CN103193294A - Reverse osmosis membrane and nanofiltration membrane combined separation method of highly concentrated brine, and apparatus thereof - Google Patents
Reverse osmosis membrane and nanofiltration membrane combined separation method of highly concentrated brine, and apparatus thereof Download PDFInfo
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- CN103193294A CN103193294A CN2012100024238A CN201210002423A CN103193294A CN 103193294 A CN103193294 A CN 103193294A CN 2012100024238 A CN2012100024238 A CN 2012100024238A CN 201210002423 A CN201210002423 A CN 201210002423A CN 103193294 A CN103193294 A CN 103193294A
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Abstract
The invention discloses a reverse osmosis membrane and nanofiltration membrane combined separation method and an apparatus thereof. The combined separation method comprises the following steps: utilizing one or more reverse osmosis membranes to concentrate a solution until ions in the solution reach an ion limiting concentration in order to obtain a limiting concentration solution having an ion concentration of about 6%, and utilizing one or more nanofiltration membranes to continuously concentrate the limiting concentration solution until the ion concentration is above 10%. The method and the apparatus have the advantages of high concentration efficiency, low energy consumption, low cost, arbitrary increase or decrease of the numbers of the reverse osmosis membranes and the nanofiltration membranes as needed, and capability of concentrating the solution containing different ions comprising NaCl, CaCl2, Na2SO4, MgCl2 or other ions or molecules which can be intercepted through the reverse osmosis membrane and the nanofiltration membrane.
Description
Technical field
The present invention relates to a kind of water handling reclamation or the material separation method in concentrating, be specifically related to combination separation method and the device of a kind of reverse osmosis membrane and nanofiltration membrane.
Background technology
The ion-selective permeability that utilizes organic film was thrown in into market with regard to the commodity that are utilized to manufacture reverse osmosis or nanofiltration membrane at the fifties end in last century and initial stage in the sixties; the initial application of reverse osmosis membrane comprises the desalination of seawater and brackish water; because industrial circle is to the protection water source; reduce energy consumption; control is polluted and the demand that reclaims valuable substance from waste water increases day by day; the purposes of reverse osmosis membrane and nanofiltration membrane is constantly expanded; also entered the field that material concentrates; with respect to traditional distillation method; the membrane separating concentration technique is saved energy consumption more; can not cause simultaneously product thermolysis and rotten yet, therefore extensively be thought one of effective and the most economic isolation technique.Reverse osmosis membrane is the most accurate embrane method liquid separation technology, and it can stop all solvability salt and molecular weight greater than 100 organism, but allows water molecules to see through, and reverse osmosis membrane composite membrane ratio of desalinization commonly used is generally greater than 98%.The difference of nanofiltration membrane and reverse osmosis is that nanofiltration membrane is not perfect blocking layer to solvability salt or solute, be called low pressure reverse osmosis or loose reverse osmosis in early days, because of its molecular weight cut-off between 200～2000, membrane pore size is about 1nm, suitable separation size is about the dissolved constituents of 1nm, so be called " nanofiltration ".Nanofiltration membrane can the effectively catching divalence and high valence ion and molecular weight be higher than 200 organic molecule, nanofiltration membrane is because of structure and the aperture difference of its film, it sees through and can larger difference be arranged because of the kind of salt or solute and the kind of concentration height and nanofiltration membrane solute.
The above-mentioned ratio of desalinization of carrying refers to remove the percentage of the impurity concentration of total solubility by reverse osmosis or nanofiltration membrane from system's water inlet, the difference of saltiness and water outlet saltiness is divided by the percentage ratio of water inlet saltiness in namely intaking, and the influent concentration that adopts in this ratio of desalinization and the testing method, intake pressure, the rate of recovery, pH, temperature is relevant with the test duration.Wherein the rate of recovery refers to that feedwater transforms into the percentage that produces water or see through liquid in the film system.It is 15 kilograms at intake pressure that the testing method of the reverse osmosis membrane that commercialization at present is general adopts 2000ppm NaCl solution more, the rate of recovery is 15%, pH7～8, the test condition of 25 ℃ and 20～30 minutes is reported its ratio of desalinization, requiring higher last its testing method of sea water desaltination reverse osmosis membrane of sea water desaltination application then to adopt 32000ppm NaCl solution to the ion remaval rate is 55 kilograms at intake pressure, the rate of recovery is 8%, the test condition of pH7～8,25 ℃ and 20～30 minutes is reported its ratio of desalinization.Be 5 kilograms and the general testing method of commodity nanofiltration membrane adopts the 2000ppm Adlerika more at intake pressure, the rate of recovery is 15%, pH7～8, the test condition of 25 ℃ and 20～30 minutes is reported its ratio of desalinization, can this test condition can not the correct response nanofiltration membrane be suitable for that what is high in salt to be concentrated, so the ratio of desalinization of nanofiltration membrane employing 60000ppm sodium-chlor or calcium chloride solution are 20 kilograms at intake pressure in this application, the rate of recovery is 50%, the test condition of pH7～8,25 ℃ and 20～30 minutes is reported its ratio of desalinization
In the sepn process of taking reverse osmosis membrane or nanofiltration membrane, the feed liquid of separating can be separated into two strands of liquid to the selection of water intermediate ion difference separatory with feed liquid because of film, one for containing the few fresh water of ionic weight (claiming penetrating fluid or clear liquid again), another strand is the dense water (or claiming concentrated solution or dope) of ion enrichment, and the water colunm pressure difference of the ionic concn difference in the film both sides when causing balance is called osmotic pressure, separation is constantly carried out, just must constantly pressurize at the liquid feeding side of film and make the high what osmotic pressure of its pressure, fresh water could see through film and flow out, the principle of operation of Here it is reverse osmosis membrane, and in actually operating, this osmotic pressure has also limited the ionic concn in its dense water, when if the ionic concn of the both sides of film is 1mole/L, its osmotic pressure can reach 24.4Bar, and the total ion concentration in the seawater is about 1.1mole/L, its osmotic pressure namely reaches about 27Bar, as the domestic fresh water that will take out 50% in the seawater, then its dense water side osmotic pressure is namely up to 54Bar, and this high osmotic pressure causes high energy consumption and the crushing resistance of film resistor is also had very high requirement.So when generally adopting reverse osmosis membrane, the concentration limit of its dense water many 2mole/L (1mole/L chlorion and 1mole/L sodium ion) just sodium chloride concentration about 6% (mass percent).Along with the demand of water reuse is increasingly sharpened, concentrated requirement to reverse osmosis membrane is also constantly risen, in some waste water recycling, the dense water of reverse osmosis membrane can not discharge arbitrarily because saltiness is too high, and the evaporation process that need carry out zero release to it, can significantly reduce the required heat energy of evaporation and reduce working cost and improve ionic concn in this dense water, therefore need a kind of technology that the content of salt in the dense water is increased to more than 10% from present 6%, to reduce investment and the working cost of evaporation again.Though electrodialysis at present is another method that concentrates, but its facility investment and running cost are also all than higher, so at this demand, this patent invention has proposed a kind of combined system of utilizing reverse osmosis and nanofiltration membrane to be concentrated salt solution can to bring up to more than 10%.
Present document does not all have relevant content with patent retrieval, only in patent CN1268390A, mention the osmotic pressure that how to reduce in the reverse osmosis membrane separation, but its device and operation scheme complexity are difficult to large-scale operation, also do not adopt different films to reduce the problem of osmotic pressure.
Summary of the invention
The objective of the invention is to solve above-mentioned the deficiencies in the prior art, combination separation method and the device of a kind of reverse osmosis membrane and nanofiltration membrane are provided, the principle of described combination separation method be to utilize described reverse osmosis membrane with the ion in the solution (as sodium-chlor, calcium chloride etc.) threshold concentration that is concentrated into described ion obtains threshold concentration solution, the concentration of ion is about 6% described in the described threshold concentration solution, it is more than 10% that the described nanofiltration membrane of recycling continues to be concentrated into described ionic concn with described threshold concentration solution, thickening efficiency height of the present invention, energy consumption is low, cost is low, and can increase and decrease reverse osmosis membrane and nanofiltration membrane quantity as required arbitrarily, can concentrate at different ions and comprise sodium-chlor, calcium chloride, sodium sulfate, magnesium chloride or other can be concentrated by the lewis' acid that reverse osmosis and nanofiltration membrane are held back.
For achieving the above object, the present invention is by the following technical solutions:
The combination separation method of a kind of reverse osmosis membrane and nanofiltration membrane, comprise: the threshold concentration that earlier ion in the solution is concentrated into described ion with described reverse osmosis membrane obtains two strands of solution, one is dense water, another strand is fresh water, and then utilizes described nanofiltration membrane that described dense water is continued to be concentrated into desired ion concentration; Described reverse osmosis membrane is general reverse osmosis membrane, ratio of desalinization is more than 99%, preferred ratio of desalinization is more than 99.5%, and more preferably the special-purpose film ratio of desalinization of sea water desaltination is more than 99.6%, and the purpose that adopts the reverse osmosis membrane of high desalination rate is the fresh water (claiming penetrating fluid or clear liquid again) that obtains low ion concns; Described nanofiltration membrane ratio of desalinization is 10%～50%, preferred ratio of desalinization is 20%～40%, more preferably ratio of desalinization is 20%～33%, this ratio of desalinization can rise with work concentration process intermediate ion concentration and descend, so the nanofiltration membrane that is suitable for is to decide by the ratio of desalinization in the concentration process and its suffered working pressure and membrane flux, the too low purpose that concentrates ion that then do not reach of ratio of desalinization, too high too high working pressure rising and the membrane flux of making of osmotic pressure that cause of ratio of desalinization reduces.
When using described reverse osmosis membrane, the described rate of recovery is the rate of recovery of described ionic concn when reaching capacity concentration, when for example feed liquor is 2% saltiness, the rate of recovery is 66%, this moment, the saltiness of dense water was 6%, and when being 3% saltiness as feed liquor, the rate of recovery namely can only be 50%.
When using described nanofiltration membrane, the described rate of recovery is 50%, requiredly when the rate of recovery is low reaches certain membrane area that concentrates ratio and can rise, increase the facility investment expense, when the rate of recovery was high, its concentrated concentration rising can cause osmotic pressure to rise and need to improve working pressure, caused the energy consumption of operation to rise.
Preferable, described reverse osmosis membrane working pressure is 50～60kg.
Preferable, described nanofiltration membrane working pressure is 20～40kg.
In a preferred embodiments, described reverse osmosis membrane ratio of desalinization is more than 99%, and described reverse osmosis membrane working pressure is 50～60kg; Described nanofiltration membrane ratio of desalinization is 10%～50%, and described nanofiltration membrane working pressure is 20～40kg; The rate of recovery of described reverse osmosis membrane is the rate of recovery of described ionic concn when reaching capacity concentration, and the rate of recovery of described nanofiltration membrane is 50%.
As long as working pressure described in the present invention satisfies under the described rate of recovery, the product water flux of film per hour gets final product as 15 to 40 liters of every square meters at general suitable flux.
The present invention also provides the combination tripping device of a kind of reverse osmosis membrane and nanofiltration membrane, comprising: reverse osmosis membrane system and nanofiltration membrane system; Described reverse osmosis membrane system comprises: reverse osmosis membrane, with integrated high pressure shell, the liquid feeding pump that pressure is provided and the high-pressure pump of reverse osmosis membrane, security personnel's filter that protective membrane is polluted by particulate matter or scratches, and required pipeline, instrument and valve; Described nanofiltration membrane system comprise nanofiltration membrane, with integrated high pressure shell, the liquid feeding pump that pressure is provided and the high-pressure pump of nanofiltration membrane, security personnel's filter that protective membrane is polluted by particulate matter or scratches, and required pipeline, instrument and valve.
The liquid that will concentrate in operation is delivered to described security personnel's filter via described liquid feeding pump with liquid and is entered described high-pressure pump again; the dress aperture is that 5 microns filter core is to remove the particulate matter in the water in described security personnel's filter; protective membrane is not scratched by these particulate matter; described high-pressure pump enters described membrane element and separates sending into described high pressure shell after the feed liquor pressurization, and the fresh water after the separation is discharged dense water by the pipe core of described high pressure shell and then flowed out by the side of described high pressure shell.
In a preferred embodiments, described combination tripping device comprises a described reverse osmosis membrane system and two described nanofiltration membrane systems (first section nanofiltration membrane system and second section nanofiltration membrane system), solution is by described reverse osmosis membrane system feed liquor, and the dense water of gained concentrates through first section nanofiltration membrane system, second section nanofiltration membrane system successively.
In another preferred embodiments, described combination tripping device comprises a reverse osmosis membrane system and three nanofiltration membrane systems (first section nanofiltration membrane system, second section nanofiltration membrane system and the 3rd section nanofiltration membrane system), solution is by described reverse osmosis membrane system feed liquor, and the dense water of gained concentrates through described first section nanofiltration membrane system, described second section nanofiltration membrane system, described the 3rd section nanofiltration membrane system successively.
In another preferred embodiments, described combination tripping device comprises first section reverse osmosis membrane system, second section reverse osmosis membrane system, first section nanofiltration membrane system and second section nanofiltration membrane system, solution is by described first section nanofiltration membrane system feed liquor, and the dense water of gained concentrates through described second section nanofiltration membrane system; Described first section nanofiltration membrane system gained fresh water separates with described second section reverse osmosis membrane system again through described first section reverse osmosis membrane system successively.
In another preferred embodiments, described associated plant comprises a reverse osmosis membrane system, first section nanofiltration membrane system, second section nanofiltration membrane system and the 3rd section nanofiltration membrane system, solution is by feed liquor between described second section nanofiltration membrane system and described the 3rd section nanofiltration membrane system, the final dense water of gained flows out through described the 3rd section nanofiltration membrane system, and final gained fresh water flows out through described reverse osmosis membrane system.
The present invention can increase and decrease reverse osmosis membrane or nanofiltration membrane quantity arbitrarily as required in practice.
High ion concentration described in the present invention is defined as and surpasses the compressible limit of general reverse osmosis membrane, and namely more than about 6% the ionic concn, described low ion concns is defined as and is lower than 6% ionic concn.
The water quality of more high its fresh water of the ratio of desalinization of reverse osmosis membrane described in the present invention is more good, and described nanofiltration membrane preferably water throughput under the identical condition of ratio of desalinization is high.
Fresh water of the present invention claims penetrating fluid or clear liquid again.
The rate of recovery of the present invention is defined as: refer to that feedwater transforms into the percentage that produces water or see through liquid in the film system.
Ratio of desalinization of the present invention is defined as: remove the percentage of the impurity concentration of total solubility by reverse osmosis membrane or nanofiltration membrane from system's water inlet, the difference of saltiness and water outlet saltiness is divided by the percentage ratio of water inlet saltiness in namely intaking.
The special-purpose film ratio of desalinization of sea water desaltination of the present invention condition determination is: 32000ppm NaCl solution is 55 kilograms at intake pressure, and the rate of recovery is 8%, pH7～8,25 ℃ and reaction times to be measured ratio of desalinization under 20～30 minutes conditions.
General reverse osmosis membrane ratio of desalinization condition determination of the present invention is: 2000ppm NaCl solution is 15 kilograms at intake pressure, and the rate of recovery is 15%, pH7～8,25 ℃ and reaction times to be measured ratio of desalinization under 20～30 minutes conditions.
Nanofiltration membrane ratio of desalinization condition determination of the present invention is: 60000ppm NaCl solution is 20 kilograms at intake pressure, and the rate of recovery is 50%, pH7～8,25 ℃ and reaction times to be measured ratio of desalinization under 20～30 minutes the condition.
Working pressure of the present invention is defined as the filter pressure that is applied on the membrane element, also can be described as intake pressure.
The bright described permeable membrane of this law and described nanofiltration membrane all can be bought or homemade film is as long as its ratio of desalinization meets the demands and just can be used for this invention by the commercial channel.
Membrane flux described in the present invention is: in the unit time, see through the flow of film with the unit membrane area, usually with per hour every square metre rise expression;
Adopt described reverse osmosis membrane that the described nanofiltration membrane that enters multistage after the feasible limit of its industry that is concentrated into that solution carries out the first step is concentrated into the ionic concn that needs among the present invention, and the fresh water of described nanofiltration membrane is back to the feed liquor of film system the last period, continue to concentrate, the fresh water of final system obtains the reuse water of low ion concns after by reverse osmosis membrane filtration.
Degree to solution concentration among the present invention can be realized by the ratio of desalinization of described nanofiltration membrane and the hop count of its series connection.
At the ionic concn of different solutions, can realize the purpose that it concentrates by the position that changes its feed liquor among the present invention.
Can adopt two-stage or multistage reverse osmosis to carry out purifying when among the present invention the ionic concn in the recycle-water require to continue being reduced.
Among the present invention to the ionic concn in the recycle-water when requiring, also can only adopt the multistage nanofiltration membrane to concentrate, and need not adopt reverse osmosis membrane.
Among the present invention, per-cent (%) is mass percent.
Nanofiltration membrane described in the present invention is lower because of its ratio of desalinization, when selecting the nanofiltration membrane of suitable ratio of desalinization, because of the ionic concn of its fresh water higher, ionic concn when the ionic concn difference of the both sides of film is moved far below reverse osmosis membrane is poor, and its osmotic pressure is descended greatly, concentrating and separating still can reasonably realized under the working pressure, because when selecting the nanofiltration membrane of low ratio of desalinization to concentrate, after nanofiltration membrane concentrates each time, its concentration is not if reach the ultimate density that needs, then dense water can be entered again next section nanofiltration membrane concentration systems, and adopt the nanofiltration membrane of different ratio of desalinization and different operating pressure to remove to overcome the osmotic pressure that different ions concentration produces, the final realization is increased to ionic concn more than 10%, and the fresh water of nanofiltration membrane contains part because its ratio of desalinization is low ion continues to concentrate before then being back to reverse osmosis membrane again.
Advantage of the present invention is: the present invention adopts the combination of reverse osmosis membrane and nanofiltration membrane that ionic concn can be concentrated into more than 10% to surpass general embrane method concentrates 6% the limit, needing that water is converted to water vapor in the time of need be as evaporation concentration because this concentration process just utilizes film to the selection separation property of ion separates again, therefore can save the energy consumption when concentrating in a large number, the energy consumption when this embrane method concentrates can be utilized the energy recycle device that adopts in the similar what sea water desaltination and its energy consumption is reduced more than 30% again.Adopting another benefit of membrane separating namely is to separate under the normal temperature, therefore can be with the concentrating of some heat-sensitive substances of what, and as milk, fruit juice, concentrating of coffee ﹠ tea drink and do not influence its smell and composition.The reverse osmosis membrane and the nanofiltration membrane system that are adopted by this invention of what have been the mature equipment that commercialization and wide model are used, and the stability of facility investment and operation and operation conveniency all are better than other technology, as technology such as electrodialysis and evaporation concentration.
Description of drawings
Fig. 1 is the schema of embodiment 1.
Fig. 2 is the schema of embodiment 2.
Fig. 3 is the schema of embodiment 3.
Fig. 4 is the schema of embodiment 4.
Fig. 5 is the schema of embodiment 5.
Embodiment
In following examples:
Described reverse osmosis membrane system consists of: reverse osmosis membrane, with integrated high pressure shell, the liquid feeding pump that pressure is provided and the high-pressure pump of reverse osmosis membrane, security personnel's filter that protective membrane is polluted by particulate matter or scratches, and required pipeline, instrument and valve.
Described nanofiltration membrane set of systems becomes: nanofiltration membrane, with integrated high pressure shell, the liquid feeding pump that pressure is provided and the high-pressure pump of nanofiltration membrane, security personnel's filter that protective membrane is polluted by particulate matter or scratches, and required pipeline, instrument and valve.
The special-purpose film ratio of desalinization of described sea water desaltination condition determination is: 32000ppmNaCl solution is 55 kilograms at intake pressure, and the rate of recovery is 8%, pH8.0, and 25 ℃ and reaction times are measured ratio of desalinization under 30 minutes conditions.
Described general reverse osmosis membrane ratio of desalinization condition determination is: 2000ppm NaCl solution is 15 kilograms at intake pressure, and the rate of recovery is 15%, pH8.0, and 25 ℃ and reaction times are measured ratio of desalinization under 30 minutes conditions.
Described nanofiltration membrane ratio of desalinization condition determination is: 60000ppm NaCl solution is 20 kilograms at intake pressure, and the rate of recovery is 50%, pH8.0, and 25 ℃ and reaction times are measured ratio of desalinization under 30 minutes the condition.
The mensuration of described ionic concn adopts Switzerland's ten thousand 883 logical ion chromatographs to carry out ion analysis, and instrumental analysis is sent in the reverse osmosis freshwater direct sampling, and high concentration liquid is that dense water is tested with same procedure after diluting 1000 times.
Embodiment 1: the separation of sodium chloride waste water:
Fig. 1 is the schema of present embodiment: the combination tripping device of reverse osmosis membrane described in the present embodiment and nanofiltration membrane is made up of reverse osmosis membrane system (RO), first section nanofiltration membrane system (NF1) and second section nanofiltration membrane system (NF2); Described reverse osmosis membrane is the special-purpose film of sea water desaltination, and described reverse osmosis membrane ratio of desalinization is 99.7%, and described first section nanofiltration membrane ratio of desalinization is 33%, and described second section nanofiltration membrane ratio of desalinization is 25%.
Concrete operational conditions: filter operation pressure is 55Kg in the described reverse osmosis membrane system; Filter operation pressure 30Kg in described first section nanofiltration membrane system; Filter operation pressure is 35Kg in described second section nanofiltration membrane system; The sodium chloride waste water pH value of solution is 8.0, and the system response temperature is 25 ℃.
Be that the sodium chloride waste water of 2% (mass percent) is sent into reverse osmosis membrane system (RO) earlier with concentration, be concentrated into about 6% (mass percent) of threshold concentration; Again the sodium chloride waste water of 6% (mass percent) is sent into first section nanofiltration membrane system (NF1), under the rate of recovery of 50% (mass percent), the sodium chloride waste water of 6% (mass percent) is concentrated into the concentration of 8% (mass percent), again the sodium chloride waste water of 8% (mass percent) is sent into second section nanofiltration membrane system (NF2), under the rate of recovery of 50% (mass percent), the sodium chloride waste water of 8% (mass percent) is concentrated into the concentration of 10% (mass percent).Fresh water among the described NF1 can be back to and continue among the RO to concentrate, and the fresh water among the described NF2 can be back to and continue among the NF1 to concentrate, and the fresh water ionic concn of described reverse osmosis system is 200～300ppm, meets the requirement of reuse washing.The mensuration of sodium-chlor ionic concn in an embodiment adopts Switzerland's ten thousand 883 logical ion chromatographs to carry out the sodium ion analysis, and instrumental analysis is sent in the direct sampling of reverse osmosis clear liquid, and high concentration liquid is tested with same procedure after diluting 1000 times.
Embodiment 2: the separation of calcium chloride waste water:
As Fig. 2: the combination tripping device of reverse osmosis membrane described in the present embodiment and nanofiltration membrane is made up of reverse osmosis membrane system (RO), first section nanofiltration membrane system (NF1), second section nanofiltration membrane system (NF2) and the 3rd section nanofiltration membrane system (NF3); Described reverse osmosis membrane is general reverse osmosis membrane, and its ratio of desalinization is 99.5%, and described first section nanofiltration membrane ratio of desalinization is 35%, and described second section nanofiltration membrane ratio of desalinization is 25%, and described the 3rd section nanofiltration membrane ratio of desalinization is 20%.
Concrete reaction conditions: the filter pressure of operating in the described reverse osmosis membrane system is 50Kg, and the rate of recovery is 66%; Filter pressure is 20Kg in described first section nanofiltration membrane system, and the rate of recovery is 50%; Filter pressure is 25Kg in described second section nanofiltration membrane system, and the rate of recovery is 50%; Filter pressure is 30Kg in described the 3rd section nanofiltration membrane system, and the rate of recovery is 50%; Calcium chloride waste water solution pH is 8.0, and the system response temperature is 25 ℃.
The concentration of calcium chloride is 2% in the waste water, described reverse osmosis membrane system is concentrated into threshold concentration concentration 6% with calcium chloride concentration in the waste water earlier, dense water is concentrated into 12% by first section, second section and the 3rd section nanofiltration membrane system more successively, every section nanofiltration membrane increases by 2% concentration, fresh water among the described NF1 can be back to and continue among the RO to concentrate, fresh water among the described NF2 can be back to and continue among the NF1 to concentrate, and the fresh water among the described NF3 can be back to and continue among the NF2 to concentrate; The fresh water ionic concn of described reverse osmosis membrane system is less than 200ppm, the mensuration of calcium chloride ionic concn in an embodiment adopts Switzerland's ten thousand 883 logical ion chromatographs to carry out the calcium ion analysis, instrumental analysis is sent in the direct sampling of reverse osmosis clear liquid, and high concentration liquid is tested with same procedure after diluting 1000 times.
Because common reverse osmosis membrane namely has very high calcium chloride rejection, therefore described reverse osmosis membrane system can adopt general reverse osmosis membrane concentrating as the first step in the present embodiment.Crossing that this case can illustrate can be with high density salt solution concentrating gradually as long as select suitable nanofiltration membrane and increase the hop count of nanofiltration membrane.
The separation of the concentrated seawater of embodiment 3:6% saltiness (sodium-chlor) concentrates
Fig. 3 is the schema of present embodiment, and the combination tripping device of reverse osmosis membrane described in the present embodiment and nanofiltration membrane is made up of first section reverse osmosis membrane system (RO1), second section reverse osmosis membrane system (RO2), first section nanofiltration membrane system (NF1) and second section nanofiltration membrane system (NF2); Use the seawater desalination reverse osmosis film among the described RO1, its ratio of desalinization is 99.7%, uses general reverse osmosis membrane among the described RO2, its ratio of desalinization is 99.5%, and the nanofiltration membrane of using among the described NF1, ratio of desalinization are 33%, the nanofiltration membrane of using among the described NF2, ratio of desalinization are 25%.
Concrete reaction conditions: working pressure is 60 kilograms in described first section reverse osmosis membrane system, and the rate of recovery is 50%; Working pressure is 20kg in described second section reverse osmosis membrane system, and the rate of recovery is 85%; Working pressure is 40Kg in described first section nanofiltration membrane system, and the rate of recovery is 50%; Working pressure is 30Kg in described second section nanofiltration membrane system, and the rate of recovery is 50%; Described seawater pH is 8.0, and the system response temperature is 25 ℃.
6% seawater is by the NF1 feed liquor, dense water directly enters second section sodium filter membrane system and concentrates, the fresh water of first section sodium filter membrane system then is back to before first section reverse osmosis membrane system, first section reverse osmosis membrane that reverse osmosis membrane system adopts sea water desaltination to use, the fresh water of first section reverse osmosis membrane system enters second section reverse osmosis membrane system because ionic concn is too high, this moment is on the low side than the ionic concn in first section reverse osmosis membrane system because of ionic concn, can adopt general reverse osmosis membrane to get final product, be lower than 30ppm through the fresh water ionic concn after second section reverse osmosis membrane system separation, satisfy the requirement of reuse.Dense water is through two sections nanofiltration membrane systems, and every section concentrates the ionic concn that can reach after 2% more than 10% respectively.
The present embodiment explanation, through adjusting the position of water inlet, reverse osmosis membrane and nanofiltration membrane can realize concentrating of high ion concentration, and can make the fresh water ionic concn of recovery near the requirement of pure water by increasing the two-pass reverse osmosis system.
The salt water sepn of embodiment 4:10% saltiness (sodium-chlor) concentrates
Fig. 4 is the present embodiment schema: the combination tripping device of reverse osmosis membrane described in the present embodiment and nanofiltration membrane is made up of reverse osmosis membrane system (RO), first section nanofiltration membrane system (NF1), second section nanofiltration membrane system (NF2) and the 3rd section nanofiltration membrane system (NF3); The seawater desalination reverse osmosis film that uses among the described RO, its ratio of desalinization are 99.7%, and the nanofiltration membrane of using among the described NF1, ratio of desalinization are 33%, and the nanofiltration membrane of using among the described NF2, ratio of desalinization are 25%, and the nanofiltration membrane of using among the described NF3, its ratio of desalinization are 20%.
Concrete reaction conditions: working pressure is 60Kg in described first section reverse osmosis membrane system, and the rate of recovery is 50%; Working pressure is 40Kg in described first section nanofiltration membrane system, and the rate of recovery is 50%; Working pressure is 35Kg in described second section nanofiltration membrane system, and the rate of recovery is 50%; Working pressure is 30Kg in described the 3rd section nanofiltration membrane system, and the rate of recovery is 50%; Described salt solution pH is 8.0, and the system response temperature is 25 ℃.
Because salt is than higher, the feed liquor of the salt solution of 10% saltiness is changed between second section nanofiltration membrane system and the 3rd section nanofiltration membrane system, by the 3rd section nanofiltration membrane system 10% salt solution being concentrated into ion content is 12% dense water, and the fresh water of the 3rd section nanofiltration membrane system is back to before second section nanofiltration membrane system, and the fresh water of second section nanofiltration membrane system returns before first section nanofiltration membrane system, and the fresh water of first section nanofiltration membrane system is back to before the reverse osmosis membrane system again, this moment, the fresh water from reverse osmosis membrane system can obtain ionic concn less than 200ppm, general fresh water reuse at 160ppm, present embodiment explanation, reverse osmosis membrane of the present invention and nanofiltration membrane combination separation method and device can concentrate the also water of reuse low ion concns to the water inlet of different ions concentration by adjusting the water inlet position.
The salt water sepn of embodiment 5:10% saltiness (sodium-chlor) concentrates
Fig. 5 is the present embodiment schema: the combination tripping device of reverse osmosis membrane described in the present embodiment and nanofiltration membrane is made up of first section reverse osmosis membrane system (RO1), second section reverse osmosis membrane system (RO2), first section nanofiltration membrane system (NF1), second section nanofiltration membrane system (NF2), the 3rd section nanofiltration membrane system (NF3), the 4th section nanofiltration membrane system (NF4) and the 5th section nanofiltration membrane system (NF5); The seawater desalination reverse osmosis film that described RO1 and RO2 use, ratio of desalinization is 99.7%, the nanofiltration membrane of using among the described NF 1, and ratio of desalinization is 33%, the nanofiltration membrane of using among the described NF2, ratio of desalinization is 25%, and the nanofiltration membrane of using among the described NF3, ratio of desalinization are 20%, the nanofiltration membrane of using among the described NF4, ratio of desalinization is 33%, and the nanofiltration membrane of using among the described NF5, ratio of desalinization are 20%.
The concrete operations condition: working pressure is 50Kg among the described RO1, and the rate of recovery is 50%; Working pressure is 55Kg among the described RO2, and the rate of recovery is 50%; Working pressure is 30Kg among the described NF1, and the rate of recovery is 50%; Described NF2 working pressure is 30Kg, and the rate of recovery is 50%; Working pressure is 35Kg among the described NF3, and the rate of recovery is 50%; Working pressure is 40Kg among the described NF4, and the rate of recovery is 50%; Working pressure is 40Kg among the described NF5, and the rate of recovery is 50%; Described salt solution pH is 8.0, and the system response temperature is 25 ℃.
The feed liquor of the salt solution of 10% saltiness is placed between second section nanofiltration membrane system and the 3rd section nanofiltration membrane system, through the 3rd section nanofiltration membrane system it is concentrated into 12%, enter the 4th section nanofiltration membrane system again it is concentrated into 15%, enter the 5th section nanofiltration membrane system again and be concentrated into 18%, the fresh water of every section nanofiltration membrane system then is back to two sections entrance and continue concentrates, the fresh water that is NF5 is back to before the NF3, the fresh water of NF4 is back to before the NF2, the fresh water of NF3 is back to before the NF1, the fresh water of NF2 is back to before the RO2, the fresh water of NF1 is back to before the RO1, and the ionic concn of the fresh water of RO1 and RO2 can direct reuse at 200ppm.
Claims (9)
1. the combination separation method of a reverse osmosis membrane and nanofiltration membrane, comprise: the threshold concentration that earlier ion in the solution is concentrated into described ion with described reverse osmosis membrane obtains two strands of solution, one is dense water, another strand is fresh water, and then utilizes described nanofiltration membrane that described dense water is continued to be concentrated into desired ion concentration; Or earlier concentrate described solution with described nanofiltration membrane, and the feed liquor that the fresh water that obtains is back to film system the last period continues concentrated, and the dense water that obtains enters next section film system and continues to be concentrated into desired ion concentration, and described fresh water flows out after by reverse osmosis membrane filtration.
2. combination separation method according to claim 1, it is characterized in that: described reverse osmosis membrane ratio of desalinization is more than 99%.
3. combination separation method according to claim 1, it is characterized in that: described nanofiltration membrane ratio of desalinization is 10%～50%.
4. combination separation method according to claim 2, it is characterized in that: the working pressure of described reverse osmosis membrane is 50～60kg.
5. combination separation method according to claim 3, it is characterized in that: the working pressure of described nanofiltration membrane is 20～40Kg.
6. according to the described combination separation method of one of claim 1～5, it is characterized in that: the rate of recovery of described reverse osmosis membrane is the rate of recovery of described ionic concn when reaching capacity concentration.
7. according to the described combination separation method of one of claim 1～5, it is characterized in that: the rate of recovery of described nanofiltration membrane is 50%.
8. combination separation method according to claim 6, it is characterized in that: the rate of recovery of described nanofiltration membrane is 50%.
9. one kind is utilized the reverse osmosis membrane of the described combination separation method of claim 1 and the combination tripping device of nanofiltration membrane, comprising: reverse osmosis membrane system and nanofiltration membrane system; Described reverse osmosis membrane system comprises: requisite assembly when described reverse osmosis membrane and the described reverse osmosis membrane of use permeate; Described nanofiltration membrane system comprises: described nanofiltration membrane and requisite assembly when using described nanofiltration membrane to permeate.
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