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CN105143099A - 用于烃类气体部分氧化的反应器 - Google Patents

用于烃类气体部分氧化的反应器 Download PDF

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CN105143099A
CN105143099A CN201480021330.7A CN201480021330A CN105143099A CN 105143099 A CN105143099 A CN 105143099A CN 201480021330 A CN201480021330 A CN 201480021330A CN 105143099 A CN105143099 A CN 105143099A
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S·E·多林斯基
A·A·杰尔加乔夫
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Abstract

用于烃类原料部分氧化的反应器可在有机合成、石油和天然气工业中用来生成合成气或富氢气体。反应器包括带有反应产物从反应器出料的出口和至少一个将原料或原料组分送入催化剂套筒的入口的外壳，所述催化剂套筒位于反应器内、与外壳有一个间隙、装填有催化剂且其下部包括产物出口，其特征在于催化剂套筒配备至少部分毗邻催化剂套筒的圆柱壁的夹套，所述催化剂套筒做成在所述毗邻区域有开口孔，反应器配备将冷却催化剂套筒的冷却剂送入夹套的入口，所述冷却剂冷却催化剂套筒、然后穿过圆柱壁的孔进入催化剂套筒。催化剂套筒的冷却使得制造催化剂套筒材料的耐热和耐腐蚀规格要求得以降低。

Description

用于烃类气体部分氧化的反应器
本发明涉及用于烃类气体通过水蒸汽-氧气重整工艺进行氧化转化以得到化学工业用氢气或合成气的接触式设备。
已发现在氧气和水蒸汽存在下烃类原料的催化部分氧化反应(水蒸汽-氧气重整)是一种很有前途的方法，因为相比由游离氧所进行的部分氧化反应，它允许在更低温度下获得合成气，且如果其原料具有一定组成，在自热重整的情况下与水蒸汽重整一样不需要向反应区输入热量。
烃原料的水蒸汽-氧气重整反应按如下所述实施。将加热的各个组分-烃原料、水蒸汽和氧气或含氧气体(通常为空气或富氧空气)进行混合并送入其中放置有催化剂的反应器中。原料与催化剂的接触区域形成反应区。在反应区上部发生甲烷氧化的快速放热反应且与其一起的其它烃类发生烃蒸汽重整的吸热反应，后者在下游料流中份额增加从而降低了催化剂床出口处的温度。沿催化剂床层高度的温度分布在前部床层(10％至15％的总高度)具有很明显的驼峰。理论上，在部分氧化催化剂的前部床层中气体混合物的加热温度超过1200℃，并且只能通过开始高吸热的水蒸汽分子离解反应而受到限制。反应产物-氢气、碳氧化物和水蒸汽的混合物以不高于1000℃的温度从反应区移出、冷却、与水分离并送去进一步的处理，例如，借助费-托工艺的烃合成。在一些情况下，产物冷却步骤包括通过与水直接热交换或在特定装置中或在反应器中反应区下游的淬冷区进行淬冷处理(US5358696，US6797022)。
用于将烃类原料转化成合成气的催化剂可以松散材料形式，或是具有延展外表面(其上沉积有催化活性基质层)的陶瓷或金属合金制成的导热元件的块状形式(包括板、带、发泡材料)。催化剂床温度升高会加速其结构劣化和降低催化活性。
催化剂过热问题在等温反应器中或多或少地得到成功解决。为在反应区中创建接近等温的条件，使用了管式热交换器型反应器(如专利US8216531中的管式反应器)、导热元件(如专利RU2175799中反应器内催化剂层中的导热板)以及在反应区中特别设置的传质和传热条件(US4888131中的流化床，专利申请WO2013008020中反应器流动的湍流流态)。
如果水蒸汽-氧气重整催化剂具有足够的耐热性且其前部床层温度升至1200℃前不会导致其快速失活和不希望反应器设计及其操作系统的复杂性(如用在边远地区合成气生产的成套设备的情况下)，利用导热催化剂载体和催化剂层中特定的导热元件似乎对整个反应区的温度均衡是足够的。可透气的块状催化剂可被放置在一个金属套筒(杯)内，其外径小于所述反应器外壳的内径，外壳与套筒的间隙填充有隔热材料。具有这样元件的反应器公开于发明RU2012107731的申请中作为原型。制作套筒的金属合金在反应区工作温度即1200℃和更高温度的条件下应该足够耐热和耐腐蚀，但这种合金成本很高。催化剂套筒壁温度降低到1000℃和更低将允许其由相对廉价的耐热合金如ХН45Ю级合金来制造，高至1200℃温度下它是耐腐蚀的。
本发明要解决的技术任务是-将催化剂套筒壁温度降低至1000℃及更低。技术措施是将催化剂套筒用冷却剂-水蒸汽和/或反应条件下惰性的气体或这些气体的混合物如氮气、合成气进行冷却。供应夹套的冷却剂冷却催化剂套筒筒壁并穿过催化剂套筒壁的开口孔进入套筒内的催化剂层。
所提出的用于烃类原料部分氧化的反应器包括带有一个反应产物出口和至少一个将原料或原料组分送入催化剂套筒的入口的外壳，所述催化剂套筒位于反应器内、与外壳有一个间隙、装填有催化剂且其下部包括产物出口，其特征在于催化剂套筒配备至少部分毗邻催化剂套筒筒壁的夹套，所述催化剂套筒筒壁做成在所述毗邻区域有开口孔，和反应器配备将冷却催化剂套筒的冷却剂送入夹套的入口，然后穿过筒壁的孔进入催化剂套筒。
冷却催化剂套筒的夹套位于其筒壁外侧且至少部分与其表面毗邻。所述夹套可包住催化剂套筒筒壁的全部或其上面最热的部分。通过与冷却剂直接接触而被冷的催化剂套筒筒壁被做成沿整个高度或仅上部-催化剂的温度超过1000℃的区域带有开口孔。必须要对孔尺寸、孔数量，孔之间的距离和供应催化剂套筒夹套的冷却剂量进行选择以保证催化剂套筒壁的温度不高于所定义的限定值。例如，催化剂套筒壁的温度至少降到1000℃的情况下，其可以使用ХН45Ю级钢来制造，ХН45Ю级钢在高至1200℃温度下是耐腐蚀的。通过催化剂套筒筒壁开口孔流入催化剂层的冷却剂可避免催化剂套筒筒壁与反应混合物的氧在此区域内发生接触从而抑制材料的腐蚀。
可以使用水蒸汽或反应器中得到的合成气作为冷却剂，且可在后面的反应器产物处理阶段冷却下来。优选利用水蒸汽，其进入催化剂套筒与其中装填的催化剂进行接触并参与烃类原料的蒸汽重整反应。夹套配有至少一个冷却剂入口。
烃类原料和其部分氧化反应所必需的组分-氧气或含氧气体、水、有时需要的二氧化碳-以单一的混合料流形式或原料混合物或各个组分采用分布式入口的方式被送入反应器。原料供应的方式不涉及本发明的实质内容。
图1代表一个用于烃类气体部分氧化的反应器的方案，所述反应器沿催化剂套筒全高度带有冷却夹套。配备夹套5的催化剂套筒4放置在反应器外壳1内，其间隙7填充有隔热材料。催化剂套筒4中放置用于烃类原料部分氧化的催化剂3。催化剂套筒筒壁做成有开口孔6且其底部配备产物从催化剂套筒出料的出口9。反应器配备原料(原料混合物)进入催化剂套筒4的入口2、产物从反应器出料的出口10以及冷却剂进入催化剂套筒夹套的入口8。
反应器按如下所述操作。加热的原料混合物通过原料入口进入催化剂套筒，与放置其中的催化剂进行接触以形成反应产物。冷却剂通过入口进入催化剂套筒夹套、将其冷却并穿过催化剂套筒筒壁的孔进入到里面并与反应介质混合。含有冷却剂或其与催化剂接触时转化反应产物的产物料流借助催化剂套筒的产物出口从催化剂套筒流出，并借助反应器出口从反应器流出，然后送去进行包括冷却的进一步处理。
图2代表一个用于烃类气体部分氧化的反应器的方案，所述反应器在催化剂套筒上部区域带有冷却夹套并具有反应产物冷却室。配有夹套5的催化剂套筒4放置在反应器外壳1内，其间隙7填充有隔热材料。催化剂套筒4中放置用于烃类原料部分氧化的催化剂3。催化剂套筒筒壁做成有开口孔6且其底部配备有产物从催化剂套筒进入位于反应容器下游的反应产物冷却室13的出口9。催化剂套筒夹套5配备有冷却剂入口8。反应器配有原料(原料混合物)进入催化剂套筒4的入口2、产物从反应器出料的出口10、冷却剂进入催化剂套筒夹套的入口8以及进入反应产物冷却室的水入口11和喷淋气体入口12。
反应器按如下所述操作。加热的原料混合物通过原料入口进入催化剂套筒，与放置其中的催化剂进行接触以形成反应产物。冷却剂通过入口进入催化剂套筒夹套、将其冷却并穿过催化剂套筒筒壁的孔进入到里面并与反应介质混合。含有冷却剂或其与催化剂接触时转化反应产物的产物料流借助催化剂套筒的产物出口从催化剂套筒流出，然后进入送入水和喷淋气体的产物冷却室，用水蒸汽和喷淋气体冷却下来的产物借助反应器的产物出口从反应器流出，然后送去进一步处理。
反应器的设计和用于冷却催化剂套筒筒壁的冷却剂量根据其温度、反应器的生产能力、冷却表面的面积和冷却剂的规格的需要而确定。催化剂套筒筒壁的温度最好不超过1000℃，尽管包括利用冷却夹套冷却催化剂套筒热负荷最大区域的其它选择也是可以的。

Claims (6)

1.用于烃类原料部分氧化的反应器，包括带有一个反应产物出口和至少一个将原料或原料组分送入催化剂套筒的入口的外壳，所述催化剂套筒位于反应器内、与外壳有一个间隙、装填有催化剂且其下部包括产物出口，其特征在于催化剂套筒配备至少部分毗邻催化剂套筒筒壁的夹套，所述催化剂套筒筒壁做成在所述夹套毗邻区域有开口孔，和反应器配备将冷却催化剂套筒的冷却剂送入夹套的入口，然后穿过筒壁的孔进入催化剂套筒。
2.按照权利要求1的反应器，其特征在于水蒸汽、合成气或它们的混合物用作冷却剂。
3.按照权利要求1的反应器，其特征在于催化剂套筒夹套和反应器外壳之间的间隙装填有隔热材料。
4.按照权利要求1的反应器，其特征在于它还包括用水冷却产物的冷却室，其借助催化剂套筒的产物出口与催化剂套筒连接，借助反应器配备的水入口将水供入冷却室。
5.按照权利要求1的反应器，其特征在于它还配备水喷淋气体进入产物冷却室的入口。
6.按照权利要求1的反应器，其特征在于冷却剂进入催化剂套筒夹套的入口做成可以按足以将催化剂套筒冷却到至少1000℃的量供应冷却剂。
CN201480021330.7A 2014-01-13 2014-02-28 用于烃类气体部分氧化的反应器 Pending CN105143099A (zh)

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