CN104803448A - Forward osmosis treatment method of wastewater with high salinity and high organic matter concentration - Google Patents
Forward osmosis treatment method of wastewater with high salinity and high organic matter concentration Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a forward osmosis treatment method of wastewater with high salinity and high organic matter concentration. The forward osmosis treatment method comprises a wastewater concentration process and an absorbing liquid cyclic regeneration process; in the wastewater concentration process, a forward osmosis technology is adopted to concentrate wastewater, and an adsorbing liquid subjected to hyperosmosis is used for concentrating high salinity and high COD wastewater, so as to obtain a diluted driving liquid and concentrated wastewater; in the absorbing liquid cyclic regeneration process, a multi-stage evaporation technology is adopted to dehydrate the diluted driving liquid to obtain purified water and a regenerative adsorbing liquid to be used for the forward osmosis process. The high salinity and high COD wastewater subjected to hyperosmosis is concentrated to obtain the diluted driving liquid and the concentrated wastewater; the multi-stage evaporation technology is adopted in the adsorbing liquid subjected to hyperosmosis to dehydrate the diluted driving liquid to obtain the purified water and the regenerative adsorbing liquid to be used for the forward osmosis process. The forward osmosis treatment method has the advantages of being stable in operation, low in cost, wide in application range and the like.
Description
Technical field
What the present invention relates to is a kind of sewage water treatment method.The specifically positive osmosis processing method of a kind of high salinity, high organic concentration (chemicaloxegen demand, COD) waste water.
Background technology
High salt high-COD waste water refers to have high density solvability inorganic salt, COD at the waste water of more than 2000mg/L, the waste water of main representative comprises, the fermentation that the dyeing waste water of discharging as pharmaceutical intermediate wastewater, textile industry production and food-processing industry are discharged and scavenging solution, oil field waste etc.These waste water have the features such as saltiness is high, BOD, COD are high, biodegradability is poor, go back the method that neither one efficiently processes high salt high-COD waste water at present, therefore, study the high efficiency of high salt high-COD waste water, innoxious treating processes is of great significance preventing the destruction tool of water pollution and ecotope.
Current high salt high-COD waste water main methods comprises ion-exchange, electrodialysis, reverse osmosis and multistage flash evaporation, membrane distillation, just permeates.Ion exchange technique is ripe, can carry out desalting treatment.But the ion-exchange production cycle is long, operation is complicated, be only applicable to process Low-salinity waste water.Electrodialysis desalination is not too thorough, can only partial deionization.Reverse osmosis is widely used in process brine waste, but process high-salt wastewater like this, adopt conventional reverse osmosis treatent method it effectively can not be concentrated, and the concentrated waste water that reverse osmosis produces also is a more scabrous problem.In a word, the investment of these treatment processs is large, complex process, energy consumption are high, processing cost is high.Such as publication number is the treatment process disclosing a kind of high-salt wastewater in the patent document of CN101928087A, adopt the treatment scheme of alkali adjusting and hardness removing+immersed microfiltration+neutralization+membrane distillation, employing adds alkali and removes into hardness, micro-filtration desalination, the PH narrow range, wayward be suitable for, microfiltration membrane easily produces pollution, and micro-filtration mainly removes bacterium and suspended substance, is not also suitable for the high salt high-concentration waste water of process; Publication number is " treatment process of high COD, high ammonia nitrogen, high salinity trade effluent " disclosed in the patent document of CN101618920A, adopt chemical treatment, microbiological treatment, membrane bioreactor advanced treatment, reverse osmosis composite membrane desalination processing treatment process integration process height salt high-COD waste water, whole technical process more complicated, certainly will add running cost.And wherein micro-organism treatment process needs domestication and the culturing process of microorganism, the cycle of operation is long; Publication number is the method for the high dense trade effluent treatment of wastes with processes of wastes against one another of high salt a kind of disclosed in the patent document of CN102311211A " in; adopt MVR, three-dimensional potential electrolysis process, composite bacteria biochemical process anaerobism, oxygen of holding concurrently, aerobic, gas reuse four part composition; run machinery expenses high, microorganism is wayward; Publication number is a kind of disclosed in the patent document of CN103739136A treatment process of high salt organic waste water " in; adopt air lift+resin absorption+charcoal absorption step, gas process is too complicated, overall flow is long, floor space is large, adsorption process may relate to the processes such as the regeneration of gac; Publication number is a kind of disclosed in the patent document of CN203653386U treatment system of high salinity high organic substance content wastewater " in; employing grille well, adsorption tank, Fenton oxidation pond, pH regulator pond, UBF anaerobic reactor, contact-oxidation pool and mudpan combination process, technical process length is wayward, cost is high, floor space is not suitable for greatly the larger waste water of process salinity.
On the whole, above method all exists that processing cost is high, fouling membrane is serious, amount of investment is large, for shortcomings such as the high salt high-COD waste water poor effect of process.Can not be widely used in the high salt high-COD waste water of process, especially reverse osmosis technology, although be widely used in sea water desaltination, pure water treatment process.But pressure needed for reverse osmosis process high thus directly with reverse-osmosis treated high-salt wastewater in energy consumption, put into practice in be infeasible.And the dense water produced in reverse osmosis process does not also have effective treatment process at present.Therefore, the new direction that brand-new, an efficient treatment process makes future development is found.
Just permeating the recent studies on achievement with Multi-effect Evaporation Processes embrane method treatment technology.Compared to other treatment technologies, just permeating and to be described as 21 century most advanced, the most rising water technology with multistage evaporation.
Forward osmosis membrane isolation technique is the high efficient separation technology based on novel material.Its principle of work utilizes selectivity semipermeable partition for separating medium, and the permeable pressure head of film both sides is motivating force, does not need the effect of impressed pressure, and water molecules automatically enters the side of high osmotic pressure under the effect of motivating force.Because forward osmosis membrane has crown_interception to the salinity in stock liquid and other pollution substances, therefore in whole process, former feed liquid (Hyposmolality) is concentrated, and draws liquid (high osmotic pressure) and is diluted.The features such as its process has simply, stablize, easy handling.Because this process is spontaneous carrying out, select the suitable liquid that draws just can carry out the concentrating of stock liquid, green technology that this process has less energy-consumption, Sustainable development.Multistage evaporation is the secondary steam that produced by the previous vaporizer primary steam as next vaporizer, and is condensed into condensed water and distilled water in next vaporizer, by that analogy, just becomes multi-effect evaporation system.Multiple-effect evaporation technology concentrates the driving liquid after dilution, obtains pure water and concentrated driving liquid.Obtain pure water, can reuse be directly used in.Draw liquid for positive process of osmosis.
Summary of the invention
The object of the present invention is to provide a kind of stable, cost is low, the positive osmosis processing method of the high salinity height organic concentration waste water of applied range.
The object of the present invention is achieved like this:
Comprise Waste water concentrating technique and draw liquid and circulate in raw technique; Described Waste water concentrating technique adopts positive infiltration technology to concentrate waste water, concentrated high salt high-COD waste water by the liquid that draws of high osmotic pressure, obtains the driving liquid after dilution and concentrated waste water; Described liquid cyclic regeneration technique of drawing adopts multistage evaporation technology to dewater to the driving liquid after dilution, and what obtain pure water and regeneration draws liquid, for aforesaid positive process of osmosis; The quality of the salt of described high salt high-COD waste water is that more than 1%, COD reaches more than 2000mg/L, pH=7.0-10.0 than concentration.
The present invention can also comprise:
1, in described positive infiltration technology, forward osmosis membrane used is adopted and is obtained with the following method: by one or more combinations in cellulose acetate, triacetate fiber, polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile, be dissolved in macromolecule solvent and additive, heated and stirred forms film-casting liquid, be support with polyester screen, adopt phase conversion method knifing shaping; One or more in described macromolecule solvent Isosorbide-5-Nitrae dioxane, acetone, N-N N,N-DIMETHYLACETAMIDE; Described additive is one or more in methyl alcohol, lactic acid, PEG.
2, described multistage evaporation technology is: multiple evaporator series, previous evaporator evaporation secondary steam is out imported next vaporizer as heating steam, in next vaporizer, be condensed into distilled water simultaneously, the heating chamber of rear stage vaporizer becomes the condenser of the secondary steam that previous stage vaporizer produces, raw steam only consumes in first evaporator, and solution evaporates together in multiple vaporizer.
3, drawing liquid is one or more in inorganic type, organic type, polyelectrolyte, magnetic nano-particle, described inorganic type is one or more in the aqueous solution of the aqueous solution of sodium-chlor, sodium bicarbonate, magnesium sulfate, magnesium chloride, ammonia and carbonic acid gas, sulfurous gas, and described organic type is one or more in sucrose, glucose, fructose and mixed solution thereof, ethanol, ethylenediamine tetraacetic acid (EDTA), polyoxyethylene glycol, organic ion salts solution, novel tree-like macromole, polyalcohol hydrogel etc.
4, the aperture of described forward osmosis membrane is the film of 0.1-1um.
The invention provides a kind of positive osmosis processing method of high salt high-COD waste water, comprise Waste water concentrating technique and draw liquid and circulate in raw technique, wherein Waste water concentrating technique adopts positive infiltration technology, by the liquid that draws of high osmotic pressure, high salt high-COD waste water is concentrated, obtain the driving liquid after dilution and concentrated waste water, drawing liquid cyclic regeneration technique adopts multistage evaporation technology to dewater to the driving liquid after dilution, and what obtain pure water and regeneration draws liquid, for aforesaid positive process of osmosis.The method has stable, the plurality of advantages such as cost is low, applied range.
Advantage of the present invention is:
1. pair salt has higher rejection.
2. the active coating of forward osmosis membrane has wetting ability, the little and reversible easy recovery of the pollution of film.
3., without external pressure effect, motivating force is the osmotic pressure of solution.
4. without strong brine emission problem, environmental friendliness.
5. equipment is simple, and mould material is without particular requirement.
Accompanying drawing explanation
Fig. 1: positive osmotic treated height salt height COD schematic diagram.
Fig. 2: positive osmotic treated height salt height COD schema.
Fig. 3: forward osmosis membrane sectional drawing.
Embodiment
In the treatment process of high salt height COD of the present invention, described high-salt wastewater concentration at least reaches more than 1%, COD and reaches more than 2000mg/L, pH7.0-10.0.Comprise the following steps:
1) Waste water concentrating technique
First carry out pre-treatment by entering the stock liquid just permeated, its pre-treatment step comprises: except hardness, coagulation, the simple pre-treatment step of filtration, removes suspended substance in waste water and solid matter and part COD.Forward osmosis membrane assembly is entered through pretreated stock liquid, draw one or more in the aqueous solution of the aqueous solution that liquid is inorganic type sodium-chlor, sodium bicarbonate, magnesium sulfate, magnesium chloride, ammonia and carbonic acid gas, sulfurous gas, one or more in organic type sucrose, glucose, fructose and mixed solution thereof, ethanol, ethylenediamine tetraacetic acid (EDTA), polyoxyethylene glycol, organic ion salts solution, novel tree-like macromole, polyalcohol hydrogel etc., one or more in polyelectrolyte, magnetic nano-particle.The aperture of described forward osmosis membrane process is the film of 0.1-1um, the positive osmotic pressure that the pressure of described positive osmotic treated is stock liquid and draws between liquid, without the need to the effect of impressed pressure.The water flux of forward osmosis membrane keeps stable.After the process of forward osmosis membrane assembly, stock liquid is concentrated, draw liquid is diluted.Concentrated waste water does further advanced treatment and discharges.
2) the cyclic regeneration technique of liquid is drawn
Liquid will be drawn after above-mentioned dilution, regulate pH to neutral left and right, to its heat temperature raising, then carry out multistage evaporation system, multiple-effect evaporation processed is carried out to the driving liquid after dilution.The heat utilization ratio of this process is high, the water outlet of multiple-effect evaporation good (distilled water), directly can carry out reuse production, improve the economy of evaporation operation.The liquid that draws in said process is concentrated, and concentrated draws liquid reusable edible, and accomplish the regeneration of drawing liquid, utilization ratio is high.
3) liquid is drawn in the regeneration of drawing the acquisition of liquid circulation technology and be again applied to Waste water concentrating technique, realize the cycling and reutilization drawing liquid, and the lasting process of high salt high-COD waste water.
The present invention is prior art for the treatment of the pre-treatment of high salt high-COD waste water, its objective is the suspended substance, solid matter and the part COD that remove in waste water, prevents obstruction and the pollution of follow-up forward osmosis membrane.Pre-treatment can adopt coagulation sedimentation to remove suspended solids and part COD in waste water.
The positive infiltration technology of the present invention's application is new separation technology, and forward osmosis membrane used is one or more combinations in cellulose acetate, triacetate fiber, polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile.Be dissolved in one or more in macromolecule solvent Isosorbide-5-Nitrae dioxane, acetone, DMAC (N-N dimethylacetamide solvent), in additive methyl alcohol, lactic acid, PEG one or more, heated and stirred formed film-casting liquid; Be support with polyester screen, adopt inversion of phases principle and make with manual knifing machine.The asymmetry structure of obtained forward osmosis membrane is made up of supporting layer, active coating usually.To the rejection of sodium-chlor more than 90%.Be can multivalent ion concentration in very big less sewage compared to reverse osmosis, nanofiltration, its advantage of ultrafiltration, decrease dirt, can at high temperature grasp, have great rejection; The fouling membrane produced is little and be reversible, just makes it recover by simply processing; Water flux has higher recovery rate.Compared to other membrane separating process, extend the work-ing life of film.
The present invention's application multiple-effect evaporation technology carries out the processed of diluent, and multi-effect evaporation system is formed by multiple evaporator series.Import next vaporizer by previous evaporator evaporation secondary steam out, it can be used as heating steam, be condensed into distilled water simultaneously in next vaporizer, so order is undertaken by effect number successively.Like this, the heating chamber of rear 1st effective evaporator has just become the condenser of the secondary steam that front 1st effective evaporator produces, and raw steam only consumes in the first single-effect evaporator, and solution evaporates together in multiple vaporizer.Therefore, adopt multiple-effect evaporation can reach the object making full use of heat energy, namely by multiple-effect evaporation, the recycling of secondary steam, can reduce the consumption of raw steam, thus improves the economy of evaporation operation.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Just permeate-multiple-effect evaporation coupling technique treatment of dyeing and printing
The index of dyeing waste water is as shown in Table 1:
Table one: dyeing waste water index:
Just permeating the coupling technique with multiple-effect evaporation, the liquid liquid that draws just permeated adopts 2MNaCl solution, and forward osmosis membrane adopts cellulose acetate flat sheet membrane, adopts active coating towards drawing liquid PRO pattern; Evaporation adopts multiple-effect evaporation technology (flat flow).Forward osmosis membrane assembly flows out and is driven the concentration of liquid to be 1.5M by dilution, and after multiple-effect evaporation process, the concentration of regenerative drives liquid reaches 2M.
Result:
Run through continuous print, FO membrane flux is at 15-5LMH.The generation kept stable of pure water in Multi-effect Evaporation Processes, produces water conductivity and is less than 300 μ s/cm, higher than national drinking water standard.Stock liquid after dilution is concentrated significantly, can continue as drawing liquid in positive process of osmosis.It is actual that show just to permeate can the carrying out of continous-stable with multiple-effect evaporation technique.
Embodiment 2: high-salt wastewater in solvay soda process
In ammonia alkali, the index of high salt high-COD waste water is as shown in Table 2:
Table two: ammonia alkali height salt high-COD waste water index
Adopt the waste water just permeated in multiple-effect evaporation coupling technique process ammonia alkali production process, forward osmosis membrane adopts the blend of CA, CTA to be material, take polyester screen as propping material, adopts phase inversion process to prepare forward osmosis membrane.Draw the MgCl that liquid adopts 15%
2solution.Adopt PRO pattern, what evaporation adopted is multistage evaporation technology (reverse-flow).
Result:
Run through continuous print, FO membrane flux is at 15-10LMH.System produces water can carry out industrial application, and waste liquid concentrates can the volume of less 30-50%.Whole process stable water outlet, concentrated solution can reach the concentration requirement drawing liquid.
Embodiment 3: shale gas fracturing waste water
The index of shale gas fracturing waste water is as shown in Table 3:
Table three: shale gas fracturing waste water index
Adopt forward osmosis membrane multiple-effect evaporation coupling technique process shale gas fracturing waste water, forward osmosis membrane adopts the blend of CTA and PVP to be material, and PVP is a kind of synthesizing water-solubility macromolecular compound, has excellent solubility property.Take polyester screen as propping material, adopt phase inversion process to prepare forward osmosis membrane.Drawing liquid adopts massfraction to be the NaCl solution of 15%, and forward osmosis membrane device adopts active coating towards stock liquid FO pattern.Evaporative applications be multiple-effect evaporation technology.
Result:
Through the operation of continous-stable, the flux of forward osmosis membrane keeps stable, remains between 15-20LMH.The rejection of salt is up to 94%, and the water purity that multi-effect evaporation system produces is high, can directly apply.The concentrated solution that multi-effect evaporation system produces also can be used for the concentration technology of waste water.Reach the object of recycle, save energy, reduction cost.
Embodiment four: epoxy resin production waste-water
Epoxy resin production waste-water index is as shown in Table 4:
Table four: epoxy resin production waste-water index
NaCl 22％-26％
Average COD concentration 12000mg/L-20000mg/L
pH 8-10
Adopt positive osmosis process process epoxy resin waste-water.Forward osmosis membrane adopts cellulosetri-acetate to be mould material, and Isosorbide-5-Nitrae-dioxane and acetone are solvent, methyl alcohol and lactic acid is additive, polyester screen is propping material.Draw the Al that liquid adopts 30%
2(SO
4)
3solution, the active coating of forward osmosis membrane is towards driving liquid.The liquid calcium hydroxide that draws after dilution makes it precipitate, and makes it be separated with water, obtains purer product water.
Result:
Will through pretreated stock liquid by forward osmosis membrane, flux keeps being stabilized between 15-20LMH, reaches more than 90% to the rejection of salt, draws liquid and is separated only through simple chemical reaction, produce pure water through precipitate and separate.
Embodiment five: hot pickled mustard tube factory effluent
Hot pickled mustard tube factory effluent index is as shown in Table 5:
Table five: hot pickled mustard tube factory effluent index
Adopt and just permeating and solar heating coupling technique process hot pickled mustard tube factory effluent.Forward osmosis membrane adopts cellulosetri-acetate to be mould material, and Isosorbide-5-Nitrae-dioxane and acetone are solvent, methyl alcohol and lactic acid is additive, polyester screen is supporting layer.Inversion of phases is adopted to prepare the forward osmosis membrane of high-throughput, high rejection.More optimizedly adopt the aqueous solution of the mixed gas of ammonia and carbonic acid gas for drawing liquid, sodium bicarbonate has higher solubleness, the drawing liquid and can produce huge osmotic pressure of formation, and motivating force makes water molecules penetrate film.Drawing liquid and can decompose solute wherein by heating evaporation and obtain recycle after dilution, with overcome compared with evaporation of water heat, drive the energy in liquid needed for solute thermolysis lower, the ammonia after decomposition and carbon dioxide reclaim to be dissolved into drive in liquid by condensation again and reuse.Eliminate dissolved ammonia and the later water of carbonic acid gas is purer product water.Because just can be decomposed at a lower temperature, the present invention adopts solar heating method to be separated and draws liquid.
Result:
The preserved szechuan pickle waste water of typical high salt height organic concentration, will through simple pre-treatment, remove the waste water of main suspended substance and particulate matter in waste water by forward osmosis membrane assembly, water flux is comparatively stable, between 10-15LMH, 95%, COD clearance is reached to the rejection of salt and reaches about 80%, simple physical reaction is only passed through in the separation of drawing liquid, energy-saving and environmental protection, Sustainable development.
Claims (9)
1. a positive osmosis processing method for high salinity height organic concentration waste water, is characterized in that: comprise Waste water concentrating technique and draw liquid and circulate in raw technique; Described Waste water concentrating technique adopts positive infiltration technology to concentrate waste water, concentrated high salt high-COD waste water by the liquid that draws of high osmotic pressure, obtains the driving liquid after dilution and concentrated waste water; Described liquid cyclic regeneration technique of drawing adopts multistage evaporation technology to dewater to the driving liquid after dilution, and what obtain pure water and regeneration draws liquid, for aforesaid positive process of osmosis; The quality of the salt of described high salt high-COD waste water is that more than 1%, COD reaches more than 2000mg/L, pH=7.0-10.0 than concentration.
2. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 1, it is characterized in that: in described positive infiltration technology, forward osmosis membrane used is adopted and obtained with the following method: by one or more combinations in cellulose acetate, triacetate fiber, polysulfones, polyethersulfone, polyvinylidene difluoride (PVDF), polyacrylonitrile, be dissolved in macromolecule solvent and additive, heated and stirred forms film-casting liquid, be support with polyester screen, adopt phase conversion method knifing shaping; One or more in described macromolecule solvent Isosorbide-5-Nitrae dioxane, acetone, N-N N,N-DIMETHYLACETAMIDE; Described additive is one or more in methyl alcohol, lactic acid, PEG.
3. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 1 and 2, it is characterized in that: described multistage evaporation technology is: multiple evaporator series, previous evaporator evaporation secondary steam is out imported next vaporizer as heating steam, in next vaporizer, be condensed into distilled water simultaneously, the heating chamber of rear stage vaporizer becomes the condenser of the secondary steam that previous stage vaporizer produces, raw steam only consumes in first evaporator, and solution evaporates together in multiple vaporizer.
4. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 1 and 2, it is characterized in that: drawing liquid is inorganic type, organic type, polyelectrolyte, one or more in magnetic nano-particle, described inorganic type is sodium-chlor, sodium bicarbonate, magnesium sulfate, magnesium chloride, the aqueous solution of ammonia and carbonic acid gas, one or more in the aqueous solution of sulfurous gas, described organic type is sucrose, glucose, fructose and mixed solution thereof, ethanol, ethylenediamine tetraacetic acid (EDTA), polyoxyethylene glycol, organic ion salts solution, novel tree-like macromole, one or more in polyalcohol hydrogel etc.
5. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 3, it is characterized in that: drawing liquid is inorganic type, organic type, polyelectrolyte, one or more in magnetic nano-particle, described inorganic type is sodium-chlor, sodium bicarbonate, magnesium sulfate, magnesium chloride, the aqueous solution of ammonia and carbonic acid gas, one or more in the aqueous solution of sulfurous gas, described organic type is sucrose, glucose, fructose and mixed solution thereof, ethanol, ethylenediamine tetraacetic acid (EDTA), polyoxyethylene glycol, organic ion salts solution, novel tree-like macromole, one or more in polyalcohol hydrogel etc.
6. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 2, is characterized in that: the aperture of described forward osmosis membrane is the film of 0.1-1um.
7. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 3, is characterized in that: the aperture of described forward osmosis membrane is the film of 0.1-1um.
8. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 4, is characterized in that: the aperture of described forward osmosis membrane is the film of 0.1-1um.
9. the positive osmosis processing method of high salinity height organic concentration waste water according to claim 5, is characterized in that: the aperture of described forward osmosis membrane is the film of 0.1-1um.
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| CN105712560A (en) * | 2016-04-13 | 2016-06-29 | 北京新源国能科技集团股份有限公司 | Device and method for treating high-salinity wastewater with forward osmosis technique |
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