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TWI730056B - 藉由ｓｏｅｃ而最佳化的一氧化碳生產方法 - Google Patents

藉由ｓｏｅｃ而最佳化的一氧化碳生產方法 Download PDF

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TWI730056B
TWI730056B TW106105927A TW106105927A TWI730056B TW I730056 B TWI730056 B TW I730056B TW 106105927 A TW106105927 A TW 106105927A TW 106105927 A TW106105927 A TW 106105927A TW I730056 B TWI730056 B TW I730056B
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Abstract

本發明係關於一種自包含二氧化碳(CO2)及天然氣及/或石腦油之進料流生產一氧化碳(CO)的方法，該方法包含合成氣產生步驟、CO2移除步驟及CO純化步驟，且該方法進一步包含SOEC單元，該SOEC單元自CO2流產生CO，該方法尤其適合於增大現有已知CO生產設備之容量。

Description

藉由SOEC而最佳化的一氧化碳生產方法
本發明屬於在固態氧化物電解池(solid oxide fuel cell；SOEC)堆疊中進行之電解的領域。固態氧化物電解池為以逆向模式運作之固態氧化物燃料電池(solid oxide fuel cell，SOFC)，其使用固態氧化物或陶瓷電解質藉由電解水來產生(例如)氧氣與氫氣。其包含SOEC核心，其中SOEC堆疊與製程氣體之入口及出口容納在一起。進料氣體(通常被稱作燃料氣體)被引導至堆疊之陰極部分，來自電解之產物氣體自該陰極部分排出。堆疊之陽極部分亦被稱作氧氣側，此係因為氧氣在此側上產生。
本發明將基於蒸汽重整之CO設備中之一氧化碳(CO)生產與在固態氧化物電解池(solid oxide electrolysis cell；SOEC)或SOEC堆疊中自二氧化碳(CO2)生產一氧化碳(CO)之方法關聯，其中藉由經施加電流將CO2引導至堆疊之燃料側，且將過量氧氣輸送至堆疊之氧氣側，視情況使用空氣或氮氣沖洗氧氣側，且其中來自含有與CO2混合之CO的SOEC之產物流經受分離製程。
在本發明中，SOEC堆疊強化基於現有蒸汽重整之CO生產設施中的CO生產，該CO生產設施藉助於經蒸汽重整之合成氣體及後續低溫或薄膜CO純化而操作。
藉由蒸汽重整之CO生產得到氫氣之共生產，此可取決於局部環境而具有高價值或低價值。在氫氣具有低價值之情況下，可藉由使用具有高C/H比率之原料(諸如，石腦油)、在低S/C比率及/或高溫下操作重整器、自CO2移除單元再循環CO2及/或添加匯入CO2來抑制氫氣生產。
然而，歸因於重整觸媒上之增加的碳形成可能性，眾所周知對於任何給定原料存在在應用以上技巧之蒸汽重整器中可達到的H2/CO比率的下限。因此，在碳形成開始或達至設備之熱傳遞限度之前，大自然設定了給定大小之重整器可生產之CO量的限制。在已達至此點時需要額外CO容量之情況下，生產額外CO之唯一選項為增加蒸汽重整容量。增加重整容量典型地僅在相對大的遞增方面可行以達成合理的規模經濟，合成氣設備之其餘部分上的負載隨著所增加之重整容量增加成本、時間及改進現有設施之複雜化而線性增加(或若應用六邊形重整，則負載更大)。因此，遞增的CO商機必須具有足夠大小以獲得必要規模經濟以用於使新型合成氣設備可行或消除現有設施之瓶頸。
已知可藉由電解自CO2製備CO。因此，US 2007/0045125 A1描述一種使用鈉傳導電化電池自二氧化碳及水製備合成氣體(合成氣包含一氧化碳及氫氣)之方法。合成氣亦藉由在固態氧化物電解池中共電解二氧化碳及蒸汽來產生。
US 8,138,380 B2描述藉由還原性地轉換二氧化碳來生產甲醇之環境有益方法，該方法包括在電化電池中將經再循環二氧化碳還原成一氧化碳之步驟。
自US 2008/0023338 A1已知一種藉由高溫電解生產至少一種 合成氣組份之方法。可藉由在固態氧化物電解池中分解二氧化碳及水或蒸汽以形成一氧化碳及氫氣來形成合成氣組份氫氣及一氧化碳，可利用所謂逆向水煤氣轉移(water gas shift；WGS)反應使氫氣之一部分與二氧化碳反應以形成一氧化碳。
US 2012/0228150 A1描述一種在連續製程中使用與YSZ電解質整合之缺氧鐵氧體(oxygen deficient ferrites；ODF)之電極將CO2分解成C/CO及O2的方法。ODF電極可藉由跨越電極施加小的電位偏置來保持主動。亦可同時電解CO2及水以持續產生合成氣(H2+CO)及O2。從而，CO2可轉型成允許烴燃料之CO2中性使用的寶貴燃料源。
最後，US 8,366,902 B2描述利用來自含碳燃料之熱化學轉換的熱生產合成氣以支持使用一或多個固態氧化物電解池分解水及/或二氧化碳的方法及系統。可藉由一或多個固態氧化物電解池同時分解二氧化碳及水以產生氫氣及一氧化碳。
除了上文所提及之專利及專利申請案以外，在固態氧化物電解池中電解CO2之概念亦描述於香港理工大學倪萌(Meng Ni)之出版物「Modeling of a Solid Oxide Electrolysis Cell for Carbon Dioxide Electrolysis」中，且亦由Sune Dalgaard Ebbesen及Mogens Mogensen描述於題為「Electrolysis of Carbon Dioxide in Solid Oxide Electrolysis Cells」(Journal of Power Sources 193,349-358(2009))之文章中。
具體言之，在本發明中吾人主張基於蒸汽重整之CO設備的SOEC去瓶頸，從而使得操作者/擁有者能夠利用超出其當前CO生產容量且 投資及停用時間相對較少之遞增CO商機。SOEC在低壓CO2上操作(較佳CO2移除單元廢氣，此係因為其不含觸媒毒物，而匯入CO2可能含有污染物)且將其5%至99%轉換成CO。優點為不改變CO2壓縮及合成氣產生負載，亦即，無需修改或投資。
CO2移除單元上之負載增加，然而與額外重整容量相比小得多，因此僅需要較少修改/投資/停工時間。乾燥器及CO純化單元上之負載增加基本上受限於額外CO(+可能在SOEC產物中之低水平的H2、N2)，亦即，很可能無需或需要較少修改/投資/停工時間。
SOEC中之電解製程需要在650℃與850℃之間的操作溫度。取決於特定操作條件、堆疊組態及堆疊之整合性，總體操作可消耗熱(亦即，為吸熱的)，其可為熱中性的，或其可產生熱(亦即，為放熱的)。在此類高溫下進行之任何操作亦導致顯著的熱量損耗。此意謂典型地其將需要外部加熱來達至並維持所要操作溫度。
當在SOEC堆疊中在足夠大的電流下進行操作時，將最終產生必要的熱，但同時堆疊之降級將增加。因此，在方法之另一具體實例中，使用外部加熱器來加熱氧氣側及燃料側上之入口氣體，以便將熱供應至SOEC堆疊，從而緩解此問題。此類外部加熱器亦在啟動期間可用，此係因為其可提供熱以幫助SOEC達至其操作溫度。適合的進料氣體溫度將為大約700℃至850℃。外部加熱器可為電氣的，但亦可使用氣體或液體燃料外部加熱器。
除了使用入口氣體加熱器來獲得必要操作溫度以外，亦可利用氧氣側及燃料側上之熱廢氣來加熱入口氣體。此為維持SOEC之適合操 作溫度且同時減少加熱器上之負載的另一方式。因此，藉由在氧氣側及燃料側兩者上併入進料流出熱交換器(feed effluent heat exchanger)，進一步緩解了與高溫操作及熱量損耗有關之問題。根據SOEC操作之性質，物質(O2)自燃料側傳遞至氧氣側，此產生僅在燃料側上之進料流出熱交換器中可達至之最大溫度的限度。由於此，在氧氣側上貫穿SOEC將存在質量之增加，此導致在SOEC氧氣出口流中之熱過量。此亦又導致來自氧氣側上之進料流出熱交換器之出口流中的熱過剩。因此，為了利用氧氣側上之此過量的熱，實施第三進料流出熱交換器，該第三熱交換器將熱自氧氣側上之進料流出熱交換器之熱出口側轉移至燃料側上之進料流出熱交換器之冷入口。藉由與加熱器與熱交換器之間以及熱交換器、加熱器與堆疊之間的連接管道上之高溫絕緣體組合地使用電示蹤，可進一步保留SOEC堆疊中之所要溫度水平。
本發明之特徵
1.一種自包含二氧化碳(CO2)及天然氣及/或石腦油之進料流生產一氧化碳(CO)的方法，該方法包含˙合成氣產生步驟，其中自該進料流產生第一合成氣流，˙CO2移除步驟，其中自該第一合成氣流移除CO2之至少一部分，且從而產生之CO2再循環流係再循環回至該合成氣產生步驟，且在該CO2移除步驟中產生第二合成氣流，及˙CO純化步驟，其中自該第二合成氣流產生CO，其中該方法進一步包含由CO2流進料之SOEC單元，該SOEC單元產生進料回至該第一合成氣流中之CO，從而提高該第一合成氣流中之CO濃 度。
2.如特徵1之方法，其中進料至該SOEC單元之該CO2流為包含該CO2再循環流之至少一部分的再循環旁通流。
3.如前述特徵中任一項之方法，其包含進料至該合成氣產生步驟之CO2匯入流。
4.如前述特徵中任一項之方法，其包含進料至該SOEC單元之CO2匯入流。
5.如特徵2之方法，其中該SOEC單元包含壓縮器，該壓縮器經調適以使得該CO2再循環旁通流能夠克服來自該CO2再循環流之壓力差、穿過該SOEC單元及管道且回至該第一合成氣流中。
6.如特徵5之方法，其中該SOEC單元包含該CO2再循環流下游之減壓閥，該減壓閥用以保護該SOEC單元免受過量壓力。
7.如前述特徵中任一項之方法，其中該SOEC單元將進料至該SOEC單元之CO2之5%至99%轉換成CO。
8.如前述特徵中任一項之方法，其中該SOEC單元將進料至該SOEC單元之CO2之20%至60%轉換成CO。
9.如前述特徵中任一項之方法，其中該第一合成氣流之壓力為2Bar(g)至25Bar(g)。
10.如前述特徵中任一項之方法，其中該第一合成氣流之壓力為15Bar(g)至25Bar(g)。
11.如前述特徵中任一項之方法，其中該CO2再循環流之壓力為0Bar(g)至5Bar(g)。
12.如前述特徵中任一項之方法，其中該合成氣產生步驟包含氫化、脫硫、預重整及重整。
13.如前述特徵中任一項之方法，其中該CO純化步驟包含低溫或薄膜CO純化。
01:進料流
02:合成氣產生步驟
03:第一合成氣流
04:CO2移除步驟
05:CO2再循環流
06:第二合成氣流
07:CO純化步驟
08:SOEC單位
09:CO2流
10:CO2匯入流
藉由展示本發明之具體實例之實例的附圖進一步說明本發明。
圖1展示根據本發明之一具體實例之方法的圖，且圖2展示根據本發明之另一具體實例之方法的圖。
圖1中之圖展示根據本發明之一具體實例之CO生產方法。將包含天然氣及/或石腦油進料之進料流01引導至合成氣產生步驟02，其中藉由催化反應將進料流轉型成合成氣。隨後將從而產生之第一合成氣流03引導至CO2移除步驟，此產生藉助於CO2再循環壓縮器再循環回至進料流中之CO2再循環流及經由合成氣乾燥器進一步傳遞至CO純化步驟07之第二合成氣流06。藉由在CO純化步驟中發生之反應自第二合成氣流形成CO產物流。
為了增加此已知方法之效率，將SOEC單元添加至該方法，SOEC單元自CO2產生CO。在本具體實例中，SOEC單元由在CO2移除步驟中產生之CO2再循環流之至少一部分進料。在SOEC中產生之CO隨後進料回至第一合成氣流中，從而增加此流之CO濃度且增大現有方法之總CO生產容量。當現有方法之容量增大時，將CO2匯入流10施加至系統可 為可行的，CO2匯入流10可進料至CO2再循環流中。因此，本發明較適用於改進現有CO生產設備，增大其CO生產容量而無主要設備替換。
在本發明之根據圖2之具體實例中，SOEC單元直接由CO2匯入流進料。此具體實例可為有利的，此係因為其至少需要管道及現有設備之改進。
01‧‧‧進料流
02‧‧‧合成氣產生步驟
03‧‧‧第一合成氣流
04‧‧‧CO2移除步驟
05‧‧‧CO2再循環流
06‧‧‧第二合成氣流
07‧‧‧CO純化步驟
08‧‧‧SOEC單位
09‧‧‧CO2流
10‧‧‧CO2匯入流

Claims (13)

  1. 一種自包含二氧化碳(CO2)及天然氣及/或石腦油之進料流生產一氧化碳(CO)的方法，該方法包含合成氣產生步驟，其中自該進料流產生第一合成氣流，CO2移除步驟，其中自該第一合成氣流移除該CO2之至少一部分，且從而產生之CO2再循環流係再循環回至該合成氣產生步驟，且在該CO2移除步驟中產生第二合成氣流，及CO純化步驟，其中自該第二合成氣流產生CO，其中該方法進一步包含由CO2流進料之SOEC單元，該SOEC單元產生進料回至該第一合成氣流中之CO，從而提高該第一合成氣流中之CO濃度。
  2. 如申請專利範圍第1項之方法，其中進料至該SOEC單元之該CO2流為包含該CO2再循環流之至少一部分的再循環旁通流。
  3. 如申請專利範圍第1項或第2項之方法，其包含進料至該合成氣產生步驟之CO2匯入流。
  4. 如申請專利範圍第1項或第2項之方法，其包含進料至該SOEC單元之CO2匯入流。
  5. 如申請專利範圍第2項之方法，其中該SOEC單元包含壓縮器，該壓縮器經調適以使得該CO2再循環旁通流能夠克服來自該CO2再循環流之壓力差、穿過該SOEC單元及管道且回至該第一合成氣流中。
  6. 如申請專利範圍第5項之方法，其中該SOEC單元包含該CO2再循環流下游之減壓閥，該減壓閥用以保護該SOEC單元免受過量壓力。
  7. 如申請專利範圍第1項或第2項之方法，其中該SOEC單元將5%至99%進料至該SOEC單元之該CO2轉換成CO。
  8. 如申請專利範圍第1項或第2項之方法，其中該SOEC單元將20%至60%進料至該SOEC單元之該CO2轉換成CO。
  9. 如申請專利範圍第1項或第2項之方法，其中該第一合成氣流之壓力為2Bar(g)至25Bar(g)。
  10. 如申請專利範圍第1項或第2項之方法，其中該第一合成氣流之壓力為15Bar(g)至25Bar(g)。
  11. 如申請專利範圍第1項或第2項之方法，其中該CO2再循環流之壓力為0Bar(g)至5Bar(g)。
  12. 如申請專利範圍第1項或第2項之方法，其中該合成氣產生步驟包含氫化、脫硫、預重整及重整。
  13. 如申請專利範圍第1項或第2項之方法，其中該CO純化步驟包含低溫或薄膜CO純化。
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