CN104936679B - 用于从烟道气或废气中同时除去一氧化碳和氮氧化物的方法和催化剂 - Google Patents
用于从烟道气或废气中同时除去一氧化碳和氮氧化物的方法和催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003546 flue gas Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002912 waste gas Substances 0.000 title claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 75
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 60
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- FXVIUOOYXNDBDN-UHFFFAOYSA-N palladium vanadium Chemical compound [V].[Pd].[Pd].[Pd].[Pd].[Pd].[Pd].[Pd].[Pd] FXVIUOOYXNDBDN-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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Abstract
本发明涉及用于同时除去一氧化碳和NOx的方法和催化剂，其中使含有有害的一氧化碳、有机化合物(VOC)和NOx的烟道气或废气与层状催化剂接触，在所述层状催化剂中，第一层包含氧化催化剂且在下层中包含NH3‑SCR催化剂。
Description
本发明涉及用于同时除去包含在烟道气(flue gas)或废气(exhaust gas)中的一氧化碳和氮氧化物(NOx)的方法和催化剂。
更特别地，本发明提供用于同时除去一氧化碳和NOx的方法，其中使含有有害的一氧化碳、有机化合物(VOC)和NOx的烟道气或废气与层状催化剂接触，在所述层状催化剂中，第一层包含氧化催化剂且在下层中包含NH3-SCR催化剂。
通常通过使用两种不同的催化剂组合物来从烟道气或废气中去除NOx、VOC以及CO，其中将氧化催化剂设置在SCR催化剂的上游，并在催化剂之间注入还原剂。通常通过用整体形式的(monolithic form)基于氧化钒或沸石的催化剂上的氨的选择性催化还原(SCR)来进行NOx的去除。将氨注入到SCR催化剂的上游并使其与催化剂表面上的NOx反应。对于基于氧化钒的催化剂而言，最佳的温度窗口为200-400℃，而基于沸石的催化剂在温度>400℃时活性更高。
在通过催化氧化除去CO和VOC的情况下，铂金属是最常见的选择，这是由于其在温度>200℃时已经具有高反应性。
含有CO、VOC二者以及NOx的烟道气的例子是来自依靠天然气运行的涡轮机的烟道气。传统上，在HRSG设计中，CO氧化催化剂(通常基于铂)位于SCR催化剂和氨注入格栅(gird)(“AIG”)的上游。选择这个位置主要是由于这样的事实：氧化催化剂在NH3氧化成NOx的过程中是非常活泼的，这是高度不希望的。使CO氧化催化剂位于AIG上游确保不浪费NH3，但是所有量的注入氨到达SCR催化剂限制了设备的运行成本。
在可替换的构造中，将氧化催化剂设置在SCR催化剂的下游。当以这种方式设置时，氧化催化剂在比常规布局低的温度下操作。这种构造的问题在于，如果设计不正确，则氧化催化剂可能将逸出(slip)到NOx的NH3氧化，因此降低设备整体的NOx去除。可能地，氧化催化剂可以以将NH3转化成N2的方式设计，但是这样的催化剂通常比常规的氧化催化剂更昂贵，这是由于用于其生产的贵金属的种类和量。
在上述构造中，所得到的反应器由两个分开的催化剂单元(即一个SCR催化剂单元和一个氧化催化剂单元)组成。更准确地说，安装的催化剂的总体积将通过SCR催化剂单元的尺寸加上氧化催化剂单元的尺寸来确定。
为了减小反应器的尺寸，已经尝试将这两种催化剂部分地组合在相同载体上并在一些情况下实现。
美国专利7 390 471公开了一种用于减少废气流中的NOx、HC和CO浓度的废气处理装置。处理装置包括多功能催化元件，该多功能催化元件具有仅用于还原的上游部分和位于氨注入装置的下游的用于还原加氧化的下游部分。通过注入过量于化学计量浓度的氨而在催化元件的上游部分中促进NOx的选择性催化还原(SCR)，所产生的逸出氨在催化元件的下游部分中被氧化。通过氨的氧化而产生的任何额外的NOx在输送到大气之前在下游部分中被进一步还原。仅用于还原的催化剂可以是钒/TiO2，且用于还原加氧化的催化剂包括具有用2.8g/ft 3的铂和钯中的每一种浸渍的1.7wt％的钒/TiO2的还原催化剂。
然而，氧化催化剂的SCR活性显著低于仅用于SCR的催化剂的SCR活性，这意味着所安装的催化剂总体积将等于氧化催化剂的体积加上补偿氧化催化剂的低SCR活性所需要的SCR催化剂的体积。
在例如燃气涡轮机烟道气的清洗中，从实用性角度看，第一要务是尽可能降低总的催化剂体积。大的体积实际上意味着跨催化剂床的高压降和HRSG的总体较低的效率。压降对涡轮机可实现的净功率有直接影响，并对热通量(即，可以通过HRSG从烟道气提取的热量)有间接影响。
为了将催化剂体积降低到最小，必须使氧化催化剂的SCR活性增高到与仅用于SCR的催化剂同样高的水平。用于获得这点的一个必要条件是使用这样的氧化催化剂：其在氧化CO和VOC时非常活泼，但是其不与NH3反应。另一个重要条件是，氧化催化剂必须仍具有与仅用于氧化的催化剂相同的氧化活性。
通过本发明实现了这两个条件，所得到的用于CO和VOC二者以及NOx的合并去除的催化剂的总体积等于位于氧化专用的催化剂和SCR专用的催化剂之间的最大催化剂的体积，其取决于具体设备所需的CO、VOC以及NOx的去除。
因此，本发明提供了用于降低烟道气或废气中的一氧化碳、挥发性有机化合物和氮氧化物的量的方法，所述方法包括以下步骤：
向烟道气或废气中引入氨和/或其前体；
如果前体存在的话，则将前体转化为氨；
使气体和氨在高达350℃的温度下与层状(layered)催化剂接触，该层状催化剂沿气体流动方向包括具有氧化催化剂的上层第一催化剂层和具有NH3-SCR催化剂的完全负载该第一层的下层第二催化剂层；以及使至少部分量的一氧化碳和挥发性有机化合物在上层的第一层中氧化而不影响气体中还含有的氨，且通过与氨反应而使氮氧化物的量在下层的第二催化剂层中降低。
已经开发出用于根据本发明的方法中的CO和VOC的氧化催化剂，其在高达350℃的温度下在NH3氧化中是不活泼的。
因此，在本发明的实施方式中，在第一层中的氧化催化剂由钯、氧化钒和氧化钛组成。
通过将该催化剂涂覆在市售的NH3-SCR催化剂(例如根据本发明的另一实施方式包含钨、钼、钒和钛的氧化物的NH3-SCR催化剂)上，所得到的催化剂由氧化CO和VOC但不氧化氨的第一催化剂层和仅用于NH3-SCR的第二催化剂层组成。
参照图1，在图中在气体温度高达350℃时，CO和VOC将在层状催化剂1的第一氧化层2中被氧化为CO2，而用于NOx去除的所有注入的NH3将同时扩散通过氧化层2并在下层的SCR催化剂层3上反应。
通过增加第一催化剂层的孔隙结构和厚度，NOx和NH3将容易接近下层的SCR催化剂，并且由于反应物穿过氧化催化剂层的扩散速率，SCR活性的损失将非常有限。
因此，在本发明的另一个实施方式中，第一催化剂层具有10至200微米、优选10至50微米的层厚度。
在根据本发明的如上所述的方法中，烟道气或废气还可以用常规的非层状的位于该层状催化剂的上游或下游的SCR催化剂处理。
本发明还提供用于同时氧化一氧化碳和挥发性有机化合物以及通过与氨反应从而选择性还原氮氧化物的催化剂，该催化剂包含氧化催化剂的第一层和完全负载第一层的NH3-SCR催化剂的第二层。
优选地，氧化催化剂由钯、钒氧化物和钛氧化物组成。
根据本发明的实施方式，优选的氧化催化剂还具有某些SCR活性，这是由于TiO2和钒氧化物二者的存在。因此，在无需提高所加入的氨的情况下保留了全部的SCR活性。以这种方式，用显著减小的催化剂体积可以实现期望的CO和NOx二者的去除。
在本发明的实施方式中，第一催化剂层具有10至200微米、优选10至50微米的层厚度。
当以整体形式构建层状催化剂时，所得到的整体催化剂将具有跨整体长度的均匀的催化剂组成。CO、VOC和NOx的去除沿该整体的整个长度同时进行。
实施例
用由TiO2上的0.45wt％的Pd和4.5wt％的V2O5组成的催化剂涂覆基于V/Ti的市售SCR催化剂。测量NOx去除效率并与没有用氧化催化剂涂覆的相同SCR催化剂的NOx去除效率相比较。该测试的结果和条件示于下表1中：
表1
| 除NOx，％ | 除CO，％ | NH3逸出，ppmv | |
| SCR | 93.5 | 0 | 5.7 |
| 氧化+SCR | 92.9 | 97.8 | 4.4 |
测试条件：气体入口组成：50ppmv的NOx、55ppmv的NH3、100ppmv的CO、15体积％的O2、10体积％的H2O、余量为N2。气体空速，NHSV＝27 000h-1。温度：350℃。
如从表1中明显的，在两个测试中获得了相同的(在实验的不确定性之内)NOx去除效率。
Claims (11)
1.用于降低烟道气或废气中的一氧化碳、挥发性有机化合物和氮氧化物的量的方法，所述方法包括以下步骤：
向所述烟道气或废气中引入氨和/或其前体；
如果前体存在的话，则将所述前体转化为氨；
使所述烟道气或废气和所述氨在高达350℃的温度下与层状催化剂接触，所述层状催化剂包括具有氧化催化剂的上层第一催化剂层和具有NH3-SCR催化剂的完全负载所述第一层的下层第二催化剂层；以及使至少部分量的一氧化碳和所述挥发性有机化合物在上层的第一层中氧化而不影响所述气体中还含有的氨，且通过与所述氨反应而使所述氮氧化物的量在下层的第二催化剂层中降低，其中在所述第一层中的所述氧化催化剂由钯、氧化钒和氧化钛组成。
2.如权利要求1所述的方法，其中所述氧化催化剂由负载在氧化钛上的0.45wt％的钯和4.5wt％的五氧化二钒组成。
3.如权利要求1或2所述的方法，其中所述第一催化剂层具有10至200微米的层厚度。
4.如权利要求1或2所述的方法，其中所述第一催化剂层具有10至50微米的层厚度。
5.如权利要求1或2所述的方法，其中在所述第二催化剂层中的所述NH3-SCR催化剂包含钨、钼、钒和钛的氧化物。
6.如权利要求1或2所述的方法，其中所述烟道气或废气还用位于所述层状催化剂上游或下游的常规的非层状SCR催化剂处理。
7.一种用于同时氧化一氧化碳和挥发性有机化合物以及通过与氨反应而选择性还原氮氧化物的催化剂，所述催化剂包括氧化催化剂的第一层和完全负载所述第一层的NH3-SCR催化剂的第二层，其中所述氧化催化剂由钯、钒氧化物和钛氧化物组成。
8.如权利要求7所述的催化剂，其中所述氧化催化剂由负载在氧化钛上的0.45wt％的钯和4.5wt％的五氧化二钒组成。
9.如权利要求7或8所述的催化剂，其中所述第一催化剂层具有10至200微米的层厚度。
10.如权利要求7或8所述的催化剂，其中所述第一催化剂层具有10至50微米的层厚度。
11.如权利要求7或8所述的催化剂，其中在所述第二催化剂层中的所述NH3-SCR催化剂包含钨、钼、钒和钛的氧化物。
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