CN103073146A - Waste water treatment method and device based on forward osmosis and membrane distillation - Google Patents
Waste water treatment method and device based on forward osmosis and membrane distillation Download PDFInfo
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- CN103073146A CN103073146A CN2013100479401A CN201310047940A CN103073146A CN 103073146 A CN103073146 A CN 103073146A CN 2013100479401 A CN2013100479401 A CN 2013100479401A CN 201310047940 A CN201310047940 A CN 201310047940A CN 103073146 A CN103073146 A CN 103073146A
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Abstract
The invention belongs to the field of sewage treatment, and particularly relates to a waste water treatment method and device based on forward osmosis and membrane distillation. The waste water treatment method based on the forward osmosis and membrane distillation comprises a waste water concentration process and a drive liquid circulation process, wherein the waste water concentration process adopts a forward osmosis technology to concentrate waste water with high salt content and high chemical oxide demand (COD) concentration through drive liquid so as to obtain the concentrated waste water and diluted drive liquid; the drive liquid circulation process adopts a membrane distillation technology to dehydrate the diluted drive liquid so as to obtain the purified water and renewable drive liquid; and the renewable drive liquid is repeatedly used for the waste water concentration process so as to continuously concentrate the waste water. Due to the adoption of the method and device for treating the waste water with high salt content and high COD concentration, the waste water of different sources and fields can be treated, and the advantages such as wide applicability for waste water, stability in running and low treatment cost can be realized.
Description
Technical field
The invention belongs to sewage treatment area, be specifically related to a kind of method of wastewater treatment and device based on just permeating with membrane distillation.
Background technology
High slat-containing wastewater is the waste water that is difficult to effectively process qualified discharge that a kind of industrial production faces at present, main representative waste water comprises shale gas pressure break waste water, glyphosate trade effluent, Silver Nitrate waste water, titanium dioxide waste water, the copper sulfate trade effluent, pharmacy waste water, dyeing waste water, oil field waste etc., these waste water not only have very high saltiness, usually also contain very high chemical oxygen demand cod, and have very low biodegradability.The treatment technology method that neither one has the economical and efficient of the wider model scope of application is gone back in processing for the waste water of the high COD concentration of high saliferous.
At present the main methods of high slat-containing wastewater comprises that chemical agent processes, and regulates the acid-basicity of waste water, distillation, or precipitation, ion-exchange, electrodialysis and multiple-effect evaporation, reverse osmosis, membrane bioreactors etc. are united use, and multi-step is gone out the salinity in the waste water, reach the standard of discharging.The investment of these treatment processs is large, complex process, energy consumption are high, and processing cost is high.For example Chinese patent CN101798150A " treatment process of high slat-containing wastewater and treatment unit thereof " has announced a kind for the treatment of process take the RO treatment process as core, in order to reach the water inlet requirement of RO system, employing adds acid for adjusting pH value and carbonate hardness, adopts Na-ion exchanger to remove permanent hardness, adopts the weak acid ion-exchanger to remove carbonate hardness, remove deliquescent CO
2Method satisfy the water inlet index request of RO, the cost of the method ion-exchange when processing high level solvability salt waste water is too high, also is not suitable for the waste water of high COD content, range of application is narrow, and processing cost is high.Patent CN101857321 " reverse osmosis concentrated water and the complicated wastewater treatment of high saliferous and reuse method and equipment " has announced and has adopted tubular membrane to separate the method for processing through the RO device again, the method needs a large amount of chemical agents, processing cost is high, is not suitable for the lower high slat-containing wastewater of heavy metal ion and high-COD waste water.Patent CN102001776 has announced a kind of " process for reclaiming of highly salt containing organic waste water and device ", adopt the method that adds the chemical agent sedimentation and filtration to remove heavy metal ion in the water, adopt the method for salt concn in electro-adsorption desalination, the electrolytic chlorine Techniques For Reducing water, the method processing cost is high, energy consumption is high, and same range of application is narrower; Patent CN102583876 has announced a kind of " treatment unit of high saline sewage and treatment process thereof ", adopt electrodialytic method to reduce salt concn, adopt the COD in the biochemistry pool reduction waste water, the method when salt concn is very high in waste water the electrodialysis cost very high, desalting efficiency reduces, when wastewater biodegradability is low, remove the poor effect of COD, have equally a lot of limitation; Among the patent CN102092887 " the high saliferous industrial wastewater treatment system of high density and method ", adopt equalizing tank, neutralization tank, settling tank, electrocoagulation, A/O biological contact oxidation pond, precipitation late, a series for the treatment of process such as activated carbon filtration sterilization, technical process is complicated, take up an area large, investment and running cost are high, also are not suitable for the processing of the relatively poor high saliferous high-COD waste water of biodegradability; Among the patent CN102616973 " treatment process of highly salt containing organic waste water and treatment unit thereof ", the Technology that adopts multiple-effect evaporation to be combined with the MVR system, can effectively reduce energy consumption with respect to general multiple-effect evaporation, but for the high high slat-containing wastewater of corrodibility, facility investment is high, and energy consumption is still very high; Among the patent CN102390902 " the dense water drying and other treatment of high saliferous system ", adopt the treatment process of multiple-effect evaporation crystallization, facility investment is high, and operation energy consumption is high, and the scope of application is little; Among the patent CN102616996 " a kind of method and dedicated system of processing the composite waste of supersalinity ", adopt the technique of processing through employing RO behind the ultrafiltration membrance filter again behind the A2/O biochemical processing process, facility investment is higher, floor space is large, and the high slat-containing wastewater low for biodegradability can't effectively move; Among patent CN102642947 " supercritical water oxidation treatment system of highly salt containing organic waste water ", the patent CN102249461 " supercritical water oxidation treatment system of the high chlorine organic wastewater of high saliferous ", the treatment technology that adopts supercritical water oxidation treatment system (SCWO) to combine with evaporation, facility investment is high, and operation energy consumption is high; Among the patent CN102363546 " a kind for the treatment of system of high salinity pharmaceutical wastewater ", adopt the treatment process in catalysis and micro-electrolysis+hydrogen peroxide catalytic oxidation+photosynthetic bacteria anaerobic system+photosynthetic bacteria aerobic system+coagulation decoloration pond, mainly for pharmaceutical industry specific some have the processing of the high-COD waste water of certain saltiness; During patent CN101402509 " processes Sewage treatment systems and the treatment process of high slat-containing wastewater ", adopt biochemical treatment system to combine with the salt crystal system, wherein the salt crystal system adopts the technique of membrane bioreactor (MBR)+ultrafiltration+two-pass reverse osmosis, the integrated artistic long flow path, floor space is large, investment and working cost are high, and it is poor to surpass the poor water treatment effect of 5% waste water or biodegradability for salts contg.
All in all, there are respectively the shortcomings such as processing cost is high, investment is large, the RO film is seriously polluted, processing water source salt concn is on the low side in above method, for the poor deficiencies such as waste water weak effect of biodegradability, in the processing of the high COD concentration of high saliferous waste water, can not be promoted on a large scale.Particularly reverse osmosis process has been widely used in sea water desaltination, boiler water processing, since its large-scale application, the cost reduced year by year.But reverse osmosis process must overcome the high osmotic pressure of waste water, no matter all is infeasible on practice and energy consumption so directly utilize reverse osmosis process to process high slat-containing wastewater.The concentrated water discharge problem of reverse osmosis has more and more caused concern in addition, because such dense draining has become the source of pollution of new class.Therefore, the alternative method of searching reverse osmosis has become new research direction.
Just permeating the recent studies on achievement with membrane distillation process Membrane Separation for Water Treatment.Than reverse osmosis, just permeating with membrane distillation and be described as a new generation, less energy-consumption desalination technology.
The principle of just permeating is for utilizing the selectivity semi-permeable membranes to be separating medium, and take the permeable pressure head of the solution of film both sides as impellent, under the effect that does not need impressed pressure, water molecules is penetrated into high osmotic pressure side (driving the liquid side) from feeding side automatically.In this process, feeding liquid is concentrated, and drives liquid and is diluted.Because process is spontaneous, select suitable driving solution just can realize concentration to charging, thereby this process compare with reverse osmosis process, it is low to have energy consumption, eco-friendly advantage.Membrane distillation then is take hydrophobic membrane as separating medium, in the situation away from the boiling point of water, utilizes that the vapor partial pressure of film both sides is poor to be impellent, realizes the concentrated and reuse to waste water.Membrane distillation adopts hydrophobic mould material, can only allow air penetrating film, water then can not see through film, the partial pressure that its separation motivating force is the film both sides is poor, membrane distillation feed side solution generally needs higher temperature that higher partial pressure is provided, and opposite side adopts the liquid of lesser temps or the mode that vacuumizes to reduce partial pressure, therefore film distillation technology is divided into again direct contact membrane distillation (DCMD) technology and vacuum membrane distillation (VMD) technology, adopts in addition the method for gas purging also can effectively reduce the partial pressure of producing the water side.Because the membrane distillation film can only allow vapour transmission, all have higher rejection, can process the aqueous solution of high density.It is concentrated to can be used for biological products, food-processing, and the processing of high slat-containing wastewater.Theoretically, membrane distillation be unique one once going on foot the membrane process that can obtain pure water.
Simultaneously, film distillation technology is with respect to general distillation technique, its mould material is generally macromolecular material, has good corrosion resistance nature, saved the cost of distillation plant costliness, the membrane distillation film provides the high-specific surface area that common distillation did not have simultaneously, and the saturating amount of water vapor can meet the demands under lower service temperature, generally can utilize low-grade thermal source (such as used heat, sun power, underground heat etc.), have good economic performance.The membrane distillation process is compared with reverse osmosis, and it is low to have energy consumption, can process the characteristics applied widely of water.
But the membrane pollution problem of membrane distillation process is to affect the bottleneck that membrane distillation is used.The generation of the pollution of membrane distillation process comprises that the existence of organism in the solution, microorganism and some easy structure salts causes the hydrophobicity of film to reduce, even film is wetting thereby move unsuccessfully.Therefore film pollutes and causes the suitability of membrane distillation process greatly to reduce.Determine, form the operation stability that feeding liquid relatively single, less scaling and that be difficult for polluted membrane will improve membrane distillation if use component, but actual should in water quality go very complicatedly, all can't solve membrane pollution problem so directly send sharp a lot of waste water with membrane distillation.
Corresponding, positive process of osmosis is utilized high osmotic pressure, and the driving liquid that component is determined concentrates charging, drive liquid in the operational process and be diluted, and drive liquid effectively, less energy-consumption is reclaimed is the key of positive infiltration applications.Because the driving liquid that is just permeating reclaims the pollution problem of problem and membrane distillation, the present invention is in connection with the advantage of just permeating with membrane distillation, utilize positive process of osmosis that high slat-containing wastewater is processed, utilize film distillation technology to align osmotic drive liquid and reclaim, realize less energy-consumption processing and the reuse of high slat-containing wastewater.
Summary of the invention
The object of the present invention is to provide a kind of method of wastewater treatment and device of processing pesticide wastewater, the high COD concentration of the contour saliferous of trade effluent.
The present invention at first discloses a kind of method of wastewater treatment based on just permeating with membrane distillation, comprises Waste water concentrating technique and drives the liquid circulation technology; Wherein, described Waste water concentrating technique is for adopting positive infiltration technology, by driving liquid the high COD concentration of high saliferous waste water is concentrated, the waste water after obtaining to concentrate and the driving liquid after the dilution, the osmotic pressure of described driving liquid is higher than the osmotic pressure of the high COD concentration of high saliferous waste water; Described driving liquid circulation technology dewaters the water (purified water) behind the acquisition purifying, and regenerative drives liquid for the driving liquid after adopting film distillation technology to dilution; Described regenerative drives liquid is re-used in Waste water concentrating technique, continues on for waste water is concentrated.
More excellent, described method of wastewater treatment based on just permeating with membrane distillation, its step is as follows:
1) Waste water concentrating technique: at first the high COD concentration of high saliferous waste water is carried out pre-treatment, remove suspended substance and/or solid matter in the waste water; Pretreated waste water enters and just permeates assembly, and under the effect of osmotic pressure, the water in the waste water sees through the forward osmosis membrane that is just permeating assembly and enters driving liquid, after just permeating assembly, and the waste water after obtaining respectively to concentrate and the driving liquid after the dilution; Discharging after waste water after concentrated is further processed;
2) drive the liquid circulation technology: the driving liquid after the dilution flows out from just permeating the assembly, is heated to 40～65 ℃, obtains heat and drives liquid; Described heat drives liquid and enters the membrane distillation assembly; Under the poor driving of steam partial pressure, heat drives dewatering microporous film that the water in the liquid sees through the membrane distillation assembly with the form of water vapour and enters and produce the water side; Enter and obtain purified water after the water vapor condensation that produces the water side reclaims, it is concentrated that heat drives the liquid dehydration, obtains regenerative drives liquid;
3) will drive the regenerative drives liquid that the liquid circulation technology obtains and again be applied to Waste water concentrating technique, realize driving the recycle of liquid, and the lasting processing of the high COD concentration of high saliferous waste water.
The high COD concentration of high saliferous of the present invention waste water be total dissolved solid content at 100000～200000mg/l, COD content is less than or equal to the waste water of 2000mg/l.Further, the high COD concentration of high saliferous of the present invention waste water comprises shale gas pressure break waste water, glyphosate trade effluent, Silver Nitrate waste water, titanium dioxide waste water, copper sulfate trade effluent, pharmacy waste water, dyeing waste water, oil field waste etc.
The pending high COD concentration of high saliferous waste water among the present invention, and drive the liquid concentration crystallization concentration that all do not reach capacity.The osmotic pressure that drives liquid is higher than the osmotic pressure of pending waste water.
When adopting positive osmose process place that waste water is concentrated, forward osmosis membrane drives the liquid side, and the temperature range that drives liquid is 5～95 ℃; Be preferably 10～45 ℃; Optimum is 15～40 ℃.
The pre-treatment of the high COD concentration of high saliferous of the present invention waste water is prior art, and its purpose is suspended substance, solid matter and the part COD etc. that remove in the waste water, is convenient to the further processing of follow-up waste water.More excellent, the described pre-treatment of step 1) adopts more medium filter and activated charcoal filter to carry out filtration treatment for adopting coagulation sedimentation to remove suspended substance and part COD in the water, perhaps adopts cartridge filter to filter, and removes larger solid matter in the water.
The material of forward osmosis membrane of the present invention and structure are prior art.More excellent, the described forward osmosis membrane material of step 1) is selected from one or more the combination in cellulosetri-acetate, cellulose acetate, polysulfones, polyethersulfone, polyacrylonitrile, sulfonated polyether-ether-ketone, polyvinylidene difluoride (PVDF), the polyimide.The membrane structure of forward osmosis membrane comprises the symmetric double cortex construction, asymmetric single skin structure composite film, and interfacial polymerization film.Preferably, the interception capacity of forward osmosis membrane NaCl of the present invention is not less than 90%.Take the NaCl aqueous solution of 0.5M as driving solution, pure water is charging, its water flux dense layer surface in the face of the prerequisite that drives liquid under, the ratio of its reverse salt transmission rates and water flux is lower than 3g/L.
The osmotic pressure that the present invention drives liquid should be higher than the osmotic pressure of the high COD concentration of high saliferous waste water, could be under the driving effect of osmotic pressure, and make water in the waste water see through forward osmosis membrane and enter driving liquid.Because the difference that mould material both sides liquid infiltration is pressed, the osmotic pressure of waste water side is lower than the osmotic pressure that drives the liquid side, water enters under the driving of osmotic pressure from the waste water side and drives the liquid side, the salt and the organism that exist with ion or complex compound form in the waste water are trapped in feed side by FO film (forward osmosis membrane), exit at forward osmosis membrane, waste water by concentrate near crystallization concentration, thereby reach once purpose with the pollutent concentrating and separating.
The further processing of the waste water after concentrated in the step 1) is selected from crystallisation by cooling, evaporation or further concentrated by just permeating assembly again.Volume through waste water after concentrated greatly reduces, and can technique at lower cost further process rear discharging.
Driving liquid of the present invention can adopt the driving liquid of prior art.More excellent, described driving liquid solute is selected from any in inorganic salts, organic molecule, organic molecule salt, complex polyelectrolyte particle, protein, the minuteness particle, and described driving liquid solvent is water.
More excellent, described inorganic salts is selected from NaCl, KCl, MgCl
2, KNO
3, NaNO
3, NH
4HCO
3, Na
2SO
4, K
2SO
4, Ca(NO
3)
2, (NH
4)
2HPO
4, (NH
4)
3PO
4, Na
3PO
4In one or more combination; Described organic molecule is selected from vitamins C, glucose, sucrose, fructose, glycerine, ethylene glycol and oligomer thereof, the combination of one or more in the amino acid; Described organic molecule salt is selected from one or more the combination in quadrol, EDTA, DTPA, magnesium acetate, the sodium acetate; Described complex polyelectrolyte particle is selected from one or more the combination in polyvinylamine, polyacrylic acid, polyamide-based amine hydrochlorate, vitriol, the sulfonated polystyrene; Described protein is selected from a kind of in bovine serum albumin, the magnetic storage ferritin or both combinations; Described minuteness particle is selected from one or more the combination in modification magnetic nano-particle, the modification Jenner grain of rice, dendrimer polyamide-based amine, the Temperature Responsive Polymer As gel.
More excellent, step 2) described film distillation technology (MD) is selected from direct contact membranes distil process (DCMD), vacuum membrane distillation technique (VMD) or sweep gas membrane distillation technique.
More excellent, when adopting the driving liquid after direct contact membranes distil process (DCMD) is processed dilution, make the external source pure water enter the product water side of membrane distillation assembly, the water vapor that sees through dewatering microporous film by external source pure water cooling and absorbing after, leave the membrane distillation assembly with the external source pure water, cooling obtains purified water.The advantage of this technique is that technique is simple, and is lower to equipment requirements, and shortcoming is that thermo-efficiency is lower.
More excellent, when adopting the driving liquid after vacuum membrane distillation technique (VMD) processing is diluted, dewatering microporous film produces the water side and adopts vacuum pump to extract the water vapour that enters product water side through the membrane distillation film, and then water vapor condensation obtains purified water.In the method, uncooled water vapour and non-condensable gas be by vacuum pump suction discharging, and the advantage of this technique is can Effective Raise membrane distillation film both sides steam partial pressure poor, and thermo-efficiency can be utilized preferably, and shortcoming is higher to equipment requirements.
More excellent, when adopting the driving liquid after the sweep gas membrane distillation technique is processed dilution, membrane distillation produces the water side inlet mouth and air outlet, the vacuum pump suction is adopted in the air outlet, inlet mouth communicates with atmosphere,, with air intake membrane distillation element the steam purging that sees through dewatering microporous film is collected by the vacuum pump suction, obtained purified water after the condensation.The method can effectively reduce the steam partial pressure that produces the water side, and reduced product water side temperature, thereby improve film both sides water vapour pressure reduction, this technological advantage is the investment that has reduced the membrane distillation components of system as directed, do not need special low-temperature receiver, be adapted at using under residual heat resources are abundant and water resources is the not in short supply condition.
Driving liquid after the present invention adopts membrane distillation technique to dilution carries out thickening, with respect to direct evaporation concentration technique or multiple-effect evaporation concentration technique, the operating temperature range that its advantage is mainly membrane distillation is relatively low, the general work scope is 10-100 ℃, the recommended work temperature range is 30-80 ℃, more preferably 40-65 ℃, in this temperature range, can adopt factory's used heat, sun power, low-grade thermal source such as underground heat, and do not need the thermal source of high-quality high value, reach the purpose that reduces cost.
In driving the liquid circulation technology, after driving liquid is warming up to 40～65 ℃, heat drives liquid and enters membrane distillation assembly feed side, the mould material of membrane distillation adopts high hydrophobic material to make, therefore liquid water can not see through film, only having the gas such as water vapour can see through film enter and produce the water side, because it is higher to drive liquid temp, its water vapour is higher than product water side steam partial pressure, under the poor driving of film both sides steam partial pressure, water vapor enters product water side from driving the liquid side, and driving liquid dries out and is concentrated, get back to positive osmosis system as regenerative drives liquid at last, thereby reached the purpose that drives the liquid recycle.
More excellent, method of wastewater treatment of the present invention also comprises the heat utilization process, and described heat utilization process is for adopting the waste-heat heating step 2 of regenerative drives liquid) driving liquid after the dilution, obtain heat and drive liquid; And/or the waste-heat heating step 2 of employing product water side purified water) the driving liquid after the dilution obtains heat driving liquid.
The regenerative drives fluid residual heat:
Owing to also have certain temperature from membrane distillation assembly feed side regenerative drives liquid out, before entering the forward osmosis membrane assembly, need to cool off, in order effectively to utilize heat energy wherein, adopt the method for thermal exchange, carry out heat exchange with the driving liquid after the lower dilution of the temperature that flows out from the forward osmosis membrane assembly, both utilize heat energy, reduced again the cooling load that needs.
More excellent, when adopting the waste heat of regenerative drives liquid, described heat utilization process is: the regenerative drives liquid that the band that will flow out from the membrane distillation assembly has surplus heat is transported to interchanger, by the method for direct heat exchange, and carries out heat exchange from the driving liquid that just permeates after the dilution that assembly flows out; The regenerative drives liquid that the band that perhaps will flow out from the membrane distillation assembly has surplus heat is transported to the vaporizer of thermal-pump unit, and interchanger and the driving liquid after the dilution of just permeating assembly outlet outflow through thermal-pump unit carries out heat exchange again.
Can make the heat energy that changes into temperature higher (grade is higher) with the regenerative drives liquid of waste heat by heat pump techniques, be used for follow-up thermal exchange.
On the one hand, driving the fluid residual heat heating technique can adopt driving liquid directly to carry out thermal exchange through interchanger, process flow diagram is seen Fig. 4, also have certain temperature from membrane distillation assembly feed side regenerative drives liquid out, before entering the forward osmosis membrane element, need to cool off, in order effectively to utilize heat energy wherein, adopt the technology of direct heat exchange, enter interchanger and carry out heat exchange with the cold driving liquid that exports from the forward osmosis membrane element, both utilized heat energy, reduced again the cooling load that needs.
On the other hand, drive the fluid residual heat heating technique and can also adopt heat pump techniques, process flow diagram is seen Fig. 5, enter vaporizer the thermal-pump unit from the membrane distillation assembly regenerative drives liquid with waste heat out, heating heat pump heat transferring medium, drive liquid temp and be cooled to normal temperature, then enter in the forward osmosis membrane assembly, and heat pump compresses after heat transferring medium is heated up, temperature further rises, enter the interchanger heating from forward osmosis membrane assembly cold driving liquid out, reached so the efficient purpose of utilizing of waste heat.
Produce water side purified water waste heat
When step 2) when adopting the driving liquid after direct contact membrane distillation technique (DCMD) is processed dilution, produce the utilization of water side purified water waste heat and can adopt hot water direct heat exchange technology and/or hot water heat pump technology; When step 2) when adopting the driving liquid after vacuum membrane distillation technique (VMD) or sweep gas membrane distillation technique are processed dilution, produce the utilization of water side purified water waste heat and can adopt steam direct heating technology, steam heat pump technology and/or vapor recompression intensification heating technique.
More excellent, described hot water direct heat exchange technology is: the product water side purified water that the band that flows out from the membrane distillation assembly the is had surplus heat interchanger of flowing through, by the method for direct heat exchange, and carry out heat exchange from the driving liquid that just permeates after the dilution that assembly flows out.
This techniqueflow of hot water direct heat exchange technology is simple, reduced investment, but heat utilization rate is lower, see Fig. 6, membrane distillation adopts direct contact type DCMD technique, namely produces the water side and utilizes the circulation of external source pure water to absorb the water vapour that sees through film, water temperature after absorbing water vapour raises, this part water enters interchanger after leaving the membrane distillation assembly, and preheating is from just permeating the assembly cold driving liquid out, and hot water has also reached the purpose of cooling simultaneously.
More excellent, described hot water heat pump technology is: the product water side purified water that the band that will flow out from the membrane distillation assembly has surplus heat is transported to the vaporizer of thermal-pump unit, and interchanger and the driving liquid after the dilution of just permeating the assembly outflow through thermal-pump unit carries out heat exchange again.
Produce water side purified water when flowing through the vaporizer of thermal-pump unit, low grade heat energy can be changed into higher-grade heat energy, be used for follow-up thermal exchange.
It is in order to improve the utilization efficiency of heat energy of hot water direct heat exchange technology that the present invention adopts the purpose of hot water heat pump technology, and its process flow diagram is seen Figure of description 7.Product water side at the membrane distillation assembly, temperature raise after the external source pure water absorbed in the membrane distillation assembly and sees through the water vapour of film, enter vaporizer in the heat pump after leaving the membrane distillation assembly, heating heat pump heat transferring medium, hot water self obtains cooling, and the heat pump heat exchanging medium temperature raises and enters interchanger by further rising of overdraft temperature, and heating drives liquid from forward osmosis membrane assembly low temperature out, improved like this heat transfer temperature difference, heat energy obtains better utilised.
More excellent, described steam direct heating technology is: suction sees through the water vapour of dewatering microporous film, carries out heat exchange by interchanger and from the dilution rear-guard hydrodynamic that just permeates the assembly outflow.
When membrane distillation adopts vacuum membrane distillation (VMD) technique, the water vapour that sees through the membrane distillation film extracts by vacuum pump or compressor, the utilization of the heat energy of this part water vapour can be adopted the utilization of direct heat exchange technology, see Fig. 8, similar with hot water heat transfer technology technique, this technical process is simple, reduced investment, but heat energy utilization is slightly low, but specific heat water direct heat-exchange technology is slightly good.Detailed process is left the membrane distillation assembly and is directly entered the interchanger heating from just permeating assembly low temperature driving liquid out for the hot steam that sees through the membrane distillation film is sucked, hot steam is cooled into water and leaves interchanger.
More excellent, described steam heat pump technology is: suction sees through the water vapour of dewatering microporous film, is transported to the vaporizer of thermal-pump unit, and interchanger and the driving liquid after the dilution of just permeating the assembly outflow through thermal-pump unit carries out heat exchange again.
Adopting the purpose of steam heat pump technology is in order to improve the thermo-efficiency of steam direct heat exchange technology, its process flow diagram is seen Figure of description Fig. 9, the hot steam who sees through dewatering microporous film enters the heat pump vaporizer after being sucked and leaving the membrane distillation assembly, heating heat pump heat transferring medium, water vapour is cooled into water, the heat pump heat exchanging medium is heated and compresses rear temperature and further raises, enter the interchanger heating of thermal-pump unit from just permeating assembly cold driving liquid out, improved like this heat transfer temperature difference, heat energy obtains better utilised.The advantage of this technique is that low-grade heat energy obtains better utilised, and shortcoming is that the heat pump investment is higher, is fit to fairly large system.
More excellent, described vapor recompression intensification heating technique is: suction sees through the water vapour of dewatering microporous film, at first compresses, then carries out heat exchange through interchanger and the driving liquid after the dilution of just permeating the assembly outflow by compression fan.
Concentration by vapor compressor heating liquid technical matters schematic flow sheet is seen Figure 10, detailed process raises through pressure and temp after leaving the membrane distillation assembly after the compressor suction and entering the compression fan compression for the water vapor that sees through dewatering microporous film, this part hot steam temperature is higher, the Temperature Difference Ratio steam direct heating technology temperature difference strengthens, enter the cold driving liquid that the interchanger heating is flowed out from just permeating assembly, hot steam is condensed into hot water, improved heat exchange efficiency, this technology has improved utilization efficiency of heat energy with respect to steam direct heat exchange technology, with respect to the steam heat pump technology, technical process is simpler, has reduced investment.
The phylogenetic relationship that takes full advantage of of heat resource arrives economy of the present invention.The present invention adopts the regenerative drives fluid residual heat to utilize technology, produces water side purified water or produces water side water vapor UTILIZATION OF VESIDUAL HEAT IN technology and combination technique reaches the purpose that heat energy takes full advantage of, and reduces newly-increased energy demand, realizes superior economic performance.
Second aspect present invention discloses a kind of device that adopts preceding method to process the high COD concentration of high saliferous waste water, comprises the Waste water concentrating system, drives fluid circulation and pure water collection system;
The described Waste water concentrating of a system comprises waste tank, wastewater feed pump, pre-processing device, strainer and is just permeating assembly that the described assembly that just permeating comprises the waste liquid entrance, waste liquid outlet, driving liquid entrance and the outlet of driving liquid;
The described driving fluid circulation of b comprises the driving liquid bath, drives liquid fresh feed pump, interchanger, recycle pump and membrane distillation assembly; Described membrane distillation assembly comprises the stock liquid entrance, and the stock liquid outlet is produced the water side entrance and produced the water side outlet;
The described pure water collection of c system comprises interchanger and header tank;
Described waste tank, wastewater feed pump, pre-processing device, strainer and the waste material entrance that is just permeating assembly connect successively by pipeline; Described driving liquid bath, the driving liquid entrance that drives the liquid fresh feed pump and just permeating assembly connect successively by pipeline, described driving liquid outlet of just permeating assembly is connected by pipeline successively with recycle pump, the interchanger that drives fluid circulation, the stock liquid entrance of membrane distillation assembly, and the stock liquid outlet of described membrane distillation assembly is connected with the driving liquid entrance that just permeates assembly by pipeline; The product water side outlet of described membrane distillation assembly is connected with header tank with the interchanger of pure water collection system successively by pipeline.
More excellent, described driving liquid outlet of just permeating assembly is communicated with the driving liquid bath by reflux line; Described driving fluid circulation also comprises dashpot and dashpot fresh feed pump, the stock liquid outlet of described membrane distillation assembly is communicated with the entrance of dashpot by reflux line, the outlet of described dashpot is connected with the dashpot fresh feed pump, and is communicated with the stock liquid entrance of membrane distillation assembly by pipeline.
More excellent, when adopting direct contact membranes distil process, described pure water collection system also comprises the header tank fresh feed pump, and described header tank, header tank fresh feed pump and membrane distillation assembly produce the water side entrance and connect successively by pipeline.
When the driving liquid after the waste-heat intensification dilution that utilizes product water side purified water, drive fluid circulation and pure water collection system and can adopt same interchanger.
The advantages such as method of wastewater treatment of the present invention and equipment can be processed the waste water in different sources and field, and recycle driving liquid, collect purified water, have the broad applicability of waste water, and stable, processing cost is low.
Description of drawings
Fig. 1: FO-DCMD coupling technique schema
Fig. 2: FO-VMD coupling technique schema
Fig. 3: FO-sweep gas membrane distillation technique schematic flow sheet
Fig. 4: drive fluid residual heat direct heat exchange schematic flow sheet
Fig. 5: the heat pump techniques utilization drives the fluid residual heat schematic flow sheet
Fig. 6: DCMD produces water waste heat direct heat exchange schematic flow sheet
Fig. 7: heat pump techniques utilizes DCMD to produce water waste heat schematic flow sheet
Fig. 8: VMD produces water side steam direct heat exchange schematic flow sheet
Fig. 9: heat pump techniques utilizes VMD to produce water side steam waste heat schematic flow sheet
Heat exchange process synoptic diagram behind Figure 10: the VMD product water side vapor recompression
1. waste tank 2. wastewater feed pumps 3. pre-processing devices 4. strainers 5. are just permeating assembly 6. driving liquid baths 7. driving liquid fresh feed pumps 8. recycle pumps 9. interchanger 10. membrane distillation assemblies 11. compression fans 12. header tank fresh feed pumps 14. header tanks 15. heat pumps 16. surge tanks 17. vacuum pumps 18. dashpots 19. dashpot fresh feed pumps
Embodiment
Embodiment 1:FO-MD coupling technique is processed shale gas pressure break waste water
Shale gas pressure break waste water index is as shown in table 1:
Table 1: shale gas pressure break waste water index
Adopt the technique of just permeating with the membrane distillation coupling, process flow sheet is seen Fig. 1, and positive osmotic drive liquid adopts the MgCl of 2.55M
2Solution, the FO film adopts the CTA flat sheet membrane, adopts the AL-DS pattern; Membrane distillation adopts direct contact membranes distillation (DCMD) technique, and the MD film adopts CF
4The PES hollow-fibre membrane that hydrophobization is processed, its film surface water contact angle are just permeating the driving liquid MgCl after the assembly outlet is diluted greater than 170 °
2Concentration is 2.4M, processes through membrane distillation, and regenerative drives liquid concentration reaches 2.55M, 55-65 ℃ of membrane distillation operating temperature.
When the driving liquid after adopting direct contact membranes distillation (DCMD) technique to dilution concentrates, the part of heat energy that drives the liquid heat temperature raising is come self-produced water side waste heat: adopt pure water collection to see through the water vapour of dewatering microporous film, obtain the product water side purified water that band has surplus heat, the product water side purified water that band is had surplus heat is delivered to interchanger, and carries out heat exchange from the driving liquid that just permeates after the dilution that assembly outlet flows out.Produce water side waste heat direct heat exchange schema as shown in Figure 6.And the energy recycling step of present embodiment adopts same interchanger with driving the liquid circulation technology, realizes producing the thermal exchange between the driving liquid after water side purified water and the dilution, obtain heat and drive liquid and be used for driving concentrating of liquid, and cooled purified water.
Result:
Through continuously operation, the FO membrane flux maintains 15-10LMH, and along with waste strength rises and descends, it is basicly stable that the MD membrane flux maintains 10-13LMH.Raw material pressure break waste water can concentrate nearly 1 times, and its waste water total amount reduces half, and MD produces water conductivity less than 300 μ s/cm, is higher than national Indicator for Drinking Water Quality.Two process system couplings of FO and MD form integrated artistic can the continuous effective operation.
Embodiment 2:FO-MD coupling technique is processed the glyphosate trade effluent
Glyphosate waste water influent quality index is as shown in table 2:
Table 2: waste water influent quality index after pretreatment
| Project | Index | Remarks |
| Glyphosate (g/L) | 8.5 | Through after the pre-treatment |
| TOC(g/L) | 15.4 | Through after the pre-treatment |
| NaCl(g/L) | 122 | Through after the pre-treatment |
| Na 2HPO 3(g/L) | 15 | Through after the pre-treatment |
| pH | 9.5 | Through after the pre-treatment |
Adopt just to permeate-membrane distillation coupling technique processing glyphosate waste water, forward osmosis membrane drives liquid and adopts 23% sodium chloride aqueous solution for adopting the surface treated forward osmosis membrane material of polysulfone material (PSF), employing AL-DS operational mode; Membrane distillation adopts vacuum membrane distillation (VMD) technique, process flow sheet is seen Fig. 2, vacuum tightness is 0.3-0.4bar, adopt the heat-exchange integrated membrane module of distillation, see through the vapour stream of film through the pre-thermal wastewater of interchanger, thereby reach the purpose that reduces energy consumption, the MD mould material adopts the PES film through the CF4 hydrophobic treatment, and its contact angle reaches more than 150 °.60 ℃ of membrane distillation operating temperatures.
When the driving liquid after membrane distillation adopts vacuum membrane distillation (VMD) technique to dilution concentrated, the part of heat energy that drives the liquid heat temperature raising was come self-produced water side waste heat, specifically adopts the steam direct heating technology, and its process flow sheet is seen Fig. 8.
Result:
System produces water and reaches the process water quality requirements, the concentrated volume that can reduce 30-50% of waste liquid, thereby greatly reduced the cost of further processing, the membrane flux that is just permeating reaches 6-10LMH, the membrane flux of membrane distillation reaches 10LMH, and this system moves 72 hours continuously, kept stable, illustrate that technique is feasible, can carry out industrialized application through further optimization.
Embodiment 3:FO-MD coupling technique treatment of nitric acid silver waste water
Petrochemical industry adopts precious metal chemical complex to make catalyzer, is the effective means that reduces cost with the precious metal recycling use of spent catalyst.Silver catalyst adopts steam direct evaporation concentration technology not only to consume a large amount of steam after adopting nitric acid dissolve, and the nitric acid galactic pole is unstable, at high temperature decomposes aggravation, and is very high to equipment requirements, in order to reduce cost, adopts the FO-MD coupling technique to process.
The leading indicator of Silver Nitrate waste water is: Silver Nitrate content: 3-3.5%; Excessive nitric acid content: 1-2%, on a small quantity other impurity.
Experiment adopts FO-VMD technique to carry out concentration after with the Silver Nitrate waste water filtering, and process flow sheet is seen Fig. 2.The FO membrane element that FO adopts HTI company to produce drives liquid and adopts the 1.5M potassium nitrate solution, adopts the AL-DS pattern; Membrane distillation adopts VMD technique, and the heat circulation is adopted and produced water side waste-heat technology, is specially vapor recompression intensification heating technique, and the heat exchange process synoptic diagram of vapor recompression heat temperature raising technology is seen Figure 10.In the membrane distillation process, 50～55 ℃ of saltpetre feeding temperatures, about 40 ℃ of temperature outs, adopt lobed rotor compressor, per hour produce water 400Kg, power consumption 11KW, vapor temperature is elevated to from 45 ℃ enters preheater about 70 ℃ and again heat potassium nitrate solution, the ton water vapor is amounted to only about 27.5KWh of power consumption, and this technique can be concentrated into silver nitrate solution the concentration of 10-12%, greatly reduces the concentrated cost of steam direct evaporation.
Embodiment 4:FO-MD coupling technique is processed oil field reinjection water
Water-quality guideline after oil field extracted water is processed through oily water separation:
Table 3: the water-quality guideline after oil field extracted water is processed through oily water separation
| Analysis project | Unit | Index | Remarks |
| Mn | mg/l | 2.61 | ? |
| Cu 2+ | mg/l | 0.33 | ? |
| SO 4 2- | mg/l | 0.33 | ? |
| Fe | mg/l | 15.9 | ? |
| Al | mg/l | 0.013 | ? |
| Ca 2+ | mg/l | 1269 | ? |
| Mg 2+ | mg/l | 203 | ? |
| Ba 2+ | mg/l | ? | Exceed sensing range |
| Cr | mg/l | 0.015 | ? |
| Cl - | mg/l | 157.2 | ? |
| SiO 2 2+ | mg/l | 44.9 | ? |
| TDS | g/l | 53.3 | ? |
Membrane distillation adopts vacuum membrane distillation (VMD) technique (see figure 2), and forward osmosis membrane adopts the CTA mould material, drives liquid and adopts the 1M sodium chloride solution, adopts the AL-FS operator scheme; Drive 65-45 ℃ of liquid chlorine sodium solution temperature out temperature, 55 ℃ of medial temperatures.The heat exchange process synoptic diagram was seen Figure 10 after VMD produced water side vapor recompression.
Just permeate the operation membrane flux and reaching 15-20LMH, the membrane distillation membrane flux is 12-20LMH, about 52 ℃ of lobed rotor compressor steam inlet, outlet is higher than 70 ℃, the comprehensive power consumption of ton water is less than 35KWh, this technique can effectively reduce the pollution of film, former water discharge reduction 70-80%, produce water can re-injection or further process after as boiler feedwater.
Claims (10)
1. a method of wastewater treatment is characterized in that, comprises Waste water concentrating technique and drives the liquid circulation technology; Wherein, described Waste water concentrating technique is for adopting positive infiltration technology, by driving liquid the high COD concentration of high saliferous waste water is concentrated, the waste water after obtaining to concentrate and the driving liquid after the dilution, the osmotic pressure of described driving liquid is higher than the osmotic pressure of the high COD concentration of high saliferous waste water; Described driving liquid circulation technology obtains purified water for the driving liquid after adopting film distillation technology to dilution dewaters, and regenerative drives liquid; Described regenerative drives liquid is re-used in Waste water concentrating technique, continues on for waste water is concentrated.
2. method of wastewater treatment as claimed in claim 1 is characterized in that, step is as follows:
1) Waste water concentrating technique: at first the high COD concentration of high saliferous waste water is carried out pre-treatment, remove suspended substance and/or solid matter in the waste water; Pretreated waste water enters and just permeates assembly, and under the effect of osmotic pressure, the water in the waste water sees through the forward osmosis membrane that is just permeating assembly and enters driving liquid; After just permeating assembly, the waste water after obtaining respectively to concentrate and the driving liquid after the dilution; Discharging after waste water after concentrated is further processed;
2) drive the liquid circulation technology: the driving liquid after the dilution flows out from just permeating the assembly, is heated to 40～65 ℃, obtains heat and drives liquid; Described heat drives liquid and enters the membrane distillation assembly; Under the poor driving of steam partial pressure, heat drives dewatering microporous film that the water in the liquid sees through the membrane distillation assembly with the form of water vapour and enters and produce the water side; Enter and obtain purified water after the water vapor condensation that produces the water side reclaims, it is concentrated that heat drives the liquid dehydration, obtains regenerative drives liquid;
3) will drive the regenerative drives liquid that the liquid circulation technology obtains and again be applied to Waste water concentrating technique, realize driving the recycle of liquid, and the lasting processing of the high COD concentration of high saliferous waste water.
3. method of wastewater treatment claimed in claim 2, it is characterized in that, the described pre-treatment of step 1) adopts more medium filter and activated charcoal filter to carry out filtration treatment for adopting coagulation sedimentation to remove suspended substance and part COD in the water, and/or adopts cartridge filter to filter.
4. claim 1 or the described method of wastewater treatment of 2 arbitrary claims is characterized in that the solute of described driving liquid is selected from any in inorganic salts, organic molecule, organic molecule salt, complex polyelectrolyte particle, protein, the minuteness particle; The solvent that drives liquid is water.
5. method of wastewater treatment claimed in claim 4 is characterized in that, described inorganic salts is selected from NaCl, KCl, MgCl
2, KNO
3, NaNO
3, NH
4HCO
3, Na
2SO
4, K
2SO
4, Ca(NO
3)
2, (NH
4)
2HPO
4, (NH
4)
3PO
4, Na
3PO
4In one or more combination; Described organic molecule is selected from vitamins C, glucose, sucrose, fructose, glycerine, ethylene glycol and oligomer thereof, the combination of one or more in the amino acid; Described organic molecule salt is selected from one or more the combination in quadrol, EDTA, DTPA, magnesium acetate, the sodium acetate; Described complex polyelectrolyte particle is selected from one or more the combination in polyvinylamine, polyacrylic acid, polyamide-based amine hydrochlorate, vitriol, the sulfonated polystyrene; Described protein is selected from a kind of in bovine serum albumin, the magnetic storage ferritin or both combinations; Described minuteness particle is selected from one or more the combination in modification magnetic nano-particle, the modification Jenner grain of rice, dendrimer polyamide-based amine, the Temperature Responsive Polymer As gel.
6. claim 1 or the described method of wastewater treatment of 2 arbitrary claims is characterized in that described film distillation technology is selected from direct contact membranes distil process, vacuum membrane distillation technique or sweep gas membrane distillation technique.
7. claim 1 or the described method of wastewater treatment of 2 arbitrary claims, it is characterized in that, described method of wastewater treatment also comprises the heat utilization process, described heat utilization process is to utilize the waste heat of regenerative drives liquid, by interchanger heat temperature raising step 2) driving liquid after the dilution, obtain heat and drive liquid, and/or utilize the waste heat that produces water side purified water, by interchanger heat temperature raising step 2) driving liquid after the dilution, obtain heat and drive liquid.
8. a device that adopts the described method of wastewater treatment of the arbitrary claim of claim 1-7 to process the high COD concentration of high saliferous waste water comprises the Waste water concentrating system, drives fluid circulation and pure water collection system; Wherein,
1) described Waste water concentrating system comprises waste tank, wastewater feed pump, pre-processing device, strainer and is just permeating assembly, and the described assembly that just permeating comprises the waste liquid entrance, and waste liquid outlet drives the liquid entrance and drives the liquid outlet;
2) described driving fluid circulation comprises the driving liquid bath, drives liquid fresh feed pump, interchanger, recycle pump and membrane distillation assembly; Described membrane distillation assembly comprises the stock liquid entrance, and the stock liquid outlet is produced the water side entrance and produced the water side outlet;
3) described pure water collection system comprises interchanger and header tank; Described waste tank, wastewater feed pump, pre-processing device, strainer and the waste material entrance that is just permeating assembly connect successively by pipeline; Described driving liquid bath, the driving liquid entrance that drives the liquid fresh feed pump and just permeating assembly connect successively by pipeline, described driving liquid outlet of just permeating assembly is connected by pipeline successively with recycle pump, the interchanger that drives fluid circulation, the stock liquid entrance of membrane distillation assembly, and the stock liquid outlet of described membrane distillation assembly is connected with the driving liquid entrance that just permeates assembly by pipeline; The product water side outlet of described membrane distillation assembly is connected with header tank with the interchanger of pure water collection system successively by pipeline.
9. device as claimed in claim 8 is characterized in that, described driving liquid outlet of just permeating assembly is communicated with the driving liquid bath by reflux line; Described driving fluid circulation also comprises dashpot and dashpot fresh feed pump, the stock liquid outlet of described membrane distillation assembly is communicated with the entrance of dashpot by reflux line, the outlet of described dashpot is connected with the dashpot fresh feed pump, and is connected with the stock liquid entrance of membrane distillation assembly by pipeline.
10. the application in the wastewater treatment of the high COD concentration of high saliferous of the described method of wastewater treatment of the arbitrary claim of claim 1-7, and claim 8 or 9 described devices.
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| CN111875140A (en) * | 2020-07-27 | 2020-11-03 | 扬州大学 | High-phosphorus wastewater treatment device and method based on forward osmosis-membrane distillation technology |
| CN113105053A (en) * | 2021-04-09 | 2021-07-13 | 自然资源部天津海水淡化与综合利用研究所 | Energy-saving two-stage forward osmosis coupling double-effect membrane distillation wastewater high-concentration treatment system |
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