CN111957346B - 甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂及其制备方法 - Google Patents
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Abstract
本专利申请提供一种甲醇‑叔丁醇制备甲基叔丁基醚的醚化催化剂及其制备方法。甲醇‑叔丁醇制备甲基叔丁基醚的醚化催化剂,是由油相和分散相共存中悬浮共聚,经抽提、干燥、筛分取得共聚白球,后经磺化、洗涤后制得,其中的油相包括苯乙烯、甲基丙烯酸甲酯、二乙烯基苯单体,致孔剂、引发剂,所述的分散相,包括水和聚乙烯醇。本技术方案经实际验证,叔丁醇转化率>60%,表现出优良的反应催化活性。
Description
技术领域
本专利申请涉及石油化工合成的催化剂技术领域,尤其涉及的是由甲醇和叔丁醇合成制备甲基叔丁基醚的离子树脂催化剂及其制备方法。
背景技术
甲基叔丁基醚的制备,目前主要利用石油碳四中的异丁烯馏分与甲醇在酸性催化剂催化作用下合成来获得。甲醇原料虽较为充足,但异丁烯物料供给有限,尤其在甲基叔丁基醚需求急剧增加的现实中,异丁烯原料供给已越来越不能满足实际规模化工业生产需求。因此,开发甲基叔丁基醚的非异丁烯制备路线,其中由叔丁醇和甲醇制取甲基叔丁基醚是一条极有价值的可取工艺线路,叔丁醇容易从丙烯-异丙烷氧化制取环氧丙烷的过程中联产得到。但现有的阳离子树脂催化剂在甲醇-叔丁醇合成甲基叔丁基醚的催化表现却并不理想。
专利文献CN110586185A公开了一种叔丁醇甲醇醚化树脂催化剂及其制备技术方案,其催化剂以苯乙烯-二乙烯苯交联共聚白球为母体,再实施均一相共聚包裹,后经功能基团稳定化得到叔丁醇甲醇醚化树脂催化剂。其催化剂树脂是经聚合白球之上再聚合制得,因此其磺化深度不够,导致酸性不强,催化活性差;另外,其合成过程中不能及时将水移除催化剂,抑制了催化剂的活性。
发明内容
本专利申请的发明目的在于,面对异丁烯原料有限、供给越来越紧张的现实,为甲基叔丁基醚制备开辟由叔丁醇和甲醇合成的工艺方法同时,提供一种在合成反应中能够持久展现出高催化活性的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂及其制备方法。
本专利申请提供的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂技术方案,其主要技术内容是:一种甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,是由油相和分散相共存中悬浮共聚,经抽提、干燥、筛分取得共聚白球,后经磺化、洗涤后制得,其特征在于,按重量份计,油相包括苯乙烯60~80份、甲基丙烯酸甲酯20~40份、二乙烯基苯单体60~100份,致孔剂24~55份、引发剂0.4~1.0份,所述的致孔剂为液体石蜡,所述的引发剂为过氧化苯甲酰;所述的分散相,包括水300~400份和聚乙烯醇1.0~2.0份;
(1)聚合
所述油相和分散相混合悬浮共聚反应,反应后冷却、出料、洗涤、抽提、干燥聚合白球,至含水量为5~10%重量百分比,筛选粒径为0.4~0.5mm的白球;
(2)磺化
将第(1)筛选白球浸入磺化剂,在100℃~120℃、反应8~20h,所述的磺化剂为溶解氯磺酸的发烟硫酸;
(3)洗涤
磺化反应后冷却,树脂球由去离子水冲洗至中性,分离获得催化剂树脂,其含水量为40-55%。
上述整体方案中的之一优选技术手段,将苯乙烯、甲基丙烯酸甲酯、二乙烯基苯、致孔剂和引发剂按量加入混合罐,搅拌均匀得油相;聚合釜加入水和聚乙烯醇,升温、搅拌至完全溶解,加入油相,搅拌转速90转/分~100转/分,缓慢升温至80℃聚合反应8~18小时,反应后交替用热水和冷水洗涤,得聚合白球。
上述整体方案中的之一优选技术手段,所述的抽提为:聚合白球加入抽提釜,蒸馏釜加入过量溶剂,蒸馏冷凝至抽提釜,抽提釜混合溶液达到指定高度时排回蒸馏釜,如此反复6-20次,将聚合白球内致孔剂抽提干净。
上述整体方案中的之一优选技术手段,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1:(6~10):(1~3)。
上述整体方案中的之一优选技术手段,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1: 6:1。
上述整体方案中的之一优选技术手段,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1: 10:3。
本专利申请还提供了一种上述甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂的制备方法。
本专利申请公开的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂技术方案,于聚合中参入甲基丙烯酸甲酯,其作用一方面是均衡苯乙烯和二乙烯苯聚合速度,使两者聚合速度相当,解决交联剂二乙烯苯聚合完毕时还有未聚合苯乙烯的难题,从而获得更均匀、且颗粒较小的聚合树脂白球,特别是使树脂球孔道内均布有酯基,酯基的疏水特性,能够使甲醇-叔丁醇制备甲基叔丁基醚合成中生成的水脱离反应体系,从而使催化剂本体持久的保持和发挥催化活性;小颗粒聚合树脂白球能够减少物料内扩散时间,反应物料进出催化剂快,提升了催化剂催化性能发挥效率;磺化工艺采用发烟硫酸和氯磺酸做磺化试剂,加强了磺化深度,获得高催化活性催化剂。取所制得的催化剂400ml装入内径50mm、长1000mm的固定床反应器中制备甲基叔丁基醚,其中甲醇、叔丁醇摩尔比为1:1,反应工艺条件为:压力1.0-1.5Mpa、空速0.5-4h-1、温度70℃-100℃,经实际验证,叔丁醇转化率>60%,表现出优良的反应催化活性。
具体实施方式
下面将通过以下实施例详细说明本申请技术方案。
实施例1
催化剂A
(1)聚合
将苯乙烯60份、甲基丙烯酸甲酯20、二乙烯基苯60、致孔剂24和引发剂0.4按量加入混合罐,搅拌0.5小时,得均匀油相;聚合釜加入水300份和聚乙烯醇1.0份,搅拌升温至40℃完全溶解,加入油相,根据单体分散情况调整搅拌转速90转/分,缓慢升温至80℃、聚合反应8小时,反应后冷却、出料,交替用热水和冷水洗涤,分离出聚合白球;
聚合白球加入抽提釜,蒸馏釜加入过量溶剂,溶剂可以选用丁酮或苯等,蒸馏冷凝至抽提釜,抽提釜混合溶液达到指定高度时排回蒸馏釜,如此反复6次,将聚合白球内致孔剂抽提干净,聚合白球通风干燥至含水量为5~10%重量百分比,筛选粒径为0.4mm白球为磺化基体;
(2)磺化
将第(1)筛选白球浸入磺化剂,在100℃反应8h,所述的磺化剂为溶解氯磺酸的发烟硫酸,且白球、发烟硫酸、氯磺酸的质量比为1:6:1;
(3)洗涤
磺化反应后冷却,树脂球移至水洗柱,用去离子水冲洗至中性,分离获得催化剂树脂,其含水量为40-55%。
取上述新鲜的树脂催化剂400ml,装入内径50mm、长1000mm的固定床反应器中,实施甲醇-叔丁醇醚化制备甲基叔丁基醚合成试验。其中甲醇、叔丁醇的摩尔比为1:1,在固定床反应条件为:压力1.0Mpa、空速0.5h-1、反应温度为70℃,其叔丁醇转化率达到63.7%。
实施例2:
催化剂B:
(1)聚合
将苯乙烯80份、甲基丙烯酸甲酯40、二乙烯基苯100、致孔剂44和引发剂1.0按量加入混合罐,搅拌2.0小时,得均匀油相;聚合釜加入水400份和聚乙烯醇2.0份,搅拌升温至50℃完全溶解,加入油相,根据单体分散情况调整搅拌转速100转/分,缓慢升温至80℃、聚合反应18小时,反应后冷却、出料,交替用热水和冷水洗涤,分离出聚合白球;
聚合白球加入抽提釜,蒸馏釜加入过量溶剂,蒸馏冷凝至抽提釜,抽提釜混合溶液达到指定高度时排回蒸馏釜,如此反复20次,将聚合白球内致孔剂抽提干净,聚合白球通风干燥至含水量为5~10%重量百分比,筛选粒径为0.4~0.5mm 白球为磺化基体;
(2)磺化
将第(1)筛选白球浸入磺化剂,在120℃反应20h,所述的磺化剂为溶解氯磺酸的发烟硫酸,且白球、发烟硫酸、氯磺酸的质量比为1:10:3;
(3)洗涤
磺化反应后冷却,树脂球移至水洗柱,用去离子水冲洗至中性,分离获得催化剂树脂,其含水量为40-55%。
取上述新鲜的树脂催化剂400ml,装入内径50mm、长1000mm的固定床反应器中,实施甲醇-叔丁醇醚化制备甲基叔丁基醚合成试验。其中甲醇、叔丁醇的摩尔比为1:1,在固定床反应条件为:压力1.5Mpa、空速4h-1、反应温度为100℃,其叔丁醇转化率达到64.1%。
实施例3:
催化剂C:
(1)聚合
将苯乙烯70份、甲基丙烯酸甲酯30、二乙烯基苯80、致孔剂39.6和引发剂0.6,按量加入混合罐,搅拌1.0小时,得均匀油相;聚合釜加入水400份和聚乙烯醇2.0份,搅拌升温至45℃完全溶解,加入油相,根据单体分散情况调整搅拌转速95转/分,缓慢升温至80℃、聚合反应10小时,反应后冷却、出料,交替用热水和冷水洗涤,分离出聚合白球;
聚合白球加入抽提釜,蒸馏釜加入过量溶剂,蒸馏冷凝至抽提釜,抽提釜混合溶液达到指定高度时排回蒸馏釜,如此反复10次,将聚合白球内致孔剂抽提干净,聚合白球通风干燥至含水量为5~10%重量百分比,筛选粒径为0.4~0.5mm 白球为磺化基体;
(2)磺化
将第(1)筛选白球浸入磺化剂,在110℃反应10h,所述的磺化剂为溶解氯磺酸的发烟硫酸,且白球、发烟硫酸、氯磺酸的质量比为1:8:2;
(3)洗涤
磺化反应后冷却,树脂球移至水洗柱,用去离子水冲洗至中性,分离获得催化剂树脂,其含水量为40-55%。
取上述新鲜的树脂催化剂400ml,装入内径50mm、长1000mm的固定床反应器中,实施甲醇-叔丁醇醚化制备甲基叔丁基醚合成试验。其中甲醇、叔丁醇的摩尔比为1:1,在固定床反应条件为:压力1.2Mpa、空速2h-1、反应温度为85℃,其叔丁醇转化率达到61.8%。
Claims (6)
1.一种甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,是由油相和分散相共存中悬浮共聚,经抽提、干燥、筛分取得共聚白球,后经磺化、洗涤后制得,其特征在于,按重量份计,油相包括苯乙烯60~80份、甲基丙烯酸甲酯20~40份、二乙烯基苯单体60~100份,致孔剂24~55份、引发剂0.4~1.0份,所述的致孔剂为液体石蜡,所述的引发剂为过氧化苯甲酰;所述的分散相,包括水300~400份和聚乙烯醇1.0~2.0份;
(1)聚合
所述油相和分散相混合悬浮共聚反应,反应后冷却、出料、洗涤、抽提、干燥聚合白球,至含水量为5~10%重量百分比,筛选粒径为0.4~0.5mm的白球;
(2)磺化
将第(1)筛选白球浸入磺化剂,在100℃~120℃、反应8~20h,所述的磺化剂为溶解氯磺酸的发烟硫酸;
(3)洗涤
磺化反应后冷却,树脂球由去离子水冲洗至中性,分离获得催化剂树脂,其含水量为40-55%。
2.根据权利要求1所述的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,其特征在于,将苯乙烯、甲基丙烯酸甲酯、二乙烯基苯、致孔剂和引发剂按量加入混合罐,搅拌均匀得油相;聚合釜加入水和聚乙烯醇,升温、搅拌至完全溶解,加入油相,搅拌转速90转/分~100转/分,缓慢升温至80℃聚合反应8~18小时,反应后交替用热水和冷水洗涤,得聚合白球。
3.根据权利要求1所述的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,其特征在于,所述的抽提为:聚合白球加入抽提釜,蒸馏釜加入过量溶剂,蒸馏冷凝至抽提釜,抽提釜混合溶液达到指定高度时排回蒸馏釜,如此反复6-20次,将聚合白球内致孔剂抽提干净。
4.根据权利要求1所述的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,其特征在于,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1:(6~10):(1~3)。
5.根据权利要求2所述的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,其特征在于,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1: 6:1。
6.根据权利要求2所述的甲醇-叔丁醇制备甲基叔丁基醚的醚化催化剂,其特征在于,第(2)步磺化中,白球、发烟硫酸、氯磺酸的质量比为1: 10:3。
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