CN101676016A - 用于从气体流中减少杂质的工艺和系统 - Google Patents
用于从气体流中减少杂质的工艺和系统 Download PDFInfo
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Abstract
本发明涉及用于从气体流中减少杂质的工艺和系统，具体地涉及用于从进料气体减少羰基硫化物、二硫化碳、羰基金属化合物、硫化氢和氰化氢、氨以及砷和氯化合物的工艺，其包括如下步骤：使所述气体连续地接触包括活性碳的第一净化剂、包括氧化铝的第二净化剂、包括氧化锌的第三净化剂、包括沸石的材料的第四净化剂以及包括氧化锌和氧化铜的第五净化剂。
Description
技术领域
本发明涉及用于减少气体流，特别是富氢气和一氧化碳的气体流中所含杂质的工艺和系统。
背景技术
富氢气和一氧化碳的气体通常被称为合成气。合成气是一种用于制备包括甲醇、二甲醚或氨的化学制剂的原料，或者其用于费托合成。
在本领域中众所周知，所述合成气是通过蒸汽重整从一些原料如天然气和石脑油来制备的。近来，由于天然气和液态烃来源的减少，对于利用固体和液体燃料，例如煤、石油焦、生物资源和不同特性的废弃物来制备合成气的兴趣获得了提高。
通过使用气化来制备合成气的一个问题是相对高的杂质含量，其对于随后用于所述气体到化学制品转化的特定催化剂具有中毒作用。
所述有毒的污染物主要包括含硫的化合物，尤其是羰基硫化物、羰基金属、二硫化碳和硫化氢，其与氰化氢、氨以及砷和氯化合物在一起。这些化合物会毒害具有例如铜或锌或沸石的催化剂，所述催化活性材料会以不可逆的方式形成金属硫化物、氰化物、砷化物和含氯物。
为了避免下游催化剂的严重毒害，在所述合成气中污染物的含量必须被基本减少到低ppb级，优选地低于10ppb。
在所述合成气中硫化氢的整体量在工业工艺中通常通过化学制品或者物理溶剂的洗涤工艺被降低至ppm级，包括已知的使用有机化合物作为物理溶剂的Selexol和Rectisol工艺，或者使用链烷醇胺作为化学溶剂的胺洗涤工艺，如一乙醇胺(MEA)和甲基二乙醇胺(MDEA)工艺。
而且从气体流还原痕量的含硫化合物在本领域中也是已知的。
EP 320979A2公开了通过使用铜-锌脱硫剂将烃物流脱硫至含硫量低于5ppb。
从US 4263020中得知使用铬、铁、钴、铜、镉、汞或者锌氧化铝尖晶石作为吸附剂来去除硫化氢。
在WO 2007/093225中讨论了在具有氧化铁基材料的单一保护床中将羰基硫化物、硫化氢和氰化氢从合成气物流中去除到小于2ppb。该文件进一步公开了通过用氧化锌同时或串联处理来还原氰化氢、硫化氢和氨的数量。
现有技术没有教导全部去除进料气体流中所有的杂质(所述杂质在随后用于所述供给气体到化学制品转化的催化过程中为催化剂毒物)。
发明内容
因此，本发明的主要目的是，提供一种用于去除进料气体流中许多种痕量杂质的有效工艺，其中所述杂质对下游催化剂组分来说是有毒的。
根据所述的主要目的，本发明提供了用于从进料气体减少羰基硫化物、二硫化碳、羰基金属化合物、硫化氢和氰化氢、氨以及砷和氯化合物的工艺，其包括如下步骤：
使所述气体连续地接触包括活性炭的第一净化剂、包括氧化铝的第二净化剂、包括氧化锌的第三净化剂、包括沸石材料的第四净化剂以及包括氧化锌和氧化铜的第五净化剂。
具体实施方式
要求所述活性炭在所述进料气体接触含有氧化铝的净化剂之前从所述进料气体通过吸附除去一部分所述有毒化合物。这在几个方面是有利的。活性炭是一种相对便宜的材料和消耗物料，其可以容易地用新鲜的活性炭材料替换。硫化氢和氨的吸附将会推进在所述第二床上发生的水解反应平衡向右移动：
(1)COS+H2O＝CO2+H2S
(2)CS2+2H2O＝CO2+H2S
(3)HCN+H2O＝CO+NH3
改进所述反应器的效率。在活性炭上羰基化合物的吸附节省了在后面具有更昂贵的含氧化锌净化剂床中用于去除硫化氢和砷的更昂贵的材料。而且，氯的部分吸收最小化了在后面的床中对特定吸收剂的使用。
在所述第二床中，羰基硫化物、二硫化碳以及氰化氢在氧化铝上通过所述平衡反应(1)-(3)被分别水解为硫化氢和氨。
通过以上反应形成的硫化氢必须在随后的具有氧化锌的床中被除去。
除羰基和氰化物的水解之外，存在于所述进料气体之中的氯化合物也被所述含有氧化铝的净化剂所吸收。
来自所述第二净化剂的水解排出物被通向含锌的第三净化剂，其用于去除存在于所述进料气体中的和在上述处理过程期间形成的硫化氢。除了氢吸附以外，所述含有氧化锌的净化剂除去了没有被如上所示的等式反应(1)所水解的剩余量的羰基硫化物。
通过与含有沸石材料的第四净化剂接触而吸附引入所述第一净化剂的进料气体中所含的以及在反应(3)中通过与所述第二净化剂接触而形成的氨的数量。通常，所有酸性沸石都适合用于氨的减少，包括天然存在的沸石如丝光沸石和斜发沸石，以及合成沸石如ZSM-20、ZSM-5和Y沸石。
在所述进料气体中的砷化合物被第五净化剂通过形成Cu3As和Zn3As2而捕获。
除以上公开的金属化合物之外，其它化合物可以促进所述净化剂。因此，在所述第二净化剂中优选包括1-40重量％的碳酸钾。所述第三净化剂可以含有至多20重量％的氧化铝并且所述第五净化剂可以含有至多15重量％的氧化铝。
如在上文已经提到的，本发明的工艺被设计用于减少合成气中的痕量有毒杂质。为此应当指出，在本发明中所述的“减少(abatement)”其意思是指将杂质的数量从在所述进料气体引入第一净化剂处的ppm范围降低到在所述第五净化剂出口处的ppb范围。
在根据本发明所述的工艺中例如含硫化合物像硫化氢的大量去除(bulk removal)可以借助于在第一净化剂上游对所述进料气体用化学制品或物理溶剂的常规洗涤来进行。
所述净化剂优选地以固定床布置。在吸附净化的情况下，如床1、3和4，所述净化剂可以被布置为两个平行的床。这允许用过的净化剂通过杂质的脱附而再生，或者用新鲜的净化剂替换用过的净化剂，而不中断所述净化过程。
可以通过加热、化学反应或者通过简单取代来再生用过的净化剂。
此外，本发明提供一种用于从合成气减少污染物的系统，其连续地包括具有包括活性碳的净化剂的第一床、具有包括氧化铝的净化剂的第二床、具有包括氧化锌的净化剂的第三床、具有包括沸石材料的净化剂的第四床以及具有包括氧化锌和氧化铜的净化剂的第五床。
上面已经描述了所述系统的不同的净化剂的功能以及所述净化剂中各自所含的任选的促进剂的含量。
在本发明所述系统中，所述第一、第三和第四床可以被复制为两个平行床的形式。
除所述第一床的第一净化剂优选在20-260℃的温度下和至多140bar的压力下运行之外，根据本发明所述的工艺和系统优选在200-250℃的温度下以及15-140bar的压力下运行。
Claims (12)
1.用于从进料气体中减少羰基硫化物、二硫化碳、羰基金属化合物、硫化氢和氰化氢、氨以及砷和氯化合物的工艺，其包括如下步骤：
使所述气体连续地接触包括活性碳的第一净化剂、包括氧化铝的第二净化剂、包括氧化锌的第三净化剂、包括沸石的材料的第四净化剂以及包括氧化锌和氧化铜的第五净化剂。
2.权利要求1所述的工艺，其中所述第二净化剂还包括碳酸钾。
3.权利要求1所述的工艺，其中所述第三净化剂还包括氧化铜。
4.权利要求1所述的工艺，其中所述第四净化剂由酸性沸石组成。
5.权利要求1所述的工艺，其中所述第五净化剂还包括氧化铝。
6.前面权利要求任何一项所述的工艺，还包括在用所述第一净化剂接触所述气体之前用化学或物理溶剂洗涤的步骤。
7.用于从合成气减少污染物的系统，其连续地包括具有包括活性碳的净化剂的第一床、具有包括氧化铝的净化剂的第二床、具有包括氧化锌的净化剂的第三床、具有包括沸石材料的净化剂的第四床以及具有包括氧化锌和氧化铜的净化剂的第五床。
8.权利要求7所述的系统，其中所述第二净化剂还包括碳酸钾。
9.权利要求7所述的系统，其中所述第三净化剂还包括氧化铜。
10.权利要求7所述的系统，其中所述第四净化剂由酸性沸石组成。
11.权利要求7所述的系统，其中所述第五净化剂还包括氧化铝。
12.根据前述权利要求中任一项的系统，其中至少所述第一、第三和第四床各自布置为两个平行的床。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103201012A (zh) * | 2010-11-08 | 2013-07-10 | 3M创新有限公司 | 含氧化锌的过滤介质及其形成方法 |
| CN103201012B (zh) * | 2010-11-08 | 2016-05-18 | 3M创新有限公司 | 含氧化锌的过滤介质及其形成方法 |
| CN114653167A (zh) * | 2022-02-18 | 2022-06-24 | 青岛润华士科技有限公司 | 湿法voc治理系统及其方法 |
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| ATE503553T1 (de) | 2011-04-15 |
| EP2156877B1 (en) | 2011-03-30 |
| AU2009208128B2 (en) | 2013-10-10 |
| JP5479812B2 (ja) | 2014-04-23 |
| RU2009130709A (ru) | 2011-02-20 |
| BRPI0902758A2 (pt) | 2010-05-25 |
| CN101676016B (zh) | 2013-03-13 |
| US20100037774A1 (en) | 2010-02-18 |
| DE602009000975D1 (de) | 2011-05-12 |
| CA2675007A1 (en) | 2010-02-13 |
| JP2010047469A (ja) | 2010-03-04 |
| CA2675007C (en) | 2015-01-13 |
| PL2156877T3 (pl) | 2011-11-30 |
| RU2508155C2 (ru) | 2014-02-27 |
| EP2156877A1 (en) | 2010-02-24 |
| US8551218B2 (en) | 2013-10-08 |
| MX2009008598A (es) | 2010-03-22 |
| ZA200905588B (en) | 2012-09-26 |
| AU2009208128A1 (en) | 2010-03-04 |
| DK200801093A (en) | 2010-02-14 |
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