the electrodialysis process is carried out in electric dialyzator.
The processing method of above-mentioned water-soluble liquid treating system, it is specially：
(1) accessing pending water solution is pre-processed in pretreatment unit, and nanofiltration device is entered after pressurized in 0.5~40bar
Nanofiltration processing is carried out under pressure；
(2) analysis obtained after nanofiltration is handled point is permeable enters the permeable tank of analysis point, and the analysis point for entering back into electrodialysis plant is saturating
Hydroecium；Analyse fractionation water and enter analysis fractionation water pot, enter back into the analysis fractionation hydroecium of electrodialysis plant.In the presence of dc source,
Analyse the anion analysed in fractionation hydroecium in fractionation water to migrate to anode, enter the weight close to anode side through anion-exchange membrane
Drip chamber, stopped during continuing to migrate to anode by cation-exchange membrane and stay in the rearrangement hydroecium；Analyse fractionation water
The cation in fractionation water is analysed in room to cathodic migration, the rearrangement hydroecium through cation-exchange membrane into close negative electrode side,
Stopped during continuing to cathodic migration by anion-exchange membrane and stay in the rearrangement hydroecium.In the permeable room of analysis point
Anion during analysis point is permeable migrates to anode, enters through anion-exchange membrane close to the dense room of anode side, continues to face south
Pole is stayed in the rearrangement hydroecium by the stop of anion-exchange membrane when migrating；Cation during analysis is point permeable to cathodic migration,
Enter the rearrangement hydroecium close to negative electrode side through cation-exchange membrane, continue to be hindered by cation-exchange membrane to during cathodic migration
Keep off and stay in the rearrangement hydroecium.By electrodialytic transformation, cation and analysis fractionation during analysis obtained by nanofiltration is point permeable
Anion in water is combined into a kind of new salt, the cation group in anion and analysis fractionation water during analysis point obtained by nanofiltration is permeable
Another salt is synthesized, to be reassembled into the very big salt of solubility molten so that each ion easily in fouling salting liquid is split
Liquid.
Compared with prior art, the invention has the advantages that：
The present invention proposes a kind of ion weight combination technology, and this technology combines nanofiltration and electrodialysis, and utilization is electrodialytic
Transformation, the anion in cation and analysis fractionation water of the analysis point obtained by nanofiltration in permeable is combined into a kind of new salt, received
Anion during filter gained analysis is point permeable with the cation combination in concentrate into another salt so that easily fouling salting liquid
In the analysis of each ion point be rearranged into the very big salting liquid of solubility, each ion institute energy in the very big salting liquid of the solubility
The ionic product of forming salt is the 0.001~99.99% of its solubility product.
Meanwhile the life-span of film and equipment is improved using system of the present invention, solve zero-emission near-zero release,
Caused scale problems in the systems such as counter-infiltration, electrodialysis, distillation/evaporation.
Brief description of the drawings
Fig. 1 is the artwork of water-soluble liquid treating system of the present invention；
Fig. 2 is that electrodialysis analysis is allocated as using schematic diagram in water-soluble liquid treating system of the present invention；
Fig. 3 is the structure drawing of device of water-soluble liquid treating system described in the embodiment of the present invention 1；
1- hoppers, 2- feed pumps, 3- accumulators, 4- pressure-relief valves, 5- enter film pressure table, 6- nanofiltration devices, and 7- goes out film pressure
Table, 8- flow valves, 9- dc sources, 10- pole room tanks, the permeable tank of 11- analysis point, 12- analysis fractionation water pots, 13- reset water pot one,
14- reset water pot two, 15- flowmeters, 16- product pumps, 17- positive plates, 18- minus plates, 19- cation-exchange membranes, 20- the moon from
Proton exchange, the permeable room of 21- analysis point, 22- rearrangement hydroeciums one, 23- analysis fractionation hydroeciums, 24- rearrangement hydroeciums two, 25- anode chambers,
26- cathode chambers, 27- pretreatment units.
Embodiment
Below in conjunction with several specific embodiments, exemplary illustration and help further understand the present invention, but embodiment has
Body details does not represent whole technical schemes under present inventive concept merely to the explanation present invention, therefore should not be construed as to this
Total technical scheme to be invented to limit, some are changed without departing from the unsubstantiality of utility model design in technical staff, such as
Simply change or replace with the technical characteristic with same or similar technique effect, belong to the scope of the present invention.
As shown in figure 1, water-soluble liquid treating system of the present invention mainly includes three parts：Pretreatment unit, nanofiltration
Device and electrodialysis plant.
More specifically, the system includes hopper 1, pretreatment unit 27, nanofiltration device, the permeable tank 11 of analysis point, analysis
Fractionation water pot 12 and electrodialysis plant, electrodialysis plant include pole room tank 10, reset water pot, electric dialyzator and dc source electrode
9。
Electric dialyzator includes positive plate 17, minus plate 18, cation-exchange membrane 19, anion-exchange membrane 20, dividing plate, analysis point
Stay hydroecium 23, the permeable room 21 of analysis point, reset hydroecium, anode chamber 25 and cathode chamber 26.
Wherein, the permeable outlet of the analysis point of nanofiltration device 6 is connected with the entrance of the permeable tank 11 of analysis point, the outlet of the permeable tank 11 of analysis point
It is connected with the entrance of the permeable room 21 of analysis point, the outlet of the permeable room 21 of analysis point is connected with the entrance of the permeable tank 11 of analysis point, nanofiltration device 6
Entrance of the analysis fractionation water out simultaneously with analysis fractionation water pot 12 and hopper 1 is connected, outlet and the analysis fractionation of analysis fractionation water pot 12
The entrance of hydroecium 23 is connected, and the outlet of analysis fractionation hydroecium 23 is connected with analysing the entrance of fractionation water pot 12, resets going out for hydroecium 1
Mouth is connected with resetting the entrance of water pot 1, and the outlet for resetting water pot 1 is connected with resetting the entrance of hydroecium 1, rearrangement water
The outlet of room 2 24 is connected with resetting the entrance of water pot 2 14, resets entrance phase of the outlet of water pot 2 14 with resetting hydroecium 2 24
Even, the positive pole of dc source 9 is connected with positive plate, and the negative pole of dc source 9 is connected with minus plate.
Feed pump 2, accumulator 3, pressure-relief valve 4 are additionally provided between the pretreatment unit 27 and nanofiltration device 6 and enters mould
Power table 5.
Preferably, membrane pressure gauge 7 and flow valve 8 are provided with the concentrated solution outlet pipeline of the nanofiltration device 6.
The pole room tank 10, analysis, which divide on the export pipeline of permeable tank 11, analysis fractionation water pot 12 and rearrangement water pot, to be provided with
Flowmeter 15 and product pump 16.
NF membrane in the nanofiltration device 6 is any one in flat film, hollow fiber form film, rolled film or tubular membrane
Or at least two combination.
The electric dialyzator includes 1 group with upper diaphragm.
Preferably, every group of diaphragm includes 2 cation-exchange membranes 19 and 2 anion-exchange membranes 20.
Preferably, the current density during electric dialyzator operation is 0.1~1000A/m2。
Embodiment 1：
As shown in figure 3, present embodiments provide following water-soluble liquid treating system：
A kind of water-soluble liquid treating system, the system are permeable including hopper 1, pretreatment unit 27, nanofiltration device, analysis point
Tank 11, analysis fractionation water pot 12 and electrodialysis plant, electrodialysis plant include pole room tank 10, reset water pot 1, reset water pot two
14th, electric dialyzator and dc source 9.
Electric dialyzator includes positive plate 17, minus plate 18, cation-exchange membrane 19, anion-exchange membrane 20, dividing plate, analysis point
Hydroecium 23, the permeable room 21 of analysis point are stayed, hydroecium 1 is reset, resets hydroecium 2 24, anode chamber 25 and cathode chamber 26.
Wherein, the permeable outlet of the analysis point of nanofiltration device 6 is connected with the entrance of the permeable tank 11 of analysis point, the outlet of the permeable tank 11 of analysis point
It is connected with the entrance of the permeable room 21 of analysis point, the outlet of the permeable room 21 of analysis point is connected with the entrance of the permeable tank 11 of analysis point, nanofiltration device 6
Entrance of the analysis fractionation water out simultaneously with analysis fractionation water pot 12 and hopper 1 is connected, outlet and the analysis fractionation of analysis fractionation water pot 12
The entrance of hydroecium 23 is connected, and the outlet of analysis fractionation hydroecium 23 is connected with analysing the entrance of fractionation water pot 12, resets going out for hydroecium 1
Mouth is connected with resetting the entrance of water pot 1, and the outlet for resetting water pot 1 is connected with resetting the entrance of room 1, rearrangement hydroecium
2 24 outlet is connected with resetting the entrance of water pot 2 14, and the outlet for resetting water pot 2 14 is connected with resetting the entrance of room 2 24,
The outlet of pole room tank 10 is connected with the entrance of anode chamber 25 and cathode chamber 26 simultaneously, and the outlet of anode chamber 25 and cathode chamber 26 is simultaneously
It is connected with the entrance of pole room tank 10, the positive pole of dc source 9 is connected with positive plate, and the negative pole of dc source 9 is connected with minus plate.
Feed pump 2, accumulator 3, pressure-relief valve 4 are provided between the pretreatment unit 27 and nanofiltration device 6 and enters film pressure
Table 5.
Membrane pressure gauge 7 and flow valve 8 are provided with the analysis fractionation water outlet line of the nanofiltration device 6.
The pole room tank 10, the permeable tank 11 of analysis point, fractionation water pot 12 is analysed, reset water pot 1 and resets going out for water pot 2 14
Flowmeter 15 and product pump 16 are provided with mouth pipeline.
NF membrane in the nanofiltration device 6 is flat film.
The electric dialyzator includes 2 groups of diaphragms, and every group of diaphragm includes 2 cation-exchange membranes 19 and 2 anion exchanges
Film 20, current density when electric dialyzator is run is 500A/m2, the electric dialyzator is common electrodialysis.
Embodiment 2：A kind of water-soluble liquid treating system
Except the NF membrane in the nanofiltration device 6 is hollow fiber form film, the electric dialyzator includes 1 group of diaphragm, every group
Diaphragm includes 2 cation-exchange membranes 19 and 2 anion-exchange membranes 20, and current density when electric dialyzator is run is 1000A/
m2, the electric dialyzator is that other devices are in the same manner as in Example 1 outside bipolar membrane electrodialysis.
Embodiment 3：A kind of water-soluble liquid treating system
Except the NF membrane in the nanofiltration device 6 is tubular membrane, the electric dialyzator includes 5 groups of diaphragms, every group of diaphragm bag
2 cation-exchange membranes 19 and 2 anion-exchange membranes 20 are included, current density when electric dialyzator is run is 0.1A/m2, it is described
Electric dialyzator is that other devices are in the same manner as in Example 1 outside pole-reversing electroosmosis.
Embodiment 4：
A kind of water-soluble liquid treating system
Except the electric dialyzator includes 10 groups of diaphragms, every group of diaphragm includes 2 cation-exchange membranes 19 and 2 anion
Exchange membrane 20, the electric dialyzator are that other devices are in the same manner as in Example 1 outside bipolar membrane electrodialysis.
Embodiment 5：
The aqueous solution is handled using system as described in example 1 above, wherein electrodialysis process principle is as shown in Fig. 2 described
Contain Ca in the aqueous solution2+0.01mol/L, Na+0.1mol/L, SO4 2-0.01mol/L, Cl-0.1mol/L。
6 are put into nanofiltration device after the accessing pending water solution is pressurized and nanofiltration separation is carried out under 12bar pressure, contained
Ca2+0.029mol/L, Na+0.14mol/L, SO4 2-0.03mol/L, Cl-0.138mol/L analysis fractionation water and containing Ca2+
0.0008mol/L, Na+0.08mol/L, Cl-0.082mol/L analysis point is permeable, and the analysis fractionation water has basically reached CaSO4It is full
And solubility.
The analysis obtained after nanofiltration is handled point is permeable to enter the permeable tank 11 of analysis point, and the analysis point for entering back into electrodialysis plant is permeable
Room 21；Analyse fractionation water and enter analysis fractionation water pot 12, enter back into the analysis fractionation hydroecium 23 of electrodialysis plant.In the effect of dc source
Under, analyse the anion in fractionation hydroecium in 23 analysis fractionation water and migrated to positive plate 17, enter through anion-exchange membrane 20 and reset
Hydroecium 1, stopped during continuing to migrate to positive plate 17 by cation-exchange membrane 19 and stay in and reset hydroecium one
22；The cation analysed in analysis fractionation hydroecium 23 in fractionation water migrates to minus plate 18, enters through cation-exchange membrane 19 and resets
Hydroecium 2 24, stopped during continuing to migrate to minus plate 18 by anion-exchange membrane and stay in and reset hydroecium 2 24.
In the permeable room 21 of analysis point, the anion during analysis point is permeable migrates to positive plate 17, enters through anion-exchange membrane 20 and resets water
Room 2 24, continue to be stayed in by the stop of anion-exchange membrane 20 when migrating to positive plate 17 and reset hydroecium 2 24；Analysis point is saturating
Cation during analysis point is permeable in hydroecium 21 migrates to minus plate 18, enters through cation-exchange membrane 19 and resets hydroecium 1,
Continue by cation-exchange membrane 19 to be stopped when migrating to minus plate 18 and stay in and reset hydroecium 1.
The analysis point is permeable and analysis divides concentrated water in the presence of electric field and anions and canons exchange membrane, by the permeable He of room 21 of analysis point
The intermediate ion of analysis fractionation hydroecium 23 pulls respectively to double drip chamber, realizes that the analysis point of ion is reset.By electrodialysis, can obtain
Containing Ca2+0.097mol/L, Na+0.47mol/L, Cl-The 0.66mol/L aqueous solution and containing Ca2+0.007mol/L, Na+0.66mol/
L, SO4 2-0.10mol/L, Cl-The 0.46mol/L aqueous solution.0.097mol/L Ca are obtained in the case of completely no fouling2+It is molten
Liquid and 0.10mol/L SO4 2-Solution, far below its saturation solubility, salinity is higher four times than directly using reverse osmosis concentration, most
The rate of recovery of the whole aqueous solution is increased to 90% by 60%..
Embodiment 6：
The aqueous solution is handled using system as described in example 1 above, contains Ni in the aqueous solution2+0.5mol/L, Na+
1.7mol/L, SO4 2-0.5mol/L and Br-1.7mol/L。
Nanofiltration separation is carried out under 20bar pressure into nanofiltration device 6 after the accessing pending water solution is pressurized, is contained
Ni2+1.5mol/L, Na+2.0mol/L, SO4 2-1.5mol/L, Br-2.0mol/L analysis fractionation water and containing Na+1.5mol/L, Br-
1.5mol/L analysis point is permeable.The analysis point is permeable and analysis fractionation water is in the presence of electric field and anions and canons exchange membrane, will wherein
Ion pull to double drip chamber, realize that the analysis point of ion is reset respectively.By electrodialysis, can obtain containing Ni2+5.3mol/
L, Na+7.1mol/L, Br-The 10.6mol/L aqueous solution and containing Na+10.6mol/L SO4 2-5.3mol/L, Br-It is 7.1mol/L water-soluble
Liquid.5.3mol/L Ni are obtained in the case of completely no fouling2+Solution, 10.6mol/L Na+Solution, 10.6mol/L Br-
Solution and 5.3mol/L SO4 2-Solution, less than its saturation solubility, salinity is higher 3.5 times than directly using reverse osmosis concentration, most
The rate of recovery of the whole aqueous solution is increased to 90% by 66%..
Embodiment 7：
The aqueous solution is handled using system as described in example 1 above, contains Ca in the aqueous solution2+0.03mol/L, Na+
0.2mol/L, benzoate anion 0.06mol/L, Cl-0.2mol/L。
Nanofiltration separation is carried out under 5bar pressure into nanofiltration device 6 after the accessing pending water solution is pressurized, is contained
To containing Ca2+0.09mol/L, Na+0.25mol/L, benzoate anion 0.18mol/L, Cl-0.25mol/L analysis fractionation water and containing Na+
0.18mol/L, Cl-0.18mol/L analysis point is permeable.Both solution respectively enter the permeable room of different analysis point of electric dialyzator,
In the presence of electric field and anions and canons exchange membrane, freshwater room intermediate ion is pulled to two rearrangement hydroeciums respectively, realizes ion
Analysis point reset.By electrodialysis, can obtain containing Ca2+1.8mol/L, Na+5.0mol/L, Cl-3.6mol/L rearrangement water and
Containing Na+3.6mol/L, benzoate anion 3.6mol/L, Cl-5.0mol/L.1.8mol/L is obtained in the case of completely no fouling
Ca2+Solution and 3.6mol/L benzoate anion solution, far below its saturation solubility, salinity ratio is directly improved with distillation and concentration
20 times, the rate of recovery of the final aqueous solution is increased to 98% by 66%.
Embodiment 8：
In addition to carrying out nanofiltration separation under 40bar pressure into nanofiltration device 6 after the accessing pending water solution is pressurized, its
He operates and material amounts are in the same manner as in Example 5.
Embodiment 9：
In addition to carrying out nanofiltration separation under 0.5bar pressure into nanofiltration device 6 after the accessing pending water solution is pressurized,
Other operations and material amounts are in the same manner as in Example 5.
Integrated embodiment 1-9 can be seen that the present invention and propose a kind of ion weight combination technology, and this technology is by nanofiltration and electricity
Dialysis combines, using electrodialytic transformation, by cation and analysis fractionation water of the analysis point obtained by nanofiltration in permeable it is cloudy from
Subgroup synthesizes a kind of new salt, anion during analysis point obtained by nanofiltration is permeable and analyses cation combination in fractionation water into other one
Kind salt, so that each ion analysis point easily in fouling salting liquid is rearranged into the very big salting liquid of solubility, the solubility is non-
Often in big salting liquid each ion institute can the ionic product of forming salt be the 0.001~99.99% of its solubility product；
Meanwhile the life-span of film and equipment is improved using system of the present invention, solve zero-emission near-zero release,
Caused scale problems in the systems such as counter-infiltration, electrodialysis, distillation/evaporation.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (20)
1. a kind of water-soluble liquid treating system, it is characterised in that the system includes hopper (1), pretreatment unit (27), nanofiltration
Device, the permeable tank (11) of analysis point, analysis fractionation water pot (12) and electrodialysis plant, electrodialysis plant include pole room tank (10), reset
Water pot, electric dialyzator and dc source (9)；
Electric dialyzator include positive plate (17), minus plate (18), cation-exchange membrane (19), anion-exchange membrane (20), dividing plate,
Analyse fractionation hydroecium (23), the permeable room (21) of analysis point, reset hydroecium, anode chamber (25) and cathode chamber (26)；
Wherein, the permeable outlet of the analysis of nanofiltration device (6) point is connected with the entrance of the permeable tank (11) of analysis point, and analysis point permeable tank (11) goes out
Mouth is connected with the entrance of the permeable room (21) of analysis point, and the outlet of the permeable room (21) of analysis point is connected with analysing the entrance of point permeable tank (11),
Entrance of the analysis fractionation water out of nanofiltration device (6) simultaneously with analysis fractionation water pot (12) and hopper (1) is connected, and analyses fractionation water pot
(12) outlet is connected with the entrance of analysis fractionation hydroecium (23), the outlet of analysis fractionation hydroecium (23) and entering for analysis fractionation water pot (12)
Mouth is connected, and the outlet for resetting hydroecium is connected with resetting the entrance of water pot, and the outlet for resetting water pot is connected with the entrance of rearrangement hydroecium,
The positive pole of dc source (9) is connected with positive plate (17), and the negative pole of dc source (9) is connected with minus plate (18).
2. water-soluble liquid treating system according to claim 1, it is characterised in that the pretreatment unit (27) and nanofiltration device
(6) feed pump (2), accumulator (3), pressure-relief valve (4) are additionally provided between and enters film pressure table (5).
3. water-soluble liquid treating system according to claim 1, it is characterised in that the analysis fractionation water of the nanofiltration device (6) goes out
Membrane pressure gauge (7) and flow valve (8) are provided with mouth pipeline.
4. water-soluble liquid treating system according to claim 2, it is characterised in that the feed pump (2) is centrifugal pump, back and forth
Any one in pump, rotary pump or peripheral pump or at least two combination.
5. water-soluble liquid treating system according to claim 1, it is characterised in that the pole room tank (10), the permeable tank of analysis point
(11), analyse and be provided with flowmeter (15) and product pump (16) on the entrance pipe of fractionation water pot (12) and rearrangement water pot.
6. water-soluble liquid treating system according to claim 5, it is characterised in that the product pump (16) is centrifugal pump, past
Any one in multiple pump, rotary pump or peripheral pump or at least two combination.
7. water-soluble liquid treating system according to claim 1, it is characterised in that the NF membrane in the nanofiltration device (6) is
Any one in flat film, hollow fiber form film, rolled film or tubular membrane or at least two combination.
8. water-soluble liquid treating system according to claim 1, it is characterised in that the electric dialyzator includes more than 1 group film
Piece.
9. water-soluble liquid treating system according to claim 8, it is characterised in that every group of diaphragm includes 2 cation exchanges
Film (19) and 2 anion-exchange membranes (20).
10. water-soluble liquid treating system according to claim 1, it is characterised in that the electric current during electric dialyzator operation
Density is 0.1~1000A/m2。
11. water-soluble liquid treating system according to claim 1, it is characterised in that the electric dialyzator be common electrodialysis,
Any one in bipolar membrane electrodialysis, pole-reversing electroosmosis, liquid film electrodialysis or electrolytic electro-dialysis or at least two combination.
12. the processing method of the water-soluble liquid treating system according to claim any one of 1-11, it is characterised in that the place
Reason method comprises the following steps：
(1) accessing pending water solution carries out nanofiltration processing after pretreatment；
(2) aqueous solution after nanofiltration is handled carries out electrodialysis process.
13. processing method according to claim 12, it is characterised in that the accessing pending water solution is natural water body, certainly
Any one in water, industrial water, trade effluent, sanitary wastewater and bitter or at least two combination.
14. processing method according to claim 12, it is characterised in that CaSO is included in the accessing pending water solution4、
MgSO4、CaCO3、MgCO3、CaCl2、MgCl2、Na2SO4、Na2CO3、K2SO4、K2CO3, it is any one in fatty acid calcium or calcium oxalate
Kind or at least two combination.
15. processing method according to claim 12, it is characterised in that pretreatment described in step (1) is flocculation, mixed
Any one in solidifying, sedimentation, filtering, husky filter, micro-filtration, ultrasound, flotation, acidolysis, alkaline hydrolysis or pyrolysis or at least two combination.
16. processing method according to claim 12, it is characterised in that the pressure that nanofiltration is handled in step (1) for 0.5~
40bar。
17. processing method according to claim 16, it is characterised in that the current density of electrodialysis process in step (2)
For 0.1~1000A/m2。
18. processing method according to claim 12, it is characterised in that pretreatment fills in pretreatment described in step (1)
Put in (27) and carry out.
19. processing method according to claim 12, it is characterised in that the nanofiltration processing is entered in nanofiltration device (6)
OK.
20. processing method according to claim 12, it is characterised in that the electrodialysis process is entered in electric dialyzator
OK.
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| CN106693710A (en) * | 2017-01-19 | 2017-05-24 | 浙江大维高新技术股份有限公司 | Electrodialyzer and solution treating method thereof |
| CN107265734B (en) * | 2017-08-03 | 2020-07-10 | 国家海洋局天津海水淡化与综合利用研究所 | Reverse osmosis concentrated seawater treatment system and method |
| CN107522268B (en) * | 2017-08-15 | 2020-11-03 | 中国科学院青岛生物能源与过程研究所 | Device for water treatment and material separation and separation method thereof |
| CN108793544A (en) * | 2018-04-26 | 2018-11-13 | 浙江大维高新技术股份有限公司 | A kind of Zero discharge treatment method of desulfurization wastewater |
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| CN108793522B (en) * | 2018-07-14 | 2021-03-09 | 浙江大维高新技术股份有限公司 | Concentration and reduction process for desulfurization wastewater |
| CN110038440B (en) * | 2019-05-30 | 2021-07-27 | 河北工业大学 | Bipolar membrane electrodialysis device and method for seawater decalcification |
| CN110980883A (en) * | 2019-12-24 | 2020-04-10 | 天津膜天膜科技股份有限公司 | Method for removing divalent ions in water by whole membrane method |
| CN111620483A (en) * | 2020-05-07 | 2020-09-04 | 金达泰克电子系统(北京)有限公司 | Non-dosing zero-emission membrane softening system and method for radiation environment |
| CN113233662A (en) * | 2021-05-31 | 2021-08-10 | 南开大学 | Integrated membrane process treatment system and method for seawater desalination concentrated seawater |
| CN114890511A (en) * | 2022-03-03 | 2022-08-12 | 佰仕邦水处理环保科技(大连)有限公司 | Dialysis membrane stack |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US12040517B2 (en) | 2022-11-15 | 2024-07-16 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell and methods of use thereof |
| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
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