技术领域technical field
本发明涉及一种疏水性强的改性聚丙烯中空纤维膜的制备方法及其在支撑液膜体系中的应用。The invention relates to a preparation method of a modified polypropylene hollow fiber membrane with strong hydrophobicity and its application in a supporting liquid membrane system.
背景技术Background technique
随着全球工业化进程的快速发展，对能源的需求随之激增。煤气化技术在应对能源需求的快速增长时起到了重要作用。然而，煤化工废水是现代煤化工行业所面临的重要问题。由于煤化工废水中酚类等有机污染物含量高使其难以被传统的生物法降解处理。With the rapid development of the global industrialization process, the demand for energy has surged. Coal gasification technology has played an important role in responding to the rapid growth in energy demand. However, coal chemical wastewater is an important problem faced by the modern coal chemical industry. Due to the high content of organic pollutants such as phenols in coal chemical wastewater, it is difficult to be degraded by traditional biological methods.
支撑液膜萃取技术是近年来开发的一种基于膜分离与萃取过程结合形成的废水处理技术，通过将疏水性微孔膜材料支撑体浸在溶解有机萃取剂的膜液中，在表面张力作用下膜液充满支撑体微孔而形成支撑液膜；以其为料液相与反萃相提供分隔界面，料液相中的酚类有机物在支撑液膜的一侧表面被膜液中的有机萃取剂萃取，以络合物的形式在支撑体微孔内扩散传递至支撑液膜的另一侧表面，再被反萃而实现废水除酚效果。与传统的萃取技术相比，具有投资运行成本低、能耗低、萃取剂用量小、运行操作简单和易于放大等技术优势，在废水处理和资源回收领域前景广阔。然而，支撑体中液膜相的流失是导致支撑液膜体系稳定性较差主要原因，这一问题是当前该技术无法实现大规模工业化应用的主要瓶颈。液膜相的流失主要是由于支撑体微孔逐渐被润湿，支撑体中的液膜相逐渐溶解流失到水溶液中造成。因此，需要选用疏水性强的膜材料做支撑体并通过对膜材料的改性强化其疏水性能，以达到强化支撑液膜体系稳定性的目的。Supported liquid membrane extraction technology is a wastewater treatment technology developed in recent years based on the combination of membrane separation and extraction process. By immersing the support body of hydrophobic microporous membrane material in the membrane liquid dissolved in organic extractant, under the action of surface tension The lower membrane liquid fills the micropores of the support body to form a support liquid film; it provides a separation interface for the feed liquid phase and the stripping phase, and the phenolic organics in the feed liquid phase are organically extracted in the film liquid on one side of the support liquid film In the form of a complex, it diffuses in the micropores of the support and transfers to the surface of the other side of the supporting liquid membrane, and then is back-extracted to achieve the effect of removing phenol from wastewater. Compared with traditional extraction technology, it has technical advantages such as low investment and operation cost, low energy consumption, small amount of extractant, simple operation and easy scale-up, etc. It has broad prospects in the fields of wastewater treatment and resource recovery. However, the loss of the liquid film phase in the support is the main reason for the poor stability of the supported liquid film system. This problem is currently the main bottleneck for the large-scale industrial application of this technology. The loss of the liquid film phase is mainly due to the micropores of the support are gradually wetted, and the liquid film phase in the support is gradually dissolved and lost into the aqueous solution. Therefore, it is necessary to choose a membrane material with strong hydrophobicity as the support body and strengthen its hydrophobic performance by modifying the membrane material, so as to achieve the purpose of strengthening the stability of the supported liquid membrane system.
聚丙烯中空纤维膜因其价格低廉、机械强度好、化学稳定性和热稳定性优良而被广泛应用到水处理的各个领域。同时聚丙烯中空纤维膜表面还具有一定的疏水性能，可以被用作支撑液膜体系的支撑体，但是在与水溶液的长期接触过程中仍然会被润湿导致支撑液膜体系中的液膜相从支撑体中流失。采用表面能低的疏水改性剂对聚丙烯膜表面进行接枝改性将大大提升聚丙烯膜的疏水性能，进而提升以聚丙烯中空纤维膜作支撑体的支撑液膜体系的稳定性，为支撑液膜技术的工业化应用奠定基础。Polypropylene hollow fiber membranes are widely used in various fields of water treatment because of their low price, good mechanical strength, excellent chemical stability and thermal stability. At the same time, the surface of the polypropylene hollow fiber membrane also has certain hydrophobic properties, which can be used as a support for the liquid membrane system, but it will still be wetted during the long-term contact with the aqueous solution, resulting in the liquid membrane phase in the supported liquid membrane system. drain from the support. Grafting the surface of the polypropylene membrane with a hydrophobic modifier with low surface energy will greatly improve the hydrophobic performance of the polypropylene membrane, and then improve the stability of the supported liquid membrane system with the polypropylene hollow fiber membrane as the support. Lay the foundation for supporting the industrial application of liquid membrane technology.
当前膜表面疏水改性的方法主要有表面涂覆法、表面接枝法和等离子体接枝法等技术。但现有的方法接枝率低，处理工艺复杂且费用普遍较高难以进行大规模的工业化推广应用。CN102688704A公开了一种聚丙烯膜的疏水改性方法，该方法分别将含不饱和双键的氟醋和含长烷基链的丙烯酸醋、二硫醇和光引发剂溶于丙酮溶液中配制改性溶液，将常压等离子体处理的聚丙烯膜浸泡在上述改性溶液中并进行紫外光照，最后水洗并晾干，即制得含氟和长烷基链接枝改性的聚丙烯膜材料。但是该方法的改性过程流程复杂，需要等离子体和紫外辐射处理能耗较高，整体改性费用较高，难以实现大规模的推广应用。The current methods of hydrophobic modification of membrane surface mainly include surface coating method, surface grafting method and plasma grafting method. However, the existing method has low grafting rate, complicated treatment process and generally high cost, making it difficult to carry out large-scale industrial application. CN102688704A discloses a method for hydrophobic modification of polypropylene film. In this method, fluorine ester containing unsaturated double bonds, acrylate ester containing long alkyl chains, dithiol and photoinitiator are dissolved in acetone solution to prepare modified solution, immersing the polypropylene film treated with atmospheric pressure plasma in the above modification solution and subjecting it to ultraviolet light, and finally washing with water and drying in the air, so as to obtain the polypropylene film material containing fluorine and long alkyl chain graft modification. However, the modification process of this method is complicated, requires high energy consumption for plasma and ultraviolet radiation treatment, and the overall modification cost is high, making it difficult to achieve large-scale popularization and application.
发明内容Contents of the invention
为了解决上述方法处理工艺复杂、能耗与费用较高难以进行大规模的工业化推广应用的问题，本发明提供了一种强疏水性聚丙烯中空纤维膜的制备方法及其应用。In order to solve the above-mentioned problems of complex treatment process, high energy consumption and high cost, and difficulty in large-scale industrial application, the present invention provides a preparation method and application of a strongly hydrophobic polypropylene hollow fiber membrane.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种强疏水性聚丙烯中空纤维膜的制备方法，包括如下步骤：A preparation method for a strongly hydrophobic polypropylene hollow fiber membrane, comprising the steps of:
（1）配置浓度为1~30wt%的（NH4）2SO4溶液并水浴加热升温至35~85℃，之后在蠕动泵的推动下于聚丙烯中空纤维膜组件管程和壳程中循环流动，对聚丙烯中空纤维膜表面进行1~40min的预处理；(1) Prepare (NH4 )2 SO4 solution with a concentration of 1-30wt% and heat it in a water bath to 35-85°C, and then circulate in the tube side and shell side of the polypropylene hollow fiber membrane module under the push of a peristaltic pump Flow, pretreatment of the surface of the polypropylene hollow fiber membrane for 1~40min;
（2）配置改性液：将二氧化硅纳米颗粒混入0.01~0.15mmol/L的十七氟癸基三乙氧基硅烷溶液中，超声搅拌1~60min，二氧化硅纳米颗粒在改性液中的浓度为0.1~0.5wt%，改性液中所用溶剂为正己烷、氯仿或异丙醇等常见有机溶剂；(2) Configure the modification solution: mix the silica nanoparticles into the 0.01~0.15mmol/L heptadecafluorodecyltriethoxysilane solution, stir ultrasonically for 1~60min, and the silica nanoparticles are mixed in the modification solution The concentration in the modified solution is 0.1~0.5wt%, and the solvent used in the modified solution is a common organic solvent such as n-hexane, chloroform or isopropanol;
（3）使用蠕动泵推动步骤（2）配置的改性液在步骤（1）预处理后的聚丙烯中空纤维膜组件的管程和壳程中循环流动1~60min，每循环1~10min改变一次流动的方向，经去离子水清洗后在35~85℃的干燥箱中烘干，得到强疏水性聚丙烯中空纤维膜。(3) Use a peristaltic pump to push the modifying solution prepared in step (2) to circulate in the tube side and shell side of the polypropylene hollow fiber membrane module pretreated in step (1) for 1-60 minutes, and change the value of each cycle for 1-10 minutes. In the direction of the primary flow, it is washed with deionized water and then dried in a drying oven at 35-85°C to obtain a strongly hydrophobic polypropylene hollow fiber membrane.
上述方法制备的强疏水性聚丙烯中空纤维膜可作为支撑体应用在支撑液膜体系中用于去除煤化工废水中的有机酚，具体应用方法如下：液膜相在蠕动泵的推动下在中空纤维膜组件的管程和壳程中流动5~30min，并浸入到支撑体的微孔中，共同组成支撑液膜体系。其中：所述液膜相为10~30vol%的萃取剂与70~90vol%的煤油所形成的混合液；所述萃取剂为磷酸三丁酯、三烷基氧化膦和二（2-乙基己基）磷酸中的一种或多种。The strong hydrophobic polypropylene hollow fiber membrane prepared by the above method can be used as a support in a supported liquid membrane system to remove organic phenols in coal chemical wastewater. The fiber membrane module flows in the tube side and the shell side for 5-30 minutes, and is immersed in the micropores of the support body to form a supported liquid membrane system. Wherein: the liquid film phase is a mixture of 10-30vol% extractant and 70-90vol% kerosene; the extractant is tributyl phosphate, trialkylphosphine oxide and bis(2-ethyl One or more of hexyl) phosphoric acid.
相比于现有方法，本发明具有如下优点：Compared with existing methods, the present invention has the following advantages:
1、本发明对聚丙烯中空纤维膜采用（NH4）2SO4作羟基化预处理，采用纳米二氧化硅和十七氟癸基三乙氧基硅烷两种疏水改性剂进行表面协同疏水改性处理，改性后的膜的接触角增大10~45%，疏水性能大幅提升。1. In the present invention, (NH4 )2 SO4 is used as hydroxylation pretreatment for polypropylene hollow fiber membranes, and two hydrophobic modifiers, nano-silica and heptadecafluorodecyltriethoxysilane, are used for surface synergistic hydrophobicity. After modification treatment, the contact angle of the modified film increases by 10-45%, and the hydrophobic performance is greatly improved.
2、整个改性工艺流程简单方便、改性条件温和、费用较低、便于工业化推广。2. The entire modification process is simple and convenient, the modification conditions are mild, the cost is low, and it is convenient for industrialization.
3、本发明制备的强疏水性聚丙烯中空纤维膜在支撑液膜体系的应用中延缓了萃取剂的流失，大幅地提升了体系的稳定性，使得支撑液膜体系的稳定提高了5~30%，为支撑液膜技术的工业化推广奠定了技术基础。3. The strong hydrophobic polypropylene hollow fiber membrane prepared by the present invention delays the loss of the extractant in the application of the supported liquid membrane system, greatly improves the stability of the system, and improves the stability of the supported liquid membrane system by 5-30 %, laying a technical foundation for supporting the industrialization of liquid membrane technology.
附图说明Description of drawings
图1为聚丙烯中空纤维膜疏水改性装置（亦为支撑液膜萃取装置）示意图，图中：1-改性剂罐（亦为废液罐）；2-磁力转子；3-蠕动泵；4-压力表；5-聚丙烯中空纤维膜组件；6和8-阀门；7-改性剂罐（亦为碱液罐）。Figure 1 is a schematic diagram of a polypropylene hollow fiber membrane hydrophobic modification device (also a supporting liquid membrane extraction device), in which: 1-modifier tank (also a waste liquid tank); 2-magnetic rotor; 3-peristaltic pump; 4-pressure gauge; 5-polypropylene hollow fiber membrane module; 6 and 8-valve; 7-modifier tank (also lye tank).
具体实施方式detailed description
下面结合实施例对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。The technical solution of the present invention will be further described below in conjunction with the examples, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention within the scope of protection.
实施例1：Example 1:
本实施例提供的十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜的制备方法在图1所示聚丙烯中空纤维膜疏水改性装置中进行，该装置亦为支撑液膜萃取装置。具体步骤如下：The preparation method of the heptadecafluorodecyltriethoxysilane- SiO hydrophobically modified polypropylene hollow fiber membrane provided in this example is carried out in the polypropylene hollow fiber membrane hydrophobic modification device shown in Figure 1, which is also Support liquid membrane extraction device. Specific steps are as follows:
（1）配置浓度为20wt%的（NH4）2SO4溶液并水浴加热升温至65℃，之后在蠕动泵的推动下于聚丙烯中空纤维膜组件管程和壳程中循环流动，对聚丙烯中空纤维膜表面进行30min的预处理；(1) Prepare (NH4 )2 SO4 solution with a concentration of 20wt% and heat it in a water bath to 65°C, and then circulate in the tube side and shell side of the polypropylene hollow fiber membrane module under the push of a peristaltic pump. The surface of the propylene hollow fiber membrane is pretreated for 30 minutes;
（2）配置改性液：将二氧化硅纳米颗粒混入0.03mmol/L的十七氟癸基三乙氧基硅烷-正己烷溶液中，超声搅拌30min，二氧化硅纳米颗粒在改性液中的浓度为0.15wt%；(2) Configure the modification solution: mix the silica nanoparticles into the 0.03mmol/L heptadecafluorodecyltriethoxysilane-n-hexane solution, stir ultrasonically for 30min, and the silica nanoparticles are in the modification solution The concentration is 0.15wt%;
（3）使用蠕动泵推动步骤（2）配置的改性液在步骤（1）预处理后的聚丙烯中空纤维膜组件的管程和壳程中循环流动30min，每循环10min改变一次流动的方向，经去离子水清洗后在65℃的干燥箱中烘干，得到十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜。(3) Use a peristaltic pump to push the modified liquid prepared in step (2) to circulate in the tube side and shell side of the polypropylene hollow fiber membrane module pretreated in step (1) for 30 minutes, and change the flow direction every 10 minutes , washed with deionized water and dried in a drying oven at 65°C to obtain heptadecafluorodecyltriethoxysilane-SiO2 hydrophobically modified polypropylene hollow fiber membranes.
以十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜作支撑体，20vol%磷酸三丁酯和80vol%煤油作液膜相，应用蠕动泵推动萃取剂在膜组件的管程和壳程中循环流动15min，构建支撑液膜体系去除煤化工废水中的有机酚。与未经疏水改性的原始膜体系相比，经疏水改性后的支撑液膜体系经过3天的持续运行后有机酚的去除率仍然能够保持在62.22%，支撑液膜的稳定性提升了约22.34%。Using heptadecafluorodecyltriethoxysilane-SiO2 hydrophobically modified polypropylene hollow fiber membrane as the support, 20vol% tributyl phosphate and 80vol% kerosene as the liquid membrane phase, a peristaltic pump was used to drive the extractant in the membrane module The tube side and the shell side circulated for 15 minutes to build a supported liquid membrane system to remove organic phenols in coal chemical wastewater. Compared with the original membrane system without hydrophobic modification, the organic phenol removal rate of the supported liquid membrane system after hydrophobic modification can still be maintained at 62.22% after 3 days of continuous operation, and the stability of the supported liquid membrane has been improved. About 22.34%.
实施例2：Example 2:
本实施例与实施例1不同的是，所述制备方法如下：The difference between this embodiment and Example 1 is that the preparation method is as follows:
（1）配置浓度为15wt%的（NH4）2SO4溶液并水浴加热升温至65℃，之后在蠕动泵的推动下于聚丙烯中空纤维膜组件管程和壳程中循环流动，对聚丙烯中空纤维膜表面进行30min的预处理；(1) Configure (NH4 )2 SO4 solution with a concentration of 15wt% and heat it in a water bath to 65°C, and then circulate in the tube side and shell side of the polypropylene hollow fiber membrane module under the push of a peristaltic pump. The surface of the propylene hollow fiber membrane is pretreated for 30 minutes;
（2）配置改性液：将二氧化硅纳米颗粒混入0.04mmol/L的十七氟癸基三乙氧基硅烷-异丙醇溶液中，超声搅拌35min，二氧化硅纳米颗粒在改性液中的浓度为0.2wt%；(2) Configure the modification solution: mix the silica nanoparticles into the 0.04mmol/L heptadecafluorodecyltriethoxysilane-isopropanol solution, stir ultrasonically for 35min, and the silica nanoparticles in the modification solution The concentration in is 0.2wt%;
（3）使用蠕动泵推动步骤（2）配置的改性液在步骤（1）预处理后的聚丙烯中空纤维膜组件的管程和壳程中循环流动30min，每循环10min改变一次流动的方向，经去离子水清洗后在65℃的干燥箱中烘干，得到十七氟癸基三乙氧基硅烷-疏水改性聚丙烯中空纤维膜。(3) Use a peristaltic pump to push the modified liquid prepared in step (2) to circulate in the tube side and shell side of the polypropylene hollow fiber membrane module pretreated in step (1) for 30 minutes, and change the flow direction every 10 minutes , washed with deionized water and then dried in a drying oven at 65° C. to obtain heptadecafluorodecyltriethoxysilane-hydrophobic modified polypropylene hollow fiber membrane.
以十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜作支撑体，20vol%三烷基氧化膦和80vol%煤油作液膜相，应用蠕动泵推动萃取剂在膜组件的管程和壳程中循环流动15min，构建支撑液膜体系去除煤化工废水中的有机酚。与未经疏水改性的原始膜体系相比，经疏水改性后的支撑液膜体系经过3天的持续运行后有机酚的去除率仍然能够保持在54.31%，支撑液膜的稳定性提升了约14.43%。Using heptadecafluorodecyltriethoxysilane-SiO2 hydrophobically modified polypropylene hollow fiber membrane as the support, 20vol% trialkylphosphine oxide and 80vol% kerosene as the liquid membrane phase, a peristaltic pump was used to drive the extractant through the membrane The tube side and shell side of the module circulate for 15 minutes to build a supported liquid membrane system to remove organic phenols in coal chemical wastewater. Compared with the original membrane system without hydrophobic modification, the organic phenol removal rate of the supported liquid membrane system after hydrophobic modification can still be maintained at 54.31% after 3 days of continuous operation, and the stability of the supported liquid membrane has been improved. About 14.43%.
实施例3：Example 3:
本实施例与实施例1不同的是，所述制备方法如下：The difference between this embodiment and Example 1 is that the preparation method is as follows:
（1）配置浓度为25wt%的（NH4）2SO4溶液并水浴加热升温至65℃，之后在蠕动泵的推动下于聚丙烯中空纤维膜组件管程和壳程中循环流动，对聚丙烯中空纤维膜表面进行30min的预处理；(1) Prepare (NH4 )2 SO4 solution with a concentration of 25wt% and heat it in a water bath to 65°C, and then circulate in the tube side and shell side of the polypropylene hollow fiber membrane module under the push of a peristaltic pump. The surface of the propylene hollow fiber membrane is pretreated for 30 minutes;
（2）配置改性液：将二氧化硅纳米颗粒混入0.02mmol/L的十七氟癸基三乙氧基硅烷-氯仿溶液中，超声搅拌40min，二氧化硅纳米颗粒在改性液中的浓度为0.1wt%；(2) Prepare modification solution: mix silica nanoparticles into 0.02mmol/L heptadecafluorodecyltriethoxysilane-chloroform solution, stir ultrasonically for 40min, the concentration of silica nanoparticles in the modification solution The concentration is 0.1wt%;
（3）使用蠕动泵推动步骤（2）配置的改性液在步骤（1）预处理后的聚丙烯中空纤维膜组件的管程和壳程中循环流动60min，每循环10min改变一次流动的方向，经去离子水清洗后在65℃的干燥箱中烘干，得到十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜。(3) Use a peristaltic pump to push the modified liquid prepared in step (2) to circulate in the tube side and shell side of the polypropylene hollow fiber membrane module pretreated in step (1) for 60 minutes, and change the flow direction every 10 minutes , washed with deionized water and dried in a drying oven at 65°C to obtain heptadecafluorodecyltriethoxysilane-SiO2 hydrophobically modified polypropylene hollow fiber membranes.
以十七氟癸基三乙氧基硅烷-SiO2疏水改性聚丙烯中空纤维膜作支撑体，20vol%二（2-乙基己基）磷酸和80vol%煤油作液膜相，应用蠕动泵推动萃取剂在膜组件的管程和壳程中循环流动15min，构建支撑液膜体系去除煤化工废水中的有机酚。与未经疏水改性的原始膜体系相比，经疏水改性后的支撑液膜体系经过3天的持续运行后有机酚的去除率仍然能够保持在56.24%，支撑液膜的稳定性提升了约16.43%。Using heptadecafluorodecyltriethoxysilane-SiO2 hydrophobically modified polypropylene hollow fiber membrane as the support, 20vol% di(2-ethylhexyl) phosphoric acid and 80vol% kerosene as the liquid membrane phase, driven by a peristaltic pump The extractant circulates in the tube side and shell side of the membrane module for 15 minutes to build a supported liquid membrane system to remove organic phenols in coal chemical wastewater. Compared with the original membrane system without hydrophobic modification, the organic phenol removal rate of the supported liquid membrane system after hydrophobic modification can still be maintained at 56.24% after 3 days of continuous operation, and the stability of the supported liquid membrane has been improved. About 16.43%.
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| CN104548950A (en)* | 2013-10-16 | 2015-04-29 | 中国石油化工股份有限公司 | Inorganic nanoparticle enhanced type polypropylene hollow fiber microporous membrane and preparation method thereof |
| CN105396474A (en)* | 2014-09-05 | 2016-03-16 | 中国石油化工股份有限公司 | A method of modifying polyolefin hollow fiber membrane with special hydrophilic organosilicon |
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| CN109537282A (en)* | 2018-09-27 | 2019-03-29 | 天津工业大学 | A kind of method of polypropylene hollow fiber membrane modifying super hydrophobicity |
| CN111644067A (en)* | 2020-06-17 | 2020-09-11 | 东北电力大学 | Preparation method of nano micro-column super-amphiphobic composite membrane |
| CN112608412A (en)* | 2020-11-06 | 2021-04-06 | 临海伟星新型建材有限公司 | Preparation method of fluorine-containing grafted polyolefin material |
| CN114789001A (en)* | 2022-05-11 | 2022-07-26 | 河南迈纳净化技术有限公司 | Polyolefin hollow fiber porous membrane with super-hydrophobic outer surface and preparation method thereof |
| CN115487676A (en)* | 2022-09-02 | 2022-12-20 | 北京理工大学 | Preparation method of antibacterial modified hollow fiber ultrafiltration membrane |
| CN115487676B (en)* | 2022-09-02 | 2024-05-03 | 北京理工大学 | Preparation method of antibacterial modified hollow fiber ultrafiltration membrane |
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