TWI463135B - 用於線上分析氣相加工物流之方法 - Google Patents
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Description
本發明係有關利用近紅外光光譜術(NIR),線上分析於烴類之水蒸氣重整中之氣相加工物流。
習知用於諸如甲醇等化學品製造上之合成氣體已經由烴典型為石腦油或天然氣,於催化劑存在下,進行水蒸氣重整而衍生。藉水蒸氣重整反應所製造之合成氣包含一氧化碳、氫氣及二氧化碳之混合物。大致上,所製造之一氧化碳:氫氣之莫耳比用於下游化學加工諸如甲醇之製造上並非最適當。如此,常見實務性移除於重整反應中共同製造的二氧化碳且將期望數量回收回該重整器。二氧化碳添加至重整器進料,變更一氧化碳:氫氣之莫耳比。審慎控制回收再利用之二氧化碳數量,允許達成期望之一氧化碳:氫氣比例。於習知實務中,經由使用溶劑典型為水性烷醇胺類進行吸收汽提(absorption stripping),可達成二氧化碳之分離,接著為壓縮來達到循環返回重整器所需之壓力。若於水蒸氣重整反應中所製造之二氧化碳數量可經調整或最小化者為較佳。
進給至水蒸氣重整反應之進料組分為水(水蒸氣)、烴及任選地,二氧化碳。進料組分典型經預熱至至少500℃溫度且於至少15barg壓力進給至該重整器。於此等情況下,進料組分係呈氣體存在。
習知氣相分析技術為氣體層析術。但當採用氣體層析
術時,發現可能發生某些組分諸如水蒸氣之冷凝,因而難以獲得具有可接受的精度之組成資料。因此高度期望於分析期間維持該加工物流於氣相。但不期望於極高溫之加工物流進行分析,諸如水蒸氣重整器中所採用之高溫,原因在於可忍受如此高溫之分析設備可能不易獲得或價格昂貴。
如此,本發明提供一種線上分析一加工物流之方法,該加工物流為一水蒸氣重整器之進料流或流出流,該加工物流具有至少200℃之溫度,該加工物流之各組分係於氣相,該方法包含:(a)由該加工物流取得一滑流;(b)將該滑流冷卻至高於其露點之溫度;(c)藉近紅外線(NIR)光譜術分析已冷卻的滑流而獲得特徵化該加工物流之該等NIR吸收性組分之一光譜;以及(d)使用化學計量技術找出該所得之光譜與由NIR光譜術已建立的校準模型間之交互關係來判定該加工物流之NIR吸收性組分中之一者或多者之濃度及/或判定其分壓。
典型地,於烴之水蒸氣重整中,組分:水蒸氣、烴及任選地,二氧化碳於高溫及高壓進給至重整器。烴例如可為石腦油或天然氣。天然氣主要包含甲烷,但也可含有較小量之低碳脂肪族烴如乙烷及丙烷。如此,加工物流包含組分物流、甲烷及二氧化碳。二氧化碳可得自含二氧化碳之回收流或得自任何其他來源。較佳,於二氧化碳循環進
料之接頭後方之一點可由重整器之進料流中取得滑流。
水蒸氣重整反應製造包含一氧化碳、氫氣、未轉化之烴及二氧化碳之一流出流。如此,加工物流包含一氧化碳、氫氣、甲烷及二氧化碳等組分。典型地,於商業實務上,二氧化碳係由流出流中分離,且至少部分二氧化碳循環返回重整器。較佳,於二氧化碳由流出流分離之前之一點,由該重整器之流出流中取得滑流。
水蒸氣重整器可為任何適當重整器單元,諸如市售重整器單元且可為單通式重整器或二階段式重整器。典型地,重整器為含有平行管排組其中填充以習知水蒸氣重整催化劑諸如經礬土支載之氧化鎳之燒製爐。
於本發明方法中,加工物流之各組分係於氣相,但各組分也可接受加壓。加工物流之溫度及壓力將取決於水蒸氣重整加工之本質。本發明方法適合用於分析水蒸氣重整器之進料流及/或流出流,其具有至少200℃,諸如200℃至500℃例如200℃至350℃之溫度。加工物流可於大氣壓下或更高壓下,例如於至少10 barg諸如10 barg至100 barg之壓力。
滑流係由部分加工物流所組成。滑流之體積並無特殊限制;但可進行滑流之冷卻之速度將隨著滑流體積之減少而增高。滑流之較快速冷卻將允許更頻繁進行本發明之方法。
滑流之冷卻可藉空氣冷卻執行。另外,滑流之冷卻可使用水夾套執行。
經由將滑流冷卻至高於其露點之溫度,亦即滑流之各組分將開始冷凝之溫度,滑流各組分維持於氣相。如此,因可避免分析期間組分的冷凝,故本發明允許以高精度測定組成資料。
實際上,滑流適當冷卻至高於滑流之露點至少20℃之溫度以防滑流中有冷點的形成。較佳,滑流係維持於200℃至300℃範圍之溫度。
近紅外線(NIR)光譜技術可用於決定吸收光譜中之近紅外線部分之分子之特性。NIR光譜術允許進行定性分析及定量分析二者。NIR分析儀於市面上可購得。NIR分析儀之主要組件包括一檢測器、一光源、將光信號傳輸至檢測器之裝置及一光譜儀。該檢測器係耦接至將光信號傳輸至光源之裝置及光譜儀。
藉技藝界已知之適當裝置,將波長10000至4000厘米-1
之光發射至檢測器。典型地,此種傳輸裝置包括光纖纜線,例如低OH二氧化矽光纖纜線。較佳為了用於高溫,光纖纜線塗覆以對於高於200℃溫度分解為不敏感之塗層。例如光纖纜線可塗覆以聚醯亞胺材料或塗覆以金屬諸如金。
光源並無特殊限制,例如光源可為石英鹵素光源或近紅外線發光二極體。
滑流之分析係於近紅外線區(10000厘米-1
至4000厘米-1
)操作之檢測器進行。
為了用於本發明方法,其中各組分係於氣相,較佳採用流動光試管型檢測器。流動光試管於市面上可購得例如
購自史貝凱克有限公司(Specac Limited)。
NIR流動光試管之選擇為於以冷卻之滑流之溫度及壓力條件下可達成組分之分析。例如流動光試管可藉電子加熱至高於滑流之露點之溫度。適合用於本發明方法之NIR流動光試管包括台芬(Typhoon)-T光試管(史貝凱克有限公司)。
較佳流動光試管之本體係由高品質不鏽鋼諸如316L級不鏽鋼雙工不鏽鋼或哈斯特合金(Hastelloy)C所製成。
較佳光試管窗係由對近紅外線為透明,於以冷卻之滑流之條件下具有化學抗性及機械強勁之材料製成。適當光試管窗材料例如為藍寶石。
光試管窗藉密封材料黏著至光試管窗本體,該密封材料可忍受以冷卻之滑流之溫度及壓力。例如採用適當以環氧樹脂為主之密封劑。
所使用之光試管徑長係依據所分析之組分之特定壓力及溫度決定。增加光譜強度,導致吸收強度與濃度間之非線性交互關係。非線性交互關係不合所需,原因在於可能造成分析結果錯誤。因此,較佳被分析組分之光譜具有小於1.5吸收單位之吸收。
光譜強度隨壓力而增高。如此,當欲分析組分之壓力增高時,光試管徑長須相對應地縮短。例如,若欲分析之組分之壓力係於12至25 barg之範圍,則光試管徑長可於5厘米至10厘米之範圍。典型地,天然氣水蒸氣重整器之進料流及流出流係於約17 barg之壓力,光試管徑長係於7.0厘
米至8.0厘米之範圍,諸如7.5厘米將允許定量水蒸氣、甲烷、二氧化碳及其他於近紅外光區吸收之組分。
多種類型之NIR光譜儀為市面上可得且可用於本發明方法。例如,NIR光譜儀可為富利葉轉換紅外線光譜儀(FTIR光譜儀)或二極體陣列光譜儀。如技藝界業界眾所周知,FTIR光譜儀於高解析度操作提供無失真之光譜,而於低解析度操作則允許更頻繁分析加工物流之各個組分。較佳,測量頻率係可達成有效之加工控制之頻率。使用FTIR光譜儀,發現於0.1至2厘米-1
範圍之解析度允許於約30秒頻率達成無失真之光譜。但使用高於4厘米-1
諸如4至16厘米-1
範圍之解析度將允許達成更快速之回應時間。
可定量水、甲烷及二氧化碳之光譜區為7500至4800厘米-1
。
所得光譜記錄於NIR光譜儀。光譜於使用化學計量技術與加工物流組分之參考資料產生交互關聯,來單純對各分析組分之濃度及/或各分析組分之分壓算出直接數值。有用之技術包括部分最小平方(PLS)、多次線性迴歸(MLR)及主要組分迴歸(PCR)。PLS型分析軟體為商業上可得,例如葛蘭提克有限公司(Galactic Limited)出售之GRAMS及美斯索夫公司(Mathsoft Inc.)出售之MATLAB。MATLAB也可用於MLR型及PCR型分析。
典型地,於天然氣之水蒸氣重整中,水蒸氣重整器之進料流將包含甲烷、二氧化碳及水蒸氣。校準混合物可藉流動攙混技術而離線產生。於流動攙混技術中,氣態組分
與液體組分於期望之壓力下攙混且加熱至期望溫度而形成以攙混之氣相混合物。然後氣相混合物通過NIR流動光試管來產生光譜。液體及氣體流動之控制可利用質量流量控制器達成。液體可由已經使用氮氣加壓之不鏽鋼瓶進給以防止流動呈現脈波狀態。來自於NIR流動光試管之氣相回流經冷卻,液體冷凝物收集於頂出瓶。然後氣體用來控制系統壓力隨後送至換氣。然後由氣相混合物所產生之NIR光譜用來建立校準模型。
除了離線校準資料外,經由從加工物流取得試樣且藉標準分析技術諸如氣相層析術分析試樣,可驗證校準模型之準確度及/或改良模型。經由採用具有適當容量諸如300毫升之不鏽鋼瓶可進行氣相加工物流之取樣。於使用前,鋼瓶以不存在於欲分析之加工物流中之惰性氣體加壓掃除。惰性氣體之選擇也取決於層析術。較佳,惰性氣體為氪。此外,小量溶劑(約5毫升)透過隔膜注射入不鏽鋼瓶內。如此為定量洗滌出冷凝於瓶子內壁上之試樣組分所需。再度所使用之溶劑不可於加工物流內而必須與已冷凝的組分可相溶混。於重整器進料流之情況下,適合使用甲醇作為溶劑。甲醇中須存在有內部標準來輔助定量。當架設於工場時,瓶子極為短時間(約0.5秒)對加工物流開放。如此允許經過超音波處理之試樣流入瓶內來減少惰性氣體或溶劑的損耗。然後由工場內取出不鏽鋼瓶,藉氣相層析術離線分析氣體及/或液體內容物。任何容納於瓶內之液體皆須藉氣相層析術移除及分析。同理,藉氣相層析術分析氣體。
由氪之稀釋程度可算出實際收集之試樣體積。然後算出各項中之各組分之莫耳數,如此容易允許以vo1%測定氣相濃度。然後此資料用來驗證及/或改良校準模型之準確度。
本發明方法可用於測定進給至水蒸氣重整器或由其中流出之加工物流之NIR吸收性組分中之一者或多者之濃度。
另外,本發明方法可用於測定進給至水蒸氣重整器或由其中流出之加工物流之NIR吸收性組分中之一者或多者之分壓。
當加工物流包含水、甲烷及二氧化碳時,使用化學計量技術求出所得光譜與參考資料間之交互關聯來測定水、甲烷及二氧化碳中之一者或多者之濃度。一旦已知此等組成資料,若有所需,可調整進料組分之流速,藉此改良加工效率。
另外,水、甲烷及二氧化碳所得光譜可使用化學計量技術求出與參考資料間之交互關聯,來判定水、甲烷及二氧化碳中之一者或多者之分壓。某些氣體諸如氫氣及/或氮氣不具有偶極,因而不會吸收紅外線輻射。結果此等氣體無法藉NIR分析。但氮氣可能存在於重整器之進料流而氫氣係存在於重整器之流出流。習知,化學工場包括重整器具有相關流之壓力檢測器。壓力檢測器諸如轉換器可測定加工物流之總氣體壓力。如此經由使用本發明方法,可測定加工物流之多個NIR吸收性組分之分壓和。藉本發明之NIR方法測定之壓力值與例如得自壓力轉換器之絕對氣體壓力資料作比較,將允許測定剩餘氣態組分例如氮氣及氫氣之
壓力。於天然氣中存在之氮氣量改變,例如可能發生於天然氣之供應來源改變時之情況下特別有價值。
本發明方法之優點之一為可於加工壓力及高於加工物流之露點之溫度下快速測定氣相加工物流之組成資訊。於實施本發明時,根據本發明之以冷卻之滑流之水蒸氣及/或烴諸如甲烷及/或二氧化碳之濃度測定可連續進行,例如頻繁至每30秒測量一次。
當連續操作本發明方法時,較佳滑流之冷卻溫度維持恆定。此點為較佳,原因在於所得光譜強度不受溫度改變之影響,因而可減化光譜與已確立的校準模型間之交互關聯。
進一步,本發明方法之連續操作允許該方法適合用於執行加工控制。舉例言之,經由連續監視來自於重整器之流出流中之未經轉化之甲烷濃度,甲烷流至重整器之流速(濃度)可經調整來最大化一氧化碳之製造量,藉此改良重整方法之效率。
如此,本發明進一步提供一種於水蒸氣重整製程中執行製程控制之方法,該製程具有一加工物流其為一水蒸氣重整器之進料流或流出流,該加工物流具有至少200℃之溫度,該加工物流之各組分係於氣相,其中該方法包含:(a)由該加工物流取得一滑流;(b)將該滑流冷卻至高於其露點之溫度;(c)藉近紅外線(NIR)光譜術分析已冷卻的滑流而獲得特徵化該加工物流之該等NIR吸收性組分之一光譜;以及
(d)使用化學計量技術找出該所得之光譜與由NIR光譜術已建立的校準模型間之交互關係來判定該加工物流之NIR吸收性組分中之一者或多者之濃度及/或判定其分壓;及(e)回應於所測得之濃度及/或分壓,調整於進料流中之各組分中之至少一種組分之濃度。
基於由得自水蒸氣重整器之進料流及/或流出流之滑流之近紅外線分析所得資訊,進行化學製程之製程控制可為手動控制或自動控制。較佳,得自近紅外線分析之資料饋至電腦化控制單元,其自動調整水蒸氣重整器之進料組分來達成各組分之期望流速。
另外,資料可饋至顯示單元,且由手動調整進料組分之流速之操作員加以解譯。
現在將藉下列非限制性實例及參照第1圖及第2圖舉例說明本發明之方法。第1圖以示意圖形式顯示適合用於建立藉物流攙混所產生之氣相混合物之已確立的校準模型之裝置。第2圖顯示二氧化碳、甲烷及水之氣相混合物。
該裝置包含多個溫度質量流量控制器(1)、一已加熱之控制式蒸發器混合器(CEM)(2)、一NIR流動光試管(3)、光纖纜線(4)及一NIR光譜儀(5)。
於使用中,呈液相之組分經由管線(6)進給至已加熱之控制式蒸發器混合器(2),於該處氣化而形成蒸氣。氣態組
分經管線7及8進給至已加熱之控制式蒸發器混合器(2),於該處與氣化後之液體混合。液體組分及氣態組分之流至已加熱之控制式蒸發器混合器(2)可藉溫度質量流量控制器(1)來調節。於已加熱之控制式蒸發器混合器(2)中所產生之氣相混合物送至NIR流動光試管(3)。來自於NIR流動光試管(3)之流出流通過熱交換器(9)及透過頂出液體之冷凝器(10)及控制系統壓力之壓力調節器(11)換氣。NIR流動光試管(3)係藉光纖纜線(4)而耦接至NIR光譜儀(5)。流動光試管(3)中之氣相混合物藉NIR光譜儀(5)分析,使用於10000至4000厘米-1
之可變解析度多次掃描且採用於氮氣下之流動光試管或纖維回路作為參考。
第1圖所示裝置配置係用來產生二氧化碳、水蒸氣及甲烷之校準混合物之NIR光譜。該裝置包含布朗克斯特英國公司(Bronkhurst (US) Ltd.)所製造之溫度質量流量控制器(1)及已加熱之控制式蒸發器混合器(2)。NIR光譜儀(5)為布魯克(Bruker)美崔斯(Matrix)FTNIR光譜儀(布魯克光學公司),具有整合式機械多工器且裝配有熱電式冷卻InGaAs檢測器及石英分束器。NIR光譜儀(5)藉低OH二氧化矽光纖(200微米核心/280微米護套,0.29數值孔徑,經聚醯胺塗覆額定至350℃,得自聖特尼克公司(Sentronic GmbH)連結至NIR流動光試管(3)。所使用之NIR流動光試管為具有藍寶石窗、徑長7.5厘米且額定至50巴及300℃之不鏽鋼台芬T光試
管(史貝凱克公司)。流動光試管及蒸氣管線藉電熱加熱至高於蒸氣混合物之露點。
水蒸氣、甲烷及二氧化碳之校準混合物製備如下。水(0至10克/小時)經氣化,於控制式蒸發器混合器內混合甲烷(0至3奈升/小時)及二氧化碳(0至3奈升/小時),且於200℃至280℃及15巴至20巴總壓力進給至流動光試管。如此製造含有8至12巴水蒸氣,2至6巴甲烷及1至4巴二氧化碳之蒸氣混合物。使用於氮氣下之流動光試管於作為參考之測量溫度,於2波數解析度於10000至4000波數間記錄混合物之NIR光譜。
顯示二氧化碳(2.60巴)、甲烷(3.64巴)及水蒸氣(10.81巴)吸收於總壓力17.05巴及240℃之試樣光譜顯示區顯示於第2圖(純質組分光譜出現於商業實驗室,諸如由華盛頓里齊朗美國能源部太平洋西北國家實驗室公告)。由產生之NIR光譜所得資料用來建立校準模型。使用PLSplus/IQ化學計量學軟體(熱電子公司(Thermo Electron Corporation))使用避開過度水吸收之光譜區(9500至7400、7100至5520及5160至4925波數),對甲烷、水、二氧化碳及溫度建立部分最小平方校準模型。
得自於約278℃溫度及約17 barg壓力之包含水蒸氣、二氧化碳及甲烷之水蒸氣重整器進料流之滑流藉空氣冷卻至250℃至260C溫度,隨後使用前述NIR光譜儀、NIR流動光式管及光纖纜線於30秒間隔期間以2波數解析度記錄10000
至4000波數間之NIR光譜。部分最小平方校準模型應用至所產生之NIR光譜,測定於重整器進料流中之組分亦即甲烷、水蒸氣及二氧化碳之濃度。回應於所測得之各組分甲烷、水蒸器及二氧化碳之濃度,可調整進給至水蒸氣重整器之進料流中之甲烷濃度。
1‧‧‧熱質量流量控制器
2‧‧‧控制式蒸發器混合器(CEM)
3‧‧‧近紅外線(NIR)流動光試管
4‧‧‧光纖纜線
5‧‧‧NIR光譜儀
6、7、8‧‧‧管線
9‧‧‧熱交換器
10‧‧‧冷凝器
11‧‧‧壓力調節器
第1圖以示意圖形式顯示適合用於建立藉物流攙混所產生之氣相混合物之已確立的校準模型之裝置。
第2圖顯示二氧化碳、甲烷及水之氣相混合物。
1‧‧‧熱質量流量控制器
2‧‧‧控制式蒸發器混合器(CEM)
3‧‧‧近紅外線(NIR)流動光試管
4‧‧‧光纖纜線
5‧‧‧NIR光譜儀
6、7、8‧‧‧管線
9‧‧‧熱交換器
10‧‧‧冷凝器
11‧‧‧壓力調節器
Claims (26)
- 一種線上分析一加工物流之方法,該加工物流為一水蒸氣重整器之進料流或流出流,該加工物流具有至少200℃之溫度,該加工物流之各組分係於氣相,該方法包含:(a)由該加工物流取得一滑流;(b)將該滑流冷卻至高於其露點之溫度;(c)藉近紅外線(NIR)光譜術分析已冷卻的滑流而獲得特徵化該加工物流之該等NIR吸收性組分之一光譜;以及(d)使用化學計量技術找出該所得之光譜與由NIR光譜術已建立的校準模型間之交互關係來判定該加工物流之NIR吸收性組分中之一者或多者之濃度及/或判定其分壓。
- 如申請專利範圍第1項之方法,其中該加工物流包含組分水蒸氣、甲烷及二氧化碳。
- 如申請專利範圍第1項之方法,其中該加工物流包含組分一氧化碳、氫氣、甲烷及二氧化碳。
- 如申請專利範圍第2項之方法,其中該加工物流進一步包含氮氣。
- 如申請專利範圍第3項之方法,其中該加工物流進一步包含氮氣。
- 如申請專利範圍第1項之方法,其中該加工物流之溫度係於200℃至500℃之範圍。
- 如申請專利範圍第1項之方法,其中該滑流係於二氧化 碳循環再利用進料之接頭後方一點處得自該進料流。
- 如申請專利範圍第1項之方法,其中該滑流係在由該流出流中分離二氧化碳前之一點處得自該流出流。
- 如申請專利範圍第1項之方法,其中該滑流係經冷卻至高於露點至少20℃之溫度。
- 如申請專利範圍第1項之方法,其中該經冷卻之滑流係維持於200℃至300℃範圍之溫度。
- 如申請專利範圍第9項之方法,其中該經冷卻之滑流係維持於200℃至300℃範圍之溫度。
- 如申請專利範圍第1項之方法,其中該加工物流係於10至100barg範圍之壓力。
- 如申請專利範圍第1項之方法,其中該化學計量技術係選自於部分最小平方、多次線性迴歸及主要組分迴歸。
- 如申請專利範圍第1項之方法,其中該近紅外線光譜術係使用一種包含NIR光譜儀、光纖纜線、及NIR流動光試管(NIR flow cell)之裝置來進行。
- 如申請專利範圍第14項之方法,其中該NIR光譜儀為富利葉轉換紅外線光譜儀。
- 如申請專利範圍第15項之方法,其中該富利葉轉換紅外線光譜儀係於0.1至2厘米-1 之範圍之解析度使用。
- 如申請專利範圍第14項之方法,其中該光纖纜線為低OH二氧化矽光纖纜線。
- 如申請專利範圍第14項之方法,其中該光纖纜線係以聚醯亞胺材料或金屬予以塗覆。
- 如申請專利範圍第17項之方法,其中該光纖纜線係以聚醯亞胺材料或金屬予以塗覆。
- 如申請專利範圍第14項之方法,其中該NIR流動光試管包含不鏽鋼本體及藍寶石窗。
- 如申請專利範圍第14項之方法,其中該NIR流動光試管具有於5厘米至10厘米範圍之光徑長度。
- 如申請專利範圍第20項之方法,其中該NIR流動光試管具有於5厘米至10厘米範圍之光徑長度。
- 如申請專利範圍第21項之方法,其中該光徑長度係於7.0厘米至8.0厘米之範圍。
- 如申請專利範圍第22項之方法,其中該光徑長度係於7.0厘米至8.0厘米之範圍。
- 如申請專利範圍第1項之方法,其中該接受分析之組分之光譜具有小於1.5吸收單位之吸收。
- 一種於水蒸氣重整製程中執行製程控制之方法,該製程具有一加工物流,其為一水蒸氣重整器之進料流或流出流,其中該加工物流具有至少200℃之溫度,該加工物流之各組分係於氣相,其中該方法包含:(a)由該加工物流取得一滑流;(b)將該滑流冷卻至高於其露點之溫度;(c)藉近紅外線(NIR)光譜術分析已冷卻的滑流而獲得特徵化該加工物流之該等NIR吸收性組分之一光譜;以及(d)使用化學計量技術找出該所得之光譜與由NIR 光譜術已建立的校準模型間之交互關係來判定該加工物流之NIR吸收性組分中之一者或多者之濃度及/或判定其分壓;及(e)回應於所測得之濃度及/或分壓,調整該進料流中之各組分之至少一者之濃度。
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CN101707919A (zh) | 2010-05-12 |
JP5654343B2 (ja) | 2015-01-14 |
EP2158472A1 (en) | 2010-03-03 |
RU2491532C2 (ru) | 2013-08-27 |
WO2008152351A1 (en) | 2008-12-18 |
RU2010101005A (ru) | 2011-07-20 |
UA97671C2 (ru) | 2012-03-12 |
EP2158472B1 (en) | 2010-12-01 |
TW200912305A (en) | 2009-03-16 |
MY148026A (en) | 2013-02-28 |
ES2357463T3 (es) | 2011-04-26 |
KR101494920B1 (ko) | 2015-02-23 |
ATE490457T1 (de) | 2010-12-15 |
CN101707919B (zh) | 2012-02-01 |
BRPI0812731A2 (pt) | 2014-12-23 |
DE602008003803D1 (de) | 2011-01-13 |
RS51628B (en) | 2011-08-31 |
KR20100017804A (ko) | 2010-02-16 |
CA2690078A1 (en) | 2008-12-18 |
JP2010530067A (ja) | 2010-09-02 |
US20100127217A1 (en) | 2010-05-27 |
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