CN112295412B - Ultra-filtration degradation regeneration method for ultraviolet reinforced oxidation waste reverse osmosis membrane - Google Patents

Abstract

The invention relates to a degradation and regeneration method of a waste reverse osmosis membrane, in particular to an ultra-filtration degradation and reuse method of an ultraviolet reinforced oxidized waste reverse osmosis membrane. The ultrafiltration degradation recycling method of the waste reverse osmosis membrane is characterized in that firstly, the waste reverse osmosis membrane is subjected to anatomical separation to obtain the waste reverse osmosis membrane, then the waste reverse osmosis membrane is cleaned, the cleaned membrane is subjected to ultraviolet irradiation and the soaking surface modification treatment of chlorine-containing solution, and then the filtration performance is further optimized through one or more of a surfactant, a complexing agent and a chelating agent, so that ultrafiltration recycling of the waste reverse osmosis membrane is realized. The ultraviolet reinforced oxidation waste reverse osmosis membrane ultrafiltration degradation recycling method can not only realize the recycling of the waste reverse osmosis membrane, but also increase the types of the ultrafiltration membrane at the present stage, and the degradation recycling process is simpler, and the degradation recycling time is greatly shortened.

Description

Translated fromChinese

一种紫外强化氧化废弃反渗透膜超滤化降级再生方法A method for ultrafiltration downgrading regeneration of waste reverse osmosis membrane by ultraviolet enhanced oxidation

技术领域technical field

本发明涉及水处理技术领域，具体为一种紫外强化氧化废弃反渗透膜超滤化降级再生方法。The invention relates to the technical field of water treatment, in particular to a method for ultrafiltration and downgrading regeneration of waste reverse osmosis membranes through ultraviolet enhanced oxidation.

技术背景technical background

反渗透分离技术由于系统简单，操作方便，结构紧凑，运行可靠等优点，已经在海水和苦咸水淡化，废水处理，生物，环境工程，食品，医疗等领域得到广泛应用，并取得了很好的经济和社会效益。但在反渗透运行过程中，膜污染现象往往不可避免地发生，表现为产水量的下降和段间压差的上升。当膜污染达到一定程度后，可通过物理清洗和化学清洗有效地去除大部分污染物，恢复膜的性能。随着清洗次数的增加，难清洗污染物逐渐积累，导致清洗效果越来越差，膜通量难以恢复。一旦膜不能达到工业过程中设定的目标，它们就被认为是废物，最终主要是在垃圾填埋场，加重了企业的负担。随着时间的推移，大量废弃的反渗透膜不仅给环境带来了巨大压力，而且还造成了资源的浪费。Due to the advantages of simple system, convenient operation, compact structure and reliable operation, reverse osmosis separation technology has been widely used in seawater and brackish water desalination, wastewater treatment, biology, environmental engineering, food, medical and other fields, and has achieved good results. economic and social benefits. However, in the process of reverse osmosis operation, the phenomenon of membrane fouling often inevitably occurs, which is manifested as the decrease of water production and the increase of pressure difference between stages. When the membrane fouling reaches a certain level, most of the pollutants can be effectively removed by physical cleaning and chemical cleaning, and the performance of the membrane can be restored. With the increase of cleaning times, difficult-to-clean pollutants gradually accumulate, resulting in poor cleaning effect and difficult recovery of membrane flux. Once the membranes fail to meet the targets set in the industrial process, they are considered waste and end up mostly in landfills, burdening businesses. Over time, a large number of discarded reverse osmosis membranes not only bring great pressure to the environment, but also cause a waste of resources.

由于废弃反渗透膜浪费严重等问题，Mohamedou等人(Desalination，2010，253(1-3)：62-70.)将膜片进行简单的氧化或者修复处理，使膜片依然具备过滤能力，达到回收利用的目的，而且经过他们清洗过的膜片应用到处理农业用水；Molina等人(Polym.Degrad.Stab.，2018，150(APR.)：46-56.)则对废弃反渗透膜进行降级利用，制备PES超滤膜，并且降级完成的反渗透膜可以达到城市三级污水处理的预处理的超滤膜的要求；苗伟(申请号202010380670.6)等人提出了一种废弃有机反渗透膜再造超滤膜的方法，通过将废弃有机反渗透膜浸泡在特殊的反渗透膜再造液中，实现了废弃有机反渗透膜的再生利用，俞三传(申请号CN201010574082.2)通过全胺溶液的浸泡改性处理，采用聚合物调节膜性能，实现了废弃反渗透膜纳滤化再生。但是现在针对于废弃反渗透膜降级为超滤膜的方法，氧化时间过长，大多数处理时间在36h以上，而且部分氧化剂为有机氧化剂，对环境污染大。Due to the serious waste of waste reverse osmosis membranes, Mohamedou et al. (Desalination, 2010, 253(1-3): 62-70.) performed a simple oxidation or repair process on the membrane, so that the membrane still has the filtering ability, reaching The purpose of recycling, and the membranes that have been cleaned by them are applied to the treatment of agricultural water; Molina et al. Downgrade utilization, prepare PES ultrafiltration membrane, and the degraded reverse osmosis membrane can meet the requirements of pretreatment ultrafiltration membrane for urban tertiary sewage treatment; Miao Wei (application number 202010380670.6) and others proposed a waste organic reverse osmosis membrane The method of remanufacturing ultrafiltration membranes by soaking waste organic reverse osmosis membranes in a special reverse osmosis membrane reconstitution solution realizes the regeneration and utilization of waste organic reverse osmosis membranes. Yu Sanchuan (application number CN201010574082. The soaking modification treatment of the solution, the use of polymers to adjust the membrane performance, realized the nanofiltration regeneration of the waste reverse osmosis membrane. However, for the current method of downgrading waste reverse osmosis membranes to ultrafiltration membranes, the oxidation time is too long, most of which take more than 36 hours, and some oxidants are organic oxidants, which cause great environmental pollution.

因而，如何通过简单、实用的方法对废弃反渗透膜进行处理，通过改变反渗透膜表面的孔径，表面结构，以及膜表面电荷，使废弃反渗透膜转化成为具有超滤分离性能的膜元件，对实现废弃反渗透膜的资源化利用，降低超滤膜的制造成本，扩大超滤膜的品种，有效拓展超滤膜的使用范围等均是十分必要和具有实际意义的。Therefore, how to treat the waste reverse osmosis membrane in a simple and practical way, and transform the waste reverse osmosis membrane into a membrane element with ultrafiltration separation performance by changing the pore size, surface structure, and membrane surface charge of the reverse osmosis membrane surface, It is very necessary and has practical significance to realize the resource utilization of waste reverse osmosis membranes, reduce the manufacturing cost of ultrafiltration membranes, expand the varieties of ultrafiltration membranes, and effectively expand the use range of ultrafiltration membranes.

发明内容Contents of the invention

针对现有反渗透膜因劣化而被大量遗弃以及现阶段降级方式时间过长等原因，提出一种废弃反渗透膜降级再利用的方法。目的是可以实现废弃反渗透膜的超滤化降级再生利用。Aiming at the reasons that the existing reverse osmosis membranes are largely abandoned due to deterioration and the current downgrading method takes too long, a method of downgrading and reusing waste reverse osmosis membranes is proposed. The purpose is to realize the ultrafiltration downgrading and recycling of waste reverse osmosis membranes.

为实现上述目的，本发明提供如下技术方案：一种紫外强化氧化废弃反渗透膜超滤化降级再生方法，包括以下步骤：In order to achieve the above object, the present invention provides the following technical solution: a method for ultrafiltration and downgrading regeneration of waste reverse osmosis membrane by ultraviolet enhanced oxidation, comprising the following steps:

(1)对废弃反渗透膜进行解剖分离，将废弃反渗透膜展开得到废弃反渗透膜片；(1) dissecting and separating the waste reverse osmosis membrane, and unfolding the waste reverse osmosis membrane to obtain the waste reverse osmosis membrane;

(2)对解剖后的废弃反渗透膜片进行清洗，清洗液温度为10-40℃，清洗时间为1-3h，然后将废弃反渗透膜片取出；(2) Cleaning the dissected waste reverse osmosis membrane, the temperature of the cleaning solution is 10-40°C, the cleaning time is 1-3h, and then the waste reverse osmosis membrane is taken out;

(3)将清洗后的废弃反渗透膜片用纯水冲洗后，浸泡在一定浓度的含氯溶液中，同时用一定强度的紫外光对浸泡在含氯溶液中的废弃反渗透膜片进行照射，一段时间后，将氧化的废弃反渗透膜片取出(3) Wash the discarded reverse osmosis membrane with pure water, soak it in a certain concentration of chlorine-containing solution, and irradiate the discarded reverse osmosis membrane soaked in the chlorine-containing solution with a certain intensity of ultraviolet light , after a period of time, take out the oxidized waste reverse osmosis membrane

(4)对氧化处理的废弃反渗透膜片用纯水冲洗后，用含有一定浓度的表面活性剂水溶液，或络合剂，或螯合剂进行浸泡处理，然后将改性后废弃反渗透膜片取出；(4) Rinse the oxidized waste reverse osmosis membrane with pure water, soak it with an aqueous solution containing a certain concentration of surfactant, or a complexing agent, or a chelating agent, and then use the modified waste reverse osmosis membrane take out;

(5)对改性后废弃反渗透膜片进行纯水冲洗处理，得到平板超滤膜。(5) Rinse the modified discarded reverse osmosis membrane with pure water to obtain a flat ultrafiltration membrane.

优选的，所述的专用的反渗透膜清洗溶液含有但不限于以下几种：Preferably, the special reverse osmosis membrane cleaning solution contains but is not limited to the following:

或，质量浓度为0.5-3％的可溶性强酸，或弱酸中的一种或几种混合物；Or, a soluble strong acid with a mass concentration of 0.5-3%, or one or a mixture of weak acids;

或，质量浓度为0.5-2％的可溶性碱中的一种或几种混合物；Or, one or several mixtures of soluble alkalis with a mass concentration of 0.5-2%;

或，质量浓度为0.01-0.3％的表面活性剂，或络合剂，或螯合剂中的一种或几种混合物。Or, a surfactant with a mass concentration of 0.01-0.3%, or a complexing agent, or one or more mixtures of the chelating agent.

优选的，所述的紫外光强度为10000-30000μW/cm²。Preferably, the ultraviolet light intensity is 10000-30000 μW/cm² .

优选的，所述的紫外光照射时间为0.5-5h。Preferably, the ultraviolet light irradiation time is 0.5-5h.

优选的，所述的含氯溶液为：次氯酸钠，次氯酸钾，次氯酸，亚氯酸，氯胺，二氧化氯，氯酸钾，氯酸钠或氯氧化合物等中的一种或几种混合物。Preferably, the chlorine-containing solution is one or more mixtures of sodium hypochlorite, potassium hypochlorite, hypochlorous acid, chlorous acid, chloramine, chlorine dioxide, potassium chlorate, sodium chlorate or oxychloride.

优选的，所述的含氯溶液浸泡改性处理的条件为浸泡时间为0.5-5h，含氯溶液质量浓度为0.5-5％，温度为20-80℃。Preferably, the modification treatment conditions by soaking in the chlorine-containing solution are as follows: the soaking time is 0.5-5 hours, the mass concentration of the chlorine-containing solution is 0.5-5%, and the temperature is 20-80°C.

优选的，所述的表面活性剂，或络合剂，或螯合剂等的水溶液浓度为50-300mg/L，温度为20-40℃，进行浸泡处理的时间为0.5-2h。Preferably, the concentration of the aqueous solution of the surfactant, complexing agent, or chelating agent is 50-300mg/L, the temperature is 20-40°C, and the soaking time is 0.5-2h.

有益效果：本发明的紫外强化氧化废弃反渗透膜超滤化降级再生方法，利用紫外和含氯溶液结合的方式，实现了废弃反渗透膜的资源化利用，还增加了现阶段超滤膜的种类，而且降级再生利用的工艺较为简单，降级再生利用的时间大大缩短。Beneficial effects: the ultraviolet enhanced oxidation waste reverse osmosis membrane ultrafiltration degradation regeneration method of the present invention uses the combination of ultraviolet light and chlorine-containing solution to realize the resource utilization of waste reverse osmosis membranes, and also increases the cost of ultrafiltration membranes at the present stage. species, and the process of downgrading and recycling is relatively simple, and the time for downgrading and recycling is greatly shortened.

具体实施specific implementation

下述实施例是对本发明内容的进一步说明以作为对本发明技术内容的阐释，但是本发明的实质内容并不仅限于下述具体实施例所述，任何对制备过程的简单变化均属于本发明所要求的保护范围。The following examples are a further description of the content of the present invention as an explanation of the technical content of the present invention, but the essence of the present invention is not limited to the following specific examples, and any simple changes to the preparation process all belong to the requirements of the present invention scope of protection.

一种紫外强化氧化废弃反渗透膜超滤化降级再生方法，包括以下步骤：废弃反渗透膜进行解剖分离，将废弃反渗透膜展开得到废弃反渗透膜片，废弃反渗透膜片的清洗处理：用清洗剂对废弃反渗透膜片进行清洗，清洗剂为常用的反渗透膜清洗剂，可以但不限于包含酸、碱、表面活性剂、螯合剂、络合剂等中的一种或几种。清洗浸泡温度为10-40℃，清洗时间为1-3h。清洗后用清水对废弃反渗透膜片进行冲洗处理。A method for downgrading and regenerating waste reverse osmosis membranes by ultraviolet enhanced oxidation, comprising the following steps: dissecting and separating the waste reverse osmosis membranes, unfolding the waste reverse osmosis membranes to obtain waste reverse osmosis membranes, and cleaning the waste reverse osmosis membranes: Use a cleaning agent to clean the waste reverse osmosis membrane. The cleaning agent is a commonly used reverse osmosis membrane cleaning agent, which can, but is not limited to, contain one or more of acids, alkalis, surfactants, chelating agents, complexing agents, etc. . The cleaning soaking temperature is 10-40°C, and the cleaning time is 1-3h. After cleaning, rinse the waste reverse osmosis membrane with clean water.

废弃反渗透膜片的含氯溶液浸泡清洗处理：将上述经过清洗液清洗后的废弃反渗透膜片浸入一定量的含氯溶液，同时用紫外光对含氯溶液和废弃反渗透膜片进行光照处理，含氯溶液为次氯酸钠，次氯酸钾，次氯酸，亚氯酸，氯胺，二氧化氯，氯酸钾，氯酸钠或氯氧化合物中的一种或几种混合物，含氯溶液质量浓度为0.5-5％，温度为40-60℃，紫外光强度为10000-30000μW/cm²，含氯溶液浸泡改性处理时间为0.5-5h。浸泡处理后用清水对废弃反渗透膜片进行冲洗处理。Soaking and cleaning treatment of waste reverse osmosis membranes in chlorine-containing solution: immerse the above-mentioned waste reverse osmosis membranes after cleaning with a certain amount of chlorine-containing solution, and at the same time illuminate the chlorine-containing solution and waste reverse osmosis membranes with ultraviolet light Treatment, the chlorine-containing solution is one or more mixtures of sodium hypochlorite, potassium hypochlorite, hypochlorous acid, chlorous acid, chloramine, chlorine dioxide, potassium chlorate, sodium chlorate or oxychloride, and the mass concentration of the chlorine-containing solution is 0.5-5%, the temperature is 40-60°C, the ultraviolet light intensity is 10000-30000μW/cm² , and the modification treatment time is 0.5-5h in chlorine-containing solution. After the soaking treatment, rinse the waste reverse osmosis membrane with clean water.

用含表面活性剂、络合剂、螯合剂其中一种或几种的水溶液对经含氯溶液浸泡改性处理的废弃反渗透膜片进行浸泡处理，常用的含表面活性剂、络合剂、螯合剂水溶液的浓度为0.5-300mg/L，温度为20-40℃，进行浸泡处理的时间为0.5-2h。Use an aqueous solution containing one or more of surfactants, complexing agents, and chelating agents to soak the waste reverse osmosis membranes that have been modified by soaking in chlorine-containing solutions. Commonly used surfactants, complexing agents, The concentration of the aqueous solution of the chelating agent is 0.5-300mg/L, the temperature is 20-40°C, and the soaking time is 0.5-2h.

改性后的废弃反渗透膜片的冲洗处理：用清水对改性后废弃反渗透膜片进行冲洗处理，得到平板超滤膜。Washing treatment of the modified waste reverse osmosis membrane: wash the modified waste reverse osmosis membrane with clean water to obtain a flat ultrafiltration membrane.

膜片性能测试：Diaphragm performance test:

1.废弃反渗透膜片性能测试：1. Performance test of waste reverse osmosis membrane:

截留率和通量是评价反渗透膜片分离性能的两个重要参数。通过错留渗透试验，对反渗透膜片进行分离性能评价。Rejection rate and flux are two important parameters to evaluate the separation performance of reverse osmosis membrane. The separation performance of the reverse osmosis membrane was evaluated by the false retention osmosis test.

截留率(R)定义为：在一定的操作条件下，进料液浓度(C_f)与渗透液中盐浓度(C_p)之差，再除以进料液(C_f)，既

The rejection rate (R) is defined as: under certain operating conditions, the difference between the concentration of the feed solution (C_f ) and the salt concentration in the permeate (C_p ), divided by the feed solution (C_f ), is

通量定义：在一定条件下，单位时间(t)内透过膜片(S)的体积(V)，其单位为L/(m²·h)，既

Definition of flux: Under certain conditions, the volume (V) permeating the membrane (S) per unit time (t), the unit is L/(m² ·h), that is

本发明中反渗透膜片性能测定采用的条件为：进液为2000ppm的NaCl溶液，操作压力为125psi，操作温度为25℃，溶液pH为6.8。The conditions used in the determination of the performance of the reverse osmosis membrane in the present invention are: the inlet liquid is 2000ppm NaCl solution, the operating pressure is 125psi, the operating temperature is 25°C, and the pH of the solution is 6.8.

2.降级再生膜片性能测试：2. Performance test of degraded recycled diaphragm:

通过错流渗透试验，对降级再生膜片的牛血清白蛋白、腐殖酸的截留率和通量进行分离性能评价。Through the cross-flow permeation test, the separation performance evaluation of bovine serum albumin and humic acid rejection and flux of the degraded regeneration membrane was carried out.

本发明中降级再生反渗透膜片性能测定采用的条件为：进液为0.5g/L的牛血清白蛋白溶液，或者0.05g/L腐殖酸溶液，操作压力为0.2MPa，操作温度为25℃，溶液pH为6.8。In the present invention, the conditions used for performance measurement of degraded and regenerated reverse osmosis membranes are: the inlet liquid is 0.5g/L bovine serum albumin solution, or 0.05g/L humic acid solution, the operating pressure is 0.2MPa, and the operating temperature is 25 °C, the pH of the solution is 6.8.

结果：result:

上述实例表明：对经过反渗透膜清洗工艺清洗的废弃反渗透膜片，用紫外光进行光照同时用含氯溶液进行浸泡改性处理和用表面活性剂、螯合剂、络合剂的水溶液进行浸泡处理，可实现对废弃反渗透膜的超滤化降级再利用。更改含氯溶液的溶质种类与含量、含氯溶液的温度及浸泡处理时间、紫外光的光照强度及紫外光的照射时间、含表面活性剂、螯合剂、络合剂的水溶液种类与含量、温度及浸泡处理时间等均会影响再生超滤平板膜的性能。同时，对于不同初始性能的、不同种类的废弃反渗透膜均可实现超滤化再生。The above examples show that: for the discarded reverse osmosis membranes cleaned by the reverse osmosis membrane cleaning process, ultraviolet light is used to illuminate and simultaneously soak and modify with chlorine-containing solutions and soak with aqueous solutions of surfactants, chelating agents, and complexing agents. The treatment can realize the ultrafiltration downgrading and reuse of the waste reverse osmosis membrane. Change the solute type and content of chlorine-containing solution, the temperature and soaking treatment time of chlorine-containing solution, the intensity of ultraviolet light and the irradiation time of ultraviolet light, the type and content of aqueous solution containing surfactant, chelating agent, and complexing agent, and temperature And soaking treatment time will affect the performance of regenerated ultrafiltration flat membrane. At the same time, ultrafiltration regeneration can be realized for different types of waste reverse osmosis membranes with different initial properties.

Claims (2)

Translated fromChinese

1.一种紫外强化氧化废弃反渗透膜超滤化降级再生方法，其特征包括下述步骤：1. A method for downgrading regeneration of waste reverse osmosis membrane by ultraviolet enhanced oxidation, characterized in that it comprises the following steps:(1)对废弃反渗透膜进行解剖分离，将废弃反渗透膜展开得到废弃反渗透膜片；(1) dissecting and separating the waste reverse osmosis membrane, and unfolding the waste reverse osmosis membrane to obtain the waste reverse osmosis membrane;(2)对解剖后的废弃反渗透膜片进行清洗，清洗液温度为10-40℃，清洗时间为1-3h，然后将废弃反渗透膜片取出；(2) Cleaning the dissected waste reverse osmosis membrane, the temperature of the cleaning solution is 10-40°C, the cleaning time is 1-3h, and then the waste reverse osmosis membrane is taken out;(3)将清洗后的废弃反渗透膜用纯水冲洗后，浸泡在一定浓度的含氯溶液中，同时用一定强度的紫外光对浸泡在含氯溶液中的废弃反渗透膜进行照射，一段时间后，将氧化的废弃反渗透膜片取出；(3) Rinse the discarded reverse osmosis membrane after cleaning with pure water, soak it in a certain concentration of chlorine-containing solution, and irradiate the discarded reverse osmosis membrane soaked in the chlorine-containing solution with a certain intensity of ultraviolet light at the same time, for a period of time After a period of time, take out the oxidized waste reverse osmosis membrane;(4)对氧化处理的废弃反渗透膜片用纯水冲洗后，用含有一定浓度的表面活性剂水溶液，或络合剂，或螯合剂进行浸泡处理，一段时间后，将改性后废弃反渗透膜片取出；(4) Rinse the oxidized waste reverse osmosis membrane with pure water, soak it in an aqueous solution containing a certain concentration of surfactant, or a complexing agent, or a chelating agent, and after a period of time, remove the waste reverse osmosis membrane after modification. Remove the permeable membrane;(5)对改性后废弃反渗透膜片进行纯水冲洗处理，得到平板超滤膜；(5) Rinse the discarded reverse osmosis membrane with pure water after modification to obtain a flat ultrafiltration membrane;所述的紫外光强度为10000-30000μW/cm²；所述的紫外光照射时间为0.5-5h；所述的含氯溶液为：次氯酸钠，次氯酸钾，次氯酸，亚氯酸，氯胺，二氧化氯，氯酸钾，氯酸钠或氯氧化合物等中的一种或几种混合物；所述的含氯溶液浸泡改性处理的条件为浸泡时间为0.5-5h，含氯溶液质量浓度为0.5-5％，温度为20-80℃；所述的表面活性剂，或络合剂，或螯合剂等的水溶液浓度为50-300mg/L，温度为20-40℃，进行浸泡处理的时间为0.5-2h。The intensity of the ultraviolet light is 10000-30000μW/^cm2 ; the irradiation time of the ultraviolet light is 0.5-5h; the chlorine-containing solution is: sodium hypochlorite, potassium hypochlorite, hypochlorous acid, chlorous acid, chloramine, One or more mixtures of chlorine dioxide, potassium chlorate, sodium chlorate or oxychloride; the conditions for the soaking modification treatment of the chlorine-containing solution are that the soaking time is 0.5-5h, and the mass concentration of the chlorine-containing solution is 0.5 -5%, the temperature is 20-80°C; the concentration of the aqueous solution of the surfactant, or complexing agent, or chelating agent, etc. is 50-300mg/L, the temperature is 20-40°C, and the time for soaking treatment is 0.5-2h.2.根据权利要求1所述的一种紫外强化氧化废弃反渗透膜超滤化降级再生方法，其特征在于所述的反渗透膜清洗溶液含有但不限于以下几种：2. A kind of ultraviolet enhanced oxidation waste reverse osmosis membrane ultrafiltration degraded regeneration method according to claim 1, it is characterized in that described reverse osmosis membrane cleaning solution contains but not limited to the following:或，质量浓度为0.5-3％的可溶性强酸，或弱酸中的一种或几种混合物；Or, a soluble strong acid with a mass concentration of 0.5-3%, or one or a mixture of weak acids;或，质量浓度为0.5-2％的可溶性碱中的一种或几种混合物；Or, one or several mixtures of soluble alkalis with a mass concentration of 0.5-2%;或，质量浓度为0.01-0.3％的表面活性剂，或络合剂，或螯合剂中的一种或几种混合物。Or, a surfactant with a mass concentration of 0.01-0.3%, or a complexing agent, or one or more mixtures of the chelating agent.