CN101816896A - Method for cleaning calcium sulfate dirt of reverse osmosis membrane or nanofiltration membrane - Google Patents

Method for cleaning calcium sulfate dirt of reverse osmosis membrane or nanofiltration membrane Download PDF

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Publication number
CN101816896A
CN101816896A CN201010154514A CN201010154514A CN101816896A CN 101816896 A CN101816896 A CN 101816896A CN 201010154514 A CN201010154514 A CN 201010154514A CN 201010154514 A CN201010154514 A CN 201010154514A CN 101816896 A CN101816896 A CN 101816896A
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China
Prior art keywords
membrane
reverse osmosis
cleaning
calcium sulfate
distilled water
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CN201010154514A
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Chinese (zh)
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曹占平
张景丽
张宏伟
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Priority to CN201010154514A priority Critical patent/CN101816896A/en
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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

Abstract

The invention relates to a method for cleaning calcium sulfate dirt of a reverse osmosis membrane or a nanofiltration membrane, which comprises the following steps of: 1) inoculating sulfate reducing bacteria in distilled water, wherein the inoculation amount of the sulfate reducing bacteria is 102 to 105CFU/mL; 2) adding easily degradable organic matters to ensure that the CODCr content of the solution is 300 to 500mg/L; 3) adjusting the pH value to between 6.5 and 8.5, keeping the temperature between 20 and 35 DEG C, injecting the solution to a membrane module, soaking for 48 to 96 hours, and discharging the solution; 4) circularly cleaning for 1 to 2 hours by adopting acid solution which is prepared from muriatic acid and distilled water and has the pH value between 2 and 3, and discharging the acid solution; and 5) cleaning for 20 to 40 minutes by adopting non oxidizing bactericide in concentration between 50 and 200mg/L, discharging the non oxidizing bactericide, and washing the membrane module with distilled water to complete cleaning the membrane. The method effectively solves the problem of cleaning calcium sulfate dirt of the reverse osmosis membrane or the nanofiltration membrane, has important significance for the promotion and application of reverse osmosis and nanofiltration in the aspects such as seawater desalting, soft water making, and advanced treatment and recycling of sewage, and expands the application range of membrane technology.

Description

A kind of method of cleaning reverse osmosis membrane or NF membrane calcium sulfate dirt
Technical field
The present invention relates to the method that a kind of cleaning counter-infiltration (RO) film or nanofiltration (NF) film calcium sulfate scaling pollute, this method is mainly developed at effective cleaning of reverse osmosis membrane or the pollution of NF membrane calcium sulfate dirt, belongs to field of environment protection.
Background technology
At present, raising along with industrial expansion and reusing sewage requirement, counter-infiltration or nanofiltration begin to widely apply in fields such as boiler of power plant water supply, desalinization, the water supply of medical electron trade demineralized water and municipal wastewater advanced treating, but the operation practice shows that inorganic salts scaling fouling particularly calcium sulfate dirt is one of key factor that influences this technology application.And the removal that the combination of conventional alkali cleaning, pickling is cleaned calcium sulfate dirt does not almost have effect, has seriously restricted the application in above-mentioned field of counter-infiltration or nanofiltration, presses for the new method that reverse osmosis membrane or NF membrane calcium sulfate dirt are effectively cleaned in exploitation.
Summary of the invention
The objective of the invention is to provide a kind of method of cleaning reverse osmosis membrane or NF membrane calcium sulfate dirt effectively, advance the application of reverse osmosis membrane or NF membrane technology at the aspects such as embrane method advanced treatment and reclamation of desalinization, demineralized water production, sewage.For this reason, we have developed a kind of method of utilizing microorganism to clean reverse osmosis membrane or NF membrane calcium sulfate dirt.
Clean in order to solve conventional physics, the problem that Chemical cleaning can't effectively be removed reverse osmosis membrane or NF membrane calcium sulfate dirt, according to the anaerobic bacteria strain properties, utilize sulfate reducing bacteria to belong to (sulfate-reducing bacteria, SRB) decomposing organic matter under anaerobic, and be that electron acceptor (oxidant) carries out metabolism with the sulfate radical in the calcium sulfate dirt, sulphion in the sulfate radical under anaerobic obtains electronics and forms deliquescent hydrogen sulfide gas, make the solubility product of calcium sulfate less than saturation value, thereby calcium sulfate dirt is constantly come off from the film surface dissolution, reach the purpose of thorough cleaning.
Specific implementation method:
The method of cleaning reverse osmosis membrane of the present invention or NF membrane calcium sulfate dirt, finish by following step:
1) inoculate sulfate reducing bacteria in distilled water, the inoculation quantity of sulfate reducing bacteria is 10 2～10 5CFU/mL;
2) add the easily organic matter of degraded again, make the COD of solution CrContent is 300～500mg/L, and adds the required trace element of growth of microorganism;
3) the pH value of adjusting solution then is 6.5～8.5 and keeps 20～35 ℃ of temperature to inject membrane modules, soaks after 48～96 hours and discharges;
4) acid solution that adopts hydrochloric acid and distilled water to prepare, the pH value is between 2～3, and wash cycles was discharged after 1～2 hour;
5) compound concentration of non-oxidizable bactericide cleans discharging after 20～40 minutes between 50～200mg/L, washes down membrane module with distilled water and finishes the film cleaning.
The bacterial classification of described sulfate reducing bacteria comprises: the bacterial classification of desulfurization vibrio genus, Desulfobacter, desulfurization Mycotoruloides or desulfurization line Pseudomonas.
Described easily biodegradable organics by glucose, acetate receive, one or more mixing in starch, disaccharides, polysaccharide or the aliphatic acid provide.
Microorganism of the present invention is washed the cleaning problem that embrane method has solved reverse osmosis membrane or NF membrane calcium sulfate dirt effectively, significant to applying of counter-infiltration or nanofiltration, for the cleaning of reverse osmosis membrane or NF membrane provides new method and thinking, enlarged the Application of membrane scope.
Description of drawings
Fig. 1: the relation of soak time and sulfate reducing bacteria amount and membrane flux;
Fig. 2: reverse osmosis membrane Inlet and outlet water conductivity variations curve;
Fig. 3: reverse osmosis membrane Inlet and outlet water firmness change curve.
The specific embodiment
Embodiment 1:
In distilled water, inoculate 10 5After the CFU/mL desulfurization vibrio belongs to (Desulfovibrio) or Desulfobacter (Desulfobacterium), add again and analyze pure glucose preparation film washing liquid, make the COD of film washing liquid CrAbout 400mg/L, and in film washing liquid, add trace elements such as magnesium, iron, zinc, adjust the pH value of film washing liquid about 7.0 with analytically pure NaOH; Afterwards this film washing liquid is injected the dirty stifled reverse osmosis membrane assembly of calcium sulfate and soak, keeping temperature during immersion is 20 ℃, and the relation of soak time and sulfate reducing bacteria amount and membrane flux as shown in Figure 1.
When measuring membrane flux, with pH earlier 2.5 hydrochloric acid solution cleaning 2h, be to measure after the non-oxidizable 911 type bactericide of 200mg/L clean 40min with concentration again.
Embodiment shows: after finishing above-mentioned cleaning step, membrane flux is greatly improved before cleaning, return to calcium sulfate before polluting more than 99%, on the increment of sulfate reducing bacteria (SRB), can infer that it is dissolved matter that sulfate reducing bacteria (SRB) can well change calcium sulfate dirt, to reach the purpose of cleaning.
Clean influence, mensuration such as Fig. 2, shown in Figure 3 of after microorganism is cleaned, the reverse osmosis produced water water quality index being carried out in order to determine microorganism to reverse osmosis membrane performance.
Produce water conductivity and compare to some extent before microorganism is washed film and descend, may with clean the back and produce water flux and increase relevant; Soluble solid, hardness, COD CrIndex such as clearance with wash before basic no change; This example shows that for the dirty stifled reverse osmosis membrane of calcium sulfate adopting sulfate reducing bacteria to clean is effectively, and to the not significantly influence of character of film, the reverse osmosis membrane flux then increases significantly, and can return to more than 99% of former flux before and after cleaning.
Embodiment 2:
In distilled water, inoculate 10 2Behind CFU/mL desulfurization Mycotoruloides (Desulfomonile) or the desulfurization line Pseudomonas (Desulfonema), add technical grade acetate again and receive the preparation film washing liquid, make the COD of film washing liquid CrAbout 500mg/L, and in film washing liquid, add the part trace element, and hydro-oxidation sodium adjustment pH value is 8.0; Afterwards this solution system being injected the dirty stifled nanofiltration membrane component of calcium sulfate soaks, keeping temperature during immersion is 30 ℃, soak time is 48 hours, discharge after reaching soak time, with the pH value is that 2 hydrochloric acid solution wash cycles was discharged after 1 hour, be the non-oxidizable isothiazolinone disinfecting agent wash cycles 20 minutes of 50mg/L again with concentration, wash down with distilled water and just to have finished cleaning, clean the back membrane flux reached calcium sulfate dirty before stifled more than 98%, the character of cleaning the back NF membrane does not change, cleaning performance is good, and adopting chemical cleaning method only can return to dirty about 45% before stifled of calcium sulfate, it is dirty stifled respond well that this example proof sulfate reducing bacteria cleans NF membrane calcium sulfate.
Embodiment 3:
In distilled water, inoculate 10 4Behind the CFU/mL Desulfobacter (Desulfobacterium), add starch again, adjust the COD of solution system CrContent is 300mg/L, and hydro-oxidation sodium adjustment pH value is 8.5; Afterwards this solution system being injected the dirty stifled nanofiltration membrane component of calcium sulfate soaks, keeping temperature during immersion is 25 ℃, soak time 75 hours, discharge after reaching soak time, with the pH value is that 3 hydrochloric acid solution wash cycles was discharged after 1.5 hours, use the non-oxidizable bactericide wash cycles of HY-220 30 minutes again, wash down with distilled water at last and just finished cleaning, clean the back membrane flux reached calcium sulfate dirty before stifled more than 98%, the character of NF membrane does not change, cleaning performance is good, and adopts chemical cleaning method only can return to dirty about 55% before stifled of calcium sulfate, and this example proof sulfate reducing bacteria cleans the respond well of NF membrane.
The cleaning reverse osmosis membrane that the present invention proposes or the method for NF membrane calcium sulfate dirt, be described by embodiment, person skilled obviously can be changed or suitably change and combination content as herein described in not breaking away from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.

Claims (4)

1. method of cleaning reverse osmosis membrane or NF membrane calcium sulfate dirt is characterized in that finishing by following step:
1) inoculate sulfate reducing bacteria in distilled water, the inoculation quantity of sulfate reducing bacteria is 10 2～10 5CFU/mL;
2) and then add easily biodegradable organics, make the COD that washes coating solution CrContent is 300～500mg/L;
3) adjustment pH value is 6.5～8.5, keeps 20～35 ℃ of temperature and inject membrane module, soaks 48～96 hours;
4) adopt hydrochloric acid and distilled water preparating acid solution, the pH value between 2～3, wash cycles 1～2 hour;
5) compound concentration of non-oxidizable bactericide cleaned 20～40 minutes between 50～200mg/L, washed down membrane module with distilled water and finished the film cleaning.
2. clean the method for reverse osmosis membrane or NF membrane calcium sulfate dirt as described in claim 1, it is characterized in that the bacterial classification of described sulfate reducing bacteria comprises: the bacterial classification of desulfurization vibrio genus, Desulfobacter, desulfurization Mycotoruloides or desulfurization line Pseudomonas.
3. clean the method for reverse osmosis membrane or NF membrane calcium sulfate dirt as described in claim 1, it is characterized in that described easily biodegradable organics by glucose, acetate receive, one or more mixing in starch, disaccharides, polysaccharide or the aliphatic acid provide.
4. clean the method for reverse osmosis membrane or NF membrane calcium sulfate dirt as described in claim 1, it is characterized in that described non-oxidizable bactericide comprises: one or more of PT-ROBI0911 bactericide, isothiazolinone disinfecting agent, the non-oxidizable bactericide of HY-220, quaternary ammonium salt bactericide, glutaraldehyde or chlorophenols mix use.
CN201010154514A 2010-04-26 2010-04-26 Method for cleaning calcium sulfate dirt of reverse osmosis membrane or nanofiltration membrane Pending CN101816896A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102658035A (en) * 2012-05-09 2012-09-12 首钢总公司 Method for preventing organic matters from polluting and blocking water treatment membrane
CN110408453A (en) * 2018-04-26 2019-11-05 天津工业大学 A kind of technique of biological eliminating organic sulfur in coal
CN110898675A (en) * 2019-12-09 2020-03-24 吉林省电力科学研究院有限公司 Calcium sulfate scale cleaning agent for reverse osmosis membrane and cleaning method
CN111286313A (en) * 2020-03-05 2020-06-16 长江大学 Barium-strontium sulfate scale biological descaling liquid and descaling method thereof
CN114086190A (en) * 2021-11-01 2022-02-25 福建中晶科技有限公司 Cleaning and maintaining method for ice machine unit for scaling

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264424A (en) * 2008-04-25 2008-09-17 天津工业大学 Novel method for cleaning reverse osmosis membrane and nano filter membrance organic pollution

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264424A (en) * 2008-04-25 2008-09-17 天津工业大学 Novel method for cleaning reverse osmosis membrane and nano filter membrance organic pollution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《过滤与分离》 20071231 周军 等 反渗透膜污染及其清洗的研究 第1-3节 1-4 第17卷, 第1期 2 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102658035A (en) * 2012-05-09 2012-09-12 首钢总公司 Method for preventing organic matters from polluting and blocking water treatment membrane
CN110408453A (en) * 2018-04-26 2019-11-05 天津工业大学 A kind of technique of biological eliminating organic sulfur in coal
CN110898675A (en) * 2019-12-09 2020-03-24 吉林省电力科学研究院有限公司 Calcium sulfate scale cleaning agent for reverse osmosis membrane and cleaning method
CN111286313A (en) * 2020-03-05 2020-06-16 长江大学 Barium-strontium sulfate scale biological descaling liquid and descaling method thereof
CN111286313B (en) * 2020-03-05 2022-07-12 长江大学 Barium-strontium sulfate scale biological descaling liquid and descaling method thereof
CN114086190A (en) * 2021-11-01 2022-02-25 福建中晶科技有限公司 Cleaning and maintaining method for ice machine unit for scaling

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Open date: 20100901