CN102407077A - Regenerating method and device of abandoned reverse osmosis membrane element - Google Patents
Regenerating method and device of abandoned reverse osmosis membrane element Download PDFInfo
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- CN102407077A CN102407077A CN2011104084074A CN201110408407A CN102407077A CN 102407077 A CN102407077 A CN 102407077A CN 2011104084074 A CN2011104084074 A CN 2011104084074A CN 201110408407 A CN201110408407 A CN 201110408407A CN 102407077 A CN102407077 A CN 102407077A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
The invention discloses a regenerating method and device of an abandoned reverse osmosis membrane element. The regenerating method comprises the following steps: utilizing the regenerating device of the abandoned reverse osmosis membrane element provided by the invention to clean the reverse osmosis membrane element by repeatedly soaking in a cleaning solution, and then washing with pure water; performing cycling soaking modifying treatment on an oxidation liquor; washing the abandoned reverse osmosis membrane element, obtained after carrying out the cycling soaking modifying treatment on the oxidation liquor, with the pure water; and finally, utilizing a polyamine solution to repeatedly soak and coat the reverse osmosis membrane element. After being treated according to the method and device provided by the invention, the abandoned reverse osmosis membrane element has the characteristics of recovered filtering property, certain salt rejection rate, higher flux, lower operating pressure, and the like. The rejection performance is better than the nano-filtration effect; the desalination property is between the nano-filtration and reverse osmosis; raw materials are easily acquired; the regenerating device is simple and is low in manufacturing cost; the unique function of the regenerating device is utilized in a specific field; and the defect of a traditional technique of treating the abandoned rolled reverse osmosis membrane element is overcome.
Description
Technical field
The present invention relates to a kind of water treatment field, in particular a kind of renovation process of discarded reverse-osmosis membrane element and device thereof.
Background technology
Because the osmosis filtration technology has normal temperature, no phase transformation, advantages such as energy consumption is low, floor space is little, non-environmental-pollution, it is come out after extremely industry favor.In recent years, reverse osmosis technology has obtained high speed development, is widely used in desalinization, municipal water supply and sewage treatment area, in a plurality of industrial trades such as oil, electric power, metallurgy, chemical industry, electronics, pharmacy, food, also attains full development.According to estimates, the sales volume of domestic 8in reverse-osmosis membrane element in 2008 surpasses 200,000, and the sales volume of 4in reverse-osmosis membrane element is above 150,000; About 450,000 of the 8in reverse-osmosis membrane element of domestic operation, about 300,000 of 4in reverse-osmosis membrane element, wherein the rolling counter-infiltration accounts for 3/4.Along with counter-infiltration market goes from strength to strength, there are every year hundreds thousand of membrane components also to come true approximately because of performance descends to going out of use, this has not only polluted environment has also wasted resource.Realize the regeneration of discarded coiled reverse osmosis membrane element and utilize again, not only reduced the quantity of discarded membrane component, reduced the processing cost of discarded membrane component, realized the resource of discarded membrane component simultaneously.
In the existing discarded reverse-osmosis membrane element regeneration techniques; Jose M. Veza is at Desalination; What be primarily aimed among 157 (2003) 65-72 is the desalinization membrane component of discarding; With the surface of liquor potassic permanganate modified membrane element, make the salt rejection rate of membrane component reduce to 2%, but the more high desalination rate of discarded membrane component is not studied.Li Baoguang, the quiet journal that greatly waits in Urban Construction Institutes Of Tianjin; 14 (4) 271-274; 2008.12 in mention through Chemical cleaning and NaClO the nanofiltration research that the mode of oxidation is discarded reverse-osmosis membrane element carried out on the film surface; Membrane component after the processing has certain nano filter membrane separating property, yet the exposed out-of-flatness desalination surface of membrane component pollution directly influences the cycle of operation and the service life of membrane component very much.Yu Sanchuan, Liu Meihong mention that in application number is 201010574082.2 patent of invention the discarded membrane component after directly will cleaning contains the amine aqueous solution modification and handles; The membrane component of gained has certain NF membrane performance; But the performance of the discarded reverse-osmosis membrane element that conventional cleaning can't recover, and contain amine aqueous solution just in surface modification, original desalination pollution layer still exists; The test of short time, operation kind can, operation will certainly be influenced for a long time.
Therefore, prior art awaits to improve and development.
Summary of the invention
The object of the present invention is to provide a kind of renovation process and device thereof of reverse-osmosis membrane element, with the counter-infiltration poor effect of the reverse-osmosis membrane element that solves existing discarded reverse-osmosis membrane element regeneration techniques gained, the technical problem that service life is long.
Technical scheme of the present invention is following:
A kind of discarded reverse-osmosis membrane element renovation process comprises step:
A: discarded reverse-osmosis membrane element is carried out the circulation immersion clean with the reverse-osmosis membrane element cleaning fluid, and fluid temperature is controlled at 28 ~ 32 ℃, and washing time is 30min ~ 2h;
HCL solution or citric acid solution that said reverse-osmosis membrane element cleaning fluid is pH=2.5 ~ 3.5; Or the hydrosulfurous acid sodium solution of pH=4 ~ 6; Or the NaOH of pH=10.5 ~ 11.5 or NaOH and detergent alkylate naphthenic acid sodium mixed solution; Or the mixed solution of the sodium phosphate trimer of pH=9.5 ~ 11 and EDTA sodium salt;
B:, carry out the circulation immersion modification of oxidation soup and handle to after the reverse-osmosis membrane element of clean is with pure water rinsing; The temperature of said oxidation soup is 25 ~ 35 ℃, and the reaction time is 20min ~ 1.5h; Said oxidation soup pH value is 6 ~ 7.5; It is 0.01% ~ 3% oxidation medicament that said oxidation soup contains mass concentration;
C: to after the discarded reverse-osmosis membrane element after the oxidation medicament circulation immersion modification processing is with pure water rinsing; It is used mass concentration is 0.05 ~ 1% polyamine solution circulation immersion coating processing; Said polyamine solution temperature scope is 20 ~ 40 ℃, and soak time is 10 ~ 20min; Said polyamine solution is m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,2-ethylenediamine, 1,4-cyclohexanediamine or 1,3 hexamethylene dimethylamine solution.
Described discarded reverse-osmosis membrane element renovation process, wherein, the oxidation medicament among the said step B is KMnO
4, clorox, chlorine dioxide or hydrogen peroxide.
Described discarded reverse-osmosis membrane element renovation process, wherein, the mass concentration of the polyamine solution among the said step C is 0.7%.
A kind of discarded reverse-osmosis membrane element regenerating unit comprises liquor box, spray pump, liquid medicine filter, reverse osmosis unit, circulation line, butterfly valve and check-valves;
Said liquor box is used for the regrowth liquid medicine of the discarded reverse-osmosis membrane element of splendid attire, comprising: reverse-osmosis membrane element cleaning fluid, oxidation soup or polyamine solution, the medicine liquid outlet of said liquor box are communicated with the soup inlet of spray pump through circulation line; Institute's spray pump is used to make the regrowth liquid medicine of discarded reverse-osmosis membrane element to circulate, and the medicine liquid outlet of said spray pump is communicated with the soup inlet of liquid medicine filter through circulation line; Said liquid medicine filter is used for the regrowth liquid medicine of discarded reverse-osmosis membrane element is carried out filtration treatment, and the medicine liquid outlet of said liquid medicine filter is communicated with the soup inlet of reverse osmosis unit through circulation line; Said reverse osmosis unit is used for the discarded reverse-osmosis membrane element of splendid attire, and the medicine liquid outlet of said reverse osmosis unit is communicated with the soup inlet of liquor box through circulation line; Said check-valves and butterfly valve are arranged on the circulation line.
Described discarded reverse-osmosis membrane element regenerating unit wherein, also comprises pH meter and Pressure gauge; Said pH meter is used to test the pH value of the regrowth liquid medicine of discarding reverse-osmosis membrane element, and said Pressure gauge is used for the pressure parameter of test loop pipeline; Institute's pH meter is arranged on the circulation line between said spray pump and the liquid medicine filter, and said Pressure gauge is arranged on the circulation line between said spray pump and the liquid medicine filter and on the circulation line between medicine company filter and the reverse osmosis unit.
Described discarded reverse-osmosis membrane element regenerating unit wherein, also comprises thermometer and heating rod; Said thermometer is used for the temperature of the regrowth liquid medicine of test solution case, and said heating rod is used for the various soup heating of liquor box; Said thermometer and heating rod are arranged in the said liquor box.
Described discarded reverse-osmosis membrane element regenerating unit, wherein, said liquor box bottom is provided with sewage draining exit, is used for discharging the pollutant of liquor box, and sewage draining exit is provided with butterfly valve; The product water side of said reverse osmosis unit is provided with butterfly valve, is used to regulate the rate of recovery of reverse osmosis unit.
The discarded reverse-osmosis membrane element regenerating unit of the present invention through utilizing invention to provide; Discarded reverse-osmosis membrane element is carried out after the reverse osmosis membrane cleaning fluid carries out the circulation immersion clean; Use pure water rinsing again; Carry out the circulation immersion modification of oxidation soup again and handle, then the discarded reverse-osmosis membrane element after handling through the modification of oxidation medicament circulation immersion is used pure water rinsing, at last to it with polyamine solution circulation immersion coating processing.Adopt the discarded reverse-osmosis membrane element strainability after method provided by the invention and the apparatus processes to be restored, have certain salt rejection rate, flux is higher; Characteristics such as operating pressure is lower, cutoff performance is better than nanofiltration, and desalting performance is between nanofiltration and counter-infiltration; And raw material is easy to get, regenerating unit is easy; Low preparation cost can be brought into play its unique effect surely at specific area, has remedied the deficiency of existing discarded coiled reverse osmosis membrane element treatment technology.
Description of drawings
Fig. 1 is the flow chart of discarded reverse-osmosis membrane element renovation process among the present invention.
Fig. 2 is the structural representation of discarded reverse-osmosis membrane element regenerating unit among the present invention.
The specific embodiment
For making the object of the invention, technical scheme and advantage clearer, clear and definite, below develop simultaneously embodiment to further explain of the present invention with reference to accompanying drawing.
A kind of discarded reverse-osmosis membrane element renovation process; Shown in the flow chart of discarded reverse-osmosis membrane element renovation process among Fig. 1 the present invention; Should comprise by discarded reverse-osmosis membrane element renovation process: steps A, discarded reverse-osmosis membrane element is carried out the circulation immersion clean with the reverse-osmosis membrane element cleaning fluid.The reverse-osmosis membrane element cleaning fluid is hydrosulfurous acid sodium solution or the NaOH of pH=10.5 ~ 11.5 or sodium phosphate trimer and the mixed solution of EDTA sodium salt or other cleaning soups that is fit to the reverse-osmosis membrane element of cleaning pollution carry out single or multiple to membrane component the wash cycles completely of NaOH and detergent alkylate naphthenic acid sodium mixed solution or pH=9.5 ~ 11 of HCl solution, citric acid solution or pH=4 ~ 6 of pH=2.5 ~ 3.5; Wherein fluid temperature is controlled in 28 ~ 32 ℃ of scopes; Washing time is 30min ~ 2h, and the temperature of soup and the occurrence of the time of flushing are provided with according to the pollution level of discarded reverse-osmosis membrane element.After discarded reverse-osmosis membrane element is cleaned, membrane component is carried out performance test, the operating pressure of recording film element, pressure reduction, salt rejection rate, hold back effect and produce water flux etc., the membrane component that leaks takes place to get rid of.
Step B to after the reverse-osmosis membrane element of clean is with pure water rinsing, carries out the circulation immersion modification of oxidation soup and handles.With the oxidation medicament KMnO for preparing
4Mass concentration is 0.01% ~ 3%; The pH value be controlled at 6 ~ 7.5 oxidation soup to discarded coiled reverse osmosis membrane element circulation immersion in temperature is 25 ~ 35 ℃ oxidizing solution; Reaction time is 20min ~ 1.5h, and the temperature of soup and the occurrence of the time of flushing are provided with according to the concrete parameter of discarded reverse-osmosis membrane element.The purpose of this step is to make the desalination laminar surface generation oxidation modification of membrane component.Through the concentration of oxidation medicament is controlled within the specific limits; Unlikely original desalination layer destroys fully; Born again reverse-osmosis membrane element has certain salt rejection rate and rejection, and experiment test draws its strainability of membrane component through oxidation between ultrafiltration and nanofiltration.Described oxidation medicament KMnO
4Can use other oxidation medicaments such as clorox, chlorine dioxide, hydrogen peroxide to replace.After the circulation immersion modification of discarded reverse-osmosis membrane element being carried out the oxidation medicament is handled, membrane component is carried out performance test, the operating pressure of recording film element, pressure reduction, salt rejection rate, hold back effect and produce water flux etc., the membrane component that leaks takes place to get rid of.
Because oxidation modification caudacoria element surface is no longer level and smooth, cause it to shorten because of the contaminated unbalanced cleaning frequency.For the cycle of operation and the service life that prolongs the regeneration membrane element, it is very necessary that the membrane component after the modification is carried out post processing.
Step C to after the discarded reverse-osmosis membrane element after the oxidation medicament circulation immersion modification processing is with pure water rinsing, handles with aromatic polyamides solution circulation immersion it.This step is to adopt dip coating, makes the thin and fine and close film of discarded reverse-osmosis membrane element surface-coated one deck of oxidation.Promptly using mass concentration is 0.05 ~ 1% polyamine solution (m-phenylene diamine (MPD) (MPDA), p-phenylenediamine (PPD) (PPDA), 1; 2-ethylenediamine, 1; 4-cyclohexanediamine or 1,3 hexamethylene dimethylamine solution) circulation immersion, temperature range is controlled at 20 ~ 40 ℃; Soak time is 10 ~ 20min, and the temperature of soup and the occurrence of the time of immersion are provided with according to the surface smoothing parameter of discarded reverse-osmosis membrane element.Polyamine is high molecular polymer; The aperture of holding back much larger than ultrafiltration; And the membrane component after the oxidation modification is held back the aperture between ultrafiltration and nanofiltration; So solution can not infiltrate modified membrane element internal generation hole and ooze, and promptly can not stop up the inner filtration channel of membrane component, can not reduce the filtration flux of membrane component.Therefore, the membrane component that utilizes is again held back effect, desalting performance and is produced water flux and is guaranteed.The also available other method for preparing the new film of reverse-osmosis membrane element of this step is handled the membrane component after the oxidation modification, like interfacial polymerization, monomer in-situ polymerization method and Plasma Polymerization etc.In this step, also can apply another kind of carboxylic solution, its salt rejection rate is improved discarded reverse-osmosis membrane element.
Cleaning fluid in the above-mentioned steps, oxidation soup and polyamine solution can be referred to as the regrowth liquid medicine of discarded reverse-osmosis membrane element.
The membrane component that after above-mentioned steps is handled, obtains; Dry with leaving standstill after the thorough cleaning of pure water; Promptly obtain the regeneration reverse-osmosis membrane element of moulding; Membrane component is carried out performance test, the operating pressure of recording film element, pressure reduction, salt rejection rate, hold back effect and produce water flux etc., to get rid of the not enough membrane component of performance.
Through the reverse-osmosis membrane element that obtains that discarded reverse-osmosis membrane element renovation process provided by the invention is handled, strainability can be applicable to production practices between nanofiltration and counter-infiltration, realized the resource of discarded reverse-osmosis membrane element.The discarded membrane component of surface oxidation modification after aromatic polyamides solution coating processing, has certain salt rejection rate again, and flux is higher; Characteristics such as operating pressure is lower; Cutoff performance is better than ultrafiltration, and desalting effect is lower than nanofiltration, but because raw material is easy to get, regenerating unit is easy; Low preparation cost can be brought into play its unique effect surely at specific area.It also can be used for handling the dense water of counter-infiltration system.At present the rate of recovery of counter-infiltration system is 75% mostly, and dense water electrode utilizes or all dischargings less, means that a system is wasted with regard to 25% water resource is arranged, and the discarded reverse-osmosis membrane element of regeneration is to the recycling of dense water, conserve water resource significantly.The discarded reverse-osmosis membrane element of regeneration is held back effect much larger than ultrafiltration to suspension and microorganism, so also can be used for intermediate water reuse system, can obtain treatment effect preferably.
A kind of discarded reverse-osmosis membrane element regenerating unit; Shown in the structural representation of discarded reverse-osmosis membrane element regenerating unit among Fig. 2 the present invention, this device comprises liquor box 1, spray pump 8, liquid medicine filter 12, reverse osmosis unit 13, butterfly valve 3, check-valves 9, heating rod 5, thermometer 6, pH meter 10, Pressure gauge 11, circulation line 14.The bottom of liquor box 1 is provided with liquor box sewage draining exit 2, and the top of liquor box 1 is provided with soup loop head 4, and the bottom of liquor box 1 also is provided with soup loop exit 7.Liquor box 1, spray pump 8, liquid medicine filter 12 and reverse osmosis unit 13 are linked to be a loop through circulation line 14 successively; Wherein reverse osmosis unit 13 is communicated with the circulation soup inlet 4 of liquor box 1; The circulation medicine liquid outlet 7 of liquor box 1 is communicated with spray pump 8; The outlet of spray pump 8 is communicated with the inlet of liquid medicine filter 12, and the outlet of liquid medicine filter 12 is communicated with the dense water side of reverse osmosis unit 13.The liquor box sewage draining exit 2 of liquor box 1 is provided with butterfly valve 3.Circulation line 14 between liquor box 1 and the spray pump 8 is provided with butterfly valve 3.Be disposed with check-valves 9, butterfly valve 3, pH meter 10, Pressure gauge 11, butterfly valve 3 on the circulation line 14 between spray pump 8 and the liquid medicine filter 12.Circulation line 14 between liquid medicine filter 12 and the reverse osmosis unit 13 is provided with butterfly valve 3 and Pressure gauge 11.The product water side of reverse osmosis unit 13 is provided with butterfly valve 3.In the present embodiment; The regrowth liquid medicine of the discarded reverse-osmosis membrane element of spray tank 1 splendid attire; Spray pump 8 is used for making regrowth liquid medicine to circulate at this regenerating unit; Liquid medicine filter 12 is used for regrowth liquid medicine is carried out filtration treatment, and reverse osmosis unit 13 is used for the discarded reverse-osmosis membrane element of splendid attire, and regrowth liquid medicine carries out Regeneration Treatment to discarded reverse-osmosis membrane element in reverse osmosis unit 13.
When utilizing this device that discarded reverse-osmosis membrane element is carried out Regeneration Treatment; Discarded reverse-osmosis membrane element is contained in the reverse osmosis unit 13; With the soup medicine-chest 1 of packing into; Open corresponding valve and spray pump 8 and make soup unimpeded flowing in circulation line 14, soup gets into 13 pairs of discarded reverse-osmosis membrane elements of reverse osmosis unit and carries out circulation immersion after medicine company filter 12 filters, flow back to liquor box 1 at last again.Utilize this device also can carry out performance test, regulate the rate of recovery through dense water side of regulating reverse osmosis unit 13 and the butterfly valve that produces the water side 3, and then realize test the membrane component performance to membrane component.Circulation process has been realized fully contacting of regrowth liquid medicine and discarded reverse-osmosis membrane element, has avoided the contact dead angle, and can comprehensively carry out soup to discarded reverse-osmosis membrane element and handle, and can make full use of soup again, practices thrift dosing.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, concerning those of ordinary skills, can improve or conversion that all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (7)
1. a discarded reverse-osmosis membrane element renovation process is characterized in that, comprises step:
A: discarded reverse-osmosis membrane element is carried out the circulation immersion clean with the reverse-osmosis membrane element cleaning fluid, and fluid temperature is controlled at 28 ~ 32 ℃, and washing time is 30min ~ 2h;
HCL solution or citric acid solution that said reverse-osmosis membrane element cleaning fluid is pH=2.5 ~ 3.5; Or the hydrosulfurous acid sodium solution of pH=4 ~ 6; Or the NaOH of pH=10.5 ~ 11.5 or NaOH and detergent alkylate naphthenic acid sodium mixed solution; Or the mixed solution of the sodium phosphate trimer of pH=9.5 ~ 11 and EDTA sodium salt;
B:, carry out the circulation immersion modification of oxidation soup and handle to after the reverse-osmosis membrane element of clean is with pure water rinsing; The temperature of said oxidation soup is 25 ~ 35 ℃, and the reaction time is 20min ~ 1.5h; Said oxidation soup pH value is 6 ~ 7.5; It is 0.01% ~ 3% oxidation medicament that said oxidation soup contains mass concentration;
C: to after the discarded reverse-osmosis membrane element after the oxidation medicament circulation immersion modification processing is with pure water rinsing; It is used mass concentration is 0.05 ~ 1% polyamine solution circulation immersion coating processing; Said polyamine solution temperature scope is 20 ~ 40 ℃, and soak time is 10 ~ 20min; Said polyamine solution is m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,2-ethylenediamine, 1,4-cyclohexanediamine or 1,3 hexamethylene dimethylamine solution.
2. discarded reverse-osmosis membrane element renovation process according to claim 1 is characterized in that the oxidation medicament among the said step B is KMnO
4, clorox, chlorine dioxide or hydrogen peroxide.
3. discarded reverse-osmosis membrane element renovation process according to claim 1 is characterized in that the mass concentration of the polyamine solution among the said step C is 0.7%.
4. a discarded reverse-osmosis membrane element regenerating unit is characterized in that, comprises liquor box, spray pump, liquid medicine filter, reverse osmosis unit, circulation line, butterfly valve and check-valves;
Said liquor box is used for the regrowth liquid medicine of the discarded reverse-osmosis membrane element of splendid attire, comprising: reverse-osmosis membrane element cleaning fluid, oxidation soup or polyamine solution, the medicine liquid outlet of said liquor box are communicated with the soup inlet of spray pump through circulation line; Institute's spray pump is used to make the regrowth liquid medicine of discarded reverse-osmosis membrane element to circulate, and the medicine liquid outlet of said spray pump is communicated with the soup inlet of liquid medicine filter through circulation line; Said liquid medicine filter is used for the regrowth liquid medicine of discarded reverse-osmosis membrane element is carried out filtration treatment, and the medicine liquid outlet of said liquid medicine filter is communicated with the soup inlet of reverse osmosis unit through circulation line; Said reverse osmosis unit is used for the discarded reverse-osmosis membrane element of splendid attire, and the medicine liquid outlet of said reverse osmosis unit is communicated with the soup inlet of liquor box through circulation line; Said check-valves and butterfly valve are arranged on the circulation line.
5. discarded reverse-osmosis membrane element regenerating unit according to claim 4 is characterized in that, also comprises pH meter and Pressure gauge; Said pH meter is used to test the pH value of the regrowth liquid medicine of discarding reverse-osmosis membrane element, and said Pressure gauge is used for the pressure parameter of test loop pipeline; Said pH meter is arranged on the circulation line between said spray pump and the liquid medicine filter, and said Pressure gauge is arranged on the circulation line between said spray pump and the liquid medicine filter and on the circulation line between medicine company filter and the reverse osmosis unit.
6. discarded reverse-osmosis membrane element regenerating unit according to claim 4 is characterized in that, also comprises thermometer and heating rod; Said thermometer is used for the temperature of the regrowth liquid medicine of test solution case, and said heating rod is used regrowth liquid medicine in the liquor box is heated; Said thermometer and heating rod are arranged in the said liquor box.
7. discarded reverse-osmosis membrane element regenerating unit according to claim 4 is characterized in that, said liquor box bottom is provided with sewage draining exit, is used for discharging the pollutant of liquor box, and sewage draining exit is provided with butterfly valve; The product water side of said reverse osmosis unit is provided with butterfly valve, is used to regulate the rate of recovery of reverse osmosis unit.
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