CN107413208B - 一种高选择性汽油脱硫膜的制备方法 - Google Patents
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Abstract
本发明涉及一种高选择性汽油脱硫膜的制备方法,首先通过2,5‑双(三乙氧基硅基)噻吩的水解聚合反应制备硅溶胶;然后通过多次擦涂和多次低温热处理的方法在无机支撑体上制备得到桥联杂化硅膜。本发明的有益效果是:该杂化硅膜具有噻吩桥联结构,大大增加了对噻吩类硫化物的亲和力,提高了膜在脱硫过程中的选择性。并且该桥联结构具有较强的刚性,从而增加了膜在汽油体系中的结构稳定性。
Description
技术领域
本发明属于膜材料制备领域,涉及一种高选择性汽油脱硫膜的制备方法。
背景技术
随着世界各国对环境保护的日益重视以及环保法规的日益严格,生产低硫及超低硫汽油正逐渐为人们所关注。加氢脱硫是目前最为广泛应用的脱硫工艺,该过程虽能有效脱除无机硫和简单的有机硫化合物,但对于稠环噻吩类含硫化合物的脱除比较困难,并且普遍存在损失辛烷值、设备投资和操作费用大等不足。因此迫切需要其它低成本的汽油深度脱硫技术。
渗透汽化(PV)是一种新型高效的膜分离技术,是基于组分的分子类型差异(而非沸点的不同)完成分离过程的。渗透汽化膜分离技术具有能耗低、单级分离效率高、过程简单、不污染环境等特点,被誉为“绿色技术”,在化工单元操作中的应用越来越广泛。渗透汽化法汽油脱硫技术在炼油和膜分离领域均是崭新的技术,与传统的汽油脱硫技术相比,渗透汽化法汽油脱硫技术具有损失辛烷值很少,投资和操作费用低、可深度脱硫等优点。
渗透汽化膜是渗透汽化汽油脱硫工艺的核心部件,因此开发高性能汽油脱硫膜已成为各石油公司和相关研究者的研究热点。聚二甲基硅氧烷(PDMS)是一种目前较为常见的用于渗透汽化汽油脱硫的膜材料。但是PDMS膜材料存在着膜内自由体积受操作条件的影响变化大从而引起的稳定性差、选择性难以提高等缺陷,研究者通过各种方法对其改进,以提高该膜的稳定性及选择性。如清华大学李继定课题组利用Ag2O和Ag+Y填充改性了PDMS膜,Ag+能与噻吩形成π-络合作用,在一定程度上增强了膜的选择性;天津大学姜忠义课题组制备的Ni2+Y填充的PDMS膜,硫富集因子提高了1.67倍。通过金属离子掺杂这一物理改性方法虽然一定程度上提高了膜的选择性,但由于膜的主体仍然是PDMS基质,所以选择性提高有限。基于此,本发明采用一种结构新颖的杂化硅材料((EtO)3SiSi(OEt)3,BTEST),成功制备出了桥联杂化硅膜。该杂化硅膜具有噻吩桥联结构大大增加了对噻吩类硫化物的亲和力,并且该桥联结构具有较强的刚性,从而增加了膜在汽油体系中的结构稳定性。将该桥联杂化硅膜应用于汽油脱硫,显示出对噻吩类硫化物的高选择性和良好耐溶剂性能(对汽油体系的耐受性)。
发明内容
本发明要解决的技术问题是:基于上述问题,本发明提供一种高选择性汽油脱硫膜的制备方法。
本发明解决其技术问题所采用的一个技术方案是:一种高选择性汽油脱硫膜的制备方法,包括以下步骤:
(1)在乙醇溶剂中,硅源前驱体2,5-双(三乙氧基硅基)噻吩BTEST和水在催化剂HNO3作用下发生水解聚合反应,制备硅溶胶;
(2)分别用600目和1200目的砂纸打磨支撑体表面,然后将支撑体浸没在去离子水中煮沸15min;用砂纸打磨支撑体表面,其目的是减小支撑体表面的粗糙度使聚合物能很好地黏结在其表面并形成薄而无缺陷的活性层;
(3)将步骤(2)中得到的支撑体在去离子水中浸泡,然后把支撑体放入60℃烘箱中烘干;将支撑体在去离子水中浸泡,其目的是为了防止涂膜液大量渗透到陶瓷支撑体的孔里;
(4)将步骤(3)中得到的烘干的支撑体放入150℃烘箱中预热;
(5)将步骤(1)中得到的硅溶胶稀释10倍,通过擦涂法将稀释后的硅溶胶涂覆到步骤(4)中得到的预热的支撑体上,然后在低温下热处理,得到桥联杂化硅膜。
进一步地,步骤(1)中BTEST、水和HNO3的摩尔比为1:120:0.3,BTEST在体系中的质量分数保持在5.0wt%。
进一步地,步骤(2)中支撑体为50nm孔径的ZrO2/Al2O3管式陶瓷超滤膜。
进一步地,步骤(3)中浸泡时间为2~3h,烘干时间为1h。
进一步地,步骤(4)中预热时间为5~10min。
进一步地,步骤(5)中热处理温度为150℃,时间为30min。
进一步地,步骤(5)中先涂覆硅溶胶后热处理的操作重复2~3次。
本发明的有益效果是:选用一种结构新颖的杂化硅材料作为前驱体((EtO)3SiSi(OEt)3),该杂化硅膜具有噻吩桥联结构大大增加了对噻吩类硫化物的亲和力,提高了膜在脱硫过程中的选择性。并且该桥联结构具有较强的刚性,从而增加了膜在汽油体系中的结构稳定性。
附图说明
下面结合附图对本发明进一步说明。
图1为实施例的高选择性汽油脱硫膜制备过程的反应机理图;
图2为实施例与对比例在汽油体系中溶胀度的对比图;
图3为实施例与对比例制备的膜的选择性和渗透通量的性能对比图,其中,(a)是选择性对比图,(b)是渗透通量对比图。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例
(1)在乙醇溶剂中,25℃下BTEST和水在催化剂HNO3(摩尔比BTEST:H2O:HNO3=1:120:0.3)的作用下发生水解聚合反应制备BTEST溶胶,并将BTEST在体系中的质量分数保持在5.0wt%;
(2)分别用600目和1200目的砂纸打磨ZrO2/Al2O3(孔径:50nm)管式陶瓷支撑体表面,然后将支撑体浸没在去离子水中煮沸15min;
(3)将步骤(2)中得到的支撑体在去离子水中浸泡2h,然后把支撑体放入60℃烘箱中1h;
(4)将步骤(3)中得到的支撑体放入150℃烘箱中预热5min;
(5)将步骤(1)中得到的硅溶胶稀释10倍,通过擦涂法将稀释后的硅溶胶涂覆到步骤(4)中预热的支撑体上,然后在150℃下低温热处理30min,重复擦涂溶胶以及热处理的操作3次,得到桥联杂化硅膜。
对比例
(1)在室温(25℃)下,将3gPDMS溶解在7g正庚烷中,边搅拌边加入0.6g交联剂正硅酸乙酯TEOS,再加入催化剂二月桂酸二丁基锡(DBTL)0.12g,室温(25℃)下继续搅拌2h得到PDMS溶液,即铸膜液;
(2)将步骤(1)中所得的铸膜液静置脱泡后,采用浸渍提拉法均匀地涂覆在ZrO2/Al2O3(孔径:50nm)管式陶瓷支撑体上,室温(25℃)下干燥12h使溶剂挥发后置于120℃烘箱中12h完成交联,得到PDMS膜。
以上实施例和对比例所制备的BTEST和PDMS膜的脱硫性能见表1:
表1实施例中制备的膜渗透汽化脱硫性能对比
注:渗透汽化脱硫实验温度为25℃,进料噻吩浓度为200ppm,有效膜面积为3.52cm2。
由表1可知,BTEST膜对噻吩的选择性是PDMS膜的2.6倍,BTEST膜渗透通量是PDMS膜渗透通量的1.2倍。
图1为实施例1中高选择性汽油脱硫膜制备过程的反应机理图。由图1可知,BTEST和水在HNO3催化下,发生水解聚合反应形成了具有噻吩桥联结构的溶胶。
从图2中可以看出,随着正辛烷/噻吩混合溶液中噻吩浓度的增加,PDMS膜和BTEST膜的溶胀度均增加,但是BTEST膜的溶胀度始终低于PDMS膜的溶胀度,表明BTEST膜具有更好的耐溶剂性能。
从图3中可以看出,随着正辛烷/噻吩混合溶液中噻吩浓度的增加,PDMS膜和BTEST膜的选择性均降低,渗透通量均增加,但是BTEST膜的选择性和渗透通量始终高于PDMS膜的选择性和渗透通量。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (7)
1.一种高选择性汽油脱硫膜的制备方法,其特征是:包括以下步骤:
(1)在乙醇溶剂中,硅源前驱体2,5-双(三乙氧基硅基)噻吩BTEST和水在催化剂HNO3作用下发生水解聚合反应,制备硅溶胶;
(2)分别用600目和1200目的砂纸打磨支撑体表面,然后将支撑体浸没在去离子水中煮沸15min;
(3)将步骤(2)中得到的支撑体在去离子水中浸泡,然后把支撑体放入60℃烘箱中烘干;
(4)将步骤(3)中得到的烘干的支撑体放入150℃烘箱中预热;
(5)将步骤(1)中得到的硅溶胶稀释10倍,通过擦涂法将稀释后的硅溶胶涂覆到步骤(4)中得到的预热的支撑体上,然后在低温下热处理,得到桥联杂化硅膜。
2.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(1)中BTEST、水和HNO3的摩尔比为1:120:0.3,BTEST在体系中的质量分数保持在5.0wt%。
3.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(2)中支撑体为50nm孔径的ZrO2/Al2O3管式陶瓷超滤膜。
4.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(3)中浸泡时间为2~3h,烘干时间为1h。
5.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(4)中预热时间为5~10min。
6.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(5)中热处理温度为150℃,时间为30min。
7.根据权利要求1所述的一种高选择性汽油脱硫膜的制备方法,其特征是:所述的步骤(5)中先涂覆硅溶胶后热处理的操作重复2~3次。
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