TWI567184B - 製備陶瓷複合粒子之方法 - Google Patents

製備陶瓷複合粒子之方法 Download PDF

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TWI567184B
TWI567184B TW103121110A TW103121110A TWI567184B TW I567184 B TWI567184 B TW I567184B TW 103121110 A TW103121110 A TW 103121110A TW 103121110 A TW103121110 A TW 103121110A TW I567184 B TWI567184 B TW I567184B
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reducer
gas
ceramic composite
particles
fuel
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TW103121110A
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TW201439304A (zh
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良 喜 方
李芳興
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美國州立俄亥俄大學
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Description

製備陶瓷複合粒子之方法
本發明大體係關於轉化碳質燃料之系統及方法。一般在一或多種化學中間物存在下利用還原-氧化(Reduction-Oxidation，redox)反應轉化該等碳質燃料。
為滿足日益增加之對清潔且可負擔之能量載體的需求且確保現代經濟持續增長，非常需要將諸如煤、原油、天然氣、生物質、瀝青砂及油葉岩之碳質燃料轉化成無碳能量載體的有效且環境友好之技術。能量載體為可用於產生機械功或熱或用於操作化學或物理過程之物質或現象。
現有碳質燃料轉化技術為資本密集型(氣化或超超臨界粉煤燃燒)，效率低(次臨界粉煤燃燒)，或兩者兼具，尤其當強制進行CO2調節時。
碳質燃料與空氣/蒸汽/CO2之間經由金屬氧化物介質輔助進行之化學反應可能代表轉化該等燃料之有效方式。已提出許多使用金屬氧化物轉化碳質燃料之技術。舉例而言，Watkins之美國專利第3,027,238號描述一種產生氫氣之方法，包括在還原區中還原金屬氧化物及在氧化區中用蒸汽氧化經還原金屬以產生氫氣。Thomas等人之美國公開申請案第2005/0175533號及Fan等人之PCT申請案第WO 2007/082089號皆描述產生氫氣之方法，其係藉由在碳基燃料與金屬 氧化物之間的還原反應中還原金屬氧化物以提供經還原金屬或具有較低氧化態之金屬氧化物，以及氧化該經還原金屬或金屬氧化物以產生氫氣及具有較高氧化態之金屬氧化物。金屬或金屬氧化物係以含有該金屬或金屬氧化物之陶瓷材料之多孔複合物形式提供。
一種熟知方法為蒸汽-鐵法，其中源自煤之發生氣(producer gas)與稍後將用蒸汽再生之氧化鐵粒子反應以產生氫氣。然而，此系統中所用之流體化床造成鐵(Fe)在FeO與Fe3O4之間循環轉化，因此氣體未完全轉化，且不會產生純氣流。Ishida等人之美國專利第5,447,024號描述使用氧化鎳粒子經由化學循環方法將天然氣轉化成將在渦輪機中使用之熱的方法。然而，此技術具有有限適用性，因為其僅可將昂貴之天然氣轉化成熱/電。因此，該方法之原料與產物皆受限制。
隨著對更清潔且更有效之能量載體(諸如電、氫氣及燃料)的需求漸增，對於以較高效率及較低排放量產生上述能量載體之改良系統及其中之系統組件的需要增加。
本發明之實施例提供將固體、液體及氣體燃料轉化成有效能量載體之新穎系統及方法。在一實施例中，提供一種轉化固體、液體或氣體燃料之系統，該系統包含第一反應器，其包含複數個陶瓷複合粒子。該等陶瓷複合粒子包含置於支撐物上之至少一種金屬氧化物，且該第一反應器經配置以用燃料還原該至少一種金屬氧化物從而產生經還原金屬或經還原金屬氧化物。該系統包括第二反應器，其經配置以至少部分地再氧化該經還原金屬或經還原金屬氧化物從而產生金屬氧化物中間物。該系統亦包括空氣源及與該空氣源連通之第三反應器，該第三反應器經配置以藉由氧化該金屬氧化物中間物而再生至少一種金屬氧化物。在較佳形式中，燃料為固體燃料或氣體燃料。視情況，將燃料轉化率提高氣體(較佳包括CO2、蒸汽及/或H2)送至第一反應 器，其中氣體以與固體流動逆流之方式流動。
本發明亦提供一種製備陶瓷複合粒子(例如呈圓粒形式)之方法，其包含以下步驟：將金屬氧化物與至少一種陶瓷材料混合以形成混合物；將該混合物粒化；及乾燥該粒狀混合物。將經乾燥之粒狀混合物加工成粒子形式以使得粒子之特徵長度大於約200μm。在約500℃至約1500℃之溫度下熱處理該等粒子且視情況可在用於反應器系統中之前還原及氧化。
鑒於以下實施方式、隨附圖式及隨附申請專利範圍，將更充分瞭解由本文所述標的物之實施例提供的其他特徵及優點。
10‧‧‧系統
11‧‧‧管道
12‧‧‧第一反應器/還原器
13‧‧‧殼面
14‧‧‧燃料源/氧化器/管線
14a‧‧‧固體燃料注入口
14b‧‧‧固體燃料注入口
14c‧‧‧固體燃料注入口
15‧‧‧管面
16‧‧‧容器
18‧‧‧管線
19‧‧‧熱交換器/管道
20‧‧‧分離器
21‧‧‧管線
22‧‧‧第二反應器/氧化器/反應器
23‧‧‧管線
24‧‧‧第三反應器/燃燒器
25‧‧‧熱交換器
26‧‧‧管線
27‧‧‧分離器
28‧‧‧壓縮機/還原器12之固體出口/管線
30‧‧‧還原器12之氣體出口
32‧‧‧上級/第一級
34‧‧‧下級/第二級
35‧‧‧管線
36‧‧‧漏斗狀出口
36a‧‧‧漏斗狀出口
36b‧‧‧漏斗狀出口
36c‧‧‧漏斗狀出口
37‧‧‧管線
40‧‧‧管線/第一級之環形區域/孔口
42‧‧‧第二級之固體出口/管線
60‧‧‧膨脹器
62‧‧‧渦輪機
64‧‧‧發電機
66‧‧‧電
70‧‧‧管線
74‧‧‧管線
80‧‧‧氫氣產生反應器
82‧‧‧還原器級/還原器
84‧‧‧氧化器級/氧化器
92‧‧‧再生之粒子
94‧‧‧管線
96‧‧‧管線
98‧‧‧經氧化粒子
100‧‧‧蒸汽或電力
A‧‧‧連接
B‧‧‧連接
C‧‧‧連接
H‧‧‧箭頭
圖1為一實施例之示意圖，其中提供無需空氣分離單元(Air Separation Unit；ASU)而自煤及/或生物質產生氫氣及/或電的系統；圖2A為將煤及/或生物質轉化成CO2及蒸汽，同時將複合粒子中之Fe2O3還原成Fe及FeO之還原器的示意圖；圖2B及圖2C說明還原器中用於固體燃料注入及反應器出口之替代設計；圖3為煤焦/生物質轉化率提高流程之示意圖；圖4A及圖4B為還原器之第一級及第二級中氣固流動模式之示意圖；圖5為展示移動床還原器之實施例中煤與氧載體之轉化的圖；圖6為將碳質燃料轉化成氫氣、可封存CO2及熱量之系統之替代實施例的示意圖；圖7說明碳質燃料轉化系統之實施例的熱整合流程；圖8為將氣體燃料(諸如合成氣、甲烷及其他烴類)轉化成氫氣及/或電之系統的示意圖； 圖9為展示移動床還原器中合成氣及氧化鐵之轉化的圖；圖10為展示移動床還原器中甲烷及氧化鐵之轉化的圖；圖11為展示自移動床氧化器產生之氫氣之濃度的圖；圖12為展示根據本發明之一實施例所製得之基於Fe2O3的金屬氧化物複合粒子之抗壓強度的圖；圖13為展示多次還原氧化循環之後氧載體粒子之損耗率的圖；圖14為展示氧載體粒子關於還原氧化循環次數之還原氧化率的圖；圖15為展示與煤反應四個還原-氧化循環、與合成氣反應三個還原-氧化循環及與天然氣反應一個還原-氧化循環之後氧載體粒子之反應性的圖；圖16為說明還原器之一實施例之所要操作線的圖；圖17為自生物質產生電之實施例的示意圖；圖18為自天然氣或其他富含甲烷之氣體產生氫氣/電之實施例的示意圖；圖19為使用非機械氣體密封件及固體流動控制裝置之還原氧化系統之設計的示意圖；且圖20A至圖20D說明用於非機械氣體密封及固體流動控制之替代設計。
當結合以下圖式理解時，可最佳理解本文所述標的物之說明性實施例的以下實施方式，其中相同結構係用相同參考數字指示。
一般參看圖1及圖8，本文所述標的物之實施例係關於藉由金屬氧化物陶瓷複合物之還原氧化反應將碳質燃料轉化成無碳能量載體(諸如氫氣、熱及電)的系統及方法。圖1說明當將固體碳質燃料直接用作原料時系統配置之一實施例，而圖8說明當將氣體碳質燃料用作 原料時系統配置之一實施例。
在圖1中所說明之實施例中，系統10包括第一反應器12(本文中亦稱為還原器)，其經配置以將來自燃料源14之固體碳質燃料氧化成CO2及蒸汽，同時還原在系統中充當氧載體之基於金屬氧化物的陶瓷複合粒子。可藉由將固體燃料夾帶於諸如含氧氣體之氣流中而供給固體燃料。如圖所示，一批金屬氧化物複合粒子係儲存於容器16中且根據需要供給還原器12。其他複合粒子可根據需要經由如圖1中所示之管道11添加。還原器12中所需之熱量或產生之熱量至少部分地由金屬氧化物氧載體粒子提供或移除。燃料之燃燒產物CO2及蒸汽係經由管線18自還原器12移除。如圖所示，藉由使氣流通過熱交換器19(自管線21向其中饋入諸如水之冷卻劑)來冷凝該蒸汽。在分離器20中視情況移除諸如汞之污染物之後，將CO2氣流送至封存。通常，相對純(亦即>95%)之CO2氣流係由還原器12產生。
第二反應器22(本文中亦稱為氧化器)經配置以(部分地)用蒸汽及/或CO2氧化一部分或所有的經還原金屬氧化物氧載體粒子且產生實質純氫氣流。經由管線23自氧化器22移除氫氣。如圖所示，可使用熱交換器25將熱氫氣流用於加熱管線40中之輸入蒸汽。氫氣流中之任何污染物(諸如硫化氫氣體)皆可經由分離器27移除。氫氣可例如用於發電、合成液體燃料或其他用途。第三反應器24(本文中亦稱為燃燒器)利用例如穿過視情況選用之壓縮機28經由管線26供給之諸如空氣的含氧氣體，使來自氧化器22的部分氧化之金屬氧化物氧載體粒子及來自還原器12的剩餘經還原金屬氧化物氧載體粒子燃燒。在還原器12需要額外之熱量的情況下，將至少一部分自燃燒器24產生之熱整合至還原器。在一些情況下，可使用空氣分離單元(未圖示)自空氣中分離氧氣且將該氧氣送至還原器中以部分燃燒燃料且向還原器12提供額外之熱量。然而，該空氣分離單元之容量比具有相同燃料處理能力之習知氣 化工廠中所使用之空氣分離單元的容量小得多。因此，圖1中說明之系統及方法之一個優點為其可減小空氣分離單元之尺寸或不需要自空氣中分離氧氣之空氣分離單元。此降低構建及操作燃料轉化系統之資金成本，且提高該系統之總效率。在較佳實施例中，空氣分離單元得以完全避免。儘管圖1中說明之系統描繪固體燃料轉化，但亦可利用此系統轉化氣體燃料及液體燃料。燃燒器24中之操作壓力可與還原器及氧化器中之壓力相當，或可能不同。在前者情況下，適宜使用基於非機械之固體及氣體流動控制裝置來連接反應器。在後者情況下，應使用機械閥門。然而，燃燒器可在較低壓力下操作，使得燃燒器能量消耗減少。此外，可由自還原器排出之固體提取熱量，以便氧化器在顯著低於還原器溫度之溫度下操作。藉此，蒸汽成為氫氣之轉化率得以提高。
如圖1中所示，可將來自燃燒器24之熱廢氣視情況送至與渦輪機62及發電機64耦接之膨脹器60且用於產生電66。可將來自膨脹器之廢氣送至分離設備用於移除污染物，諸如硫氧化物及氮氧化物。
可藉助於以下舉措產生額外之熱量：i)將較小分率之經還原金屬氧化物氧載體粒子自還原器12引入氧化器14中，同時將剩餘之經還原金屬氧化物氧載體粒子直接引至燃燒器24；或ii)將低於化學計量之量的蒸汽及/或CO2引至氧化器22中以便該蒸汽及/或CO2使經還原金屬氧化物氧載體粒子不完全再生。
該氧載體包含複數個具有置於陶瓷支撐物上之至少一種金屬氧化物的陶瓷複合粒子。本發明之系統及方法中使用之合適的陶瓷複合粒子描述於Thomas美國公開申請案第2005/0175533號及Fan等人之PCT申請案第WO 2007/082089號中。除Thomas所描述之粒子及粒子配方及合成方法之外，在如下所述之另一實施例中，已開發改良陶瓷複合粒子之效能及強度之方法。
其他實施例包括將金屬氧化物與至少一種呈粉末形式之陶瓷支撐材料混合之步驟，接著為視情況選用的在添加水或諸如澱粉、矽酸鈉及/或矽酸鉀之黏合材料之情況下進行之粒化步驟。在粒化之前的混合步驟中可添加促進劑材料。隨後在空氣或氮氣中在約50℃至500℃之間的溫度下乾燥該粒狀粉末，使水分含量減少至低於10%。隨後將粒狀粉末加工成特徵長度大於約200μm之圓粒。將粒狀粉末轉化成圓粒之方法可能包括(但不限於)擠壓、粒化，及諸如造粒之加壓方法。用於產生圓粒之壓力在約0.1MPa至25MPa範圍內。
製得含金屬氧化物之陶瓷複合粒子之後，進行最終處理步驟。最終處理步驟包括在500℃至1500℃下燒結該等粒子，隨後用氫氣還原粒子中之金屬氧化物且接著用空氣氧化粒子歷時至少一個還原-氧化循環以穩定化粒子之效能。應注意到在此方法之後由反應器系統中損耗所產生之廢粉末可經再加工及再活化。
金屬氧化物組份較佳包含選自由Fe、Cu、Ni、Sn、Co、Mn、In及其組合組成之群的金屬。支撐材料包含至少一種選自由SiC；Al、Zr、Ti、Y、Si、La、Sr、Ba之氧化物及其組合組成之群的組份。此等支撐物包括天然礦石，諸如膨潤土及海泡石。陶瓷複合物包含至少約10重量%之支撐材料。在其他實施例中，粒子包含促進劑材料。促進劑包含純金屬、金屬氧化物、金屬硫化物或其組合。此等基於金屬之化合物包含一或多種來自由Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba、B、P、V、Cr、Mn、Co、Cu、Zn、Ga、Mo、Rh、Pt、Pd、Ag及Ru組成之群的元素。陶瓷複合物包含至多約20重量%之促進劑材料。在陶瓷複合物之例示性實施例中，金屬氧化物包含支撐於氧化鋁(Al2O3)與銳鈦礦(TiO2)之混合物的支撐物上之Fe2O3。
再參看還原器12中進行之還原反應，還原器利用固體碳質燃料(諸如煤、焦油、生物質、油葉岩、油砂、瀝青砂、蠟、焦炭及其類 似物)來還原陶瓷複合粒子之至少一種金屬氧化物以產生經還原金屬及/或金屬氧化物之混合物。燃料較佳以微粒形式供給還原器。可能之還原反應包括(但不限於)：2Fe2O3+C → 4FeO+CO2
C+CO2 → 2CO
C+H2O → CO+H2
Fe2O3+CO/H2 → 2FeO+CO2/H2O
FeO+CO/H2 → Fe+CO2/H2O
還原器之較佳設計包括具有一或多級之移動床反應器、多級流體化床反應器、階段反應器(step reactor)、旋轉窯或熟習此項技術者已知之任何其他合適的反應器或容器。在任何反應器設計中，使用金屬氧化物氧載體固體粒子與氣體之間逆流流動之模式來提高氣體及固體之轉化率。逆流流動模式使金屬氧化物複合物氧載體固體與氣體之逆向混合最小化。此外，逆流流動使還原器12之固體出口28維持還原性較強之環境，而還原器12之氣體出口30則維持氧化性較強之環境。因此，基於熱力學原理，氣體及固體轉化率皆得以提高。
圖16例示基於熱力學分析，利用合成氣作為原料之還原器的較佳操作線。較佳操作線(實心直線)對應於氣態合成氣燃料完全轉化(轉化率>99%)成CO2及蒸汽，同時氧載體粒子(諸如含氧化鐵之複合粒子)之還原接近50%。類似地，當使用諸如煤之固體燃料時較佳操作模式將使煤完全轉化(轉化率>99%)成CO2及蒸汽，同時視煤之等級而定使氧化鐵氧載體複合粒子還原33%-85%。一般而言，還原器中之操作條件係經配置以便至少95%之碳質燃料轉化成具有高CO2及蒸汽濃度之氣流，同時使複合粒子中之氧化鐵還原33%-85%。較佳氧化鐵還原率為約36%-85%。經還原之氧化鐵較佳應具有約1：25至3.55：1之間的金屬鐵：方鐵礦之莫耳比。
碳質燃料之轉化率定義為：X 氣體 =n o_消耗 /n o_完全轉化
no_消耗係指還原器中自氧載體轉移至燃料之氧莫耳數；no_完全轉化表示將燃料完全轉化成CO2及蒸汽所需之氧莫耳數。
氧化鐵(或上述任何類型之金屬氧化物)之轉化率定義為：
本文中，n O /n Fe 對應於Fe2O3中氧原子與鐵原子之間的莫耳比，而/對應於經還原固體產物(亦即FeOx(0<x<1.5))中氧原子與鐵原子之間的莫耳比。舉例而言，Fe2O3還原為Fe3O4對應於(3/2-4/3)/(3/2)×100%=11.11%之固體轉化率，還原為FeO對應於33.33%之轉化率，而還原為Fe則對應於100%之固體轉化率。其他金屬氧化物轉化率之定義遵循類似定義。當使用其他金屬時，類似定義適用。
圖2說明經配置用於固體碳質燃料轉化之還原器12的特定實施例。提供二級移動床。上級32(第一級)將來自下級34(第二級)之氣相及來自固體燃料之揮發物轉化成CO2及蒸汽，同時下級34轉化自管線14饋入還原器中之固體燃料，諸如粉狀(亦即微粒)煤、焦炭生物質或煤焦。經由管線70進入第一級之金屬氧化物粒子(例如含Fe2O3之粒子)以經還原金屬(例如鐵)與金屬氧化物(例如FeO)之混合物形式經由管線28離開第二級。含氧氣體及視情況選用之增強燃燒之氣體(諸如CO2、H2O或H2)係經由管線74饋入第二級之底部；熱的燃燒氣體、CO2及蒸汽經由管線18離開第一級之頂部。舉例而言，當將含Fe2O3之粒子用作氧載體時，Fe2O3轉化率介於20%與85%之間。還原器之二級設計使固體與固體以及固體與氣體皆得以良好混合。此外，可容易地達成固體移動。在某些實施例中，還原器中之氣相夾帶一部分粉狀固體燃料。因此，一部分固體燃料向上移動且在第一級與第二級中燃燒。因 此，視燃料之物理及化學性質以及反應器中之操作條件而定，反應器第二級之高度可能比反應器第一級之高度顯著較短或較長。由於反應器設計之靈活性，固體燃料之注入點可改變至還原器入口與還原器出口之間的任何位置。
在某些實施例中，經由管線14在還原器第一級32與還原器第二級34之間注入還原器中之粉狀固體燃料係由還原器中之氣相夾帶，且相對於金屬氧化物氧載體微粒固體逆流流動。在夾帶步驟期間，固體燃料轉化成CO2及蒸汽。至少95%之燃料將在離開還原器12之第一級的頂部之前轉化。一部分灰分亦可經夾帶且自還原器之第一級之頂部移除。如圖2B及圖2C中所示，粉狀固體燃料可在多個位置處注入反應器中從而使反應器中之燃料較佳分配。
還原器12之第一級及第二級中進行之反應包括：粒子還原：CH4+4Fe2O3 → CO2+2H2O+8 FeO
煤脫揮發：煤 → C+CH4
CO+FeO → Fe+CO2
C+CO2 → 2CO
煤焦(Char)氣化及粒子還原： C+CO2 → 2CO
C+H2O → CO+H2
CO+FeO → Fe+CO2
H2+FeO → Fe+H2O
與固體燃料轉化率有關之一個問題為固體燃料轉化率之提高。圖3說明藉由將CO2添加至圖2中之還原器第二級之底部來提高固體轉化率的流程。添加CO2引發碳氣化同時金屬氧化物還原之「連鎖反應」。在此過程中，將產生更多充當氣化增進劑之CO2，使反應速率進一步提高。其他氣化增進劑包括H2O及H2。應注意到：儘管CO2及 H2O之注入可能稍微影響金屬氧化物轉化率，但仍認為其為可行之氣化增進劑，因為其在燃料轉化系統中易於獲得。獲得該等增進劑之一種方法為將來自還原器第一級之廢氣的一部分(其含有CO2及蒸汽)再循環至還原器第二級之固體出口(底部)。因為CO及H2與金屬氧化物的反應比烴或固體燃料與金屬氧化物的反應快，所以上述燃料轉化率提高技術亦可應用於諸如甲烷及較高碳數烴之氣體/液體碳質燃料的轉化。
圖4另外說明還原器第一級之固體出口(底部)以及還原器第二級之固體出口(底部)的較佳設計。第一級具有受限流動出口，諸如在內壁上具有多個刀片38之漏斗狀出口36。該設計使氣體自第二級之頂部滲透至第一級。其間，基於金屬氧化物之陶瓷複合粒子將自出口36以受控方式排出。在第一級底部與第二級頂部之間形成固體粒子丘。將固體燃料分散至第一級之環形區域40處且與基於金屬氧化物之陶瓷複合粒子充分混合。第二級之固體出口42亦使用諸如漏斗形狀之受限流動設計。該漏斗較佳具有約15°至75°之角度。該角度使具有不同尺寸之固體以類似速度向下移動，進而避免較小固體以比較大固體快得多之速率離開還原器。此外，該等固體將充當氣體分配器以確保固體與氣體之間混合良好。在某些實施例中，可使用多個漏斗狀固體出口，尤其對於第一級出口而言。圖2，尤其圖2B及圖2C，說明出口設計之一實例，其中使用具有三個固體燃料注入口14a、14b及14c的三個漏斗狀出口36a、36b及36c。此設計提供更均勻之反應器中固體分配。亦可使用其他配置之漏斗狀出口及固體燃料注入口。
有效調節反應器之間的氣體及固體流動係重要的。可使用諸如旋轉閥或球閥之機械閥門台式進料機系統來控制固體及氣體移動。亦可使用非機械閥門、環封及/或帶封來調節氣體及固體流動。圖20中示意性說明若干種合適之非機械氣體密封及固體流動控制裝置。此等 裝置可安裝於反應器或反應器級之間以控制各級之間的材料流動。
圖5進一步以圖表形式說明移動床還原器中獲得的基於氧化鐵之微粒氧載體與煤之轉化率。更詳細結果列於下表1中。
一般而言，可獲得>90%之固體燃料轉化率以及約33%-85%之金屬氧化物轉化率。來自還原器之廢氣流在蒸汽冷凝後具有>95%之CO2。
現參看圖17，其中相同參考數字表示相同元件，以示意形式展示自生物質產生電之實施例。該配置與圖1中所示類似。在此實施例中，所有經還原金屬氧化物粒子係直接送至燃燒器24。因此，氧化器(未圖示)完全被繞過。圖2中展示此實施例之還原器的較佳配置。自系統產生之熱氣流可用於鍋爐/熱回收蒸汽發生器(Heat Recovery Steam Generator；HRSG)或具有膨脹器/氣體渦輪機之組合循環系統中以供發電。類似地，儘管圖1中出於說明性目的展示膨脹器，但圖1所示之實施例中之燃燒器熱氣體亦可用於鍋爐/HRSG中。可用於圖1所示之過程中之金屬包括Fe、Ni、Cu及Mn。當使用Fe2O3時，就發電目的而言較佳之固體還原率為11%至75%。表2展示自生物質氣化所獲得之實驗結果：
在一些情況下，固體燃料可含有諸如灰分、硫及汞之雜質。固體燃料中之灰分將連同基於金屬氧化物之陶瓷複合物一起離開還原器。在高溫下，一部分硫亦將以諸如FeS(Fe0.877S)之金屬硫化合物的形式離開還原器。其餘硫以H2S/SO2之形式離開還原器。硫無需處理可連同CO2一起封存。所有汞亦將連同廢氣流一起離開還原器。可使用已知技術或封存來移除汞。
再參看圖1，離開還原器12之一部分固體將進入第二反應器22(氧化器)。氧化器之較佳設計包括移動床反應器、多級流體化床反應器、階段反應器、旋轉窯或熟習此項技術者已知之任何其他合適之反應器或容器。在任何反應器設計中，使用氧載體固體粒子與氣體之間的逆流流動模式來提高氣體及固體之轉化率。逆流流動模式最小化氧載體固體與氣體之逆向混合。此外，逆流流動使反應器22之固體出口保持氧化性較強之環境，而反應器22之氣體出口則維持還原性較強之環境。因此，氣體及固體轉化率皆得以提高。
還原器12、氧化器22及燃燒器24之間的連接可為機械連接，亦即旋轉閥或閉鎖式料斗總成。在另一設計中，還原器12、氧化器22及燃燒器24係使用非機械性閥門及氣體密封件(諸如循環流體化床或流體催化裂解器中所使用者)直接連接。反應器中之壓力差以及少量通氣氣體(aeration gas)阻止產物氣體自氧化器22洩漏至還原器12中，或反之，阻止產物氣體自還原器12洩漏至氧化器22中。圖19中說明該非 機械性反應器設計。僅使用三種連接(圖19中之「A」、「B」及「C」)中之一種來控制反應器系統中之總固體循環率。較佳使用氧化器22與燃燒器24之間的連接(圖19中之連接「C」)來調節固體流動。用於反應器各級之間之此連接的合適非機械性閥門包括L-閥門、J-閥門、環封或N-閥門。此處所使用之通氣氣體可為蒸汽及/或廢氣。對於燃燒器24與還原器12之間的連接(圖19中之連接「A」)，可使用帶封或環封，以CO2及/或廢氣作為通氣氣體。對於還原器12與氧化器22之間的連接(圖19中之連接「B」)，可使用帶封或環封，以H2及/或蒸汽作為通氣氣體。非機械性氣體密封件及固體閥門之較佳設計展示於圖20A(N-閥門)、圖20B(L-閥門)、圖20C(環封)及圖20D(豎管及帶封)中。還原器12與氧化器22皆安裝相對平滑之漏斗狀反應器出口以確保反應器(具有大內徑)與非機械性裝置(具有小得多之內徑)之間的平滑連接。此減少通氣氣體之用量。燃燒器24與還原器12之間亦可安裝微粒分離裝置(未圖示)。該裝置係用來自燃燒器廢氣中分離細末。較佳分離裝置具有兩級以上。第一級自細粉末及廢氣中分離出較大微粒(例如20至200+μm)。第二級自廢氣中分離出較小細末。該等細末可經再加工成較大粒子/圓粒。
氧化器22之氣體原料可為蒸汽、CO2或其組合，且經由管線40進入。當使用蒸汽時，視氧化器溫度及還原器中之固體轉化率而定，氧化器之蒸汽轉化率可能介於約50%至99%之間。當使用基於Fe2O3之陶瓷複合粒子時，為達成最佳蒸汽轉化率，至少5%(以莫耳計)之鐵相較佳。當使用CO2時，氣體轉化率(40%至95%)亦取決於溫度及固體轉化率。當使用CO2與蒸汽之混合物時，可將氧化器產物流冷凝且部分再循環以減少最終產物流中之CO2濃度且提高氣體轉化率。
還原器12中形成之金屬硫化合物將在氧化器22中部分再生，產生H2S。因此，氧化器之產物流通常受多達750ppm之H2S污染。可經 由吸附劑技術、溶劑技術或其他傳統之酸移除技術來移除H2S。金屬氧化物陶瓷複合物中之灰分不會在氧化器中反應且將連同部分再生之金屬氧化物陶瓷複合物一起排出。當使用基於Fe2O3之陶瓷複合物時，來自氧化器之固體產物中之鐵相主要為具有一些剩餘金屬硫化合物之Fe3O4。在某些實施例中，引入低於化學計量之量的蒸汽/CO2以使經還原氧化鐵再生為低於Fe3O4之氧化態，例如Fe/FeO混合物、FeO，或FeO/Fe3O4混合物。藉此，可自後續燃燒器產生之熱量將依靠減少氧化器中氫氣/CO之產生來增加。
再參看圖1，來自氧化器之部分再生金屬氧化物陶瓷複合粒子連同來自還原器12之一部分經還原陶瓷複合粒子一起引至第三反應器24(燃燒器)。燃燒器24之較佳設計包括快速流體化床反應器、夾帶床反應器、傳輸床反應器或機械輸送系統。視情況，為提供金屬氧化物陶瓷複合物再生之足夠時間，第三反應器24可採用兩級設計。在該設計之情況下，位於底部之第三反應器之I級係以鼓泡或擾流流體化方式操作以提供足夠之固體及氣體滯留時間。當使用該設計時，I級之直徑通常比II級之直徑大。
使用燃燒器24來將基於金屬氧化物之陶瓷複合物實質上完全氧化回至其較高氧化態。空氣或其他含氧氣體可用於燃燒器中。在比入口氣體溫度高得多之溫度下，來自燃燒器之氣體產物為貧氧氣體。氣體產物亦可含有SO2及NOx。當使用基於Fe2O3之陶瓷複合物時，固體產物中之鐵相主要為Fe2O3。灰分亦將連同由損耗所產生之陶瓷複合物細粉末一起出來。一部分灰分可自還原器之氣體出口離開。
在燃燒器24中產生大量熱。在一配置中，熱量由氣體產物與固體產物帶離燃燒器。固體產物經由管線42直接注回還原器12中。因此，固體產物中所攜帶之顯熱用來補償還原器12中所需之熱量。此外，廢氣中所含之顯熱亦可經由熱交換轉移至還原器。
灰分與廢陶瓷複合物可使用諸如漩渦分離(cyclone)之機械方法分離。當使用菸煤作為固體燃料時，在機械分離15秒之情況下，證實灰分分離效率為至少75.8%，其對應於陶瓷複合物中具有小於1%之灰分含量。
現參看圖6，圖6例示燃料轉化系統之一個替代配置。在此配置中，其中相同參考數字表示相同元件，第一反應器12整合還原器與燃燒器之功能(諸如圖1之配置中所示)。第一反應器12具有殼面13及管面15。固體或氣體碳質燃料係經由管線14引入殼面13中，且自容器16供給之陶瓷複合粒子亦在殼面中轉化(亦即經還原)。來自殼面之一部分經還原固體直接經由管道19再循環至管面且與空氣燃燒。燃燒中所釋放之熱量補償殼面中所需之熱量。此外，來自第三反應器24(燃燒器)之熱固體亦將部分補償還原器12中所需之熱量。蒸汽及CO2係經由孔口40供給氧化器22，同時氫氣流係經由管線23移除。具有再生之金屬氧化物的陶瓷複合粒子自燃燒器24送回至容器16。來自彼等粒子之熱量可經捕獲且用於產生蒸汽或發電(由管線35所指示)。灰分及廢粒子係經由管線37移除。
現參看圖7，其中相同參考數字指示相同元件，圖7說明該過程中之一般化熱整合流程。在該流程中，燃燒器24中所產生之熱量用於：1)補償還原器12中之熱量需求，及2)為附加能量消耗發電。熱整 合之目標在於使系統中產生之過量熱最小化，從而使燃料至產物之能量轉化最大化。如圖所示，金屬氧化物粒子係在還原器12中還原，且經還原粒子經由管線94及96送至氧化器22及燃燒器24。經氧化粒子98自氧化器22送至燃燒器24，同時再生之粒子92再循環回至還原器12。由該等反應產生之熱量(以箭頭H顯示)用於向還原器12供給任何需要之熱量且用於產生蒸汽或電功率(在100處)。
現參看圖8，其中相同參考數字指示相同元件，圖8說明轉化氣體/液體碳質燃料之一般化系統。液體碳質燃料可包括汽油、油、石油、柴油、噴射機燃料、乙醇及其類似物；而氣體碳質燃料包括合成氣、甲烷、一氧化碳、氫氣、氣態烴氣體(C1-C6)、烴蒸氣及其類似物。
在圖8所說明之實施例中，諸如合成氣燃料或甲烷之氣體燃料經轉化，且系統可分成兩個反應器：氫氣產生反應器80及燃燒器86。氫氣產生反應器可進一步分成兩級：還原器級82及氧化器級84。亦可認為氫氣產生反應器中之各級為獨立反應器。
氫氣產生反應器之較佳設計包括具有一或多級之移動床反應器、多級流體化床反應器、階段反應器、旋轉窯或熟習此項技術者已知之任何合適的反應器或容器。在任何反應器設計中，在固體與氣體之間使用逆流流動模式來提高氣體及固體轉化率。逆流流動模式使固體與氣體之逆向混合最小化。此外，其在熱力學上提高氣體及固體之轉化率。固體之滯留時間通常在約15分鐘至約4小時範圍內。還原器滯留時間通常在約7.5分鐘至約2小時範圍內，且氧化器滯留時間通常亦在約7.5分鐘至約2小時範圍內。
在還原器82中，在還原器之底部或底部附近引入氣體燃料，且接著以相對於陶瓷複合粒子呈逆流方式移動。當使用合成氣作為燃料時，可能之反應包括： Fe2O3+CO/H2 → 2FeO+CO2/H2O
FeO+CO/H2 → Fe+CO2/H2O
當使用天然氣或其他富含甲烷之氣體氣作為燃料時，可能之反應包括：4Fe2O3+CH4 → 8FeO+CO2+2H2O
4FeO+CH4 → 4Fe+CO2+2H2O
CH4+H2O → CO+3H2
CH4+CO2 → 2CO+2H2
Fe2O3+CO/H2 → 2FeO+CO2/H2O
FeO+CO/H2 → Fe+CO2/H2O
亦可基於類似於圖3中所示之機構將諸如CO2、蒸汽及/或氫氣之燃料轉化增進劑引入還原器級82中以提高甲烷轉化率。甲烷及其他氣體/液體碳質燃料轉化之熱整合流程類似於固體燃料轉化流程中所闡述。圖18說明甲烷轉化之一實施例。
圖16中所示之實心操作線為合成氣轉化之理想操作線。甲烷及其他燃料轉化之操作線展示與圖16類似之性質。儘管操作線之斜率可在各種操作溫度、燃料組成及壓力下變化，但金屬氧化物複合粒子與氣體燃料之間的化學計量比通常維持在約3：1至1.18：1。因此，當大於95%之氣體燃料轉化成CO2及H2O時，金屬氧化物轉化率通常在33%至85%範圍內。舉例而言，當使用甲烷時，金屬氧化物轉化率通常在介於35%與70%之間的範圍內。當使用基於Fe2O3之陶瓷複合粒子時，來自還原器之產物為鐵與方鐵礦之混合物。
可預先處理氣體燃料以使其含有小於750ppm之H2S、COS及一些元素汞。還原器配置及陶瓷複合粒子將使得H2S、COS及汞離開還原器而不與陶瓷複合物反應。因此，此等污染物可連同CO2一起封存。
圖9說明當使用合成氣作為氣體燃料時，合成氣及氧化鐵在移動床還原器級中之轉化率。圖10說明當使用甲烷作為氣體燃料時，甲烷及Fe2O3在移動床還原器級中之轉化率。在兩種情況下均使用基於Fe2O3之陶瓷複合物。如圖可見，在約50% Fe2O3轉化時可達成99.8%以上之燃料轉化率。
接著將一部分經還原之陶瓷複合物引入氧化器84中。在氧化器中，在底部或底部附近引入蒸汽及/或CO2，且使其以相對於固體呈逆流方式流動。氧化器配置以及氣體及固體轉化率與先前所述之固體燃料轉化系統中之還原器類似。
圖11展示在移動床氧化器操作期間氫氣產物之濃度。達成>99%之平均氫氣純度。
圖8中所示之燃燒器與燃料轉化系統中之燃燒器類似。較佳熱整合流程利用來自燃燒器之熱量來提供還原器中之熱量需求。在較佳配置中，使用漩渦分離或其他機械分離技術將廢陶瓷複合物與其他粒子分離。
圖12展示陶瓷複合物之抗壓強度。在經由還原-氧化循環處理後，陶瓷複合粒子展示約20MPa之平均抗壓強度。
圖13展示陶瓷複合粒子之損耗率。每個還原-氧化循環中陶瓷複合粒子之平均損耗率小於0.6%。
圖14展示陶瓷複合粒子之可再循環性。當使用合成氣作為燃料時，陶瓷複合粒子可維持100個以上還原-氧化循環而不損失其反應性。
圖15展示陶瓷複合粒子之可再循環性。陶瓷複合粒子可與各種等級之煤、合成氣及烴類反應多個循環而不損失其反應性。
當還原器及氧化器為移動床且燃燒器為夾帶床時，陶瓷複合粒子之較佳尺寸介於約200μm至約40mm之間。該粒度使其在燃燒器中 流體化而不在還原器及氧化器中流體化。
將固體燃料及烴類轉化成無碳能量載體的所述系統及方法之實施例對於產生氫而言可達到至多約90%之HHV能量轉化效率，典型之能量轉換效率為約65%至80%。用於轉化合成氣燃料的所述系統及方法之實施例對於產生氫而言可達到至多約85%之HHV能量轉化效率，典型之能量轉換效率為約55%至70%。表3展示聯合產生電力與H2之生物質工廠的效能。
在一配置中，還原器可與流體化催化裂解單元整合。還原器轉化加氫裂解器中之氣態烴類同時還原陶瓷複合物。接著將經還原之陶瓷複合物引入氧化器中以產生氫氣。所產生之氫氣隨後可用於加氫裂解。
在一些情況下，諸如烴重整或水煤氣變換之反應的催化劑可與陶瓷複合物混合以提高燃料轉化率。催化劑之重量含量通常在約0.01%至約30%範圍內。
熟習此項技術者容易認識到，可在不悖離本發明之範疇的情況下作出各種改變，本發明之範疇並不視為受說明書及圖式中所述之特 定實施例限制，而是僅受隨附申請專利範圍之範疇限制。
10‧‧‧系統
11‧‧‧管道
12‧‧‧第一反應器/還原器
14‧‧‧燃料源/氧化器/管線
16‧‧‧容器
18‧‧‧管線
19‧‧‧熱交換器/管道
20‧‧‧分離器
21‧‧‧管線
22‧‧‧第二反應器/氧化器/反應器
23‧‧‧管線
24‧‧‧第三反應器/燃燒器
25‧‧‧熱交換器
26‧‧‧管線
27‧‧‧分離器
28‧‧‧壓縮機/還原器12之固體出口/管線
30‧‧‧還原器12之氣體出口
40‧‧‧管線/環形區域/孔口
42‧‧‧第二級之固體出口/管線
60‧‧‧膨脹器
62‧‧‧渦輪機
64‧‧‧發電機
66‧‧‧電
74‧‧‧管線

Claims (4)

  1. 一種製備陶瓷複合粒子之方法，其包含以下步驟：將金屬氧化物與至少一種陶瓷支撐材料混合以形成混合物，該金屬氧化物包含選自由Fe、Cu、Ni、Sn、Co、Mn、In及其組合組成之群的金屬，該陶瓷支撐材料包含至少一種選自由SiC；Al、Zr、Ti、Y、Si、La、Sr、Ba之氧化物及其組合組成之群的組份；藉由添加包含澱粉、矽酸鈉及/或矽酸鉀之黏合材料使該混合物粒化；乾燥該粒狀混合物；將該經乾燥之粒狀混合物加工成粒子形式，使得該等粒子之長度大於約200μm；在約500℃至約1500℃之溫度下熱處理該等粒子；以及還原及氧化該等粒子。
  2. 如請求項1之方法，其中該陶瓷複合粒子含有鐵。
  3. 如請求項1之方法，其中該陶瓷複合粒子可進行還原-氧化反應歷時100個循環以上而不會顯著損失其反應性。
  4. 如請求項1之方法，其中該陶瓷複合粒子可與不同等級之煤、合成氣及甲烷反應7個循環以上而不會顯著損失其反應性。
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