CN105597712B - 增强型吸油膜材料、组件及其制备方法 - Google Patents
增强型吸油膜材料、组件及其制备方法 Download PDFInfo
- Publication number
- CN105597712B CN105597712B CN201510807572.5A CN201510807572A CN105597712B CN 105597712 B CN105597712 B CN 105597712B CN 201510807572 A CN201510807572 A CN 201510807572A CN 105597712 B CN105597712 B CN 105597712B
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- China
- Prior art keywords
- oil suction
- membrane material
- enhanced oil
- suction membrane
- woven fabrics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 89
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- 238000005266 casting Methods 0.000 claims abstract description 50
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 Kynoar Substances 0.000 claims abstract description 18
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- 239000003921 oil Substances 0.000 claims description 164
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011521 glass Substances 0.000 claims description 32
- 230000002209 hydrophobic effect Effects 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000010954 inorganic particle Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
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- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
本发明公开了一种增强型吸油膜材料、组件及其制备方法,该增强型吸油膜材料,包括管状支撑体和包覆于管状支撑体外侧的吸油功能层;管状支撑体两端以内的位置分布着多个孔;吸油功能层为表面涂覆有聚合物层的无纺布。该材料吸油性能好,支撑性强,可以负压抽吸的方式连续使用,吸油效率高。其制备方法为将无纺布用碱溶液预处理后,在其表面两次涂覆组成为溶剂、石墨烯、聚偏氟乙烯、成孔剂和无机粒子的铸膜液,经固化、萃取干燥后得到吸油功能层,将吸油功能层包覆在增强体的多孔区,得到增强型吸油膜材料。制备方法简单,易于操作。增强型吸油膜材料组件在框架上加了悬浮物,使其能漂浮在水面,施加负压后能实现连续吸油。
Description
技术领域
本发明涉及吸油材料领域,特别是涉及一种增强型吸油膜材料、组件及其制备方法。
背景技术
近年来,石油泄漏、工业油性有机溶剂及废水、废弃液的泄漏,对海洋、河流以及水上生态***造成了灾难性的危害。如何快速去除水上浮油,减少含油废水污染问题已经受到全世界的关注。传统的吸油材料包括木棉、膨润土、纸浆等,虽然他们被广泛用于实际应用中,但因其吸油效率低、油水选择性差、保油能力弱等缺点,仍无法满足环境治理的要求。
为了解决传统吸油材料的不足,人们正致力于研究新型吸油材料,代表性的有吸油树脂、吸油纤维、以及多孔聚合物基石墨烯吸油材料等。Zha等用非溶剂扩散法,使甲醇或水扩散到聚偏氟乙烯,后文缩写为PVDF,与石墨烯的二甲基甲酰胺,后文缩写为DMF,分散液中获得PVDF/石墨烯凝胶,再用水替换出凝胶中的DMF,经过真空冻干后获得超疏水超亲油PVDF/石墨烯无皮多孔材料,来源于,期刊《碳》,2011年第49卷第49期第5166-5172页刊登的文章聚偏氟乙烯/石墨烯多孔材料;即Superhydrophobic polyvinylidene fluoride/graphene porous materials[J].Carbon,2011,49(49):5166-5172。Nguyen等通过浸渍法将石墨烯涂覆与三聚氰胺海绵,并用聚二甲基硅氧烷表面处理,成功制备出超疏水超亲油性海绵基石墨烯材料,其吸附量最大可达自重的165倍,来源于期刊《能源与环境科学》2012年第5卷第7期第7908-7912页刊登的论文:利用简易涂覆法制备超疏水超亲油性石墨烯基海绵,即Superhydrophobic and superoleophilic properties of graphene-basedsponges fabricated using a facile dip coating method[J].Energy&EnvironmentalScience,2012,5(7):7908-7912。王子涛等将三聚氰胺海绵浸渍于氧化石墨烯分散液中,并用水合肼在线还原制得还原氧化石墨烯基三聚氰胺海绵,缩写为GROME,该海绵具有超疏水超亲油特性,且对油品吸附量达到56-127g/g,来源于期刊《高等学校化学学报》2014年第11卷第11期第2410-2417页刊登的论文还原氧化石墨烯基三聚氰胺海绵的制备与吸附性能。专利CN103521199A公开了一种中空管状复合吸油材料的制备方法,该方法以中空管状多孔聚合物材料为基质层,通过浸渍涂覆法将石墨烯涂覆于基质层表面所制得。该方法制得的中空管装复合吸油材料对三氯乙烯、煤油、柴油的最大静态吸附量分别为169.4g/g、97.2g/g、88.6g/g。这些聚合物基石墨烯吸油材料具有油水选择性好,吸油效率高,储油量大等特点,其性能远远超过了传统的吸油材料。但这些吸油材料的吸油方式都是依靠自身吸附,吸附的过程是间歇性过程,仍然无法实现对油水体系的连续,高效分离,且力学性能都较差,所以仍很难应用于工业生产中。
专利104128166A公开了一种中空管状吸油材料的制备方法:以弹簧为芯部,弹簧外侧包裹有片状海绵,将海绵浸泡于氧化石墨烯分散液中,经由负压抽滤、水合肼蒸汽还原、冲洗、真空干燥制得。专利CN103801274A公开了一种吸油中空纤维多孔膜的制备方法,该方法以石墨烯为表面吸附层,以中空纤维多孔膜为基质层,通过溶剂处理法或稀溶液处理法强化石墨烯与中空纤维多孔膜之间的界面结合牢度制得。这些新型聚合物基石墨烯吸油材对油水选择性好,并且一端连接负压,可实现对油品动态连续吸附,克服了传统吸油材料依靠自身吸附、工作模式为间歇性的缺点。但这些吸油材料由于力学性能差、支撑性差、形态单一等缺点,仍难在实际中广泛应用。
发明内容
本发明的第一个目的在于:提供一种增强型吸油膜材料,该材料吸油性能好,支撑性强,可以负压抽吸的方式连续使用,吸油效率高。
本发明的第二个目的在于:提供上述增强型吸油膜材料的制备方法,该方法简单,用料便宜,适于实际应用。
本发明的第三个目的在于:提供一种增强型吸油膜材料组件,集油品吸附性能和油水分离性能为一体,能连续高效的完成油水分离。
为此,本发明的技术方案如下:
一种增强型吸油膜材料,包括管状支撑体和设置于所述管状支撑体外侧的吸油功能层;所述管状支撑体两端以内的位置分布着多个孔;所述吸油功能层为表面涂覆有聚合物层的无纺布。
所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布,克重130g/m2;所述聚合物层由聚偏氟乙烯、石墨烯、疏水无机粒子及残余成孔剂组成,其中,所述疏水无机粒子为疏水二氧化硅或者疏水二氧化钛。
所述管状支撑体的材料为聚氨酯、聚乙烯、聚丙烯、聚酰胺或者聚氯乙烯。
所述管状支撑体的外径为8~12mm、管壁厚度为1~2mm,且其分布着的多个孔的孔隙密度为2.54~7.62PPI、孔的直径为1~2mm。
一种增强型吸油膜材料的制备方法,包括如下步骤:
(1)无纺布的预处理:配制浓度为1~6wt.%的碱溶液,将无纺布浸渍于60~90℃的碱溶液中1~5h后,取出并于室温下干燥,制得表面刻蚀的无纺布;
(2)铸膜液的制备:铸膜液包括按照质量分数计的如下组分:
所述溶剂为聚偏氟乙烯的良溶剂;铸膜液的制备方法为:先将石墨烯分散在溶剂中,优选采用超声分散1~3h,得到石墨烯分散液;再将聚偏氟乙烯、成孔剂和无机粒子加入所述石墨烯分散液中,在60~90℃条件下搅拌3~6h,得到铸膜液;
步骤(1)、(2)不分次序,可根据时间自行安排。
(3)制备吸油功能层:将步骤(1)预处理后的无纺布平铺于玻璃板上并固定;利用步骤(2)中所用溶剂将其润湿;然后利用所述铸膜液在其表面刮膜,后将玻璃板浸入10~50℃水中,保持12~48h后取出,再将其浸入无水乙醇中12~48h萃取出成孔剂,室温干燥至恒重,得到覆盖有单层膜的无纺布;利用所述铸膜液在覆盖有单层膜的无纺布上进行二次刮膜,再将玻璃板依次浸入10~50℃水中12~48h、乙醇中12~48h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将所述吸油功能层卷绕在管状支撑体的管壁上,且完全覆盖所述管状支撑体上分布着多个孔的区域,得到所述增强型吸油膜材料。
优选,所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、磷酸三乙酯、N-甲基吡咯烷酮和二甲基亚砜中任意一种或任意两种以任意比的混合物。
优选,所述成孔剂为邻苯二甲酸二辛脂、邻苯二甲酸二正辛脂、邻苯二甲酸二丁酯和邻苯二甲酸二乙酯中任意一种或任意两种以任意比的混合物。
优选,所述疏水无机粒子为疏水二氧化硅或者疏水二氧化钛。
步骤(3)中刮膜的方法为:将玻璃板一端固定在刮膜机上,将铸膜液均匀倒在玻璃板上固定的无纺布上,运行刮膜机使铸膜液均匀涂覆在无纺布表面。二次刮膜方法相同。
步骤(4)中将吸油功能层卷绕在管状支撑体的管壁上的方法为压边卷绕法,即将所得吸油功能层裁剪成菱形,再将一端对齐于管壁上小孔的上方进行卷绕,使得每一层卷绕层的边缘处压在上一卷绕层之上,并且完全覆盖所述管状支撑体上分布多个小孔的位置,再将卷绕层的压边处粘合密封。
一种增强型吸油膜材料组件,包括框架、悬浮装置和多个并联设置于所述框架内部的增强型吸油膜材料;所述多个增强型吸油膜材料的两端均连有接头,所述接头将所述增强型吸油膜材料与所述框架组装成一个整体;所述悬浮装置设置于所述框架上,其在水中产生的浮力大于或等于所述增强型吸油膜材料组件的重力;所述框架由连接管构成且设有用于外接负压装置的接口。
优选,将增强型吸油膜材料与框架连为一体的接头是三通接头;所述框架为聚氨酯管、聚乙烯管、聚丙烯管、聚酰胺管或者聚氯乙烯管;所述悬浮装置为高密度聚苯乙烯泡沫。
一种增强型吸油膜组件的制备方法,包括如下两步:
1)将悬浮装置分别捆绑在管道组成的框架上,使悬浮装置可绕管道自由旋转从而调节悬浮装置的高度。
2)利用三通接头将增强型吸油膜材料于框架连接,使框架内部形成通路,当设置在框架上的接口与负压装置连接时,可在增强型吸油膜材料的一端或两端形成负压。
与现有技术相比,本发明具有以下有益效果:
1、本发明提供的增强型吸油膜材料以无纺布作为增强体,使用双层涂覆法制得,其不仅吸油率高,而且具有连续吸油的功能,还兼具较高断裂强度、剥离强度的性能,力学性能佳,有效延长吸油膜材料及组件的使用寿命。
2、将本发明增强型吸油膜材料连接为组件应用于油/水体系中,组件悬浮于水面,组件端口提供负压,即可连续、快速的实现对油品的动态的连续吸附与分离,大大提高了油水分离效率。其吸附与分离的传质机理为:油品与膜表面接触时,由于石墨烯的疏水亲油特性,使油品优先被膜表面的石墨烯吸附,并通过负压传动使油品穿过多孔增强膜孔壁,进入组件的中空管内,并沿管道输送至储油端。所述组件不仅对油水体系能实现够无间歇分离,而且集分离与回收油品于一体,并且易于扩大,具有广泛的前景和极大的实际应用价值。
附图说明
图1为实施例1制得的单根增强型吸油膜材料的结构示意图;
图2为实施例1制得的三根-并联式增强型吸油膜组件示意图;
图3为实施例1制得的增强型吸油膜组件连续吸油试验装置结构示意图。
具体实施方式
以下结合附图和实施例对本发明的技术方案进行描述。
实施例1
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配制浓度为3wt.%的氢氧化钠溶液,将无纺布浸渍于90℃氢氧化钠溶液中3小时,取出并于室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.5g的石墨烯与72.5g的N,N-二甲基乙酰胺混合,经超声分散2小时制得石墨烯分散液;然后将13g的聚偏氟乙烯、10g的邻苯二甲酸二辛酯和4g的疏水性二氧化硅加入石墨烯分散液中,在70℃下搅拌3小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先将预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上;,用20毫升N,N-二甲乙酰胺将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持24小时后取出,然后浸入无水乙醇中24小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用所述铸膜液在单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入10~50℃水中12~48h、乙醇中12~48h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将步骤(3)制得的吸油功能层通过压边卷绕法卷绕在聚氨酯管的有孔区的管壁上,吸油功能层两端与聚氨酯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;如图1所述;该聚氨酯管的外径为10mm、管壁厚度为2mm、长度为210mm,管的两端各留有30mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为5.927PPI,直径1mm。
利用上述增强型吸油膜材料制备组件的方法为:框架2为长方/正方形,其上预留有用于连接外接负压装置的接口4,先将悬浮装置3,即高密度聚苯乙烯泡沫,绑在作为框架4的管子不连接头的位置上;再将三根增强型吸油膜材料1用接头平行并联在框架2内部,即得组件16,如图2所示。
如图3所示,使用时,将组件16的接口4依次用管道与压力表13、阀门12、储油罐11、真空泵10相连,组件16漂浮在表面有浮油14的水15上;当真空泵10开启时,组件16中的增强型吸油膜材料1的两端形成负压,浮油16被吸油功能层吸附后进入增强型吸油膜材料内腔,继而通过作为框架的管子,从接口4被抽出后进入并存储于储油罐11。不仅能连续完成吸油作业,且能将油收集在储油罐中。
经检测,本实施例制得的增强型吸油膜材料及组件的水进入压力为1.2bar,将组件置于煤油/水体系中在0.7bar下测得其煤油通量为244.40L/m2·h。
实施例2
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配置浓度为2wt.%的氢氧化钠溶液,将无纺布浸渍于80℃氢氧化钠溶液中2小时,取出并室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.3g的石墨烯与68.7g的N,N-二甲基甲酰胺混合,经超声分散2小时制得石墨烯分散液。之后将17g的聚偏氟乙烯、10g的邻苯二甲酸二辛酯和4g的疏水性二氧化硅加入石墨烯分散液中,在60℃下搅拌3小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先将预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上,用20毫升N,N-二甲基甲酰胺将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持12小时后取出,然后浸入无水乙醇中12小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入20℃水中12h、乙醇中12h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将步骤(3)制得的吸油功能层通过压边卷绕法卷绕在聚氨酯管的有孔区的管壁上,吸油功能层两端与聚氨酯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;该聚氨酯管的外径为12mm、管壁厚度为2mm、长度为230mm,管的两端各留有40mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为3.527PPI,直径1.2mm。
制备组件及使用状态同实施例1。
经检测,本实施例制得的增强型吸油膜材料及组件的水进入压力为1.5bar,将组件置于煤油/水体系中在0.7bar下测得其煤油通量为127.60L/m2·h。
实施例3
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配置浓度为3wt.%的氢氧化钠溶液,将无纺布浸渍于80℃氢氧化钠溶液中2小时,取出并室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.3g的石墨烯与70.7g的N,N-二甲基乙酰胺混合,经超声分散3小时制得石墨烯分散液。之后将13g的聚偏氟乙烯、12g的邻苯二甲酸二辛酯和4g的疏水性二氧化硅加入石墨烯分散液中,在70℃下搅拌4小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上,用20毫升N,N-二甲基乙酰胺将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持18小时后取出,然后浸入无水乙醇中18小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用所述铸膜液在单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入20℃水中18h、乙醇中18h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将步骤(3)制得的吸油功能层通过压边卷绕法卷绕在聚丙烯管的有孔区的管壁上,吸油功能层两端与聚丙烯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;该聚丙烯管的外径为12mm、管壁厚度为2mm、长度为210mm,管的两端各留有30mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为5.927PPI,直径1mm。
制备组件及使用状态同实施例1。
经检测,本实施例制得的增强型吸油膜材料及组件的水进入压力为1.1bar,将组件置于煤油/水体系中在0.7bar下测得其煤油通量为266.92L/m2·h。
实施例4
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配置浓度为3wt.%的氢氧化钠溶液,将无纺布浸渍于80℃氢氧化钠溶液中3小时,取出并室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.5g的石墨烯与72.5g的磷酸三乙酯混合,经超声分散3小时制得石墨烯分散液。之后将12g的聚偏氟乙烯、10g的邻苯二甲酸二乙酯和5g的疏水性二氧化钛加入石墨烯分散液中,在70℃下搅拌3小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先将预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上,用15毫升磷酸三乙酯将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持24小时后取出,然后浸入无水乙醇中24小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用所述铸膜液在单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入20℃水中24h、乙醇中24h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料:将步骤(3)制得的吸油功能层通过压边卷绕法卷绕在聚氨酯管的有孔区的管壁上,吸油功能层两端与聚氨酯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;该聚氨酯管的外径为10mm、管壁厚度为2mm、长度为210mm,管的两端各留有30mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为5.488PPI,直径1.2mm。
制备组件及使用状态同实施例1。
经检测,本实施例制得的增强型吸油膜材料及组件的水进入压力为1.3bar,将组件置于煤油/水体系中在0.7bar下测得其煤油通量为217.40L/m2·h。
实施例5
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配置浓度为3wt.%的氢氧化钠溶液,将无纺布浸渍于90℃氢氧化钠溶液中3小时,取出并室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.7g的石墨烯与72.3g的N-甲基吡咯烷酮,经超声分散3小时制得石墨烯分散液。之后将12g的聚偏氟乙烯、11g的邻苯二甲酸二丁酯和4g的疏水性二氧化硅加入石墨烯分散液中,在70℃下搅拌3小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先将预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上,用15毫升N-甲基吡咯烷酮将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持24小时后取出,然后浸入无水乙醇中24小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用所述铸膜液在单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入20℃水中24h、乙醇中24h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将步骤(3)制得的吸油功能层通过压边卷绕法卷绕在聚丙烯管的有孔区的管壁上,吸油功能层两端与聚丙烯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;该聚丙烯管的外径为10mm、管壁厚度为2mm、长度为210mm,管的两端各留有30mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为4.544PPI,直径1mm。
制备组件及使用状态同实施例1。
经检测,本实施例制得的增强型吸油膜及组件的水进入压力为1.0bar,将组件置于柴油/水体系中在0.7bar下测得其柴油通量为80.64L/m2·h。
实施例6
一种增强型吸油膜材料的制备方法,包括以下步骤:
(1)无纺布的碱处理:配置浓度为3wt.%的氢氧化钠溶液,将无纺布浸渍于70℃氢氧化钠溶液中2小时,取出并室温下干燥,制得表面刻蚀的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;
(2)铸膜液的制备:将0.5g的石墨烯与73.5g的N,N-二甲基乙酰胺,经超声分散2小时制得石墨烯分散液。之后将12g的聚偏氟乙烯、10g的邻苯二甲酸二辛酯和4g的疏水性二氧化硅加入石墨烯分散液中,在70℃下搅拌4小时,得到铸膜液;
步骤(1)、(2)不分先后次序,可按实验时间安排同时进行。
(3)制备吸油功能层:首先将预处理后的无纺布平铺于玻璃板上并将边缘处利用胶带固定在玻璃板上,用12毫升N,N-二甲基乙酰胺将无纺布表面均匀润湿后水平放置于刮膜机上,一端固定;然后在将步骤(2)所配制的铸膜液均匀倒在无纺布表面,之后将刮膜棒放在已倒有铸膜液的一端,运行刮膜机使所述铸膜液均匀涂覆在无纺布表面,之后将固定有无纺布的玻璃板浸入20℃水中,保持20小时后取出,然后浸入无水乙醇中20小时萃取出成孔剂,取出后在室温下干燥至恒重,得到单层涂覆增强膜;利用所述铸膜液在单层涂敷增强膜上进行二次刮膜,再将玻璃板依次浸入20℃水中20h、乙醇中20h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将步骤(3)制得的吸油功能层通过压边卷绕法,卷绕在聚氨酯管的有孔区的管壁上,吸油功能层两端与聚氨酯管管壁表面的接触处、吸油功能层的压边处粘合密封;即得所述增强型吸油膜材料;该聚氨酯管的外径为8mm、管壁厚度为2mm、长度为180mm,管的两端各留有30mm的无孔区用来安装接头,中间150mm为有孔区,有孔区上的孔隙密度为5.563PPI,直径1.2mm。
制备组件及使用状态同实施例1。
经检测,本实施例制得的增强型吸油膜及组件的水进入压力为1.2bar,将组件置于煤油/水体系中在0.7bar下测得其煤油通量为234.64L/m2·h。
表1给出了对实施例1~6所制得的增强型吸油膜材料及其组件进行连续吸附油品与油水分离性能测试的结果。
表1 实施例1-6所制得的增强型吸油膜组件的油通量
在测定增强型吸油膜材料及其组件的通量之前,首先要测定其水进入的最高临界压力(HPP),然后在低于临界压力的条件下,测定其煤油或柴油通量。以保证组件在运行中只吸油不吸水。测试结果如表1所示,表明了所制备的增强型吸油膜组件可在连续吸附油品的同时进行油水分离,实现动态油水分离的目的。
Claims (9)
1.一种增强型吸油膜材料(1),其特征在于:包括管状支撑体和设置于所述管状支撑体外侧的吸油功能层;所述管状支撑体两端以内的位置分布着多个孔;所述吸油功能层为表面涂覆有聚合物层的无纺布;所述无纺布为聚对苯二甲酸己二醇酯/聚酰胺以比例7:3混纺的纺粘水刺无纺布;所述聚合物层由聚偏氟乙烯、石墨烯、疏水无机粒子及残余成孔剂组成。
2.如权利要求1所述增强型吸油膜材料,其特征在于:所述疏水无机粒子为疏水二氧化硅或者疏水二氧化钛。
3.如权利要求1所述增强型吸油膜材料,其特征在于:所述管状支撑体的材料为聚氨酯、聚乙烯、聚丙烯、聚酰胺或者聚氯乙烯。
4.如权利要求1所述增强型吸油膜材料,其特征在于:所述管状支撑体的外径为8~12mm、管壁厚度为1~2mm,且其分布着的多个孔的孔隙密度为2.54~7.62PPI、孔的直径为1~2mm。
5.如权利要求1所述增强型吸油膜材料的制备方法,其特征在于包括如下步骤:
(1)无纺布的预处理:配制浓度为1~6wt.%的碱溶液,将无纺布浸渍于60~90℃的碱溶液中1~5h后,取出并于室温下干燥,制得表面刻蚀的无纺布;
(2)铸膜液的制备:铸膜液包括按照质量分数计的如下组分:
所述溶剂为聚偏氟乙烯的良溶剂;铸膜液的制备方法为:先将石墨烯分散在溶剂中,得到石墨烯分散液;再将聚偏氟乙烯、成孔剂和无机粒子加入所述石墨烯分散液中,在60~90℃条件下搅拌3~6h,得到铸膜液;
(3)制备吸油功能层:将步骤(1)预处理后的无纺布平铺于玻璃板上并固定;利用步骤(2)中所用溶剂将其润湿;然后利用所述铸膜液在其表面刮膜,后将玻璃板浸入10~50℃水中,保持12~48h后取出,再将其浸入无水乙醇中12~48h萃取出成孔剂,室温干燥至恒重,得到覆盖有单层膜的无纺布;利用所述铸膜液在覆盖有单层膜的无纺布上进行二次刮膜,再将玻璃板依次浸入10~50℃水中12~48h、乙醇中12~48h,室温干燥至恒重,即得所述吸油功能层;
(4)增强型吸油膜材料的制备:将所述吸油功能层卷绕在管状支撑体的管壁上,且完全覆盖所述管状支撑体上分布着多个孔的区域,得到所述增强型吸油膜材料。
6.如权利要求5所述制备方法,其特征在于:所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、磷酸三乙酯、N-甲基吡咯烷酮和二甲基亚砜中任意一种或任意两种以任意比的混合物;所述疏水无机粒子为疏水二氧化硅或者疏水二氧化钛。
7.如权利要求5所述制备方法,其特征在于:所述成孔剂为邻苯二甲酸二辛脂、邻苯二甲酸二正辛脂、邻苯二甲酸二丁酯和邻苯二甲酸二乙酯中任意一种或任意两种以任意比的混合物。
8.利用如权利要求1~4中任意一种增强型吸油膜材料的组件,其特征在于:包括框架、悬浮装置和多个并联设置于所述框架内侧的增强型吸油膜材料;所述多个增强型吸油膜材料的两端均连有接头,所述接头将所述增强型吸油膜材料与所述框架组装成一个整体;所述悬浮装置设置于所述框架上,其在水中产生的浮力大于或等于所述增强型吸油膜材料组件的重力;所述框架由连接管构成且设有用于外接负压装置的接口。
9.如权利要求8所述组件,其特征在于:将所述增强型吸油膜材料与框架连为一体的接头是三通接头;所述框架为聚氨酯管、聚乙烯管、聚丙烯管、聚酰胺管或者聚氯乙烯管;所述悬浮装置为高密度聚苯乙烯泡沫。
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CN105561813A (zh) * | 2015-12-11 | 2016-05-11 | 天津工业大学 | 热致相分离法制备聚丙烯腈基微孔膜的方法 |
CN106087923B (zh) * | 2016-06-12 | 2018-05-18 | 中国船舶重工集团公司第七○二研究所 | 水面浮油回收装置 |
CN108212104A (zh) * | 2017-12-29 | 2018-06-29 | 吴迪 | 一种亲油稳定性纤维素基吸油材料的制备方法 |
CN109095550A (zh) * | 2018-07-25 | 2018-12-28 | 深圳全钰环保科技有限公司 | 垃圾滤液处理工艺以及垃圾滤液处理*** |
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CN110323451B (zh) * | 2019-04-28 | 2022-03-22 | 中国科学院山西煤炭化学研究所 | 一种基于石墨烯与高分子纤维的多功能复合材料及其制备方法和应用 |
CN110152504A (zh) * | 2019-06-17 | 2019-08-23 | 沈阳工业大学 | 共混改性的聚偏氟乙烯膜和制备方法及应用 |
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