CN100344352C - X型沸石膜用于苯和氮气混合物分离的方法 - Google Patents
X型沸石膜用于苯和氮气混合物分离的方法 Download PDFInfo
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Abstract
本发明属于无机膜制备技术及应用领域，涉及到一种或几种有机大分子气体与无机小分子气体混合物的分离。其特征是按照SiO2∶Al2O3＝3.85-4.2，Na2O∶SiO2＝1.2-1.5，H2O∶Na2O＝55的摩尔配比配制溶胶，采用α-Al2O3陶瓷管为载体，合成前载体管经由打磨，酸碱的处理，然后在水热条件下低温(95℃-105℃)晶化20-48h合成X型分子筛膜，将沸石膜在95℃下在0.2-0.25mol/L的硝酸银溶液中离子交换5-8h，得到AgX分子筛膜，最后将膜管置于膜分离装置中，控制两侧压差于10-60kPa，苯和氮气的分离因数在10-40之间。本发明的效果是在常温下实现了苯和氮气的分离，设备简单，能耗低，有广泛的应用前景。
Description
技术领域
本发明属于无机膜制备技术及应用领域，涉及到无机膜的合成及有机大分子气体与无机小分子气体混合物的分离应用，特别涉及到苯和氮气的分离方法。
背景技术
目前石油化工行业会有大量的苯的储存和使用，工艺上都是用氮气来密封苯，因此会产生大量的被苯饱和的氮气，苯贮罐呼吸管将100-120Nm3/h含24Mol％左右苯的苯和氮气混合气直接排放至大气，不作回收利用，不仅浪费了宝贵的资源，而且污染了环境。
目前从苯和氮气混合物的分离回收苯可采用的技术主要有冷凝分离法，吸附法及膜分离法等几种。
冷凝分离法是将混合气加压冷凝液化，再利用精馏将氮和苯分离。由于氮的沸点为-195.8℃，苯的沸点为80.4℃，若将两者的混合物液化需要高压和低温，因此其能耗很高，设备投资大，经济效益低。
吸附法是采用对苯具有很高选择吸附性能的活性炭或活性炭纤维为吸附剂，在低温下吸附苯，吸余气氮气排空。当吸附床达到饱和时，经高温解吸回收苯。苯贮罐呼吸气中苯的浓度为24％左右，采用吸附法回收苯，势必需要大量吸附剂，造成设备体积庞大，高温脱附能耗高，降温困难，设备投入高，制约了工业化应用。
膜法气体分离技术是这几十年发展起来的高新分离技术。混合气体在通过膜分离器时，一种或几种气体在压力或浓度等推动力作用下，选择性的透过膜，从而达到分离的目的。与其他分离方法相比，膜分离具有无相变，常温操作，不需加热解吸或脱附，能耗低，流程简单，投资少等优点。受到企业和科技界的普遍关注，已成研究开发，推广应用的热点。法国膜材料和过程国家实验室Guizard等人用涂布热交联法在氟化聚偏氯乙烯(Polyvinylidene Fluoride，PVDF)和聚醚砜(polyether Sulfone，PES)非对称载体上合成了三聚氟代硅氧烷有机膜(Fluorosiloxane ter-Polymers，FST)，并用该膜进行了空气——1，2-苯渗透分离试验，结果表明，当空气中1，2-苯含量为25mol％时，1，2-苯的渗透率为6.5×10-4m3/m2·s·Pa，表现出良好的分离性能。但有机膜存在透量少，抗溶剂性能差，膜结构易受溶剂破坏，膜寿命短的缺点。
沸石分子筛膜是近些年发展起来的一种新型的膜分离技术，它是通过分子筛的孔道实现分子筛分，从而得到较高的分离因数。X型分子筛孔径为0.74nm，在孔径上对苯有选择性，而银离子可以取代X型沸石分子筛中用来平衡电荷的的钠离子，通过银离子对其改性，由于银离子可以和不饱和烃在分子筛孔内形成配位键，所以化学键的作用可以是苯在膜表面形成表面吸附络合物，有高吸附容量和高选择性，同时沸石晶穴中含有阳离子，这样在阳离子周围便形成强大的电场。也正是由于静电力的关系，对不饱和及易极化分子具有优先的选择吸附作用。通过对苯的选择吸附，使其在膜孔道内发生毛细凝聚，阻止氮气通过，来实现混合气体的分离。
发明内容
本发明的目的是提供一种在常温下就可以分离苯和氮气的膜分离方法，利用该方法制备一种具有特定孔径的沸石膜，这种膜上的阳离子通过化学健力的作用可以将苯吸附到膜表面，同时苯在其孔内发生毛细凝聚现象，进而阻止无机小分子氮气的通过，来实现混合气体的分离。
本发明的关键在于合成X型分子筛膜，实现本发明的技术方案是，按照SiO2∶Al2O3＝3.85-4.2，Na2O∶SiO2＝1.2-1.5，H2O∶Na2O＝55的摩尔配比配制溶胶，其中Al2O3的原料采用三水铝石、硫酸铝或三氯化铝，SiO2的原料采用水玻璃、硅酸、硅溶胶或各种活性无定型硅石，Na2O的原料采用氢氧化钠，水为去离子水，经搅拌配成溶胶，采用α-Al2O3载体管，载体管的孔径为3-5μm，孔隙率30-50％。合成前载体管经过打磨和酸碱处理，然后在水热条件下低温95℃-105℃，晶化20-48h合成X型分子筛膜。合成的分子筛膜用去离子水漂洗至中性，然后用N2气进行渗透测试，如果有气体透过，则重复晶化，直至膜管不透气，制备出具有分离性能的X沸石膜，然后将沸石膜在95℃下在0.2-0.25mol/L的硝酸银溶液中离子交换5-8h；离子交换处理后，将膜管在室温下用去离子水漂洗，然后在100℃干燥1d，最后将膜管置于膜分离装置中，控制两侧压差于10-60kPa，苯和氮气的分离因数在10-40之间。
本发明经过Ag离子交换改性得到的沸石膜，其膜的结构和外观经过荧光光谱和扫描电镜照片分析得到证实。
本发明的效果和益处是在常温下实现了苯和氮气的分离，设备简单，节约能源，同时又能避免环境污染，回收了宝贵的资源，改善了人类的生存环境。
附图说明
附图是X型分子筛膜分离苯和氮气的装置结构示意图。
图中：1冷阱，2真空泵，3混合气，4针形阀，5压力表，6膜分离器，7膜管，8色谱，9流量计。
具体实施方式
以下结合附图详细叙述本发明的具体实施方式和最佳实施例。
实施例：
溶胶制备：以硅溶胶为硅源，异丙醇铝为铝源，氢氧化钠为碱源和去离子水为原料，按照SiO2∶Al2O3＝3.85-4.2，Na2O∶SiO2＝1.2-1.5，H2O∶Na2O＝55的摩尔配比，在强力搅拌状态下配制溶胶。
载体预处理：在合成以前首先将载体表面用400#、600#、800#砂纸打磨光滑，再用超声波震荡，洗去表面及孔内悬浮颗粒，然后用酸或碱浸泡1-2小时，超声波水洗至中性，烘干待用。
膜制备：取经过预处理的载体管，两端用聚四氟乙烯膜封死，竖直放入不锈钢晶化釜内，将溶胶沿管壁缓缓加入釜内，封好后放到事先加热到一定温度的烘箱内，晶化一定时间取出，自然冷却并用去离子水洗至中性。常温干燥1-2d，在100℃干燥1-2d，在焙烧前经N2测试，如果仍然透气，则重复晶化至不透气。
膜焙烧：在空气气氛中按照一定的升降温程序焙烧膜管，以除去膜孔内的结晶水。升温速率为：0.5-1K/min，降温速率为：1-2K/min。
阳离子改性：将自制的分子筛膜管在100℃下干燥2h后，取膜管、硝酸银和去离子水加入到三口烧瓶中，常压，恒温95度，搅拌状况下进行离子交换，交换一定时间后将改性后的膜管取出倒入烧杯中，用去离子水冲洗3-4次。
按照上述方法将制得的改性沸石膜装到附图所示的膜分离装置中，膜两端的压差控制在30Kpa，苯进气侧浓度为19.2％，进气侧流速为180ml/min；尾气浓度为2.8％，流速146ml/min，二者的分离因数为36。
Claims (1)
1.一种X型沸石筛膜用于苯和氮气混合物分离的方法，其特征是按照SiO2∶Al2O3＝3.85-4.2，Na2O∶SiO2＝1.2-1.5，H2O∶Na2O＝55的摩尔配比配制溶胶，其中Al2O3的原料可采用三水铝石、硫酸铝或三氯化铝，SiO2的原料可采用水玻璃、硅酸、硅溶胶或各种活性无定型硅石，Na2O的原料采用氢氧化钠，水为去离子水，这些原料按上述比例经搅拌配成溶胶，采用α-Al2O3载体管，载体管的孔径为3～5μm，孔隙率30-50％；合成前，载体管经过处理后，在水热条件下低温95℃-105℃晶化20-48h合成X型分子筛膜，在焙烧前经N2测试，如果仍然透气，则重复晶化至不透气，然后将沸石膜在95℃下在0.2-0.25mol/L的硝酸银溶液中离子交换5-8h；离子交换处理后，将膜管在室温下用去离子水漂洗，然后在100℃干燥1d，最后将膜管置于膜分离装置中，控制两侧压差于10-60kPa，苯和氮气的分离因数在10-40之间。
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| BR112015026567A2 (pt) * | 2013-05-07 | 2017-07-25 | Dow Global Technologies Llc | processo para efetuar a troca iônica de uma membrana de zeólito suportada em alfa-alumina |
| CN110862834A (zh) * | 2019-12-10 | 2020-03-06 | 邵帅 | 一种利用印染污泥热解气生产清洁气体燃料的方法 |
| CN114471184B (zh) * | 2021-12-20 | 2023-07-07 | 南京工业大学 | 一种阳离子修饰的分子筛膜、制备方法以及在高沸点有机溶剂脱水中的用途 |
| CN115028174B (zh) * | 2022-05-26 | 2023-11-24 | 中南大学 | 一种细化金属基体表面沸石涂层中沸石晶粒的方法 |
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| US5019263A (en) * | 1990-06-05 | 1991-05-28 | Mobil Oil Corp. | Membrane composed of a pure molecular sieve |
| US5464798A (en) * | 1994-02-24 | 1995-11-07 | Jia; Meng-Dong | Ceramic-zeolite composite membranes and use for separation of vapor/gas mixtures |
| CN1168192A (zh) * | 1995-11-17 | 1997-12-17 | 英国核燃料公共有限公司 | 气体分离 |
| CN1332671A (zh) * | 1998-12-30 | 2002-01-23 | 康宁股份有限公司 | 沸石膜及其制造方法 |
| CN1112231C (zh) * | 2000-02-24 | 2003-06-25 | 中国石油化工集团公司 | 制备x型分子筛膜的方法 |
| CN1453063A (zh) * | 2003-05-15 | 2003-11-05 | 大连理工大学 | 沸石分子筛膜用于二氯乙烷和氮气混合物的分离方法 |
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| US5019263A (en) * | 1990-06-05 | 1991-05-28 | Mobil Oil Corp. | Membrane composed of a pure molecular sieve |
| US5464798A (en) * | 1994-02-24 | 1995-11-07 | Jia; Meng-Dong | Ceramic-zeolite composite membranes and use for separation of vapor/gas mixtures |
| CN1168192A (zh) * | 1995-11-17 | 1997-12-17 | 英国核燃料公共有限公司 | 气体分离 |
| CN1332671A (zh) * | 1998-12-30 | 2002-01-23 | 康宁股份有限公司 | 沸石膜及其制造方法 |
| CN1112231C (zh) * | 2000-02-24 | 2003-06-25 | 中国石油化工集团公司 | 制备x型分子筛膜的方法 |
| CN1453063A (zh) * | 2003-05-15 | 2003-11-05 | 大连理工大学 | 沸石分子筛膜用于二氯乙烷和氮气混合物的分离方法 |
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