CN108940186B - Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法 - Google Patents
Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 5
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Abstract
Ag2O/SiO2‑TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,属于燃料油加工技术领域。该方法以正硅酸甲酯、正硅酸乙酯、硅溶胶、水玻璃等为硅源、以醋酸银、硝酸银等为银源,以钛酸四丁酯为钛源,采用溶胶凝胶—常压干燥法制得Ag2O/SiO2‑TiO2复合气凝胶。将其定量填装于固定床吸附装置中,在一定温度与空速下,注入含噻吩类硫化物的模拟汽油,在反应装置的下端出口处收集吸附后的模拟汽油,进行色谱分析。结果表明Ag2O/SiO2‑TiO2复合气凝胶对噻吩类硫化物有很好的吸附性能。本发明中Ag2O/SiO2‑TiO2复合气凝胶吸附剂的制备方法简单、成本低廉,该吸附剂可多次重复使用、经济效益高、环境友好、其吸附条件温和、对吸附设备的要求低。
Description
技术领域
本发明属于燃料油加工技术领域,具体涉及一种以π络合吸附的Ag2O/SiO2-TiO2复合气凝胶脱硫吸附剂及其制备方法和在汽油脱硫中的应用。
背景技术
随着车用工业的大力发展,汽车尾气硫化物的大量排放不仅使环境污染问题日趋严重,同样也威胁着人类的身体健康。燃料电池对燃料油中的硫含量也有相当高的要求,有机硫化物的存在,会使燃料电池电极中的催化剂中毒,使燃料电池不能有效的将柴汽油中的化学能转化成电能。因此,对燃料油的深度脱硫已经成为了全球关注的焦点。
目前,燃料油品的脱硫工艺主要有加氢脱硫技术、烷基化脱硫技术、生物脱硫技术、萃取脱硫技术、氧化脱硫技术、吸附脱硫技术等。现在的工业生产中,脱硫的主要工艺仍是传统的加氢脱硫,但其操作成本较高、耗氢量大、操作条件苛刻,降低汽油中辛烷值等缺点。且加氢脱硫只对于硫醇、硫醚、无机硫等有较好效果,对于热稳定性极高的噻吩类硫化物的脱硫效果很差。吸附脱硫由于其成本低廉,操作条件温和,脱硫效果好,不污染环境,其中π络合吸附脱硫相对于物理吸附脱硫是有选择性的,对于化学吸附脱硫更易于脱附再生,是目前最有前景的脱硫方法。
π络合吸附脱硫的关键在于制备一种高效的π络合吸附剂。常用于制备π络合脱硫吸附剂的金属离子有Cu2+、Ag+、Ni2+、Co2+等。而制备π络合脱硫吸附剂,须将这些金属离子分散在高比表面积的载体上。根据载体的不同,π络合脱硫吸附剂可分为分子筛类、活性炭类、金属氧化物类。
以分子筛为载体的π络合脱硫吸附剂。沈阳化工大学(公开号 CN 103170305 A)以负载Ag离子的13X分子筛为脱硫吸附剂,用于深度脱除汽油中的噻吩及其衍生物和苯并噻吩。其中银的元素含量占吸附剂总重量的3%~5%,银元素为离子态。中国科学院(公开号 CN1511629 A)制备了一种深度脱除硫化物的分子筛吸附剂,由Y型分子筛负载金属盐类组成。这类π络合吸附剂,载体价格低廉,制备方法简单,可循环再生。但微孔分子筛脱硫吸附剂所交换的过渡金属离子数目有限,对硫化物的吸附容量不大,且微孔分子筛自身的微孔结构,大分子的噻吩类硫化物由于分子尺寸效应无法进入孔道内与金属离子形成π络合作用,即无法达到深度脱硫。
以活性炭为载体的π络合脱硫吸附剂。沈阳化工大学(公开号 CN 103143322 A)制备了一种负载了Fe离子的活性炭吸附剂,对汽油中的噻吩及其衍生物有较大的吸附容量与选择性,且制备方法简单,再生容易,吸附剂使用寿命长。中国石油化工股份有限公司(公开号 CN 104549143 A)通过采用含Al、Zn、Ni等金属的盐和H3PO4作为助剂对活性炭进行修饰改性,较好地解决了气体原料吸附净化脱硫技术中存在单一吸附剂不能同时有效脱除多种硫化物、硫的脱除率低以及脱硫剂的穿透硫容低等问题。但活性炭的孔结构以微孔为主,改性的活性炭对噻吩类大分子硫化物的吸附容量仍然非常小,难以满足工业生产的要求。
以金属氧化物为载体的π络合脱硫吸附剂。南通大学(公开号 CN 10300787 A)以铜元素掺杂的介孔γ-Al2O3与含硫的燃料油接触,利用吸附法实现脱硫,操作成本低,吸附容量大,且再生方便。中国石油化工股份有限公司(公开号 CN 10161923 A)制备了一种脱硫吸附剂,该吸附剂包括以氧化铝为粘结剂,氧化锌为载体,再与络合剂溶液接触,然后负载金属促进剂。用于燃料油脱硫,活性高,吸附硫容量大。但在制备过程中,金属离子容易堵塞金属氧化物孔道,导致负载的活性组分在表面堆积,无法进入孔道内提供活性位,降低吸附脱硫性能,且此法较难应用于工业化生产。
发明内容
针对现有π络合吸附剂在脱除燃料油中噻吩类硫中存在的上述问题,本发明的目的在于提供一种吸附容量大、易再生的Ag2O/SiO2-TiO2复合气凝胶为吸附剂,吸附条件温和,通过π络合吸附作用和酸碱作用的协同作用脱除燃料油中噻吩类硫的方法。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于以Ag2O/SiO2-TiO2复合气凝胶为吸附剂,将该吸附剂填装入固定床吸附装置中,在0~100℃温度下,以1~10 h-1的空速通入含有噻吩类硫的模拟汽油,经吸附后得到1ppm以下硫浓度的模拟汽油。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于含有噻吩类硫的模拟汽油中的噻吩类硫为噻吩或苯并噻吩。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附剂以硅源、钛源及银源为原料,采用溶胶凝胶—常压干燥法制备而得。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于硅源为正硅酸甲酯、正硅酸乙酯、硅溶胶或水玻璃;钛源为钛酸四丁酯,银源为以醋酸银、硝酸银;优选硅源为正硅酸乙酯,银源为硝酸银。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附剂中的硅钛摩尔比为1~250 : 1,优选为25~50 : 1。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附剂中的硅银摩尔比为10~50 : 1,优选为25~50 : 1。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于通入含有噻吩类硫的模拟汽油的空速为1~5 h-1。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附噻吩类硫的模拟汽油中的噻吩类硫的温度为0~60℃。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于模拟汽油中噻吩或苯并噻吩的硫浓度为0.1~10mgS/g,优选为0.1~5 mgS/g。
所述的一种以Ag2O/SiO2-TiO2复合气凝胶为吸附剂脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附噻吩或苯并噻吩能再生利用,其再生所用的溶剂为环己烯、乙醚、苯、甲苯。
通过采用上述技术,与现有技术相比,本发明的有益效果如下:
1)本发明的Ag2O/SiO2-TiO2复合气凝胶具有典型介孔特征孔径(5~20 nm),高孔隙率(85~99%),高比表面积(600~1500 m2/g)等独特物理化学性质,因此噻吩类硫化物可无阻碍地进入气凝胶孔道内,且活性组分与硫化物能充分接触;
2)本发明的Ag2O/SiO2-TiO2复合气凝胶作为π络合脱硫吸附剂与其他π络合吸附剂相比,其结构是由纳米级骨架颗粒构成,使骨架内的活性组分可充分暴露,在气凝胶的合成过程中,可将具有π络合作用的过渡金属盐加入其中,因此其活性组分的量是可调节的;
3)本发明的Ag2O/SiO2-TiO2复合气凝胶,与Ag2O/SiO2气凝胶相比,它在气凝胶硅骨架结构中引入Ti4+,产生L酸,噻吩类化合物中S原子上的孤对电子具有碱性,气凝胶基质Ag2O/SiO2-TiO2中的L酸中心可通过酸碱作用吸附噻吩类硫化合物,π络合作用和酸碱作用的协同作用能进一步提高它对噻吩类硫的吸附性能;
4)本发明的Ag2O/SiO2-TiO2复合气凝胶π络合吸附剂对噻吩类硫化物有良好的吸附性能,通过溶剂洗涤便可再生,再生后仍然有良好的吸附性能;
5)本发明的吸附反应在常压下进行、吸附条件温和、对吸附设备的要求低、操作方便,且对噻吩类化合物有良好的吸附效果。
具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例:Ag2O/SiO2-TiO2复合气凝胶吸附剂的制备
以硅银摩尔比为50:1,硅钛摩尔比为50:1的Ag2O/SiO2-TiO2复合气凝胶吸附剂为例,其制备方法如下:
将15mL EtOH、8 mL TEOS(正硅酸乙酯)、1 mL H2O、0.12g硝酸银和0.244g钛酸四丁酯的混合溶液在酸性条件下剧烈搅拌混合均匀,加入氨水调节pH值至6.5,室温下静置约15 min得Ag2O/SiO2-TiO2复合醇凝胶,再在体积比为25:15的无水乙醇/正硅乙酸酯中老化16h,以增强凝胶的骨架结构,再用正己烷对凝胶进行溶剂置换,24 h内更换两次溶剂,除去凝胶中的乙醇、水、酸及其他有机分子。最后80℃~150 ℃下干燥2 h,得硅银摩尔比50:1,硅钛摩尔比为50:1的Ag2O/SiO2-TiO2复合气凝胶。
实施例1~5:不同硅源,银源的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
在采用溶胶-凝胶法制备的Ag2O/SiO2-TiO2复合气凝胶中,所用的硅源有正硅酸甲酯、正硅酸乙酯、硅溶胶,银源有硝酸银、醋酸银,钛源为钛酸四丁酯。将制备完成的Ag2O/SiO2-TiO2复合气凝胶进行穿透吸附脱硫实验,具体操作如下:在固定床反应器中,最底层填装适量的脱脂棉,然后填装1 g的Ag2O/SiO2-TiO2气凝胶与适量的石英砂。吸附实验开始前,用正庚烷充分润湿所填装的吸附剂。通入模拟汽油,在反应器的下端出口处收集吸附后的模拟汽油,进行色谱分析,当流出液中硫浓度为0.005mgS/g时定为穿透点。实验过程中:空速为1~5 h-1,吸附温度为0~40℃,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。所得到的噻吩与苯并噻吩的穿透吸附容量,结果见表1、表2。
表1不同硅源的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
表2不同银源的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表1、表2、可以看出,在合成Ag2O/SiO2-TiO2复合气凝胶所用的硅源、银源,当硅源选用正硅酸乙酯,银源选用硝酸银,,所合成的Ag2O/SiO2-TiO2复合气凝胶在穿透吸附实验中,对噻吩与苯并噻吩有最大的穿透吸附容量,因此优选硅源为正硅酸乙酯,银源为硝酸银。
实施例9~14:不同硅钛摩尔比的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
选用硅银摩尔比50:1,硅钛摩尔比分别5、25、50、100、150、200的Ag2O/SiO2-TiO2气凝胶,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其中空速为1~5 h-1,吸附温度为0~40℃,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。其穿透吸附实验操作同实施例1~5,吸附结果见表3。
表3不同硅钛摩尔比的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表3可以看出,硅银摩尔比为50:1,不同硅钛摩尔比的Ag2O/SiO2-TiO2气凝胶随着硅钛摩尔比的减少即钛含量的增加,对噻吩与苯并噻吩的穿透吸附容量先增后降。在硅钛摩尔比为50:1时,噻吩与苯并噻吩的穿透吸附容量达到最大,因此优选硅钛摩尔比为25:1~100:1的Ag2O/SiO2-TiO2气凝胶。
实施例15~18:不同硅银摩尔比的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
选用硅钛摩尔比50:1,硅银摩尔比分别10、20、50、100的Ag2O/SiO2-TiO2气凝胶,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其中空速为1~5 h-1,吸附温度为0~40℃,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。其穿透吸附实验操作同实施例1~8,吸附结果见表4。
表4不同硅银摩尔比的Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表4可以看出,Ag2O/SiO2-TiO2气凝胶随着硅银摩尔比的减小即银含量的增加,对噻吩与苯并噻吩的穿透吸附容量先增后减。在硅银摩尔比为50:1后,噻吩与苯并噻吩的穿透吸附容量达到最大,因此优选硅银摩尔比为20:1~50:1的Ag2O/SiO2-TiO2气凝胶。
实施案例19~23:不同空速对Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
选用硅银摩尔比50:1,硅钛摩尔比为50:1的Ag2O/SiO2-TiO2复合气凝胶。在空速分别为1 h-1、3 h-1、5 h-1、8 h-1、10 h-1下,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其中吸附温度为0~40℃,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。其穿透吸附实验操作同实施例1~5,吸附结果见表5。
表5不同空速下Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表5可以看出,空速的减小,噻吩与苯并噻吩的穿透吸附容量会逐渐增大,当空速减小到5 h-1之后,对噻吩类硫化物的穿透吸附容量变化不大,因此优选空速为1~5 h-1。
实施案例24~28:不同吸附温度对Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
选用硅银摩尔比50:1,硅钛摩尔比为50:1的Ag2O/SiO2-TiO2复合气凝胶。吸附温度分别选为0℃、25℃、40℃、80℃、100℃,对模拟汽油中噻吩类硫化物进行穿透吸附实验。其中空速为1~5 h-1,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。穿透吸附实验操作同实施例1~5,吸附结果见表6。
表6不同吸附温度下Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表6可以看出,随着吸附温度的升高,噻吩与苯并噻吩的穿透吸附容量逐渐减小,在80℃之后,噻吩与苯并噻吩的吸附穿透容量非常小,表明在此温度下,被Ag2O/SiO2-TiO2复合气凝胶吸附的噻吩与苯并噻吩已脱附。因此优先吸附温度为0~40℃。
实施案例29~34:模拟汽油中不同硫浓度下Ag2O/SiO2-TiO2复合气凝胶对噻吩类硫化物的吸附性能
选用硅银摩尔比50:1,硅钛摩尔比为50:1的Ag2O/SiO2-TiO2复合气凝胶。模拟汽油中的噻吩或苯并噻吩的硫浓度分别为0.1mgS/g、0.5 mgS/g、1 mgS/g、2 mgS/g、5 mgS/g、10mgS/g进行穿透吸附实验。其中空速为1~5 h-1,吸附温度为0~40℃。穿透吸附操作同实施例1~5,吸附结果见表7。
表7模拟汽油中不同硫浓度下Ag2O/SiO2-TiO2复合气凝胶对噻吩类硫化物的吸附性能
从表7可以看出,模拟汽油中噻吩或苯并噻吩硫浓度的增大,Ag2O/SiO2-TiO2复合气凝胶对噻吩与苯并噻吩穿透吸附容量呈下降的趋势,因此优选模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。
实施案例35~38:不同再生溶剂对Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的再生吸附性能
先用环己烯,乙醚,苯,甲苯对使用后的Ag2O/SiO2-TiO2复合气凝胶中噻吩类硫化物进行洗脱,然后再用正庚烷对Ag2O/SiO2-TiO2复合气凝胶中再生溶剂进行洗脱,再对模拟汽油中噻吩类硫化物进行穿透吸附实验。其中空速为1~5 h-1,吸附温度为0~40℃,模拟汽油中噻吩或苯并噻吩硫浓度为0.1~5 mgS/g。穿透吸附实验操作同实施例1~5,吸附结果见表8。
表8 不同再生溶剂对Ag2O/SiO2-TiO2复合气凝胶对模拟汽油中噻吩类硫化物的吸附性能
从表8 可以看出,再生Ag2O/SiO2-TiO2复合气凝胶所用的溶剂有环己烯、乙醚、苯、甲苯。选用苯时,Ag2O/SiO2-TiO2复合气凝胶对噻吩与苯并噻吩再生效果最好。因此优选再生溶剂为苯。
Claims (8)
1. Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于以Ag2O/SiO2-TiO2复合气凝胶为吸附剂,将该吸附剂填装入固定床吸附装置中,在0~100℃温度下,以1~10 h-1的空速通入含有噻吩类硫的模拟汽油,经吸附后得到1ppm以下硫浓度的模拟汽油;Ag2O/SiO2-TiO2复合气凝胶吸附剂以硅源、钛源及银源为原料,采用溶胶凝胶—常压干燥法制备而得;Ag2O/SiO2-TiO2复合气凝胶吸附剂中的硅钛摩尔比为50~100 : 1;Ag2O/SiO2-TiO2复合气凝胶吸附剂中的硅银摩尔比为50 : 1;Ag2O/SiO2-TiO2复合气凝胶吸附噻吩类硫的模拟汽油中的噻吩类硫的温度为25~40℃。
2.根据权利要求1所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于含有噻吩类硫的模拟汽油中的噻吩类硫为噻吩或苯并噻吩。
3.根据权利要求1所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于硅源为正硅酸甲酯、正硅酸乙酯、硅溶胶或水玻璃;钛源为钛酸四丁酯,银源为以醋酸银、硝酸银。
4.根据权利要求1所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于硅源为正硅酸乙酯,银源为硝酸银。
5.根据权利要求1所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于通入含有噻吩类硫的模拟汽油的空速为1~5 h-1。
6.根据权利要求2所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于模拟汽油中噻吩或苯并噻吩的硫浓度为0.1~10mg/g。
7.根据权利要求1所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于Ag2O/SiO2-TiO2复合气凝胶吸附噻吩或苯并噻吩能再生利用,其再生所用的溶剂为环己烯、乙醚、苯、甲苯。
8.根据权利要求2所述的Ag2O/SiO2-TiO2复合气凝胶吸附脱除燃料油中噻吩类硫化物的方法,其特征在于模拟汽油中噻吩或苯并噻吩的硫浓度为0.1~5 mg/g。
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