CN117282263A - 从含硫气体流中除去烟灰的方法 - Google Patents
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Abstract
本发明涉及一种用于从硫酸装置的含硫气体流中除去烟灰的方法，其中在反应器中将含有O2和大于500ppm的SO2和/或SO3以及烟灰的工艺气体与VK型催化剂接触，所述催化剂包含在多孔载体(优选二氧化硅载体)上的五氧化二钒(V2O5)，硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫和一种或多种碱金属，如Na、K、Rb或Cs。
Description
本申请是申请日为2016年4月13日，申请号为：2016800226912，名称为“从含硫气体流中除去烟灰的方法”的发明专利申请的分案申请。
技术领域
本发明涉及借助于由本申请人制备和出售的VK型催化剂通过碳氧化从含硫工艺气体流中除去烟灰。
烟灰是用于由烃类的不完全燃烧产生的不纯的碳颗粒的常用词。它是无定形碳的粉末状形式。气相烟灰含有多环芳烃(PAH)。最适当地，它限定为气相燃烧过程的产物，但它通常被延伸为包括残余热解燃料颗粒，例如煤、炭化木材、石油焦炭等，其在热解过程中变为气载的并且更适当地被认为是焦炭或木炭。
发明背景
在环境中作为气载污染物的烟灰有许多不同的来源，所有它们都是一些形式的热解的结果。其包括来自煤燃烧、内燃机、发电厂锅炉、船用锅炉、中央蒸汽加热锅炉、废物焚烧、现场燃烧、房屋火灾、森林火灾、壁炉、炉子等的烟灰。烟灰的形成强烈依赖于燃料组成。燃料组分产生烟灰的倾向性的排序是：萘类→苯类→脂族化合物。这种现象也被称为结焦。然而，脂族化合物(烷烃、烯烃、炔烃)的烟灰生成倾向性的顺序根据焚烧类型而显著地变化。认为脂族化合物和芳族化合物的烟灰生成倾向性之间的差异主要由不同的形成途径所致。脂族化合物似乎首先形成乙炔和多炔类化合物，这是一个缓慢的过程；芳族化合物可通过该途径形成烟灰，并且还可通过包括在现有芳族结构上建立环缩合或聚合反应的更直接途径来形成烟灰。
炭黑是由重质石油产品如焦油、煤焦油、乙烯裂解焦油和少量的植物油的不完全燃烧产生的烟灰的特殊变体。炭黑是类结晶碳形式，其具有高的表面积/体积比(低于活性炭的表面积/体积比)。它与普通烟灰的不同在于其高得多的表面积/体积比和显著更低(可忽略不计以及非生物可利用的)的PAH含量。然而，炭黑被广泛用作柴油氧化实验用柴油烟灰的模型化合物。炭黑主要用作轮胎和其它橡胶制品中的补强填料。在塑料、涂料和油墨中，炭黑被用作有色颜料。
烟灰的催化燃烧在汽车领域，特别是柴油发动机中是众所周知的。因此，在US 6,764,664中公开了一种催化剂组合物，其用于减少来自发动机排气，特别是来自柴油发动机的排气中的烟灰和不期望的气体排放物。催化剂含有催化活性的碱金属氧化物，优选为锂铂氧化物，其中催化活性的金属被原子隔离。为了改善柴油微粒过滤器的性能，碱金属氧化物催化剂被均匀地分散在碱金属铝酸盐如铝酸锂上。
WO 1990/012646还涉及来自柴油发动机的烟灰的催化燃烧。为了获得所述催化燃烧，废气在包含钒和铜氧化物的催化剂材料(V:Cu摩尔比为85:15至95:5，优选90:10)上传递。为了提高低温下的活性，催化剂优选还含有元素铂、钯或铑。
申请人的US2011/0283680涉及一种用于净化来自系统中的柴油发动机的废气的方法，其包括用于选择性催化还原的装置和柴油微粒过滤器，该柴油微粒过滤器优选至少部分被安装在用于选择性催化还原的装置下游的催化剂层覆盖。用于催化氧化的装置安装在用于选择性催化还原的装置的上游和/或在所述装置和柴油微粒过滤器之间。选择性催化还原优选在基于钒的催化剂存在下进行，该基于钒的催化剂为具有可能添加的钨或钼氧化物的钛氧化物上的钒氧化物。
也属于本申请人的WO 2014/169967涉及一种用于除去烟灰、灰分和重金属以及另外任选地存在于来自以重质燃料油操作的发动机的废气中的NOx和SOx的方法和系统，其中该废气中硫含量为0.1％至4.0wt％且重金属元素含量为5mg/kg至1000mg/kg。在系统中使用的催化剂优选包含二氧化钛、钒和钨的氧化物以及金属钯。
最后，US 6,013,599描述了一种低温柴油排气烟灰氧化催化剂，其包括多孔难熔金属或金属氧化物载体和涂层(wash coat)。涂层通过以下步骤形成：将酸性含铁化合物和含铜化合物混合，加入碱金属水溶液，加入含酸性钒化合物的溶液并加入碱土金属化合物溶液。含铜化合物可以是硫酸铜，且含钒化合物可以是五氧化二钒。排气可包含硫化合物，但其没有说明排气包含大于500ppm的SO2和/或SO3。
发明内容
虽然汽车领域的专利文献充分描述了烟灰经钒催化剂的催化燃烧，但对于烟灰或炭黑经VK型催化剂的燃烧并不是这种情况。迄今为止，炭黑的催化氧化似乎仅在少数科学文章中有描述，即Carbon black oxidation in the presence of Al2O3,CeO2 and Mnoxide catalysts:An EPR study,Catalysis Today,119,286-290(2007)；Catalyticoxidation of carbon black-I.Activity of catalysts and classification ofoxidation profiles,Fuel,97(3),111-119(1998)；Catalytic oxidation of anamorphous carbon black,Combustion and Flame,99,413-421(1994)；以及Effects ofozone on the catalytic combustion of carbon black,Applied Catalysis B:Environmental,54,9-17(2004)。
本发明涉及一种使用VK型催化剂通过碳氧化从不同的含硫工艺气体流中除去烟灰的方法。通常，VK催化剂可用于在硫酸装置中氧化SO2至SO3，并且它们由钒(V2O5形式)、硫(硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式)、SiO2和碱金属如Li、Na、K、Rb和Cs及其混合物作为助催化剂组成。VK催化剂可与其它催化剂类型如SCR(选择性催化去除)结合使用以去除NOx。
更具体地，本发明涉及一种用于从含硫气体流中除去烟灰的方法，其中在反应器中将含有O2和大于500ppm的SO2和/或SO3以及烟灰的工艺气体与VK型催化剂接触，所述催化剂包含在多孔载体上的五氧化二钒(V2O5)，硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫和一种或多种碱金属。
在另一方面，本发明涉及一种用于从硫酸装置的含硫气体流中除去烟灰的方法，其中该方法包括从来自静电过滤器、袋式过滤器或陶瓷过滤器的气体流中去除一定量的烟灰，由此将含有O2和大于500ppm的SO2和/或SO3以及烟灰的工艺气体导入至位于所述硫酸装置的静电过滤器、袋式过滤器或陶瓷过滤器下游的反应器中，在所述反应器中使所述工艺气体与催化剂床接触，所述催化剂床包含在多孔载体上的对于烟灰的氧化和对于SO2氧化为SO3而言是有活性的催化剂，所述催化剂包含五氧化二钒(V2O5)，硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫，和一种或多种碱金属焦硫酸盐熔体形式的碱金属。
碱金属优选选自Na、K、Rb和Cs。
催化剂的多孔载体优选为二氧化硅(SiO2)，其任选地含有少量氧化铝(多达10wt％，优选多达5wt％，且最优选多达2wt％或1wt％)。
申请人的VK催化剂的概述在下表1中给出。催化剂的燃点温度，即熔体变为活性的温度可能比工作温度低至多100℃。
表1
| VK催化剂类型 | VK38 | VK48 | VK59 | VK-WSA |
| V2O5含量，wt％ | 5-9 | 6-10 | 5-9 | 5-9 |
| 碱金属含量，wt％ | 10-16 | 10-16 | 10-16 | 10-16 |
| 工作温度，℃ | 400-630 | 400-550 | 370-450 | 400-550 |
根据本发明，如上所述，在反应器中将含有O2和SO2和/或SO3以及烟灰的工艺气体与VK型催化剂接触。工艺气体中的烟灰在暴露于VK催化剂的正常工作温度条件下不燃烧，但已经证明，当将它与所述催化剂类型接触时，它在这些温度条件下会燃烧。由于存在碱金属焦硫酸盐熔体(其在SO2和/或SO3存在下在催化剂的表面上形成)，因此燃烧发生。
这带来许多益处：首先，没有任何可能由烟灰在催化剂床中的积累所引起的压降，因此在筛选催化剂之间的较长时间是可能的。附加益处来源于例如对于100mg/Nm3/h的烟灰载量，烟灰的燃烧使催化剂床所需的入口温度降低3℃，这反过来降低了加热反应器上游的工艺气体所需的能量。此外，由于烟灰在VK催化剂上燃烧，因此在反应器上游需要去除的烟灰较少，其中通常使用静电过滤器、袋式过滤器或陶瓷过滤器。
用于本发明的方法的催化剂中的碱金属含量为2-25wt％，优选4-20wt％，且最优选8-16wt％。催化剂含有1-15wt％的V2O5，优选2-12wt％，且最优选4-10wt％的V2O5。
此外，在本发明的方法中使用的催化剂含有1-25wt％，优选2-20wt％或3-18wt％，且最优选4-16wt％或4-10wt％的硫酸盐、焦硫酸盐、三-或四硫酸盐形式的硫。
在本发明的方法中，催化剂温度为250-700℃，优选为300至650℃。
工艺气体具有>0.1mg/Nm3/h的烟灰浓度，且烟灰浓度可以大于50mg/Nm3/h，其中优选浓度为>0.5mg/Nm3/h、>1mg/Nm3/h、>2mg/Nm3/h、>5mg/Nm3/h、>10mg/Nm3/h和>20mg/Nm3/h。
工艺气体优选含有大于1000ppm的SO2和/或SO3，优选大于2500ppm的SO2和/或SO3，且最优选大于5000ppm的SO2和/或SO3。
此外，工艺气体具有包含>20wt％的C的烟灰组成。优选地，工艺气体具有包含>50wt％的C、>75wt％的C、>90wt％的C或甚至>95wt％C的烟灰组成。
在根据本发明的方法的优选实施方案中，烟灰是炭黑。炭黑可在元素组成和表面积/体积比方面与大多数其它类型的烟灰如源自内燃机的烟灰区分开。
在下面的实施例中更详细地说明本发明，但是本发明不限于此。
实施例
通过用Printex U型炭黑覆盖催化剂表面并将烟灰覆盖的催化剂暴露于反应器中的气体来测试VK-WSA催化剂在400℃下去除烟灰的能力。气体含有10vol％的SO2和10vol％的O2。
炭黑在400℃下在空气中的热氧化的比较研究表明，烟灰的去除率非常低。结果示于下表2中。
表2
Claims (21)
1.一种用于从硫酸装置的含硫气体流中除去烟灰的方法，其中该方法包括从来自静电过滤器、袋式过滤器或陶瓷过滤器的气体流中去除一定量的烟灰，由此将含有O2和大于500ppm的SO2和/或SO3以及烟灰的工艺气体导入至位于所述硫酸装置的静电过滤器、袋式过滤器或陶瓷过滤器下游的反应器中，在所述反应器中使所述工艺气体与催化剂床接触，所述催化剂床包含在多孔载体上的对于烟灰的氧化和对于SO2氧化为SO3而言是有活性的催化剂，所述催化剂包含五氧化二钒(V2O5)，硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫，和一种或多种碱金属焦硫酸盐熔体形式的碱金属。
2.如权利要求1所述的方法，其中所述催化剂的多孔载体是二氧化硅(SiO2)。
3.如权利要求2所述的方法，其中所述催化剂的多孔载体是具有<10wt％，优选<5wt％的氧化铝的SiO2。
4.如权利要求3所述的方法，其中所述催化剂的多孔载体是具有<2wt％，优选<1wt％的氧化铝的SiO2。
5.如权利要求1-4中任一项所述的方法，其中所述催化剂的碱金属含量为2-25wt％，优选4-20wt％且最优选8-16wt％。
6.如权利要求1所述的方法，其中所述催化剂含有1-15wt％的V2O5。
7.如权利要求6所述的方法，其中所述催化剂含有2-12wt％的V2O5，优选4-10wt％的V2O5。
8.如权利要求1所述的方法，其中所述催化剂含有1-25wt％的硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫。
9.如权利要求8所述的方法，其中所述催化剂含有2-20wt％，优选3-18wt％的硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫。
10.如权利要求9所述的方法，其中所述催化剂含有4-16wt％，优选4-10wt％的硫酸盐、焦硫酸盐、三硫酸盐或四硫酸盐形式的硫。
11.如权利要求1-10中任一项所述的方法，其中催化剂温度为250-700℃。
12.如权利要求11所述的方法，其中所述催化剂温度为300-650℃。
13.如权利要求1所述的方法，其中所述工艺气体具有>0.1mg/Nm3，优选>0.5mg/Nm3的烟灰浓度。
14.如权利要求13所述的方法，其中所述工艺气体具有>1mg/Nm3，优选>2mg/Nm3的烟灰浓度。
15.如权利要求14所述的方法，其中所述工艺气体具有>5mg/Nm3，优选>10mg/Nm3的烟灰浓度。
16.如权利要求15所述的方法，其中所述工艺气体具有>20mg/Nm3，优选>50mg/Nm3的烟灰浓度。
17.如权利要求13-16中任一项所述的方法，其中所述工艺气体含有大于1000ppm的SO2和/或SO3，优选大于2500ppm的SO2和/或SO3。
18.如权利要求17所述的方法，其中所述工艺气体含有大于5000ppm的SO2和/或SO3。
19.如权利要求13-16中任一项所述的方法，其中所述工艺气体中的烟灰具有包含>20wt％的C，优选>50wt％的C的组成。
20.如权利要求19所述的方法，其中所述工艺气体中的烟灰具有包含>75wt％的C，优选>90wt％的C的组成。
21.如权利要求20所述的方法，其中所述工艺气体中的烟灰具有包含>95wt％的C的组成。
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| ZA201706479B (en) | 2021-03-31 |
| EP3285913A1 (en) | 2018-02-28 |
| MX2017012456A (es) | 2018-01-30 |
| MY180603A (en) | 2020-12-03 |
| JP2018516164A (ja) | 2018-06-21 |
| PL3285913T3 (pl) | 2021-12-20 |
| US20180093225A1 (en) | 2018-04-05 |
| CA2983207A1 (en) | 2016-10-27 |
| CN107530625A (zh) | 2018-01-02 |
| ES2891751T3 (es) | 2022-01-31 |
| WO2016169822A1 (en) | 2016-10-27 |
| EP3285913B1 (en) | 2021-07-14 |
| JP6913027B2 (ja) | 2021-08-04 |
| HUE055981T2 (hu) | 2022-01-28 |
| KR102302675B1 (ko) | 2021-09-16 |
| CA2983207C (en) | 2021-08-31 |
| KR20170138418A (ko) | 2017-12-15 |
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