CN112691706A - 一种乙醇制乙腈催化剂的再生方法 - Google Patents
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Abstract
本发明公开了一种乙醇制乙腈催化剂的再生方法。本方法再生的催化剂具有化学性能衰减少,可在线操作等特点。本发明通过采用包括以下步骤:使用惰性气体充满催化剂的再生系统;将需要再生的催化剂置于一定的温度下焙烧,同时使用一定流速的含有有机胺、氧气等、水蒸气、乙醇的一种或多种气体作为活化气分5阶段对系统进行吹扫(第1~3阶段为不同体积浓度比例的氧气和有机胺混合气,第4阶段为水蒸气,第5阶段为水蒸气和乙醇的混合气);当每个阶段结束后活化气出气组成和进气一致时,继续吹扫一定时间后,再生完成。本发明催化剂再生效果好,操作简单,工业应用前景广阔。
Description
技术领域
本发明属于催化剂再生技术领域,尤其涉及乙醇制乙腈催化剂的再生。
背景技术
乙腈是一种有机腈,最明显的功用就是做溶剂,包括合成纤维的溶剂、一些特殊涂料的溶剂、除去焦油和酚等物质的溶剂、抽提丁二烯的溶剂、从动植物油中抽提脂肪酸的溶剂、制造维生素B1溶剂、氨基酸的活性介质溶剂、可代替氯化溶剂、丙烯腈合成纤维的溶剂。在合成橡胶工业中做C4馏分的抽提剂、丁二烯和脂肪酸的萃取剂、酒精变性剂。在纺织染色、乙烯基涂料、亮化工程、香料制造和感光材料制造中也有许多用途。
申请号为200910031481.1的专利介绍了一种乙醇氨化法合成乙腈的方法,原料乙醇与氨分别被汽化并预热至100-200℃,两种原料气混合反应得到乙腈,反应采用二氧化硅为载体的乙醇氨化催化剂,两种原料的反应摩尔比乙醇:氨=1:0.8-1.2。
目前尚未有一种乙醇制乙腈催化剂的再生方法,本发明填补了该项空白。本发明公开的方法,操作简单,催化剂再生后活性高,适合在线再生操作。
发明内容
本发明公开了一种乙醇制乙腈催化剂的再生方法。本方法操作简单,催化剂再生后活性高,适合在线再生操作。
本发明提供一种乙醇制乙腈催化剂的再生方法,其特征在于,使用惰性气体充满催化剂的再生系统,排出之前系统的反应涉及的气体料液等;将需要再生的催化剂置于一定的温度下焙烧,焙烧温度范围400~800℃;使用一定流速的含有有机胺、氧气、水蒸气、乙醇的一种或多种气体作为活化气分5阶段对系统进行吹扫;当5个阶段结束后出气组成和进气一致,继续吹扫0~24h时间后,再生完成。
充满系统的惰性气体为氮气、氩气、氦气等的一种或多种,优为氮气。
焙烧温度高于反应涉及气体料液的最高温度,温度范围400~800℃,优为450~600℃。
作为吹扫气体的活化气至少含有有机胺、氧气、水蒸气、乙醇等的一种或多种,可以选择含有部分惰性气体,如氮气、氩气、氦气等,优为不选择惰性气体。
有机胺为伯胺、仲胺、叔胺的一种或多种,如甲胺、乙胺、乙二胺等。
吹扫分为5个阶段:第1阶段氧气的体积浓度5.0~12.5%,有机胺体积浓度87.5~95%;第2阶段氧气的体积浓度12.5~59.7%,有机胺体积浓度40.3~87.5%;第3阶段氧气的体积浓度59.7~79.2%,有机胺体积浓度20.8~40.3%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度20.3~78.8%,乙醇体积浓度21.2~79.7%。
第1阶段~第5阶段,混合气体积空速0.5~10h-1,优为1~3h-1。
当5个阶段结束后出气组成和进气一致,继续吹扫时间0~24h,优为1~2h。
所述催化剂再生气体吹扫压力优为常压。
具体实施方式
通过实施例进一步说明本发明实施方式和所产生的效果,但本发明的保护范围并不限于实施例所列的内容。需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的特征可以相互组合。
实验室一种乙醇制乙腈实验中,单程转化率降低5%或选择性降低2%时,判定催化剂已失活,需要再生。使用氧分析仪对尾气进行检测,当尾气氧含量与进气氧含量一致时,判定出气组成和进气组成一致。
实施例1
根据专利CN 102120589 B实施例1的方法制备S-1催化剂。
将质量分数5%的四丙基氢氧化铵水溶液160L放入反应釜中,开启搅拌桨,转速为50转/min。将正硅酸乙酯和乙醇以摩尔比20∶1混合的混合液以5L/h的速度加入釜中,完成后继续搅拌10min,关闭釜盖。以1℃/min的速度升温至100℃,反应80h后停止,降至室温,所得反应液用膜过滤方法,用去离子水洗涤至滤液的pH=10-11去除杂质,去除杂质后的反应液干燥后,在500℃下焙烧8h,得到分子筛原粉;所述四丙基氢氧化铵与正硅酸乙酯的摩尔比为1∶32;将40kg分子筛加入60kg质量分数为10%的硅溶胶、100g聚乙二醇2000、10kg浓氨水、1kg田箐粉和1kg活性炭粉末,用捏合机捏合后挤条成型,然后于500℃下焙烧8h后取出。将焙烧后的产物依次放入质量比为2∶2∶96的NH3-NH3NO3-H2O的混合溶液和质量分数为0.01%的氢氟酸水溶液中于80℃下处理6h,用去离子水洗涤至洗出液的电导率在100μS/cm以下;取出后干燥且再次于500℃下焙烧8h,取出封装,即制成一种S-1全硅分子筛。S-1分子筛粒径为100-200nm。分子筛条形,直径3mm,长度10mm,作为载体A。
实施例2
根据专利CN 101602693 B实施例介绍的制备催化剂。取0.04g氢氧化钾、1.09g氢氧化镁、1.41g氧化锡、7.35g钼酸铵、259.64g催化剂A,1038.58g水一同放置旋转蒸发仪升温至60℃,旋转4h后减压抽干水分;滤饼在120℃下烘干,成型,500℃焙烧8h,制备全硅载体的K0.2Mg6Sn3Mo12O48.1催化剂,编号为催化剂B,压片碾碎筛分出20~40目催化剂进行评价实验。
实施例3
取B催化剂50g装填于固定床中,反应管内径16mm。原料乙醇与氨分别被汽化并预热至200℃,两种原料气混合之后,从反应器上部进入原料分布器后,进入催化剂床层内,两种原料的反应摩尔比是乙醇∶氨=1∶1。反应液冷却收集,取样中控。乙醇转化率96.3%,乙腈选择性78.7%。运行98h后,乙醇转化率95.4%,乙腈选择性76.6%。失活催化剂编号C。
实施例4
催化剂C在线再生活化,首先在420℃条件下,使用氮气吹扫系统2h,体积空速3h-1。系统升温至600℃,在此过程中保持氮气吹扫。温度达到600℃时,使用活化气对系统进行吹扫,吹扫分为4个阶段:第1阶段氧气的体积浓度10%,氮气体积浓度90%;第2阶段氧气的体积浓度40%,氮气体积浓度60%;第3阶段氧气的体积浓度60%,氮气体积浓度40%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度40.2%,乙醇体积浓度59.8%。活化气体积空速2h-1,当进气与出气成分一致时,继续吹扫1h。按照实施例3方法对再生活化后的催化剂进行评价,乙醇转化率96.1%,乙腈选择性77.9%。
实施例5
催化剂C在线再生活化,首先在420℃条件下,使用氮气吹扫系统2h,体积空速3h-1。系统升温至600℃,在此过程中保持氮气吹扫。温度达到600℃时,使用活化气对系统进行吹扫,吹扫分为4个阶段:第1阶段氧气的体积浓度10%,甲胺体积浓度90%;第2阶段氧气的体积浓度40%,甲胺体积浓度60%;第3阶段氧气的体积浓度60%,甲胺体积浓度40%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度40.2%,乙醇体积浓度59.8%。活化气体积空速2h-1,当进气与出气成分一致时,继续吹扫1h。按照实施例3方法对再生活化后的催化剂进行评价,乙醇转化率96.2%,乙腈选择性78.5%。
实施例6
催化剂C在线再生活化,首先在420℃条件下,使用氮气吹扫系统2h,体积空速3h-1。系统升温至600℃,在此过程中保持氮气吹扫。温度达到600℃时,使用活化气对系统进行吹扫,吹扫分为4个阶段:第1阶段氧气的体积浓度5%,甲胺体积浓度95%;第2阶段氧气的体积浓度12.5%,甲胺体积浓度87.5%;第3阶段氧气的体积浓度60.0%,甲胺体积浓度40.0%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度40.2%,乙醇体积浓度59.8%。活化气体积空速2h-1,当进气与出气成分一致时,继续吹扫1h。按照实施例3方法对再生活化后的催化剂进行评价,乙醇转化率96.1%,乙腈选择性78.3%。
实施例7
催化剂C在线再生活化,首先在420℃条件下,使用氮气吹扫系统2h,体积空速3h-1。系统升温至600℃,在此过程中保持氮气吹扫。温度达到600℃时,使用活化气对系统进行吹扫,吹扫分为4个阶段:第1阶段氧气的体积浓度5%,甲胺体积浓度85%,氮气体积浓度10%;第2阶段氧气的体积浓度12.5%,甲胺体积浓度77.5%,氮气体积浓度10%;第3阶段氧气的体积浓度60.5%,甲胺体积浓度29.5%,氮气体积浓度10%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度40.2%,乙醇体积浓度59.8%。活化气体积空速2h-1,当进气与出气成分一致时,继续吹扫1h。按照实施例3方法对再生活化后的催化剂进行评价,乙醇转化率96.0%,乙腈选择性78.1%。
实施例8
催化剂C在线再生活化,首先在420℃条件下,使用氮气吹扫系统2h,体积空速3h-1。系统升温至600℃,在此过程中保持氮气吹扫。温度达到600℃时,使用活化气对系统进行吹扫,吹扫分为4个阶段:第1阶段氧气的体积浓度5%,甲胺体积浓度85%,氮气体积浓度10%;第2阶段氧气的体积浓度12.5%,甲胺体积浓度77.5%,氮气体积浓度10%;第3阶段氧气的体积浓度60.5%,甲胺体积浓度29.5%,氮气体积浓度10%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度50.2%,乙醇体积浓度49.8%。活化气体积空速2h-1,当进气与出气成分一致时,继续吹扫1h。按照实施例3方法对再生活化后的催化剂进行评价,乙醇转化率96.1%,乙腈选择性78.3%。
以上所述,均是本发明的具体实施例,本发明并不受以上实施例的限制。任一了解熟悉本行业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质,在本发明的精神和原则之内,对以上实施例所作的任何简单的修改、等同替换与改进等,均仍属于本发明技术方案的保护范围之内。
Claims (9)
1.一种乙醇制乙腈催化剂的再生方法,其特征在于,使用惰性气体充满催化剂的再生系统;将需要再生的催化剂置于一定的温度下焙烧,焙烧温度范围400~800℃;使用一定流速的含有有机胺、氧气、水蒸气、乙醇的一种或多种气体作为活化气分5个阶段对系统进行吹扫;当每个阶段结束后活化气出气组成和进气一致时,继续吹扫0~24h时间后,再生完成。
2.根据权利要求1所述的方法,其特征在于,活化气至少含有有机胺、氧气、水蒸气、乙醇等的一种或多种。
3.根据权利要求2所述的方法,其特征在于,所述活化气还含有惰性气体。
4.根据权利要求3所述的方法,其特征在于,所述惰性气体选自氮气、氩气、氦气。
5.根据权利要求1所述的方法,其特征在于,活化气吹扫分为5个阶段:第1阶段氧气的体积浓度5.0~12.5%,有机胺体积浓度87.5~95%;第2阶段氧气的体积浓度12.5~59.7%,有机胺体积浓度40.3~87.5%;第3阶段氧气的体积浓度59.7~79.2%,有机胺体积浓度20.8~40.3%;第4阶段,水蒸气体积浓度100%;第5阶段,水蒸气体积浓度20.3~78.8%,乙醇体积浓度21.2~79.7%。
6.根据权利要求1或5所述的方法,其特征在于,焙烧温度高于反应涉及气体料液的最高温度,第1阶段到第5阶段,温度范围400~800℃。
7.根据权利要求1或5所述的方法,其特征在于,焙烧温度高于反应涉及气体料液的最高温度,第1阶段到第5阶段,温度范围400~600℃。
8.根据权利要求1或5所述的方法,其特征在于,第1阶段~第5阶段,活化气体积空速0.5~10h-1。
9.根据权利要求1所述的方法,其特征在于,当每个阶段活化气吹扫结束后且出气组成和进气一致时,继续吹扫时间为1~2h。
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