WO2017059622A1 - 一种废旧平板膜性能的综合评价方法 - Google Patents

一种废旧平板膜性能的综合评价方法 Download PDF

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WO2017059622A1
WO2017059622A1 PCT/CN2015/095725 CN2015095725W WO2017059622A1 WO 2017059622 A1 WO2017059622 A1 WO 2017059622A1 CN 2015095725 W CN2015095725 W CN 2015095725W WO 2017059622 A1 WO2017059622 A1 WO 2017059622A1
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membrane
film
contaminated
carbon
control
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French (fr)
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李秀芬
宋小莉
王新华
任月萍
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Jiangnan University
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Jiangnan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/301—Polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/90—Additional auxiliary systems integrated with the module or apparatus
    • B01D2313/903—Integrated control or detection device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/162—Use of acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/40—Automatic control of cleaning processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/20—Accessories; Auxiliary operations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a comprehensive evaluation method for the performance of waste flat membrane, belonging to the technical field of sewage and waste recycling.
  • MBR membrane bioreactor
  • PVDF polyvinylidene fluoride
  • the annual output of the world is about 33,000 tons
  • the output of China is 2,000 tons
  • the actual demand is 4,000 tons.
  • the use of PVDF membranes in wastewater treatment will increase rapidly.
  • the total area of PVDF membranes widely used in the production of sewage treatment at home and abroad is nearly 50 million m 2
  • the PVDF value for manufacturing hollow fibers is several hundred million US dollars.
  • the annual output of the lined PVDF hollow fiber membrane is nearly 10 million m 2
  • the consumption of PVDF raw materials is about 1200 tons, worth more than 200 million yuan.
  • the service life of the PVDF membrane is about 3 to 7 years. In 5 years, the replacement of the membrane module accounts for 40% of the annual membrane sales, that is, 20 million m 2 of waste film is produced every year.
  • the basis for evaluating whether the membrane module can be used or discarded is mainly the membrane flux recovery rate, that is, through various off-line chemical cleaning, if the membrane flux recovery rate is above 80%, it can continue to be used. Whether the physical and chemical properties of the cleaning film such as tensile strength and maximum pore diameter can meet the requirements for use, and the difficulty, cost and carbon emission (carbon footprint) of the cleaning process are not considered reasonable. It is worth mentioning that global warming is a severe challenge that human survival and development must face. “Carbon footprint”, “carbon emissions”, “low carbon economy”, “low carbon technology”, “low carbon city”, etc. A series of new concepts and new policies have emerged. How to correctly evaluate the pollution film cleaning effect and energy consumption, how to achieve new process theory and technology research and energy conservation and carbon reduction are new challenges faced by water treatment workers.
  • the inventors considered various factors that restrict the use efficiency and life of the film.
  • the tensile strength was taken as the main evaluation index of physicochemical properties
  • the membrane flux was taken as The main evaluation index of filtration performance, using carbon footprint as the main evaluation index of other performance, establishing a quantitative, rapid and comprehensive
  • the comprehensive evaluation system of waste film performance defines the difference between the old film and the waste film, and provides a basis for the reuse of the old film and the regeneration of the waste film, and maximizes the recycling of waste film.
  • the object of the present invention is to provide a comprehensive evaluation method for the performance of waste flat membranes, which is:
  • the surface element composition of the analytical membrane is analyzed using energy dispersive x-ray spectroscopy (EDX).
  • EDX energy dispersive x-ray spectroscopy
  • the distinguishing the pollution film is an organic pollution type film when the percentage of carbon on the surface of the film is higher than that of the control film, and the inorganic pollution type film when the percentage of carbon on the surface of the film is lower than that of the control film.
  • the pollution film is an organic pollution type film
  • a cleaning method of citric acid or grass pickling after washing with sodium hypochlorite is used;
  • the pollution film is an inorganic pollution type film
  • a cleaning method using citric acid or oxalic acid washing followed by sodium hypochlorite washing is used.
  • the organic pollution type membrane is washed by 0.1 to 5.0% sodium hypochlorite and 0.1 to 5.0% citric acid or oxalic acid, and the inorganic pollution type membrane is 0.1 to 5.0% citric acid. Or a washing method of 0.1 to 5.0% sodium hypochlorite after pickling.
  • the physicochemical properties include tensile strength (MPa) as determined using a tensile strength tester.
  • the filtration performance includes a membrane flux
  • the membrane flux is determined by placing a circular membrane into the bottom of the SCM-300 ultrafiltration cup, sealing the nitrogen, and recording from the beginning.
  • Time (t 1 , min) to end time (t 2 , min) liquid volume (A, mL) through the membrane effective area (S, m 2 ) at a pressure of 0.1 MPa, membrane standard flux (J, L/ (m 2 ⁇ h))
  • the other performance includes a carbon footprint;
  • the carbon footprint also referred to as carbon footprint, is the carbon dioxide emissions (E, g) of the off-line chemical cleaning process of the contaminated membrane, including the total of off-line chemical cleaning.
  • the energy consumption (Q i , kW ⁇ h) is calculated according to the unit carbon emission factor (f, 785g/(kW ⁇ h)) of energy consumption according to Equation 2:
  • the evaluation result is determined according to the following evaluation standard: the pollution film whose tensile strength is reduced by 50% or more than the control film is a waste film, the tensile strength is reduced by 50% or less, and the membrane flux is reduced by 30% or more compared with the control film.
  • the pollution film is waste film, the tensile strength is less than 50% lower than the control film, the membrane flux is less than 30% lower than the control film, and the carbon film with a carbon footprint higher than 188g is the waste film, otherwise it is the old film.
  • the contaminating membrane is a flat membrane.
  • the contaminated membrane is a contaminated membrane from a sewage treatment membrane bioreactor.
  • control film is a new film of the same type (flat film) as the contaminated film.
  • the contaminated film and the control film are both polyvinylidene fluoride (PVDF) or polyvinyl chloride (PVC).
  • the film surface element composition of the control film is: carbon 48.05%, fluorine 51.95%, tensile strength 20.0 MPa, and membrane flux 2000 L/(m 2 ⁇ h).
  • the invention also provides a method for detecting the performance of a waste flat membrane, comprising:
  • control membrane is a new membrane of the same type and the same material as the contaminated membrane
  • step (1) detects that the percentage of carbon on the surface of the contaminated membrane is higher than that of the control membrane, it is washed with a cleaning method of citric acid or oxalic acid after washing with sodium chlorite to obtain a sample of the membrane to be tested; otherwise, citric acid or The washing method of the sodium hypochlorite washing after the pickling of the grass is washed to obtain a sample of the film to be tested;
  • the method for detecting the performance of the waste flat membrane is to detect that the pollution film whose tensile strength is reduced by more than 50% compared with the control film is no longer recycled, the tensile strength is reduced by 50% or less, and the membrane flux is reduced by 30% compared with the control membrane.
  • the above pollution film is no longer recycled.
  • the tensile strength is less than 50% lower than the control film, the membrane flux is less than 30% lower than the control film, and the carbon film with a carbon footprint higher than 188g is no longer recycled, otherwise it is recycled.
  • the method for detecting the performance of the waste flat membrane the method for detecting the carbon element on the surface of the contaminated membrane, the cleaning solution, and the tensile strength, the membrane flux, the carbon footprint calculation method, the type of the pollution membrane, and the like are all the evaluation methods mentioned above. the same.
  • the invention firstly analyzes the element composition of the surface of the waste film by EDX to determine the type of film contamination, and then designs different cleaning schemes for organic or inorganic pollution, obtains the film sample to be tested after cleaning, and then compares the physical and chemical properties of the film sample to be tested with the control film. Nature, filtration properties, other properties, etc., determine whether the contaminated membrane is a waste membrane or an old membrane (ie, determine whether it is worth recycling).
  • the inventors conducted a large number of experiments and found that the method used in the present invention has strong objectivity and can more accurately reflect whether the film still has the value of continued use.
  • the comprehensive evaluation method for the performance of the waste film established by the invention can quantitatively, quickly and comprehensively define the difference between the old film and the waste film, and provides a basis for the selection of the waste film and the process of recycling and recycling.
  • the inventors further explained the evaluation method of the present invention by a specific experiment.
  • the PVDF-contaminated flat membrane in the municipal sewage treatment membrane bioreactor was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 19.47%, nitrogen 3.62%, oxygen 29.00%, phosphorus 11.24%, calcium 1.45%, iron 27.28%, aluminum 1.44%.
  • the contaminated membrane is of inorganic pollution type.
  • the contaminated membrane was washed with 1.0% oxalic acid for 3 h and then with 0.3% sodium hypochlorite for 3 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 20.5 MPa, a membrane flux of 1930 L/(m 2 ⁇ h), and a carbon footprint of 47 g, which was judged to be an old film as compared with the control group.
  • the monthly membrane flux decay rate is 3%, and the chemical cleaning cycle is 6-9 months, which can meet the normal operation requirements.
  • the PVDF-contaminated flat membrane in the municipal sewage treatment membrane bioreactor was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 65.63%, nitrogen 9.37%, oxygen 20.58%, fluorine 35.74%, iron 1.87%, aluminum 0.44%, and the control group. It can be seen that the contaminated membrane is of an organic pollution type.
  • the contaminated membrane was washed with 1.0% sodium hypochlorite for 2 h, and then washed with 1.0% citric acid for 1 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 18.5 MPa, a membrane flux of 2100 L/(m 2 ⁇ h), and a carbon footprint of 24 g, which was judged to be an old film as compared with the control group.
  • the monthly membrane flux decay rate is 3%, and the chemical cleaning cycle is 6-9 months, which can meet the normal operation requirements.
  • the PVDF-contaminated flat membrane in the sewage treatment membrane bioreactor of the hospital was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 53.99%, nitrogen 15.73%, fluorine 23.76%, silicon 3.22%, magnesium 2.14%, calcium 0.55%, aluminum 0.61%.
  • the contaminated membrane is organically contaminated.
  • the contaminated membrane was washed with 5% sodium hypochlorite for 2 h and then with 0.1% oxalic acid for 4 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 21.2 MPa, a membrane flux of 1890 L/(m 2 ⁇ h), and a carbon footprint of 39 g, which was judged to be an old film as compared with the control group.
  • the monthly membrane flux decay rate is 3%, and the chemical cleaning cycle is 6-9 months, which can meet the normal operation requirements.
  • the polyvinyl chloride (PVC) contaminated flat membrane in the landfill leachate treatment membrane bioreactor was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 58.63%, nitrogen 10.01%, oxygen 22.58%, magnesium 1.21%, calcium 2.18%, iron. 1.95%, aluminum 3.44%, the surface element composition of the control film: carbon 37.92%, chlorine is 62.08%, the two are relatively clear that the pollution film is organic pollution type.
  • the contaminated membrane was washed with 0.1% sodium hypochlorite for 2 h and then washed with 5.0% citric acid for 2 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 19.8 MPa, a membrane flux of 1900 L/(m 2 ⁇ h), and a carbon footprint of 31.4 g, which was judged to be an old film as compared with the control group.
  • the monthly membrane flux decay rate is 3%, and the chemical cleaning cycle is 6-9 months, which can meet the normal operation requirements.
  • the PVDF-contaminated flat membrane in the municipal sewage treatment membrane bioreactor was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 16.45%, nitrogen 2.62%, oxygen 33.98%, phosphorus 6.95%, calcium 0.69%, iron 38.98%, aluminum 0.33%.
  • the contaminated membrane is inorganically contaminated.
  • the contaminated membrane was washed with 0.1% oxalic acid for 8 h and then with 0.1% sodium hypochlorite for 4 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 18.8 MPa, a membrane flux of 1390 L/(m 2 ⁇ h), and a carbon footprint of 70.7 g, which was judged to be a waste film as compared with the control group. Still returning to the original sewage treatment project to continue to use, the results show that the system effluent water quality has not changed significantly, after one month of operation, the membrane flux is 1210L / (m 2 ⁇ h), the hydraulic retention time of the sewage is forced to extend for nearly 4h, making The plant's sewage treatment capacity has been reduced by 40% and it is unable to operate normally.
  • the PVDF-contaminated flat membrane in the municipal sewage treatment membrane bioreactor was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 21.65%, nitrogen 4.98%, oxygen 34.23%, phosphorus 5.76%, calcium 1.18%, iron 31.12%, aluminum 0.98%.
  • the contaminated membrane is inorganically contaminated.
  • the contaminated membrane was washed with 5.0% citric acid for 3 h and then washed with 0.5% sodium hypochlorite for 3 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 9.8 MPa (a decrease of about 51%), a membrane flux of 2100 L/(m 2 ⁇ h), and a carbon footprint of 47.1 g, which was judged to be a waste film as compared with the control group. Still returning to the original sewage treatment project to continue to use, the results show that the system effluent COD concentration increased by more than 10%, after one month of operation, the membrane appeared partial rupture, lost the filtering function, need to replace the new membrane, causing serious losses.
  • the PVDF-contaminated flat membrane in the sewage treatment membrane bioreactor of the hospital was analyzed by EDX.
  • the surface element composition of the membrane was: carbon 12.21%, nitrogen 11.71%, fluorine 24.86%, silicon 1.25%, magnesium 3.16%, calcium 0.75%, iron 45.15%. , aluminum 0.91%, compared with the control group, the pollution film is inorganic pollution type.
  • the contaminated membrane was washed with 2.5% oxalic acid for 24 h and then washed with 5% sodium hypochlorite for 1 h to obtain a membrane sample.
  • the obtained film sample had a tensile strength of 17.2 MPa, a membrane flux of 1920 L/(m 2 ⁇ h), and a carbon footprint of 188.4 g, which was judged to be a waste film as compared with the control group. It still returns to the original sewage treatment project and continues to use. The results show that there is no significant change in the effluent quality of the system.
  • the monthly membrane flux decay rate is 38%. After one month of operation, the membrane flux is 1190L/(m 2 ⁇ h). Chemical cleaning not only increases the cleaning cost, but also affects the normal operation of the sewage treatment plant due to frequent cleaning.

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Abstract

一种检测废旧平板膜性能的方法，包括：(1)检测污染膜表面碳元素百分比，并与对照膜比较；对照膜是与污染膜同类型、同材质的新膜；(2)如果步骤(1)检测到污染膜表面碳元素百分比高于对照膜，则采用先次氯酸钠洗后柠檬酸或草酸洗的清洗方法进行清洗，得到待测膜样品；否则采用先柠檬酸或草酸洗后次氯酸钠洗的清洗方法进行清洗，得到待测膜样品；(3)检测待测膜样品的拉伸强度；(4)检测待测膜样品的膜通量；(5)检测待测膜样品的碳足迹。及一种废旧平板膜性能的综合评价方法。

Description

一种废旧平板膜性能的综合评价方法A comprehensive evaluation strategy of waste and used flat-membrane’s property 技术领域
本发明涉及一种废旧平板膜性能的综合评价方法，属于污水及废物资源化技术领域。
背景技术
据统计，我国投入运行或在建的膜生物反应器(MBR)污水处理工程已超过300项，其中，万吨级MBR系统近10套，在污水处理膜技术应用领域，我国已成为世界增长最快的地区之一。MBR是将膜分离技术引入传统的活性污泥系统，取代二沉池，由于膜可以很好实现固液分离和大分子有机物的截留，因此，表现出传统活性污泥法所没有的优势。从20世纪70年代后期至今，MBR工艺已在水处理领域逐步得到认可，首先是北美的大规模应用，然后依次是20世纪80年代早期的日本(同期南非：厌氧膜生物反应器)，90年代中期的欧洲，90年代末期的中国。由此，分离膜在污水处理领域的用量巨大。
以聚偏氟乙烯(PVDF)为例，全世界年产量约为3.3万吨，我国产量为2000吨，实际需求量为4000吨。随着世界范围内对污水治理力度的加大，PVDF膜在污水处理中的用量将迅速增加。目前，国内外每年生产污水处理中应用广泛的PVDF膜总面积近5000万m2，用于制造中空纤维的PVDF价值达数亿美元。带衬型PVDF中空纤维膜的年产量近1000万m2，PVDF原材料的消耗量为1200吨左右，价值2亿元以上。然而，PVDF膜的使用寿命约为3～7年，以5年计，膜组件的更换占每年膜销售量的40％，即每年将有2000万m2的废旧膜产生。
通常认为，评价膜组件是否可继续使用或废弃的依据主要是膜通量回复率，即通过各种离线化学清洗，如果其膜通量回复率在80％以上，即可继续使用，并未对清洗膜的抗拉强度、最大孔径等理化性质是否能满足使用要求，也未考虑清洗过程的难度、成本及碳排放(碳足迹)是否合理。值得提到的是，全球气候变暖是人类生存和发展必须面对的严峻挑战，“碳足迹”、“碳排”、“低碳经济”、“低碳技术”、“低碳城市”等一系列新概念、新政策应运而生，如何正确评价污染膜清洗效果和能耗，如何实现新工艺理论及技术研究与节能减碳并重，是水处理工作者面临的新难题。
发明内容
针对现有的废旧膜性能评价体系存在的不足，发明人考虑制约膜的使用效率和寿命的各种因素，经大量实验研究，将拉伸强度作为理化性质的主要评价指标，将膜通量作为过滤性能的主要评价指标，将碳足迹作为其他效能的主要评价指标，建立一种定量、快速、全面地 废旧膜性能综合评价体系，由此界定旧膜与废膜之间的差异，为旧膜回用及废膜再生提供选择依据，最大限度地实现废旧膜资源化。
本发明的目的是提供一种废旧平板膜性能的综合评价方法，所述评价方法是：
(1)分析污染膜表面元素组成，辨别污染膜是有机污染型膜还是无机污染型膜，然后采用相应的化学清洗方法进行清洗，得到待测膜样品；
(2)检测待测膜样品的理化性质，得到评价指标值；
(3)检测待测膜样品的过滤性能，得到评价指标值；
(4)检测待测膜样品的其他效能，得到评价指标值；
(5)依次将步骤(2)-(4)得到的待测膜样品的指标值与对照膜的相应指标值进行进行对比，得出污染膜是旧膜还是废膜的评价结果。
在本发明的一种实施方式中，所述分析膜表面元素组成是采用能量散射x－射线光谱(EDX)进行分析。
在本发明的一种实施方式中，所述辨别污染膜，是当膜表面碳元素百分比高于对照膜时为有机污染型膜，当膜表面碳元素百分比低于对照膜时为无机污染型膜。
在本发明的一种实施方式中，所述污染膜为有机污染型膜时，采用先次氯酸钠洗后柠檬酸或草酸洗的清洗方法；
在本发明的一种实施方式中，所述污染膜为无机污染型膜时，采用先柠檬酸或草酸洗后次氯酸钠洗的清洗方法。
在本发明的一种实施方式中，所述有机污染型膜采用先0.1～5.0％次氯酸钠洗后0.1～5.0％柠檬酸或草酸洗的清洗方式，无机污染型膜采用先0.1～5.0％柠檬酸或草酸洗后0.1～5.0％次氯酸钠洗的清洗方式。
在本发明的一种实施方式中，所述理化性质包括拉伸强度(MPa)，采用拉伸强度试验机测定。
在本发明的一种实施方式中，所述过滤性能包括膜通量，膜通量测定方法为：将圆形膜片放入SCM-300超滤杯底部，密封后氮气加压，记录从开始时刻(t1，min)到结束时刻(t2，min)、0.1MPa压力下透过膜有效面积(S，m2)的液体体积(A，mL)，膜标准通量(J，L/(m2·h))按式1计算得到：
Figure PCTCN2015095725-appb-000001
在本发明的一种实施方式中，所述其他效能包括碳足迹；碳足迹也称为碳排，为污染膜 离线化学清洗过程的二氧化碳排放量(E，g)，主要包括离线化学清洗的总能耗(Qi，kW·h)，据能耗的单位碳排因子(f，785g/(kW·h))按式2计算而得：
Figure PCTCN2015095725-appb-000002
所述评价结果是根据如下评价标准确定：拉伸强度较对照膜降低50％以上的污染膜为废膜，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以上的污染膜为废膜，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以内、碳足迹高于188g的污染膜为废膜，否则为旧膜。
在本发明的一种实施方式中，所述污染膜为平板膜。
在本发明的一种实施方式中，所述污染膜为来自污水处理膜生物反应器的污染膜。
在本发明的一种实施方式中，所述对照膜是与污染膜同类型(平板膜)、同材质的新膜。
在本发明的一种实施方式中，所述污染膜和对照膜均为聚偏氟乙烯(PVDF)或聚氯乙烯(PVC)。
在本发明的一种实施方式中，对照膜(PVDF)的膜表面元素组成为：碳48.05％，氟51.95％，拉伸强度为20.0MPa，膜通量为2000L/(m2·h)。
本发明还提供一种检测废旧平板膜性能的方法，包括：
(1)检测污染膜表面碳元素百分比，并与对照膜比较；对照膜是与污染膜同类型、同材质的新膜；
(2)如果步骤(1)检测到污染膜表面碳元素百分比高于对照膜，则采用先次氯酸钠洗后柠檬酸或草酸洗的清洗方法进行清洗，得到待测膜样品；否则采用先柠檬酸或草酸洗后次氯酸钠洗的清洗方法进行清洗，得到待测膜样品；
(3)检测待测膜样品的拉伸强度；
(4)检测待测膜样品的膜通量；
(5)检测待测膜样品的碳足迹。
所述检测废旧平板膜性能的方法是检测到拉伸强度较对照膜降低50％以上的污染膜不再回收利用，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以上的污染膜不再回收利用，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以内、碳足迹高于188g的污染膜不再回收利用，否则回收利用。
所述检测废旧平板膜性能的方法中，检测污染膜表面碳元素方法、清洗溶液，以及拉伸强度、膜通量、碳足迹计算方法，污染膜类型等等，都与前面提及的评价方法相同。
本发明的有益效果：
本发明通过先EDX分析废旧膜表面的元素组成以确定膜污染的类型，然后针对有机或无机污染设计不同的清洗方案，清洗后得到待测膜样品，然后比较待测膜样品与对照膜的理化性质、过滤性质、其他效能等，确定该污染膜为废膜还是旧膜(即确定是否值得回收利用)。发明人进行了大量实验，结果发现本发明使用的方法具有较强的客观性，能够比较准确地反映膜是否还具有继续利用的价值。本发明建立的废旧膜性能的综合评价方法，可定量、快速、全面地界定旧膜和废膜之间的差异，为废旧膜的去向及再生回用工艺选择提供依据。
具体实施方式
发明人进一步通过具体实验来说明本发明的评价方法。
以下实施例便于更好地理解本发明，但并未涵盖和穷尽了发明人所做的所有实验，目的仅仅在于用那些数据来阐述本发明界定方法的直观性和准确性。
实施例1
市政污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳19.47％，氮3.62％，氧29.00％，磷11.24％，钙1.45％，铁27.28％，铝1.44％，与对照组比较可知，该污染膜属无机污染类型。将污染膜用1.0％草酸清洗3h，再用0.3％次氯酸钠清洗3h，得到膜样品。所得膜样品的拉伸强度为20.5MPa，膜通量为1930L/(m2·h)，碳足迹为47g，与对照组比较，判定该污染膜为旧膜。返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，每月的膜通量衰减速度为3％，化学清洗周期为6～9个月，能够满足常规运行需求。
实施例2
市政污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳65.63％，氮9.37％，氧20.58％，氟35.74％，铁1.87％，铝0.44％，与对照组比较可知，该污染膜属有机污染型。将污染膜用1.0％次氯酸钠清洗2h，再用1.0％柠檬酸清洗1h，得到膜样品。所得膜样品的拉伸强度为18.5MPa，膜通量为2100L/(m2·h)，碳足迹为24g，与对照组比较，判定该污染膜为旧膜。返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，每月的膜通量衰减速度为3％，化学清洗周期为6～9个月，能够满足常规运行需求。
实施例3
医院污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳53.99％，氮15.73％，氟23.76％，硅3.22％，镁2.14％，钙0.55％，铝0.61％，与对照组比较可 知，该污染膜属有机污染型。将污染膜用5％次氯酸钠清洗2h，再用0.1％草酸清洗4h，得到膜样品。所得膜样品的拉伸强度为21.2MPa，膜通量为1890L/(m2·h)，碳足迹为39g，与对照组比较，判定该污染膜为旧膜。返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，每月的膜通量衰减速度为3％，化学清洗周期为6～9个月，能够满足常规运行需求。
实施例4
垃圾渗滤液处理膜生物反应器中的聚氯乙烯(PVC)污染平板膜经EDX分析，膜表面元素组成为：碳58.63％，氮10.01％，氧22.58％，镁1.21％，钙2.18％，铁1.95％，铝3.44％，对照组膜表面元素组成为：碳37.92％，氯为62.08％，二者比较可知，该污染膜属有机污染型。将污染膜用0.1％次氯酸钠清洗2h，再用5.0％柠檬酸清洗2h，得到膜样品。所得膜样品的拉伸强度为19.8MPa，膜通量为1900L/(m2·h)，碳足迹为31.4g，与对照组比较，判定该污染膜为旧膜。返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，每月的膜通量衰减速度为3％，化学清洗周期为6～9个月，能够满足常规运行需求。
实施例5
市政污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳16.45％，氮2.62％，氧33.98％，磷6.95％，钙0.69％，铁38.98％，铝0.33％，与对照组比较可知，该污染膜属无机污染型。将污染膜用0.1％草酸清洗8h，再用0.1％次氯酸钠清洗4h，得到膜样品。所得膜样品的拉伸强度为18.8MPa，膜通量为1390L/(m2·h)，碳足迹为70.7g，与对照组比较，判定该污染膜为废膜。仍返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，运行一个月后，膜通量为1210L/(m2·h)，污水的水力停留时间被迫延长了近4h，使得该厂污水处理能力降低了40％，无法正常运转。
实施例6
市政污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳21.65％，氮4.98％，氧34.23％，磷5.76％，钙1.18％，铁31.12％，铝0.98％，与对照组比较可知，该污染膜属无机污染型。将污染膜用5.0％柠檬酸清洗3h，再用0.5％次氯酸钠清洗3h，得到膜样品。所得膜样品的拉伸强度为9.8MPa(下降了约51％)，膜通量为2100L/(m2·h)，碳足迹为47.1g，与对照组比较，判定该污染膜为废膜。仍返回原污水处理工程继续使用，结果表明，系统出水COD浓度提高了10％以上，运行一个月后，膜出现局部破裂，失去过滤功能，需更换新膜，造成严重损失。
实施例7
医院污水处理膜生物反应器中的PVDF污染平板膜经EDX分析，膜表面元素组成为：碳12.21％，氮11.71％，氟24.86％，硅1.25％，镁3.16％，钙0.75％，铁45.15％，铝0.91％，与对照组比较可知，该污染膜属无机污染型。将污染膜用2.5％草酸清洗24h，再用5％次氯酸钠清洗1h，得到膜样品。所得膜样品的拉伸强度为17.2MPa，膜通量为1920L/(m2·h)，碳足迹为188.4g，与对照组比较，判定该污染膜为废膜。仍返回原污水处理工程继续使用，结果表明，系统出水水质没有明显变化，每月的膜通量衰减速度为38％，运行一个月后，膜通量为1190L/(m2·h)，需要化学清洗，不仅增加了清洗成本，而且因频繁清洗影响了该污水处理厂的正常运行。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (10)

  1. 一种检测废旧平板膜性能的方法，其特征在于，所述方法包括：
    (1)检测污染膜表面碳元素百分比，并与对照膜比较；对照膜是与污染膜同类型、同材质的新膜；
    (2)如果步骤(1)检测到污染膜表面碳元素百分比高于对照膜，则采用先次氯酸钠洗后柠檬酸或草酸洗的清洗方法进行清洗，得到待测膜样品；否则采用先柠檬酸或草酸洗后次氯酸钠洗的清洗方法进行清洗，得到待测膜样品；
    (3)检测待测膜样品的拉伸强度；
    (4)检测待测膜样品的膜通量；
    (5)检测待测膜样品的碳足迹。
  2. 根据权利要求1所述的方法，其特征在于，所述方法是检测到拉伸强度较对照膜降低50％以上的膜不再回收利用，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以上的膜不再回收利用，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以内、碳足迹高于188g的膜不再回收利用，否则回收利用。
  3. 根据权利要求1所述的方法，其特征在于，所述步骤(2)中次氯酸钠质量浓度为0.1～5.0％，柠檬酸或草酸的质量浓度为0.1～5.0％。
  4. 根据权利要求1所述的方法，其特征在于，所述拉伸强度采用拉伸强度试验机测定；所述膜通量测定方法为：将圆形膜片放入SCM-300超滤杯底部，密封后氮气加压，记录从开始时刻t1到结束时刻t2、0.1MPa压力下透过膜有效面积S的液体体积A，膜通量J按
    Figure PCTCN2015095725-appb-100001
    计算得到；所述碳足迹为污染膜离线化学清洗过程的二氧化碳排放量E，根据
    Figure PCTCN2015095725-appb-100002
    计算得到，其中Qi为离线化学清洗的总能耗，f为能耗的单位碳排因子。
  5. 根据权利要求1所述的方法，其特征在于，所述污染膜为聚偏氟乙烯膜或聚氯乙烯。
  6. 根据权利要求1所述的方法，其特征在于，所述污染膜为来自污水处理膜生物反应器的污染膜。
  7. 根据权利要求1所述的方法，其特征在于，所述检测污染膜表面碳元素百分比是采用能量散射x－射线光谱进行分析。
  8. 一种废旧平板膜性能的综合评价方法，其特征在于，所述评价方法是：
    (1)分析污染膜表面元素组成，当膜表面碳元素百分比高于对照膜时为有机污染型膜，当膜表面碳元素百分比低于对照膜时为无机污染型膜；有机污染型膜采用先次氯酸钠洗后柠檬酸或草酸洗的清洗方法，无机污染型膜采用先柠檬酸或草酸洗后次氯酸钠洗的清洗方法，清洗，得到待测膜样品；
    (2)检测待测膜样品的理化性质；
    (3)检测待测膜样品的过滤性能；
    (4)检测待测膜样品的其他效能；
    (5)依次将步骤(2)-(4)得到的待测膜样品的检测结果与对照膜的相应值进行对比，得出污染膜是旧膜还是废膜的评价结果；其中对照膜是与污染膜同类型、同材质的新膜。
  9. 根据权利要求,8所述的方法，其特征在于，所述理化性质包括拉伸强度，过滤性能包括膜通量，其他效能包括碳足迹；评价标准是：拉伸强度较对照膜降低50％以上的污染膜为废膜，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以上的污染膜为废膜，拉伸强度较对照膜降低50％以内、膜通量较对照膜降低30％以内、碳足迹高于188g的污染膜为废膜，否则为旧膜。
  10. 根据权利要求8所述的方法，其特征在于，所述有机污染型膜采用先0.1～5.0％次氯酸钠洗后0.1～5.0％柠檬酸或草酸洗的清洗方式，无机污染型膜采用先0.1～5.0％柠檬酸或草酸洗后0.1～5.0％次氯酸钠洗的清洗方式。
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