CN105636672B - 从烟气中去除SOx和CO2的方法和设备 - Google Patents
从烟气中去除SOx和CO2的方法和设备 Download PDFInfo
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Abstract
本发明涉及一种从烟气中联合去除SO2和CO2的方法,该方法包括同时去除一个初级分馏柱以及两个精制柱中的CO2和SO2。该方法包含:a)热烟气预处理,包括通过干燥吸附剂注射去除烟气SO3;b)通过多级压缩器压缩该处理过的热烟气;c)将CO2、SO2与非冷凝气体分离;d)将该CO2和SO2送入单独的精制柱;以及e)将来自该初级分馏柱以及两个精制柱中的流合并用于能量回收。
Description
相关申请的交叉引用
本申请要求2011年11月7日递交的美国临时专利申请No.61/628,823的权益。
技术领域
本发明提供一种从氧燃料燃烧发电厂去除二氧化硫和二氧化碳的方法。
背景技术
化石燃料的燃烧产生具有稀释的SO2和CO2的烟气,该稀释的SO2和CO2难以在单一的去除工艺中去除。现有技术中去除它们是用烟气脱硫工艺(FGD)去除SO2,然后用溶剂洗涤去除CO2。该FGD工艺需要使用试剂如石灰浆,并且该工艺产生了废弃物,如需要在厂区外处置的硫酸钙。用于从该烟气中捕获CO2的现有技术是利用溶剂洗涤。许多溶剂是发展欠缺的,包括耐受燃煤锅炉烟气中的杂质以及低的溶剂再生能量的胺。现有的溶剂技术需要大量的水蒸汽以再生用于回收的废溶剂,并且会降低多至25%的发电厂输出。
另一个从烟气中捕获CO2的方法是使用氧燃料燃烧。在氧燃料燃烧锅炉中,使用高纯度的氧气,通常95%的氧气或更高,燃烧化石燃料(煤炭,油或气体)。该燃烧方法降低了烟气中氮的含量,因此有助于二氧化碳捕获。来自氧燃料燃烧锅炉中的烟气体积仅约为具有相同大小的空气燃烧锅炉中的烟气体积的25%。首先冷却该烟气以回收在烟气中的水蒸汽。与空气燃烧锅炉烟气中的约为14%的CO2相比较,干燥的氧燃料烟气含有约为90%的CO2。使用氧燃料燃烧消除了对CO2浓缩工艺如胺厂的需求。
电力行业正在开发的通用氧燃料燃烧工艺通常包括湿烟气脱硫单元(FGD)用于SO2捕获,然后CO2净化单元(CPU)。部分脱硫气体再循环回到锅炉中作为调节气体以猝灭由于氧气燃烧的炉温。该CPU包括低温型冷却和从氧气和氮气中分离CO2,该氧气和氮气由于空气泄漏在排放控制设备的 下游渗透至烟气中。
该发明提供了以联合工艺而不是以两个独立的工艺去除SO2和CO2的方法。此外,使用本发明,去除的SO2是可以在管道中传送的液体产品,并且是可销售的产品。可以控制CO2产品纯度以满足最终产品的应用。联合去除SO2和CO2的工艺不产生脱硫废弃物,并提供了用于碳捕获的低投资成本选择。该工艺优于在美国专利申请No.7,416,716中描述的联合去除SOx和CO2的工艺,其中SO2作为硫酸而不是液体产品去除。该工艺还优于在美国专利申请No.6,737,031中描述的工艺,其中需要钙基试剂以捕获SO2。
发明内容
本发明涉及一种从烟气中联合去除SO2和CO2的方法,该方法包括去除一个初级分馏柱以及两个精制柱中的CO2和SO2。该方法包含以下步骤:a)热烟气预处理,包括利用干燥吸附剂注射去除烟气SO3;b)利用多级压缩器压缩该处理过的热烟气;c)分离CO2、SO2与非冷凝气体;d)将该CO2和SO2送入单独的精制柱;以及e)将来自该初级分馏柱以及两个精制柱中的流合并用于能量回收。
附图说明
图1为联合去除工艺的流程图;
图2显示了初级分离柱结构;
图3和图4分别显示了CO2和SO2柱。
具体实施方式
在氧燃料燃烧发电厂,化石燃料在具有氧气的炉中燃烧。氧燃料燃烧的烟气主要包含二氧化碳、水蒸汽、二氧化硫和少量其他气体。本发明提供了用冷却、分馏和分离水蒸汽、二氧化硫和二氧化碳来去除这些组分的方法。二氧化硫被分离并可以以气体或液体形式输送用于出口。二氧化碳也可以被分离和压缩输送到外部用于工业用途或封存。
图1为联合去除SOx和CO2的工艺流程图。将来自化石燃料燃烧炉排气管的热烟气(1)用干燥的吸附剂处理进行SO3去除(2),其中干石灰或天 然碱可以用作所述吸附剂。在去除SO3后,烟气中的颗粒用袋滤室(3)去除。不含颗粒的气体在用于进一步清洗微量材料的水洗涤柱中洗涤并在水洗器(4)中冷却。在洗涤后,将该洗涤后的烟气输送到具有中央冷却器(5)的多级压缩单元,在该单元对CO2和SO2进行冷凝。冷凝的液体进入初级分离柱(6),在该初级分离柱对非冷凝的SO2和CO2进行分离。将来自初级分离柱的富CO2的流取出在精制柱(7)中进行进一步分馏,并从将来自初级分离柱的富SO2的流取出在精制柱(8)中进行的进一步分馏。最终产品是高纯度的SO2和CO2。
该工艺可以分为如下子系统:热烟气预处理;压缩和冷却;初级分离;CO2精制柱;SO2精制柱;以及能量回收。
预处理
热烟气(1)预处理包括通过干燥吸附剂注射(2)去除烟气SO3。候选干燥剂是天然碱,其为经商业证明用于选择性地在烟气中去除SO3的化学品。SO3存在于烟气中,尤其是如果在锅炉中燃烧的燃料是焦炭或重油,其中钒存在于燃料中时。钒是在锅炉中将SO2转化至SO3的催化剂。SO3的去除降低了烟气下游硫酸的形成。在大量的SO3被去除后,该烟气需要进一步的用袋滤室或静电沉淀器(3)清洗。然后不含颗粒的烟气在水洗器(4)中洗涤和冷却。为了控制水洗器中水的酸性,可以加入碱性材料以增加其pH值以及使用水排放(waterblowdown)控制水质。该预处理系统经商业证明是为联合去除SO2和CO2工艺制备原料气所必要的。
压缩和冷却
处理过的烟气通过具有中央冷却器(5)的多级压缩器压缩至约680psia。该压缩器的最后一级的出口气体通过制冷剂冷却至低于室温。
初级分离柱
图2显示了初级分离柱的结构。冷却的烟气进入发生SO2、CO2与非冷凝气体分离的初级分离柱(6)。该柱装配有加热的再沸器(11),以及具有气液分离罐(12)的冷却回流热交换器。排出气体(13)具有非常低的CO2 和SO2含量,并通过膨胀器(26)排放用于能量回收。供应至再沸器的热量从压缩器的中央冷却器和其他废热源回收。
从选择的进料位置(tray location)取出富CO2的流(10)。其位于临近柱的中间位置,但其确切的位置需要基于实际的项目中烟气组成而确定。该富CO2的流(10)输送至CO2精制柱(7)。
从再沸器通过其堰孔(weir well)取出富SO2的流(14)。将其输送至SO2精制柱(8)。
如果将煤炭燃烧锅炉烟气用作原料气,初级分离柱可以进行78%(重量)的CO2回收,以及99%(重量)的SO2的回收。
CO2精制柱
图3显示了CO2柱。该CO2精制柱(7)包含再沸器和具有气液分离罐(16)的制冷冷却回流冷却器。供应给再沸器(15)的热量是从发电厂回收的少量废热。回流排放物(17)主要包含非冷凝气体,并与来自其他柱的排放物合并,输送至膨胀器(26)用于能量回收。将从再沸器的堰孔取出的高纯度CO2产品(18),与来自SO2柱的柱顶回流冷凝线路(refluxoverhead condensate line)(21)中的CO2流合并,输送至压缩器(23)以增加输出压力(send-out pressure)。
SO2精制柱
图4显示了SO2柱。该SO2精制柱(8)包含再沸器和具有气液分离罐(20)的制冷冷却回流冷却器。供应给再沸器(19)的热量是从发电厂回收的少量废热。柱顶回流排放物(22)被排放至膨胀器(26),回流冷凝物(21)主要包含CO2,与流(18)合并,输送至CO2产品压缩器(23)。
能量回收
所有柱中的排放气体流是高压气体。将从初级柱排放的流(13),来自CO2精制柱的流(17),以及来自SO2精制柱的流(22)合并,并在加热器(25)中加热,然后在最终排放前被输送至膨胀器(26)用于能量回收。
性能
以下表1显示了气体组成以及CO2和SO2二者的去除效率。所使用的原料气组成基于DOE/NETL研究,No.2007.1291,修订版2,日期为2008年8月,名称为“雾化煤炭富氧燃烧发电厂(Pulverized Coal Oxycombustion Power Plants)”。参照发电厂是燃烧东部沥青煤的煤炭燃烧发电厂。其具有550MW的功率输出。如表中所示,计算机模拟的去除效率对于CO2捕获约为93.92%,对于SO2捕获约为99.96%。
表1:CO2和SO2的去除效率
原料气 | CO2产品 | SO2产品 | ||
温度 | F | 350 | 75.3 | 120 |
压力 | psia | 14.2 | 2,530 | 150 |
Ar | lb/hr | 50,745 | 2,175 | 0 |
CO2 | lb/hr | 1,283,533 | 1,199,478 | 264 |
H2O | lb/hr | 283,918 | 1 | 324 |
N2 | lb/hr | 96,439 | 2,764 | 0 |
O2 | lb/hr | 24,892 | 1,107 | 0 |
SO2 | lb/hr | 27,280 | 11.5 | 27,270 |
总计 | lb/hr | 1,766,807 | 1,205,536 | 27,858 |
去除效率 | % | 93.92% | 99.96% |
Claims (14)
1.一种从烟气中联合去除SO2和CO2的方法,包括同时去除一个初级分馏柱以及两个精制柱中的CO2和SO2,该方法包含:
a)热烟气预处理,包括利用干燥吸附剂注射去除烟气SO3;
b)利用多级压缩器压缩所述处理过的热烟气;
c)将CO2、SO2与非冷凝气体分离;
d)将该CO2和SO2送入单独的精制柱;以及
e)将来自所述初级分馏柱以及两个精制柱中的流合并用于能量回收。
2.根据权利要求1所述的方法,其中去除的所述SO2是液体产品。
3.根据权利要求1所述的方法,其中联合去除SO2和CO2过程不产生脱硫废弃物。
4.根据权利要求1所述的方法,其中利用干燥吸附剂注射去除烟气SO3。
5.根据权利要求4所述的方法,其中所述吸附剂是干石灰或天然碱。
6.根据权利要求1所述的方法,其中在去除SO3以后,用袋滤室或静电沉淀器进一步净化烟气。
7.根据权利要求6所述的方法,其中不含颗粒的烟气在水洗器中洗涤和冷却。
8.根据权利要求7所述的方法,进一步包括碱性材料。
9.根据权利要求1所述的方法,其中所述处理过的烟气被压缩至约680psia。
10.根据权利要求1所述的方法,其中通过初级分离柱将CO2、SO2与非冷凝气体分离。
11.根据权利要求10所述的方法,其中将燃煤锅炉烟气用作原料气。
12.根据权利要求11所述的方法,其中所述初级分离柱进行60%至80%重量的CO2回收,以及95%至100%重量的SO2回收。
13.根据权利要求1所述的方法,其中所述精制柱包括再沸器和具有气液分离罐的制冷冷却回流冷却器。
14.根据权利要求12所述的方法,其中所述初级分离柱进行78%重量的CO2回收,以及99%重量的SO2回收。
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