CN111056949B - 连续反应、再生、活化制苯胺反应装置及反应方法 - Google Patents
连续反应、再生、活化制苯胺反应装置及反应方法 Download PDFInfo
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Abstract
本发明涉及一种连续反应、再生、活化制苯胺反应装置及反应方法,主要解决剂耗高、催化剂容易结焦失活、无法长周期运行等问题。本发明通过一种连续反应、再生、活化制苯胺反应装置及反应方法,利用带有两个流动区的脱气罐高效脱气后,再分别采用再生器在线对结焦催化剂进行再生、活化器在线对催化剂进行活化,达到连续反应、再生与活化的长周期生产的目的,同时分别在流化床反应器、再生器与活化器内设置溅射分离构件,大幅度降低剂耗的技术方案,较好的解决了上述技术问题,可应用于硝基苯加氢制苯胺的工业生产中。
Description
技术领域
本发明涉及一种用于硝基苯加氢制苯胺反应装置及反应方法
背景技术
苯胺是一种重要的基本有机化工原料和精细化工中间体,由苯胺生产的下游产品多达300余种,广泛应用于染料、医药、农药、炸药、香料、橡胶、合成材料等行业。近年来,随着我国和世界范围内聚氨酯工业的迅速崛起,作为其主要原料MDI(4,4-二苯甲烷二异氰酸酯)不可替代的基础原料之一的苯胺,得到了超乎寻常的快速发展。
目前工业化生产苯胺的方法有三种,硝基苯催化加氢法、苯酚氨化法及铁粉还原法。其中铁粉还原法由于生成的苯胺质量较差,逐渐被淘汰。苯酚氨化法则强烈依赖于苯酚的来源。现在的硝基苯催化加氢法为大多数厂家所采用。而硝基苯催化加氢法又分为气相催化加氢工艺与液相催化加氢工艺。硝基苯液相催化加氢工艺为美国杜邦公司首先成功开发,主要是采用贵金属催化剂在无水条件下进行,该工艺有点是反应温度低、催化剂负荷高、寿命长且设备生产能力大,缺点是所需压力高、反应物与催化剂及溶剂必须进行分离,设备操作成本高,催化剂价格昂贵,且催化剂活性过高导致副产物较多。流化床气相催化加氢法是原料硝基苯加热汽化与氢气混合后,进入装有铜-硅胶催化剂的流化床反应器中进行加氢还原反应,该法较好地改善了传热状况,控制了反应温度,避免了局部过热,减少了副反应的生成,延长了催化剂的使用寿命,不足之处是操作较复杂,催化剂磨损大,操作和维修费用较高。
硝基苯气相加氢法制苯胺在国内已有几十年的生产历史,国内不少苯胺生产厂家都采用的是流化床气相催化加氢工艺。
文献CN1528737A公布了一种硝基苯气相加氢制备苯胺的装置及方法。装置包括流化床反应器,设置在反应器底部的反应原料气体入口,设置在该入口上部的第一气体分布器,设置在反应器轴向高度中部的将反应器分为两个催化剂密相区的第二气体分布器,设置在所述反应器外部或内部的分别与上下两个催化剂密相区相连的催化剂溢流装置,同时公布了利用该装置的方法,有效提高了硝基苯转化率与苯胺的选择性。
文献CN1634860A公布了一种苯胺合成流化床中的气体分布器及苯胺合成方法。该发明的气体分布器由输送气体的主管、分管及与相连的分配气体的环形管道,以及设置在环形管道上的向下喷射气体的喷嘴和向上喷射气体的喷嘴构成,同时公布了利用该装置的硝基苯气相加氢制备苯胺的方法,可降低气体分布器区的最高及平均温度,减少催化剂上的结焦,延长催化剂寿命,提高苯胺纯度。
现在的苯胺流化床反应器内部普遍都设置了内构件,用于调整内部的气固流动,但是由于苯胺催化剂的强度较低,非常容易破碎,粒径会随着运行时间逐渐变小,细粉很容易泡入稀相区后增加了旋风分离器的负荷,从而使得催化剂跑损较为严重,随之带来的影响就是反应无法长周期运行,需要停车补剂等各种问题。
现有技术的制备苯胺的流化床反应器中,反应气体原料由底部的分布器进入流化床中,因此在底部的分布器区域附近的硝基苯浓度较高,反应相对较为激烈。而硝基苯加氢的反应属于强放热反应,因此分布器附近的区域热量过大,形成局部的高温区域。现有的流化床的传质传热水平还没有完全达到能够及时将该处的过度的热量传递出去的能力,因此一方面该处容易产生副产品、影响苯胺的产品纯度;另外一方面,也极为容易将催化剂积碳,加快催化剂的失活。
综上所述,苯胺流化床反应器内细粉的存在是不可避免的,能够减少催化剂损耗一方面是提高旋风分离器的效率,另外一方面是降低旋风分离器的入口颗粒浓度(即稀相区的颗粒浓度)。由于现实旋风分离器的技术特点,提高其效率已经很难;苯胺流化床反应器内催化剂的部分失活是不可避免的,能够及时、在线地完成苯胺催化剂的再生、活化是解决苯胺反应器长周期运行的关键,本发明有针对性地解决了这些问题。
发明内容
本发明主要解决的技术问题之一是现有技术中硝基苯加氢制苯胺工业装置内剂耗高、催化剂容易结焦失活、无法长周期运行等问题,提供一种新的硝基苯加氢制苯胺的装置及方法。该装置与方法用于硝基苯加氢的工艺中,有效降低了剂耗,同时连续、在线解决了结焦催化剂的再生与活化的问题,提高了反应效率,延长了装置的长周期运行。
本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的反应方法。
为解决上述技术问题之一,本发明采用的技术方案如下:一种连续反应、再生、活化制苯胺反应装置,主要设备包括:流化床反应器3、待生脱气罐12、再生器13、待活化脱气罐16、活化器19与提升管21,其中流化床反应器3内包括下方的密相反应区4、处于中段的颗粒溅射过渡区5以及处于上方的稀相区7,待生脱气罐12分别于流化床反应器3、再生器13相连通,待活化脱气罐16分别于再生器13、活化器19相连通,提升管21分别与活化器19、流化床反应器3相连通。
上述技术方案中,所述流化床反应器3内设有气体分布器2、换热管件11、溅射分离构件6以及旋风分离器9。所述待生脱气罐12中包括脱气下行逆流区31与脱气上行并流区32,且在脱气下行逆流区31与脱气上行并流区32内分别设置脱气挡板构件33;活化脱气罐16中包括再生脱气下行逆流区51与再生脱气上行并流区52,且在再生脱气下行逆流区51与再生脱气上行并流区52内分别设置脱气挡板构件33。所述脱气挡板构件33由多组整流体经过连接件连接而成,所述整流体为流线型整流体41、菱形整流体42、斜挡板错流式整流体43中的一种或几种。
为解决上述问题之二,本发明采用的技术方案如下:一种连续反应、再生、活化制苯胺反应方法,采用上述的反应装置,包括如下几个步骤:
a、汽化后的硝基苯与氢气原料进入气室后经过气体分布器2进入流化床反应器3中,推动反应器内的催化剂流化后,在密相反应区4中进行反应,生产苯胺产物,部分气相形成气泡,在密相反应区4的顶端发生颗粒溅射,形成颗粒溅射过渡区5,溅射的颗粒经过溅射分离构件6的有效拦截后返回密相反应区4中继续进行催化作用,小部分未被拦截的颗粒穿过溅射分离构件6的通道进入稀相区7中经过旋风分离器9进行分离,颗粒返回密相反应区4,粗产品气8流出流化床反应器3进入后续分离工段;
b、在反应过程中催化剂形成部分结焦后,结焦催化剂经过待生脱气罐12脱气后进入再生器13中通氧进行烧碳再生;
c、经过再生的催化剂再经过待活化脱气罐16脱气后进入活化器19中通入氢气进行活化,活化后的催化剂进入提升管21后经提升返回流化床反应器3中继续进行催化作用。
上述技术方案中,所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为三氧化二铝或二氧化硅,催化剂平均粒径为50-600μm,且低于80μm以下的颗粒含量不小于2%。所述流化床反应器3内反应条件为:表观气速为0.2-0.8m/s,氢气与硝基苯的摩尔比为6-21,密相反应区4内平均反应温度控制在220-280℃,气体分布器2附近的温度控制在320℃以下,密相反应区4内反应压力为0.05-1MPa。所述再生器13内反应条件为:表观气速为0.1-0.6m/s,平均再生温度为350-450℃;所述活化器19内反应条件为:表观气速为0.1-0.6m/s,平均活化温度为200-250℃。
上述技术方案中,所述待生脱气罐12内脱气下行逆流区31与脱气上行并流区32表观气速之比为1/15-1,脱气剂为氮气、水蒸气、二氧化碳、甲烷、氩气中的一种或几种混合物,置换出由流化床反应器3中带出的气体组分。所述待活化脱气罐16内再生脱气下行逆流区51与再生脱气上行并流区52的表观气速之比为1/15-1,脱气剂为氮气、水蒸气、二氧化碳、氧气、氩气中的一种或几种混合物,置换出由再生器13中带出的含氧气体组分。
本发明中,脱气效率是指脱气结束后留在脱气罐中脱气剂的气体量与脱气罐内全部气体总量之比。脱气效率约接近1,说明脱气的效果越好。作为安全考虑,本发明中待生脱气罐与待活化脱气罐的脱气效率一般需达到90%以上,优选为94%以上。而本发明中的两区脱气罐具有接触面积大,传质传热水平高,脱气效率满足生产安全的需求。
采用本发明的技术方案,通过一种连续反应、再生、活化制苯胺反应装置及反应方法,利用两个两区脱气罐高效脱气后,再分别采用再生器在线对结焦催化剂进行再生、活化器在线对催化剂进行活化,达到连续反应、再生与活化的长周期生产的目的,采用上述装置及方法在硝基苯加氢制苯胺中,脱气效率提高了7%,流化床反应器内催化剂积碳量可控,取得了较好的技术效果。
附图说明
连续反应、再生、活化制苯胺反应装置及反应方法
图1为本发明所述连续反应、再生、活化制苯胺反应装置及流程示意图:
图1中,1为汽化后的硝基苯与氢气原料;2为气体分布器;3为流化床反应器;4为密相反应区;5为颗粒溅射过渡区;6为溅射分离构件;7为稀相区;8为粗产品气;9为旋风分离器;10为料腿;11为换热管件;12为待生脱气罐;13为再生器;14为再生器溅射分离构件;15为再生流化气;16为待活化脱气罐;17为活化流化气;18为活化器溅射分离构件;19为活化器;20为提升气;21为提升管;31为脱气下行逆流区;32为脱气上行并流区;33为脱气挡板构件;41为流线型整流体;42为菱形整流体;43为斜挡板错流式整流体;51为再生脱气下行逆流区;52为再生脱气上行并流区。
汽化后的硝基苯与氢气原料进入气室后经过气体分布器2进入流化床反应器3中,推动反应器内的催化剂流化后,在密相反应区4中进行反应,生产苯胺产物,部分气相形成气泡,在密相反应区4的顶端发生颗粒溅射,形成颗粒溅射过渡区5,溅射的颗粒经过溅射分离构件6的有效拦截后返回密相反应区4中继续进行催化作用,小部分未被拦截的颗粒穿过溅射分离构件6的通道进入稀相区7中经过旋风分离器9进行分离,颗粒返回密相反应区4,粗产品气8流出流化床反应器3进入后续分离工段;在反应过程中催化剂形成部分结焦后,结焦催化剂经过待生脱气罐12脱气后进入再生器13中通氧进行烧碳再生;经过再生的催化剂再经过待活化脱气罐16脱气后进入活化器19中通入氢气进行活化,活化后的催化剂进入提升管21后经提升返回流化床反应器3中继续进行催化作用。
图2为本发明所述待生脱气罐的示意图。
图2中,3为流化床反应器;12为待生脱气罐;13为再生器;31为脱气下行逆流区;32为脱气上行并流区;33为脱气挡板构件。实心三角箭头为气相主要流动方向;空心三角箭头为颗粒主要流动方向。
图3为本发明所述待活化脱气罐的示意图。
图3中,13为再生器;12为待生脱气罐;16为待活化脱气罐;19为活化器;51为再生脱气下行逆流区;52为再生脱气上行并流区;33为脱气挡板构件。实心三角箭头为气相主要流动方向;空心三角箭头为颗粒主要流动方向。
图4为本发明的待生脱气罐与待活化脱气罐的第一实施例的示意图。
图4中,33为脱气挡板构件;41为流线型整流体。实心三角箭头为气相主要流动方向;空心三角箭头为颗粒主要流动方向。
图5为本发明的待生脱气罐与待活化脱气罐的第二实施例的示意图。
图5中,33为脱气挡板构件;42为菱形整流体。实心三角箭头为气相主要流动方向;空心三角箭头为颗粒主要流动方向。
图6为本发明的待生脱气罐与待活化脱气罐的第三实施例的示意图。
图6中,33为脱气挡板构件;43为斜挡板错流式整流体。实心三角箭头为气相主要流动方向;空心三角箭头为颗粒主要流动方向。
下面通过实施例对本发明作进一步的阐述,但不仅限于本实施例。
具体实施方式
【实施例1】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.7%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表1。
【实施例2】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图5所示的两区脱气罐,所述脱气挡板构件的整流体为菱形整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为97.3%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表1。
【实施例3】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图6所示的两区脱气罐,所述脱气挡板构件的整流体为斜挡板错流式整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为97.1%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表1。
【实施例4】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.1m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.7%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.7%,结果详见表1。
【实施例5】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.6m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.7%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.3%,结果详见表1。
【实施例6】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为350℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.7%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于1%,结果详见表2。
【实施例7】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为450℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/5,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/5,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.7%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.15%,结果详见表2。
【实施例8】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1/15,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1/15,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为98.2%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表2。
【实施例9】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐如图4所示的两区脱气罐,所述脱气挡板构件的整流体为流线型整流体。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。待生脱气罐内脱气下行逆流区与脱气上行并流区表观气速之比为1,脱气剂为氮气;再生脱气下行逆流区与再生脱气上行并流区的表观气速之比为1,脱气剂为氮气。
待生脱气罐与待活化脱气罐脱气效率均为97.6%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表2。
【比较例1】
如图1所示的硝基苯加氢制苯胺装置,流化床反应器直径为45mm。在反应器内部设置有溅射分离构件。所述待生脱气罐与待活化脱气罐为现有技术的脱气罐,只有一个流动区。
所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%。所述流化床反应器内反应条件为:表观气速为0.4m/s,氢气与硝基苯的摩尔比为11,密相反应区内平均反应温度控制在240℃,密相反应区内反应压力为0.1MPa。所述再生器内反应条件为:表观气速为0.3m/s,平均再生温度为410℃;所述活化器内反应条件为:表观气速为0.3m/s,平均活化温度为220℃。
待生脱气罐与待活化脱气罐脱气效率均为91.5%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量可控制在不大于0.5%,结果详见表2。
【比较例2】
现有技术的硝基苯加氢制苯胺流化床反应器装置,不设再生器与活化器。流化床反应器直径为45mm。所用催化剂为金属负载型催化剂,以铜为主要活性组分,载体为二氧化硅,催化剂平均粒径为400μm,且低于80μm以下的颗粒含量为6%,高空速条件(0.9h-1)下反应时间为90分钟时的积碳量为3.7%,结果详见表2。
显然,采用本发明的装置及方法,可以达到解决催化剂容易结焦失活、无法长周期运行等问题,可用于硝基苯加氢制苯胺的工业生产中。
表1
表2
表3
Claims (9)
1.一种连续反应、再生、活化制苯胺反应装置,包括:流化床反应器(3)、待生脱气罐(12)、再生器(13)、待活化脱气罐(16)、活化器(19)与提升管(21),其中流化床反应器(3)内包括下方的密相反应区(4)、处于中段的颗粒溅射过渡区(5)以及处于上方的稀相区(7),待生脱气罐(12)分别与流化床反应器(3)、再生器(13)相连通,待活化脱气罐(16)分别与再生器(13)、活化器(19)相连通,提升管(21)分别与活化器(19)、流化床反应器(3)相连通;
所述待生脱气罐(12)中包括脱气下行逆流区(31)与脱气上行并流区(32)构成左、右两个区,且在脱气下行逆流区(31)与脱气上行并流区(32)内分别设置脱气挡板构件(33);待活化脱气罐(16)中包括再生脱气下行逆流区(51)与再生脱气上行并流区(52),且在再生脱气下行逆流区(51)与再生脱气上行并流区(52)内分别设置脱气挡板构件(33)。
2.根据权利要求1所述连续反应、再生、活化制苯胺反应装置,其特征在于所述流化床反应器(3)内设有气体分布器(2)、换热管件(11)、溅射分离构件(6)以及旋风分离器(9)。
3.根据权利要求1所述连续反应、再生、活化制苯胺反应装置,其特征在于所述脱气挡板构件(33)由多组整流体经过连接件连接而成,所述整流体为流线型整流体(41)、菱形整流体(42)、斜挡板错流式整流体(43)中的一种或几种。
4.一种连续反应、再生、活化制苯胺反应方法,采用权利要求1~3的装置,包括如下步骤:
(a)、汽化后的硝基苯与氢气原料进入气室后经过气体分布器(2)进入流化床反应器(3)中,推动反应器内的催化剂流化后,在密相反应区(4)中进行反应,生产苯胺产物,部分气相形成气泡,在密相反应区(4)的顶端发生颗粒溅射,形成颗粒溅射过渡区(5),溅射的颗粒经过溅射分离构件(6)的有效拦截后返回密相反应区(4)中继续进行催化作用,小部分未被拦截的颗粒穿过溅射分离构件(6)的通道进入稀相区(7)中经过旋风分离器(9)进行分离,颗粒返回密相反应区(4),粗产品气(8)流出流化床反应器(3)进入后续分离工段;
(b)、在反应过程中催化剂形成部分结焦后,结焦催化剂经过待生脱气罐(12)脱气后进入再生器(13)中通氧进行烧碳再生,所述待生脱气罐(12)内脱气下行逆流区(31)与脱气上行并流区(32)表观气速之比为1/15-1;
(c)、经过再生的催化剂再经过待活化脱气罐(16)脱气后进入活化器(19)中通入氢气进行活化,活化后的催化剂进入提升管(21)后经提升返回流化床反应器(3)中继续进行催化作用。
5.根据权利要求4所述连续反应、再生、活化制苯胺反应方法,其特征在于所述催化剂为金属负载型催化剂,以铜为主要活性组分,载体为三氧化二铝或二氧化硅,催化剂平均粒径为50-600μm,且低于80μm以下的颗粒含量不小于2%。
6.根据权利要求4所述连续反应、再生、活化制苯胺反应方法,其特征在于所述流化床反应器(3)内反应条件为:表观气速为0.2-0.8m/s,氢气与硝基苯的摩尔比为6-21,密相反应区(4)内平均反应温度控制在220-280℃,气体分布器(2)附近的温度控制在320℃以下,密相反应区(4)内反应压力为0.05-1MPa。
7.根据权利要求4所述连续反应、再生、活化制苯胺反应方法,其特征在于所述再生器(13)内反应条件为:表观气速为0.1-0.6m/s,平均再生温度为350-450℃;所述活化器(19)内反应条件为:表观气速为0.1-0.6m/s,平均活化温度为200-250℃。
8.根据权利要求4所述连续反应、再生、活化制苯胺反应方法,其特征在于所述脱气剂为氮气、水蒸气、二氧化碳、甲烷、氩气中的一种或几种混合物,置换出由流化床反应器(3)中带出的气体组分。
9.根据权利要求4所述连续反应、再生、活化制苯胺反应方法,其特征在于所述待活化脱气罐(16)内再生脱气下行逆流区(51)与再生脱气上行并流区(52)的表观气速之比为1/15-1,脱气剂为氮气、水蒸气、二氧化碳、氧气、氩气中的一种或几种混合物,置换出由再生器(13)中带出的含氧气体组分。
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CN111056949B (zh) * | 2018-10-17 | 2021-05-11 | 中国石油化工股份有限公司 | 连续反应、再生、活化制苯胺反应装置及反应方法 |
CN114426489B (zh) * | 2020-10-15 | 2024-07-30 | 中国石油化工股份有限公司 | 硝基苯加氢制苯胺的装置和方法 |
CN114649496B (zh) * | 2022-03-28 | 2023-06-27 | 中国石油大学(北京) | 一种硅复合材料的制备装置和方法 |
CN117654380B (zh) * | 2024-02-02 | 2024-04-23 | 山东东方宏业化工有限公司 | 一种废旧有机物裂解气综合回收用催化加氢裂解系统 |
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EP3868474A4 (en) | 2022-08-24 |
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JP2022505350A (ja) | 2022-01-14 |
EP3868474A1 (en) | 2021-08-25 |
WO2020078411A1 (zh) | 2020-04-23 |
TW202031635A (zh) | 2020-09-01 |
KR20210077733A (ko) | 2021-06-25 |
BR112021007336A2 (pt) | 2021-07-20 |
TW202100239A (zh) | 2021-01-01 |
WO2020078413A1 (zh) | 2020-04-23 |
JP2022512758A (ja) | 2022-02-07 |
EP3868738A1 (en) | 2021-08-25 |
CN111056949A (zh) | 2020-04-24 |
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