CN104474905A - Nanofiltration membrane cleaning agent for treating polymer flooding produced wastewater and cleaning method - Google Patents
Nanofiltration membrane cleaning agent for treating polymer flooding produced wastewater and cleaning method Download PDFInfo
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Abstract
The invention discloses a nanofiltration membrane cleaning agent for treating polymer flooding produced oil-bearing wastewater and a cleaning method. The composite cleaning agent is formed by blending EDTA, sodium pyrophosphate, SDS and water. The cleaning method comprises the following two steps: firstly, cleaning by utilizing a composite reagent provided by the invention, and then carrying out acid pickling by a diluted hydrochloric acid solution. The composite chemical cleaning reagent provided by the invention is adopted for treating the polluted nanofiltration membrane in the polymer flooding produced wastewater for chemical cleaning; the result shows that the flux recovery rate of the cleaned nanofiltration membrane can reach 99% above, and the recovered flux can be kept for a long time. In addition, a plurality of testing and representing means are further adopted for researching the cleaned nanofiltration membrane, and the result shows that the composite cleaning agent does not damage other performances of the nanofiltration membrane, and the cleaned nanofiltration membrane is almost the same with a novel membrane in desalting rate, hydrophilia, microstructure and infrared spectroscopy, thus fully showing that the polluted nanofiltration membrane is 'regenerated' by the cleaning method.
Description
Technical field
The invention belongs to poly-nanofiltration membrane treatment field of driving oil extraction waste water, relate to a kind of when driving oil extraction waste water for process is poly-contaminated NF membrane carry out effectively and Chemical cleaning without destruction time used complex cleaning and washing agent and cleaning method.
Background technology
Poly-drive oil recovery technique and effectively improve oil recovery factor applying of each elephant of China, but a large amount of clear water consumption in this process and waste water output problem to annoying this oil recovery with regard to lack of water regional always.Nanofiltration between ultrafiltration and counter-infiltration can retain small organic molecule, and there is partially desalted ability, therefore NF membrane is utilized to carry out advanced treating to the poly-oil extraction waste water that drives through hyperfiltration treatment, reduce salinity, and further remove organic matter residual in water, guarantee that nanofiltration water outlet meets to join and to be back to the poly-oil recovery process that drives after poly-quality of water requires and to be expected to solve the economic problems and environmental problem that clear water consumption and discharge of wastewater bring.
But, fouling membrane is the major obstacle that restriction NF membrane is applied, although take various control measure (as carried out pretreatment to feed liquid, operation conditions optimization, improve membrane material antifouling property etc.) fouling membrane can be alleviated, but which kind of method all can not avoid the generation of fouling membrane completely, when flux depression to a certain extent or transmembrane pressure be elevated to a certain degree, or when effluent quality deterioration can not meet the demands, just need to clean contaminated NF membrane, cleaning method can be divided into physical cleaning and Chemical cleaning, namely physical cleaning is pass through current, the disturbance of the physical actions such as gas and forcibly pollutant is peeled off film body, but when comparatively obstinate pollution layer, physical cleaning is difficult to obtain gratifying cleaning performance usually, now just need to carry out Chemical cleaning.Chemical cleaning destroys pollution layer structure by the chemical reaction between cleaning agent and pollutant, reduce the adhesion of pollutant and NF membrane, pollutant is moved under self diffusion and turbulent water effect and leaves film body, thus recovery membrane flux, ensure effluent quality, realize " regeneration " of contaminated NF membrane.
Nanofiltration process is poly-when driving oil extraction waste water, and the crude oil in water, polyacrylamide, natural organic matter and all kinds of salt ion can both cause the pollution problem of film.These pollutants are comparatively closely combined by various physics chemical action and NF membrane, are difficult to the recovery completely being realized film properties by physical cleaning, but need suitable Chemical cleaning to realize this goal.But single Chemical cleaning reagent often only has good cleaning performance to a certain pollution components, and the contaminated NF membrane in practical application is generally the combined pollution of multiple different component, in order to obtain satisfied cleaning performance, just need to adopt multiple cleaning reagent to carry out multistep cleaning, complex steps, take time and effort, and some commercially available commercial detergent are not pointed to specific pollution condition, practical application also shows commercial detergent really, and to drive the contaminated NF membrane cleaning performance that oil extraction waste water causes not good to poly-.Cleaning performance good oxidisability cleaning reagent (as liquor natrii hypochloritis) can cause irreversible destruction to the composite nanometer filtering film of polyamide material again, reduces the effluent quality of NF membrane and the service life of membrane module.Therefore, need badly a kind of process is poly-ly driven that contaminated NF membrane in oil extraction waste water is pointed, high efficiency and nondestructive composite chemical cleaning reagent and cleaning method.
Summary of the invention
Not good and to film body, there is destructive problem in order to solve existing NF membrane chemical clenaing effect, the present invention is directed to the poly-nanofiltration treatment technology driving oil extraction waste water, develop one and there is technique efficiently process is poly-targetedly and drive oil extraction waste water NF membrane cleaning agent and cleaning method.
The object of the invention is to be achieved through the following technical solutions:
A kind of process is poly-drives oil extraction waste water NF membrane cleaning agent, formulated by EDTA, sodium pyrophosphate, SDS and water, the content of each composition is: 0.03 ~ 0.07wt.%EDTA, 0.15 ~ 0.25wt.% sodium pyrophosphate, 0.15 ~ 0.25wt.%SDS, its compound method is: by 0.03 ~ 0.07%EDTA, 0.15 ~ 0.25wt.% sodium pyrophosphate and the abundant stirring and dissolving of 0.15 ~ 0.25wt.%SDS, and then with NaOH, the pH of this solution is adjusted to 10.5 ~ 11.5.
When driving that in oil extraction waste water, contaminated NF membrane carries out Chemical cleaning to process is poly-, first with above-mentioned composite chemical cleaning reagent cleaning 15 ~ 30min, then adopt the hydrochloric acid solution cleaning 10 ~ 20min of pH=2, finally again with clear water to membrane module flush clean.
Adopt composite chemical cleaning reagent of the present invention to drive contaminated NF membrane in oil extraction waste water carry out Chemical cleaning to process is poly-, result shows that the flux recovery rate of cleaning rear NF membrane can reach more than 99%, and the flux recovered can be kept for a long time.In addition, the multiple test of further employing and characterization method are studied the NF membrane through this cleaning process, result shows that this composite cleaning reagent does not damage other performances of NF membrane, clean the salt rejection rate of rear NF membrane, hydrophily, microscopic appearance and infrared spectrum all very nearly the same with new film, absolutely prove that this cleaning program effectively achieves " regeneration " of contaminated NF membrane.
Accompanying drawing explanation
Fig. 1 is the salt rejection rate of different NF membrane;
Fig. 2 is the atomic force microscope images of different NF membrane;
Fig. 3 is the contact angle of different NF membrane;
Fig. 4 is the infrared spectrum of different NF membrane.
Detailed description of the invention
Below technical scheme of the present invention is further described, but is not limited thereto, everyly technical solution of the present invention is modified or equivalent to replace, and do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Detailed description of the invention one: present embodiments provide for that a kind of process is poly-drives oil extraction waste water NF membrane cleaning agent, formulated by EDTA, sodium pyrophosphate, SDS and water, the content of each composition is: 0.05wt.%EDTA, 0.2wt.% sodium pyrophosphate, 0.2wt.%SDS, its compound method is: in clear water, add the sodium pyrophosphate of EDTA, 0.2wt.% of 0.05wt.%, the SDS of 0.2wt.%, with NaOH, the pH of this solution is modulated 11 again after abundant stirring and dissolving.
When driving that in oil extraction waste water, contaminated NF membrane carries out Chemical cleaning to process is poly-, first 20 minutes are cleaned with above-mentioned composite chemical cleaning reagent, then the hydrochloric acid solution of pH=2 is adopted to clean 15 minutes, last again with clear water to membrane module flush clean, after cleaning, the flux recovery rate of NF membrane can reach more than 99%, cleans the situation of change of the salt rejection rate of front and back NF membrane, hydrophily, microscopic appearance and infrared spectrum as Figure 1-4.
Fig. 1 shows that the salt rejection rate of contaminated NF membrane reaches 91.55%, and apparently higher than 86.21% of new film, this is because the pollution layer on film enhances the interception capacity of nanofiltration process to salt ion; When contaminated NF membrane is after optimizing the cleaning of cleaning program, by 91.55%, 87.62% has been down to the rejection of sodium chloride, with 86.21% of new film closely, illustrate that selected Chemical cleaning scheme not only effectively eliminates the pollutant on film thus, and the desalting performance of NF membrane is not damaged.
Fig. 2 shows after NF membrane is contaminated, the original convex structure in surface is covered completely by the stickum that one deck is abundant, be difficult to the bulge-structure finding that new film has again, the reason place of this also flux depression just, and after adopting the cleaning of optimization cleaning program, pollution layer closely knit in NF membrane is eliminated, concave/convex-shaped structure manifests again, and face shape characteristic is almost identical with new film, illustrate that fixed optimization cleaning program can effectively remove fouling membrane material from the angle of microscopic appearance, face inherent structure is not damaged simultaneously.
Fig. 3 shows that the contact angle polluting rear NF membrane has been increased to 78.57 ° from initial 61.16 °, and the appearance of pollution layer reduces the hydrophily of face, and this is caused by hydrophobic crude oil pollution thing.Adopt after optimizing cleaning program cleaning, NF membrane be down to 59.62 ° by 78.57 ° after polluting, and slightly lower than 61.16 ° of former film, illustrate that the pollution components on film is eliminated, recovered its comparatively hydrophilic face characteristic, contact angle is slightly lower than former film may be caused by surfactant owing to remaining on film during cleaning.
Fig. 4 shows that the NF membrane after polluting has occurred obvious absworption peak at 2850cm-1,2919 cm-1,3327 cm-1 places respectively, wherein 2850cm-1 and 2919 cm-1 is the characteristic absorption peak of crude oil pollution thing, and 3327 cm-1 are the characteristic absorption peak of APAM, after cleaning program cleaning is optimized in employing, the absworption peak at this three place is disappeared, and this two pollutant of surface is removed by cleaning.After cleaning, NF membrane is compared with former film, a more weak absworption peak has been there is respectively at 2926 cm-1 and 2855 cm-1 places, this may be that to remain in C-H in the surfactant in NF membrane on hydrophobic side in cleaning process asymmetric with symmetric shrinkage vibration absorption peak, consistent lower than the explanation of former film with the contact angle of NF membrane after cleaning.And absworption peak between 3200 cm-1 ~ 3700 cm-1 is wide compared with former film, when this may be owing to measuring, diaphragm drying is insufficient, caused by O-H in residual moisture absorbs, in addition, after cleaning, NF membrane is almost consistent with the infrared spectrum of former film, illustrates that Chemical cleaning does not cause damage to film body.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike, the content of each composition is: 0.04wt.%EDTA, 0.18wt.% sodium pyrophosphate, 0.18wt.%SDS.
Detailed description of the invention three: present embodiment and detailed description of the invention one unlike, the content of each composition is: 0.06wt.%EDTA, 0.23wt.% sodium pyrophosphate, 0.23wt.%SDS.
Claims (5)
1. a process is poly-drives oil extraction waste water NF membrane cleaning agent, it is characterized in that described cleaning agent is by the formulated complex cleaning and washing agent of EDTA, sodium pyrophosphate, SDS and water, the content of each composition is: 0.03 ~ 0.07wt.%EDTA, 0.15 ~ 0.25wt.% sodium pyrophosphate, 0.15 ~ 0.25wt.%SDS.
2. process according to claim 1 is poly-drives oil extraction waste water NF membrane cleaning agent, it is characterized in that the content of described each composition is: 0.05wt.%EDTA, 0.2wt.% sodium pyrophosphate, 0.2wt.%SDS.
3. process according to claim 1 is poly-drives oil extraction waste water NF membrane cleaning agent, it is characterized in that the content of described each composition is: 0.04wt.%EDTA, 0.18wt.% sodium pyrophosphate, 0.18wt.%SDS.
4. process according to claim 1 is poly-drives oil extraction waste water NF membrane cleaning agent, it is characterized in that the content of described each composition is: 0.06wt.%EDTA, 0.23wt.% sodium pyrophosphate, 0.23wt.%SDS.
5. utilize the poly-method of driving oil extraction waste water NF membrane cleaning agent cleaning NF membrane of process described in the arbitrary claim of claim 1-4, it is characterized in that described method step is as follows:
The first step, with complex cleaning and washing agent cleaning 15 ~ 30min;
Second step, adopts the hydrochloric acid solution of pH=2 to carry out cleaning 10 ~ 20min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056765A (en) * | 2015-08-20 | 2015-11-18 | 太仓市金鹿电镀有限公司 | Cleaning method of organic pollutants on ultrafiltration membrane surface and preparation method of cleaning solution for organic pollutants on ultrafiltration membrane surface |
| CN105443104A (en) * | 2015-06-16 | 2016-03-30 | 中国石油化工股份有限公司 | Plug removing method of acidized polymer-flooding plugged well |
| CN108031297A (en) * | 2017-12-06 | 2018-05-15 | 常州朋悦纺织品有限公司 | A kind of ceramic membrane cleaning agent |
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| WO2001023411A2 (en) * | 1999-09-30 | 2001-04-05 | New England Biolabs, Inc. | Incorporation of modified nucleotides by archaeon dna polymerases and related methods |
| US20140018250A1 (en) * | 2012-07-13 | 2014-01-16 | Alexander Abbas | Compositions and methods for the treatment of immune related diseases |
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- 2014-12-12 CN CN201410763489.8A patent/CN104474905B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023411A2 (en) * | 1999-09-30 | 2001-04-05 | New England Biolabs, Inc. | Incorporation of modified nucleotides by archaeon dna polymerases and related methods |
| US20140018250A1 (en) * | 2012-07-13 | 2014-01-16 | Alexander Abbas | Compositions and methods for the treatment of immune related diseases |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105443104A (en) * | 2015-06-16 | 2016-03-30 | 中国石油化工股份有限公司 | Plug removing method of acidized polymer-flooding plugged well |
| CN105443104B (en) * | 2015-06-16 | 2018-01-23 | 中国石油化工股份有限公司 | Polymer flooding blocks method for removing blockage after well acidizing |
| CN105056765A (en) * | 2015-08-20 | 2015-11-18 | 太仓市金鹿电镀有限公司 | Cleaning method of organic pollutants on ultrafiltration membrane surface and preparation method of cleaning solution for organic pollutants on ultrafiltration membrane surface |
| CN108031297A (en) * | 2017-12-06 | 2018-05-15 | 常州朋悦纺织品有限公司 | A kind of ceramic membrane cleaning agent |
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Effective date of registration: 20180214 Address after: Guanghua Road Qinhuai District of Nanjing City, Jiangsu province 210014 No. 129-3 Baixia Nanjing high tech Industrial Park A1 District 537 room Patentee after: Nanjing clean environment Technology Co., Ltd. Address before: 150000 Harbin, Nangang, West District, large straight street, No. 92 Patentee before: Harbin Institute of Technology |