TWI407998B - 從廢氣隔離二氧化碳之方法及裝置 - Google Patents

從廢氣隔離二氧化碳之方法及裝置 Download PDF

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TWI407998B
TWI407998B TW99112305A TW99112305A TWI407998B TW I407998 B TWI407998 B TW I407998B TW 99112305 A TW99112305 A TW 99112305A TW 99112305 A TW99112305 A TW 99112305A TW I407998 B TWI407998 B TW I407998B
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gas
carbon dioxide
fuel
reformer
reducing
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Gary Edward Metius
James M Mcclelland
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Midrex Technologies Inc
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Description

從廢氣隔離二氧化碳之方法及裝置
本非臨時專利申請案/專利請求2009年4月20日提出之美國臨時專利申請案第61/170,999號，發明名稱”Method and Apparatus for Sequestering Carbon Dioxide From a Top Gas Fuel”的優先權益，其內容在此完全併入作為參考。
本發明大致關於一種將氧化鐵直接還原成金屬鐵等程序之方法及裝置。更特定言之，本發明關於一種結合此程序而從廢氣隔離二氧化碳之方法及裝置。
許多工業程序對於以直接還原程序從二級燃料來源(如爐頂氣體燃料來源)去除二氧化碳之有效及有效率方法存有需求。換言之，許多工業程序對於從廢料燃料來源去除二氧化碳，使其可作為一級燃料來源而無排放問題之有效及有效率方法存有需求。在某些情形，政府政策已要求此二氧化碳去除，而且未來二氧化碳排放控制之需求只會增加。直接還原涉及將氧化鐵礦還原成金屬鐵粒、團塊或緊縮體，其中氧化鐵係以一種含氫及/或一氧化碳之氣體還原，造成二氧化碳副產物。
在本發明之一個例示具體實施例中，一種從爐頂氣體燃料隔離二氧化碳之方法包括：假設爐頂氣體分成程序氣體與爐頂氣體燃料：混合程序氣體與烴且將所得重組器原料氣體進料至二氧化碳與蒸氣重組器中以將重組器原料氣體重組及形成還原氣體；及將爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一些二氧化碳，而且在加入進料至二氧化碳與蒸氣重組器中之烴後形成重組器燃料氣體。此方法亦包括壓縮程序氣體與爐頂氣體燃料。此方法進一步包括從爐頂氣體產生蒸氣。此方法更進一步包括洗滌爐頂氣體以除塵。視情況地，爐頂氣體係得自還原爐。視情況地，此方法更進一步包括混合還原氣體與氧及烴以形成環管氣體，及將環管氣體進料至還原爐中。二氧化碳洗滌器亦產生二氧化碳貧乏氣體。此方法更進一步包括混合二氧化碳貧乏氣體與還原氣體。視情況地，此方法更進一步包括將二氧化碳貧乏氣體在將其混合還原氣體或作為燃料之前預熱。二氧化碳與蒸氣重組器亦產生煙道氣體。此方法更進一步包括從煙道氣體產生蒸氣。視情況地，此方法更進一步包括使用煙道氣體將其他氣體預熱。視情況地，爐頂氣體與環管氣體結合用於將氧化鐵轉化成金屬鐵之直接還原程序。
在本發明之另一個例示具體實施例中，一種從爐頂氣體燃料隔離二氧化碳之裝置包括：一或多條用於將爐頂氣體分成程序氣體與爐頂氣體燃料之導管；一或多條用於混合程序氣體與烴，而且將所得重組器原料氣體進料至二氧化碳與蒸氣重組器中以將重組器原料氣體重組及形成還原氣體之導管；及一或多條用於將爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一部分二氧化碳，而且在加入進料至二氧化碳與蒸氣重組器中之烴後形成重組器燃料氣體之導管。此裝置亦包括一或多個用於壓縮程序氣體與爐頂氣體燃料之氣體壓縮。此裝置進一步包括一種用於從爐頂氣體產生蒸氣之低壓蒸氣鍋爐。此裝置又進一步包括一種用於洗滌爐頂氣體以除塵之濕式洗滌器。視情況地，爐頂氣體係得自還原爐。視情況地，此裝置又進一步包括一或多條用於混合還原氣體與氧及烴以形成環管氣體，而且將環管氣體進料至還原爐中之導管。二氧化碳洗滌器亦產生二氧化碳貧乏氣體。此裝置又進一步包括一或多條用於混合二氧化碳貧乏氣體與還原氣體之導管。視情況地，此裝置又進一步包括一種用於將二氧化碳貧乏氣體在將其混合還原氣體或作為燃料之前預熱之預熱器。二氧化碳與蒸氣重組器亦產生煙道氣體。此裝置又進一步包括一種用於從煙道氣體產生蒸氣之低壓蒸氣鍋爐。視情況地，此裝置又進一步包括一或多條用於使用煙道氣體將其他氣體預熱之導管。視情況地，爐頂氣體與環管氣體結合用於將氧化鐵轉化成金屬鐵之直接還原程序。
在本發明之一個進一步例示具體實施例中，一種從廢氣隔離二氧化碳，而且再使用作為再生氣體而無排放顧慮之方法包括：假設氣體來源分成程序氣體與廢氣：混合程序氣體與烴且將所得原料氣體進料至重組器中以將原料氣體重組及形成還原氣體；及將至少一部分廢氣進料至二氧化碳洗滌器中以從廢氣去除至少一些二氧化碳，而且形成混合還原氣體之二氧化碳貧乏氣體。視情況地，此方法亦包括將至少一部分廢氣進料至二氧化碳洗滌器中以從廢氣去除至少一些二氧化碳，而且在加入進料至重組器中之烴後形成燃料氣體。
本發明之二氧化碳隔離程序提供一種有效率迴路，藉此可使不欲之排放最小而再捕捉一級程序未使用且排放成為廢氣之二氧化碳與氫。
參考第1圖，在本發明之一個例示具體實施例中，從爐頂氣體燃料隔離二氧化碳之裝置10固有地包括垂直軸型還原爐12等。在此實例中，還原爐12包括將氧化鐵粒、團塊或緊縮體按預定速率進料至其中之進料漏斗(未描述)。氧化鐵粒、團塊或緊縮體因重力而從進料漏斗經亦作為氣體密封管線之進料管線(未描述)下降至還原爐12中。在還原爐12之底部為進一步作為氣體密封管線之排放管線(未描述)。如電動振動進料器等之排放進料器(未描述)係配置於排放管線下方且接收金屬鐵粒、團塊或緊縮體，因而建立一種通過還原爐12之爐料重力下降系統。
大約在還原爐12之中點為環管與風嘴系統(未描述)，還原氣體經其以約700度C至約1050度C間之溫度引入。熱還原氣體向上流經還原爐12之還原區域，對粒、團塊或緊縮體之流動為逆向，而且經位於還原爐12之頂部的氣體脫離管線(未描述)離開還原爐12。進料管線在氣體脫離管線下方延伸，此幾何排列製造廢氣脫離充氣室，其使廢氣從原料線脫離且自由地流向氣體脫離管線。從環管與風嘴系統流向氣體脫離管線之熱還原氣體係用以將氧化鐵粒、團塊或緊縮體加熱，而且將其還原成金屬粒、團塊或緊縮體(即經直接還原)。熱還原氣體含氫、氮、一氧化碳、二氧化碳、甲烷、與水蒸氣，其將氧化鐵粒、團塊或緊縮體還原且產生含二氧化碳與水蒸氣之廢氣或爐頂氣體。
參考第2圖，在此利用之直接還原程序藉由事先對還原氣體調整二氧化碳貧乏氣體、天然氣與氧條件，而控制環管氣體進入還原爐12之還原條件、溫度與化學。這些直接還原程序大致敘述於美國專利第3,748,120號，發明名稱”Method of Reducing Iron Oxide to Metallic Iron”，美國專利第3,749,386號，發明名稱”Method for Reducing Iron Oxides in a Gaseous Reduction Process”，美國專利第3,764,123號，發明名稱”Apparatus for Reducing Iron Oxide to Metallic Iron”，美國專利第3,816,101號，發明名稱”Method for Reducing Iron Oxides in a Gaseous Reduction Process”，美國專利第4,046,557號，發明名稱”Method for Producing Metallic Iron Particles”，美國專利第5,437,708號，發明名稱”Iron Carbide Production in Shaft Furnace”，其全部之內容在此全部併入作為參考。
還原爐爐料作用如同大型絕熱反應器且促進環管氣體注射區中之平衡條件。在環管氣體進入還原爐12且通過爐料時，氣體反應成其平衡組成物及溫度，其係在還原爐12之上部處的爐料熱偶上觀察。
碳化反應受以下之還原氣流因素影響：
1.　起初還原氣體氫：一氧化碳比例；
2.　起初還原氣體甲烷含量；
3.　起初還原氣體溫度；
4.　對還原氣體之天然氣加入；
5.　對還原氣體之氧加入；
6.　對還原氣體之二氧化碳貧乏氣體加入；
7.　最終環管氣體還原劑：氧化劑比例；及
8.　最終環管氣體壓力。
在正常操作條件下，密切地控制起初還原氣體品質且對直接還原程序變成主要安定性因素。隨著還原氣體流向還原爐12，基於最終環管氣體之甲烷含量分析加入天然氣。如此對起初還原氣體之任何甲烷含量變動提供安定化調整，而且影響最終環管氣體之碳化可能性。將氧加入還原氣體以增加最終環管氣體之溫度且改良鐵礦還原程序之動力學。
視情況地，使用之操作條件包括將天然氣加入預熱，還原氣體甲烷含量等於或小於約12%，及氧加入流動/噸等於或小於約30牛頓立方米/噸。
在直接還原裝置之使用期間，氣體離開還原氣體來源40，而且第一感應器實行氣體分析及測量氣體之溫度。然後在天然氣入口處混合天然氣與氣體。然後在氧入口處混合氧與氣體及天然氣混合物，因而形成環管氣體。在環管氣體進入還原爐12之前，第二感應器實行氣體分析及測量環管氣體之溫度。
再度參考第1圖，依照本發明，來自還原爐12之脫離氣體管線的爐頂氣體流經另一條管線(未描述)至低壓蒸氣鍋爐14。如此可有效率地產生蒸氣以用於程序他處，如以下詳述之二氧化碳去除步驟。將鍋爐原料水進料至低壓蒸氣鍋爐14，而且如以上所提及，將產生之蒸氣經程序再循環或用於他處。
然後以水輸出將爐頂氣體導向提供以冷卻爐頂氣體及除塵之濕式洗滌器20。濕式洗滌器20可為熟悉此技藝者已知之任何習知型式，如具填充塔之細腰管(未描述)，爐頂氣體向下流經細腰管，然後對冷卻水逆流而向上流經填充物。
爐頂氣體因閥(未描述)之影響分成二流離開濕式洗滌器20。第一流代表程序氣體及第二氣體代表爐頂氣體燃料(即廢氣)。這些流之比例係由二氧化碳與連接第一流之蒸氣重組器24中之可得熱界定，其一般固定，造成1:1(使用再生二氧化碳貧乏氣體)、2:1(不使用再生二氧化碳貧乏氣體)之例示比例等。
將來自濕式洗滌器20之程序氣體進料至壓縮機22且壓縮至所需壓力，然後進料至混合器(未描述)，在此將程序氣體混合天然氣。然後將此重組器原料氣體進料至二氧化碳與蒸氣重組器24中。二氧化碳與蒸氣重組器24包括燃料燃燒器(未描述)，其經燃燒產生含氮、二氧化碳與水之經加熱煙道氣體，及多條催化重組器管(未描述)，後者利用重組器原料氣體與燃燒熱形成還原氣體，其在引入氧、天然氣與二氧化碳貧乏氣體後被反饋至還原爐12中而生成環管氣體。
來自濕式洗滌器20之爐頂氣體燃料亦在引入二氧化碳洗滌器28之前進料至壓縮機26且壓縮至所需壓力。二氧化碳洗滌器28具有低壓蒸氣輸入，其視情況地得自從爐頂氣體燃料隔離二氧化碳之裝置10的任何低壓蒸氣鍋爐14、32，及鍋爐原料水、硫與二氧化碳輸出。鍋爐原料水可輸入從爐頂氣體燃料隔離二氧化碳之裝置10的任何低壓蒸氣鍋爐14、32。二氧化碳洗滌器28之其他輸出為二氧化碳貧乏氣體，其在混合天然氣時部分變成進料至二氧化碳與蒸氣重組器24中之重組器燃料氣體。
二氧化碳洗滌器28可包括任何型式之烷醇胺(如MEA、MDEA等)、或熟悉此技藝者已知之任何型式之鉀洗滌系統。低壓蒸氣係用以再產生用於二氧化碳洗滌器28之溶液，而且離開成為鍋爐原料水。在二氧化碳洗滌程序期間，硫與二氧化碳從爐頂氣體燃料隔離。無硫與二氧化碳之爐頂氣體燃料離開二氧化碳洗滌器28成為二氧化碳貧乏氣體。再度將一部分二氧化碳貧乏氣體混合天然氣以形成重組器燃料氣體，而且經燃料燃燒器引入二氧化碳與蒸氣重組器24中。將其餘二氧化碳貧乏氣體再生且混合還原氣體，其在引入氧與天然氣之後被反饋至還原爐12中，因而形成環管氣體。視情況地，將後部二氧化碳貧乏氣體或全流在將其混合現有還原氣體或作為燃料之前引入預熱器30中。
在本發明之一個例示具體實施例中，此二氧化碳貧乏氣體/還原氣體流最終代表約20%之供應還原爐12的環管氣體，而二氧化碳與蒸氣重組器還原氣體流最終代表約80%之供應還原爐12的環管氣體，雖然在此意圖為其他之百分比。
將煙道氣體脫離管線(未描述)提供於二氧化碳與蒸氣重組器24，以在燃燒後去除含氮、二氧化碳與水之煙道氣體。煙道氣體流經一或數個熱交換器，包括低壓蒸氣鍋爐32。如此再度可有效率地產生蒸氣以用於程序他處，如以上詳述之二氧化碳去除步驟。視情況地從二氧化碳洗滌器28將鍋爐原料水進料至低壓蒸氣鍋爐32，而且如以上所提及，將產生之蒸氣經程序再循環或用於他處。低壓蒸氣鍋爐32如此可連接選用預熱器30。
雖然本發明在此已參考其較佳具體實施例及指定實例而描述及敘述，其他之具體實施例及實例可實行類似功能及/或達成同等結果對熟悉此技藝者為顯而易知的。所有此種相同具體實施例及實例均在本發明之精神及範圍內，因而意圖包含且意圖涵蓋於以下之申請專利範圍。關於此點，本發明之以上詳細說明視為非限制且完全包含最大可能範圍。
10．．．從爐頂氣體燃料隔離二氧化碳之裝置
12．．．還原爐
14．．．低壓蒸氣鍋爐
20．．．濕式洗滌器
22．．．壓縮機
24．．．二氧化碳與蒸氣重組器
26．．．壓縮機
28．．．二氧化碳洗滌器
30．．．預熱器
32．．．低壓蒸氣鍋爐
40．．．還原氣體來源
本發明在此參考各圖式而描述及敘述，其中使用同樣之元件符號適當地表示相同之方法步驟/裝置組件，及其中：
第1圖為本發明從爐頂氣體燃料隔離二氧化碳之一個方法/裝置的程序/略示圖；及
第2圖為本發明之一個直接還原程序的程序/略示圖。
10．．．從爐頂氣體燃料隔離二氧化碳之裝置
12．．．還原爐
14．．．低壓蒸氣鍋爐
20．．．濕式洗滌器
22．．．壓縮機
24．．．二氧化碳與蒸氣重組器
26．．．壓縮機
28．．．二氧化碳洗滌器
30．．．預熱器
32．．．低壓蒸氣鍋爐

Claims (24)

  1. 一種從爐頂氣體燃料隔離二氧化碳之方法，其中該爐頂氣體係在還原爐中之一原料還原後得自該還原爐，該方法包含：假設爐頂氣體分成程序氣體與爐頂氣體燃料：混合程序氣體與烴且將所得重組器原料氣體進料至二氧化碳與蒸氣重組器中以將重組器原料氣體重組及形成還原氣體；及將至少一部分爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一些二氧化碳，而且形成選擇性混合還原氣體之二氧化碳貧乏氣體；其中該程序氣體對該爐頂氣體燃料之比例對於二氧化碳以及該重組器原料氣體所進料之蒸氣重組器中可得的熱係敏感的，其中在該二氧化碳貧乏氣體係完全用於混合還原氣體時，該程序氣體對該爐頂氣體燃料之比例為1：1，及當該二氧化碳貧乏氣體並未使用於混合還原氣體時，該比例為2：1。
  2. 如申請專利範圍第1項之方法，其進一步包含將至少一部分爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一些二氧化碳，而且在加入進料至二氧化碳與蒸氣重組器中之烴後形成重組器燃料氣體。
  3. 如申請專利範圍第2項之方法，其進一步包含壓縮程序 氣體與爐頂氣體燃料。
  4. 如申請專利範圍第1項之方法，其進一步包含從爐頂氣體產生蒸氣。
  5. 如申請專利範圍第4項之方法，其進一步包含洗滌爐頂氣體以除塵。
  6. 如申請專利範圍第1項之方法，其進一步包含混合還原氣體與氧及烴以形成環管氣體，及將環管氣體進料至還原爐中。
  7. 如申請專利範圍第1項之方法，其進一步包含將二氧化碳貧乏氣體在將其混合還原氣體及作為燃料之前預熱。
  8. 如申請專利範圍第1項之方法，其中二氧化碳與蒸氣重組器亦產生煙道氣體。
  9. 如申請專利範圍第8項之方法，其進一步包含從煙道氣體產生蒸氣。
  10. 如申請專利範圍第9項之方法，其進一步包含使用煙道氣體將其他氣體預熱。
  11. 如申請專利範圍第1項之方法，其中爐頂氣體與還原氣體結合用於將氧化鐵轉化成金屬鐵之直接還原程序。
  12. 一種從爐頂氣體燃料隔離二氧化碳之裝置，其中該爐頂氣體係在還原爐中之一原料還原後得自該還原爐，該裝置包含：一或多條用於將爐頂氣體分成程序氣體與爐頂氣體燃料之導管；一或多條用於混合程序氣體與烴，而且將所得重組 器原料氣體進料至二氧化碳與蒸氣重組器中以將重組器原料氣體重組及形成還原氣體之導管；及一或多條用於將至少一部分爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一部分二氧化碳，而且形成選擇性混合還原氣體之二氧化碳貧乏氣體之導管；其中該程序氣體對該爐頂氣體燃料之比例對於二氧化碳以及該重組器原料氣體所進料之蒸氣重組器中可得的熱係敏感的，其中在該二氧化碳貧乏氣體係完全用於混合還原氣體時，該程序氣體對該爐頂氣體燃料之比例為1：1，及當該二氧化碳貧乏氣體並未使用於混合還原氣體時，該比例為2：1。
  13. 如申請專利範圍第12項之裝置，其進一步包含一或多條用於將至少一部分爐頂氣體燃料進料至二氧化碳洗滌器中以從爐頂氣體燃料去除至少一些二氧化碳，而且在加入進料至二氧化碳與蒸氣重組器中之烴後形成重組器燃料氣體之導管。
  14. 如申請專利範圍第13項之裝置，其進一步包含一或多個用於壓縮程序氣體與爐頂氣體燃料之氣體壓縮機。
  15. 如申請專利範圍第12項之裝置，其進一步包含一種用於從爐頂氣體產生蒸氣之低壓蒸氣鍋爐。
  16. 如申請專利範圍第15項之裝置，其進一步包含一種用於洗滌爐頂氣體以除塵之濕式洗滌器。
  17. 如申請專利範圍第12項之裝置，其進一步包含一或多條用於混合還原氣體與氧及烴以形成環管氣體，而且將環管氣體進料至還原爐中之導管。
  18. 如申請專利範圍第12項之裝置，其進一步包含一種用於將二氧化碳貧乏氣體在將其混合還原氣體及作為燃料之前預熱之預熱器。
  19. 如申請專利範圍第12項之裝置，其中二氧化碳與蒸氣重組器亦產生煙道氣體。
  20. 如申請專利範圍第19項之裝置，其進一步包含一種用於從煙道氣體產生蒸氣之低壓蒸氣鍋爐。
  21. 如申請專利範圍第20項之裝置，其進一步包含一或多條用於使用煙道氣體將其他氣體預熱之導管。
  22. 如申請專利範圍第12項之裝置，其中將爐頂氣體與環管氣體結合用於將氧化鐵轉化成金屬鐵之直接還原程序。
  23. 一種從廢氣隔離二氧化碳且再使用其作為再生氣體而無排放顧慮之方法，其包含：假設氣體來源分成程序氣體與廢氣：混合程序氣體與烴且將所得原料氣體進料至重組器中以將原料氣體重組及形成還原氣體；及將至少一部分廢氣進料至二氧化碳洗滌器中以從廢氣去除至少一些二氧化碳，而且形成選擇性混合還原氣體之二氧化碳貧乏氣體；其中該程序氣體對該爐頂氣體燃料之比例對於二 氧化碳以及該重組器原料氣體所進料之蒸氣重組器中可得的熱係敏感的，其中在該二氧化碳貧乏氣體係完全用於混合還原氣體時，該程序氣體對該爐頂氣體燃料之比例為1：1，及當該二氧化碳貧乏氣體並未使用於混合還原氣體時，該比例為2：1。
  24. 如申請專利範圍第23項之方法，其進一步包含將至少一部分廢氣進料至二氧化碳洗滌器中以從廢氣去除至少一些二氧化碳，而且在加入進料至重組器中之烴後形成燃料氣體。
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