TW201902560A - 用於自煙道氣移除微粒物質及有害化合物的方法及系統 - Google Patents
用於自煙道氣移除微粒物質及有害化合物的方法及系統 Download PDFInfo
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- 239000003546 flue gas Substances 0.000 title claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000013618 particulate matter Substances 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 title description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
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- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 16
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010970 precious metal Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 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 description 1
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Abstract
本發明係關於用於在低溫下自煙道氣中移除氮氧化物的方法及系統。
Description
本發明係關於用於自廢氣及煙道氣中減少微粒物質及氮氧化物(NOx)排放的方法及系統。詳言之，本發明的方法及系統在低氣體溫度下提供改良的NOx減少。
來自不同燃燒設施的煙道氣，例如固體或液體火力發電廠中的鍋爐、燃油發電機或水泥窯、生物燃料燃燒設備及垃圾焚化設備的氣體皆含有許多環境問題或甚至有毒的化合物。此等化合物包含微粒物質及NOx。
使用微粒過濾器及煙道氣的催化淨化減少了微粒物質及NOx之量，因此通常對環境有益。多數地區立法要求減少煙道氣中的氮氧化物。
例如以燭式過濾器形式的陶瓷過濾器用於許多產業，以移除來自製程氣體的微粒物質。其為可用的最有效集塵器類型之一，並且可實現對微粒超過99%的收集效率。過濾器可由各種陶瓷材料所製成，該陶瓷材料包含由鹼金屬矽酸鹽及鹼土矽酸鹽或鋁矽酸鹽所製成的陶瓷纖維。
WO 2016150464揭示基於浸漬有活性催化劑的陶瓷纖維的陶瓷過濾器，其用於移除NOX、NH3、戴奧辛、CO及不同的VOC以及粉塵。
詳言之，基於氧化釩的催化劑一般為用於在固定及汽車應用中 藉由用NH3選擇性還原NOx來還原NOx的催化劑。
此等催化劑在藉由組合氧化及與NH3的SCR反應以移除烴類(hydrocarbon；VOC)及NOx上皆具有活性。
在NOx選擇性催化還原(Selective Catalytic Reduction；SCR)中，氧化亞氮化合物藉由在催化劑上與還原劑(例如氨)反應而選擇性還原成無害的氮及水。
已知SCR活性催化劑的問題為在低於250℃的氣體溫度下催化劑的效率相對較低。特別是在起動及關閉燃燒設施時的低煙道氣溫度在藉由SCR移除NOx上產生問題。
此問題係藉由本發明在低於250℃的溫度下將NO2注入至煙道氣中以促進“快速”SCR反應而解決。
已知可將SCR反應顯著加速，並且可藉由“快速”SCR反應，在煙道氣中在等莫耳量的NO及NO2下顯著提高低溫活性：2NH3+NO+NO2 → 2N2+3H2O。
因此，本發明係基於在煙道氣管外部形成NO2並且將所製備的NO2以促進“快速”SCR反應之量注入至煙道氣中。NO2可由NH3藉由以下步驟來形成：在第一步驟中在含貴金屬的催化劑上將NH3氧化成NO，並且隨後在第二步驟中將NO氧化成NO2。
本發明在第一態樣中提供一種用於自燃燒設施的煙道氣中移除氮氧化物的方法，其包含以下步驟：將該煙道氣通過以用於選擇性還原氮氧化物的催化劑催化的一或多個陶瓷過濾器，在氨的存在下該催化劑以其本身或以其前驅物的形式添加至該煙道氣 中；在低於250℃的溫度下，將含二氧化氮的流出物氣體注入至在該一或多個陶瓷過濾器上游的該煙道氣中；按以下步驟提供含二氧化氮的流出物氣體：在氧化催化劑的存在下，用含氧氛圍將氨或其前驅物催化氧化成含一氧化氮及氧的流出物氣體；將該流出物氣體冷卻至環境溫度，並且將該冷卻的流出物氣體中之一氧化氮氧化成含二氧化氮的流出物氣體。
較佳者，陶瓷過濾器係以燭式過濾器的形式成形。
在250℃以上之煙道氣溫度下，SCR催化劑具有足夠的效率，並且當氣體溫度達到250℃時可打斷煙道氣中NO2的注入。
在煙道氣管外部將氨氧化為NO通常係在含氧氛圍的存在下在250至800℃之間的反應溫度下在具有貴金屬催化劑的反應器中進行，該貴金屬催化劑典型地為鉑或鉑與作為次要組分之其他貴金屬的合金。
為了提供所需的反應溫度，氧化反應器可藉由例如電加熱或感應加熱來加熱。
在一個具體實例中，含氧氛圍包括熱再循環煙道氣，該熱再循環氣體隨後另外提供氧化反應器部分加熱功能。
較佳者，含氧氛圍為環境空氣。
在第一步驟中藉由將與含貴金屬的催化劑接觸的NH3氧化而由NH3形成的NO隨後在第一步驟之含NO的流出物氣體中藉由將該氣體冷卻至環境溫度而被氧化成NO2，以推動平衡反應2NO+O2 2NO2而形成NO2。
本文所使用的術語「環境溫度」應指使用本發明的方法及系統的燃燒設施周圍的任何溫度。典型地，環境溫度會在-20℃至+40℃之間。
含NO的流出物氣體的冷卻及氧化可在經尺寸設定使得氣體的停留時間為約1分鐘或更久的時效反應器(aging reactor)中進行。典型地在1到2分鐘之間。
在一個具體實例中，氧化反應係在促進將NO氧化成NO2的催化劑的存在下進行。此等催化劑在本領域中為已知者，包括在TiO2上的Pt、在SiO2及活性碳上的Pt、或在氧化鋁上的Pt及/或Pd。
如上所述，所需的快速SCR反應需要等量的NO及NO2。因此，在低於250℃的溫度下控制注入至煙道氣中之NO2之量，以致使在SCR催化劑單元入口處煙道氣中氮氧化物含量之45-55體積%為NO2。
在第二態樣中，本發明提供一種用於根據本發明的方法中的系統。
該系統包含：具有一或多個用催化劑催化的陶瓷過濾器的過濾室，其在煙道氣管內，該催化劑用於選擇性還原氮氧化物；注入裝置，其在該一或多個陶瓷過濾器或該過濾室的上游，用於將氨或脲溶液注入至該煙道氣管中；注入裝置，其在該一或多個陶瓷過濾器或該過濾室的上游，用於注入含二氧化氮的流出物氣體；及氨氧化催化劑單元，其在該煙道氣管外側；及用於將自該氨氧化催化劑提取的含一氧化氮的流出物氣體冷卻並且氧化成 含二氧化氮的流出物氣體的裝置，該裝置在其出口端連接至該用於注入含二氧化氮的流出物氣體的注入裝置。
如上所述，將NO氧化成NO2的反應需要含NO氣體至少1分鐘的停留時間。典型地為1-2分鐘。
此可在氣體冷卻或水冷卻的熱交換器中或者當冷卻及氧化裝置成形為具有致使氣體通過管的所欲停留時間的長度的螺旋纏繞管時實現。
在另一個具體實例中，用於冷卻及氧化含一氧化氮的流出物氣體的裝置配置有促進將NO氧化成NO2的氧化催化劑。
在根據本發明的系統的所有具體實例中，一或多個陶瓷過濾器呈陶瓷燭式過濾器的形式。
Claims (11)
- 一種用於自燃燒設施的煙道氣中移除氮氧化物的方法，其包含以下步驟：將該煙道氣通過以用於選擇性還原氮氧化物的催化劑催化的一或多個陶瓷過濾器，在氨的存在下該催化劑以其本身或以其前驅物的形式添加至該煙道氣中；在低於250℃的溫度下，將含二氧化氮的流出物氣體注入至在該一或多個陶瓷過濾器上游的該煙道氣中；按以下步驟提供含二氧化氮的流出物氣體：在氧化催化劑的存在下，用含氧氛圍將氨或其前驅物催化氧化成含一氧化氮及氧的流出物氣體；將該流出物氣體冷卻至環境溫度，並且將該冷卻的流出物氣體中之一氧化氮氧化成含二氧化氮的流出物氣體。
- 如請求項1所述之方法，其中該含氧氛圍包含煙道氣。
- 如請求項1所述之方法，其中該含氧氛圍為環境空氣。
- 如請求項1至3中任一項所述之方法，其中將該含二氧化氮的流出物氣體以致使在該用於選擇性還原氮氧化物的催化劑的入口處該氮氧化物之45至55體積%為二氧化氮之量注入至該煙道氣中。
- 如請求項1至4中任一項所述之方法，其中將該冷卻的流出物氣體中之一氧化氮氧化成含二氧化氮的流出物氣體係在氧化催化劑的存在下進行。
- 如請求項1至4中任一項所述之方法，其中該一或多個陶瓷過濾器呈陶瓷燭式過濾器的形式。
- 一種用於如請求項1至6中任一項所述之方法中之系統，其包 含：具有一或多個用催化劑催化的陶瓷過濾器的過濾室，其在煙道氣管內，該催化劑用於選擇性還原氮氧化物；注入裝置，其在該一或多個陶瓷過濾器或該過濾室的上游，用於將氨或脲溶液注入至該煙道氣管中；注入裝置，其在該一或多個陶瓷過濾器或該過濾室的上游，用於注入含二氧化氮的流出物氣體；及氨氧化催化劑單元，其在該煙道氣管外側；及用於將自該氨氧化催化劑提取的含一氧化氮的流出物氣體冷卻並且氧化成含二氧化氮的流出物氣體的裝置，該裝置在其出口端連接至該用於注入含二氧化氮的流出物氣體的注入裝置。
- 如請求項7所述之系統，其中該用於將含一氧化氮的流出物氣體冷卻並且氧化的裝置係呈熱交換器形式。
- 如請求項7所述之系統，其中該用於將含一氧化氮的流出物氣體冷卻並且氧化的裝置係呈螺旋纏繞管形式。
- 如請求項7至9中任一項所述之系統，其中該用於將含一氧化氮的流出物氣體冷卻並且氧化的裝置配置有氧化催化劑。
- 如請求項7至10中任一項所述之系統，其中該一或多個陶瓷過濾器呈陶瓷燭式過濾器的形式。
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| US11833471B2 (en) * | 2019-03-27 | 2023-12-05 | Johnson Matthey Public Limited Company | Catalysed filter system for treating particulate-containing exhaust gas from stationary emission sources |
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| RU2760254C2 (ru) | 2021-11-23 |
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| ZA201906324B (en) | 2022-03-30 |
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