TWI308503B - Control scheme for hybrid psa/tsa systems - Google Patents

Control scheme for hybrid psa/tsa systems Download PDF

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TWI308503B
TWI308503B TW095112061A TW95112061A TWI308503B TW I308503 B TWI308503 B TW I308503B TW 095112061 A TW095112061 A TW 095112061A TW 95112061 A TW95112061 A TW 95112061A TW I308503 B TWI308503 B TW I308503B
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water
adsorption
gas
feed gas
port
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TW200640562A (en
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William Paul Schmidt
Daniel Patrick Zwilling
Andrew David Wright
Mohammad Ali Kalbassi
Christopher James Raiswell
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Air Prod & Chem
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Description

1308503 九、發明說明： 發明所屬之技術領域 - 本發明涉及一種用於從進料氣體中除去水及二氧化碳 (C〇2 )的吸附方法，該方法使用了溫度變換（即TSA )及 壓力變換（PSA )來再生吸附劑。 先前技術 # 本發明涉及一種用於從進料氣體中除去水及二氧化碳 (c〇2)的吸附方法，該方法使用了溫度變換（即TsA)及 ®力變換（PSA)來再生吸附劑。更具體而言，本發明涉 及一種方法，其中： (a )該方法採用具有用於引入進料氣體的進料口以及 用於排出產品氣體的產品口的吸附容器； (b)位於鄰近於進料口的是含有用於從進料氣體中吸 附水的水選擇性吸附劑（特別是活性氧化鋁或矽膠）的水 φ 除去區； (c )位於水除去區與產品口之間設置含有用於從進料 氣體中吸附C〇2的C〇2選擇性吸附劑（特別是分子篩）的 C02除去區； (d )該方法在吸附工序與再生工序之間循環； (e )在吸附工序中： (0 進料氣體從進料口開始流經該容器. (ii )至少一部分水選擇性吸附劑用水飽和· (出）至少一部分C〇2選擇性吸附劑用飽 1308503 和；且 (iv )產品氣體從產品口排出； (f)在再生工序中： (i ) 將容器減壓至較低壓力； (Η ) 加熱的再生氣體從產品口開始流經該 容器，提供一些再生熱以解吸（即通過溫度變換）基本上 全部在吸附工序中吸附的C〇2和部分（但不是全部）解吸 在吸附工序中吸附的水；且 (111 ) 冷卻的再生氣體從產品口開始流經該 容器，解吸（即，通過壓力變換）大部分或基本上全部在 吸附工序中吸附的殘留水份；且 (IV) 用進料氣體增壓該容器使該容器為下 一個吸附工序作好準備。 以上“併合（hybrid)” TSA/PSA方法（下文稱為併合 方法）是已知的。具體可參見Kalbassi等人（下文稱為 “Kalbassi”）的美國專利6,599,347，其教導了有關垂直 吸附容器的併合方法’在該容器中，進料口位於容器的底 部，且進料氣體在到達位於容器頂部的產品口前向上流動。 併合方法的關鍵問題在於，精確計算上述（f)(ii)中 所需的由加熱的再生氣體提供的熱量，以便除必要之外， 不浪費能量來加熱再生氣體。正如本領域技術人員所能瞭 解的，由加熱的再生氣體提供的熱量必須足以推動所產生 的熱脈衝經過C02除去區，以使它在水除去區内的某位置 (下文稱為設計位置）失效，該位置要足夠遠，以致於可 6 ' 1308503 以再生大部分的水除去區（即通過溫度變換），但沒有進入 水除去區太遠，以致於沒有充分利用冷卻的再生氣體實現 水除去區再生（即通過壓力變換）的能力。換句話說，設 計位置所對應的是位於水除去區内，由溫度變換再生向壓 力變換再生發生轉換的位置。
Kalbassi通過調節由被加熱的再生氣體提供的熱量，解 決了併合方法中所存在的這個關鍵難題，所述熱量是進料 φ 氣體水含量的函數。與基於可能遇到的最不利的環境條件 確定固定的熱量不同的是，這提供顯著地能量的節省。然 而相對於本發明，Kalbassi的方案是不完善的，與本發明 不同，Kalbassi對必要的熱量的調節，沒有考慮在再生工 序中的溫度資料及取自以設計位置為中心的水除去區的關 鍵部位（關鍵部位）内的具體溫度資料。該溫度資料可以 使人們測得熱脈衝失效的確切位置，且通過適當調節下一 個再生工序中提供的熱量，該溫度資料可以使與設計位置 • 有關的偏差一致。以這種方式，從一個週期到一個週期， 對所提供熱量的調節的調整能力進—步在Kalbassi方案中 提高了能量的節約。 通常，關鍵部位會是水除去區中除了邊緣或接近邊緣 的部位之外的任何部位，正如本領域技術人員所能瞭解 的，由於C〇2吸附劑水污染的風險，所以在併合方法中水 除去區的邊緣不是熱脈衝失效的實際設計位置。（具體而 °如果接近水除去區邊緣的設計位置鄰近於C02除去 區，則意味著水除去區通過溫度變換來實現再生即使有， 1308503
也很少的；同樣地，如果接近水除去區邊緣的設計位置在 引入進料氣體處’貝I】意味著水除去區通過壓力變換來實現 再生即使有，也很少）。更確切地說，如果人們考慮在水除 去區中水選擇性吸附劑被裝填為相同厚度的10層（層i開 始於與進料口相鄰的水除去區的—端，接下來依次到層 1〇,層1G與C02除去區相鄰），關鍵部位將包含層2到層 9之間含端值的任何3_4個連續層。已知在典型的併合“ 中’熱脈衝失效的設計位置一般位於層6到層9之間的某 個部位，由此可以判斷關鍵部位通常包含層6到層9。〆、 由編_扣等人轉讓給L，Air Liquide的游 Μ%，(2002)也公開了以上提及的併合方法。Μ〇 — 進-步教導了根據操作條件控制再生氣體的溫度，該操作 條件包括“在再生結束時由〔吸附器〕熱前緣輸出的熱分 佈圖”。或者’ Mon⑽u在第5攔第5行更具體地進行了 教導，當“熱前緣離開〔水除去區〕熱前緣” 根㈣ 分佈圖控制再生氣體的溫度。因&，溫度資料取自水除去 區的邊緣，它對應於本發明水除去區定義中…。如前 面所討論過的，這與本發明的教導不同。具體而言，該位 置意味著即使利用了水除去區容器壓力變換來實現再生的 能力，也很少，因此對再生氣體的加熱十分必要。 由 B〇SqUain 等人轉讓給以irUquid 的 USP 4,541 85 1 〇985)教導了在上述併合方法中，使用徑向吸附床，在該 併合方法中’進料π將進料氣體分佈於吸附容器的週邊， 且進料氣體在到達位於容器内部的產品口前，沿徑向向内 8 1308503 流動（如Kalbassi所述，首先通過水除去區，然後通過c〇2 除去區）。為了解決該形狀對與吸附與再生工序之間的溫度 波動相關的機械應力問題的靈敏度，B〇squain教導了採用 在極靠近水除去區（即：也對應於本發明定義的水除去區 中的層1 )的進料端的外側格柵上設置的溫度感測器，以 防止在再生期間所產生的熱脈衝到達外侧格柵。 由 Christel 等人轉讓給 pall c〇rp〇rati〇n 的 usp 4,832,711 (1989)教導了使用吸附劑從進料氣體中吸附水來 儲存吸附工序所產生的熱量，用於加熱再生氣體，在吸附 工序中測量通過吸附劑的熱脈衝的前進值，以使所產生的 熱脈衝在離開床層的產品端之前，停止吸附工序。㈤㈤ 的方案沒有外部加熱再生氣體。因此本發明所解決的問題 (卩精確確疋在再生期間需要提供的外部熱量）在 Christel的方案中沒有專門提到。 發明内容 本發月疋種用於從進料氣體中除去水及二氧化 )的吸附方法的改進的控制方案，其利用溫度變換( 及壓力變換（pSA)的併合來再生吸附劑。該控制 案包括’調節由再生教 孔體耠供的熱量，該熱量是作為承 水選擇性吸附區的關 位對應於由溫度變換再生二…枓的函數。該_ 物罢 燹換再生到由壓力變換再生所預期的奉 位置。在本發明的優者 愛選A施方案中，還按照進料氣體片 里的函數進行再生熱量的調節。 1308503 實施方式 參照圖卜本發明涉及一種用於從進料氣體（i2)中除 去水及c〇2的吸附方法，其中： U)該方法採用具有用於引人進料氣體的進料口（16) 以及用於排出產品氣體（20)的產品σ (18)的吸附容器 M4)；
(b)在進料口鄰近處設置含有用於從進料氣體中吸附 水的水選擇性吸附劑的水除去區（22 ); (c )在水除去區與產品口之間設置含有用於從進料氣 體中吸附co2的c〇2選擇性吸附劑的Cq2除去區（); (d )該方法在吸附工序與再生工序之間循環； (e)在吸附工序中： (i )進料氣體從進料口開始流經該容器·， (11 )至少一部分水選擇性吸附劑被水飽和； (in )至少一部分C〇2選擇性吸附劑被c〇2飽和； (iv)產品氣體從產品口排出； (f)在再生工序中： (i )將谷器減壓至較低（l〇wer )壓力； (11 )加熱的再生氣體從產品口開始流經該容器， 提供一些再生熱以解吸基本上全部在吸附工序中吸附的 C〇2和部分在吸附工序中吸附的水；且 (111 )冷卻的再生氣體從產品口開始流經該容器， 10 1308503 以解吸大部分或基 份；且 王邛在及附工序中吸附的殘留水 .)用進料氣體增壓該容器使之為下一 序作好準備；且 q「调吸附工 (g)水除去區内所含有的水選擇性吸附劑由等厚 成1 !始於與進料氣體口相鄰的水 =到層1〇,層位於與™相鄰的水除去:的 更具體而言，本發明是對卜+ ίχ Θ疋對上述方法的改進， 自水選擇性吸附F Μ Α 匕#依取 擇:導的一關鍵部位的溫度資料的函數調節在 11)中提及的再生熱量，如前面 ^ ^ tL 1 < π關鍵部位相 §於熱脈衝失效的設計位置，一 U 2到9之間含端 值的任何3-4·個連續層，而更為通堂沾β — 貝曰向更為通韦的疋包括層6到層9, 由圖1中水除去區的十字形陰影部分示出。 本發明的另一實施方案中，溫度資 月竹疋從關鍵部位的 兩個位置獲得的，即從層9中的位置和岸6由从/ 々增6中的位置獲得。 旦本發明的另-實施方案中，還調節作為進料氣體水含 量函數的、由被加熱的再生氣體所提供的埶旦 .、、、里 V 即：Kalbassi 中所教導的）。 本發明的另一實施方案中，進料氣體是空氣。 本發明&另一實施方案中，冑產品氣體送入低溫空氣 分離單元，並將其分離成其組成組分。 本發明的另一實施方案中’水選擇性 评注及附劑是活性氧 化銘。 ‘：1308503 *> « 本發明的另一實施方案中，水選擇性吸附劑是矽膠。 本發明的另一實施方案中，C〇2選擇性吸附劑是分子 篩。 本發明的另一實施方案中，進料氣體是天然氣。 本發明的另一實施方案中’進料氣體是包括一氧化碳 及氫氣的合成氣。 示於圖1中的本發明的實施方案，採用垂直流動容器 籲 （如Kalbassi所教導的），其中，進料口（ 14 )位於吸附容 器的底部’且進料氣體（1 〇 )在到達位於吸附容器的頂部 的產品口（ 16 )之前’向上流經吸附容器。或者，本發明 可採用徑向流動容器（如Bosquain所教導的），其中，進 料口將進料氣體分佈於吸附容器的外部，且進料氣體在到 達位於吸附容器外部的產品口前，徑向流經吸附容器（如 Kalbassi所述’首先通過水除去區，然後通過c〇2除去區）。 φ 圖式簡單說明 圖1是本發明一個實施方案的附圖。 主要元件之符號說明 1、2'3、4、5、6、7、8、9、10·.層；12.·進料氣體； 14.. 吸附容器，16.·進料口 ； 18••產品口 ； 2〇..產品氣體； 22.. 水除去區；24..C02除去區 12

Claims (1)

  1. •1308503 十、申請專利範圍：
    1、一種用於從進料氣體中除去水及C〇2的吸附方法， 其中： (a ) 該方法採用具有用於引入進料氣體的進料口 以及用於排出產品氣體的產品口的吸附容器； (b) 位於鄰近於進料口的是含有用於從進料氣體 中吸附水的水選擇性吸附劑的水除去區；
    (c ) 位於水除去區與產品口之間的是含有用於從 進料氣體中吸附C〇2的.co2選擇性吸附劑的C〇2除去區； (d ) 該方法在吸附工序與再生工序之間循環； (e) 在吸附工序中： (1 )進料氣體從進料口開始流經該容器； (Η)至少一部分水選擇性吸附劑被水飽和； (lii )至少一部分C〇2選擇性吸附劑被c〇2飽和； (b)產品氣體從產品口排出； (〇在再生工序中： (i )將容器減壓至較低壓力； (π)加熱的再生氣體從產品口開始流經該容器， 提供一些再生熱以解吸基本上全部在吸附工序中吸附的 C〇2和部分在吸附工序中吸附的水；且 (m)冷卻的再生氣體從產品口開始流經該容器， 以解吸大°卩分或基本上全部在吸附工序中吸附的殘留水 份； 13 1308503 (iv)用進料氣體增壓該容器使之為下—個 序作好準備；且 (g)水除去區内所含有的水選擇性吸附劑由等厚的十 層組成1 1始於與進料氣體口相鄰的水除去區的—端， 依次到層1〇,層10位於與c〇2除去區相鄰的水 一端； 其改進之處包括依取自水選擇性吸附區的一關鍵部位 的溫度資料的函數對再生熱量進行調節，制鍵部位包含 曰2到9之間含端值的任何3_4個連續層。 2、如申請專利範圍第1項所述的方法，其中，水選擇 性吸附區的關鍵部位包含層6到9。 如申叫專利乾圍第2項所述的方法，其中，溫度資 料是從關鍵部位的兩個位置獲得的，即從層9中的位置和 層6中的位置獲得。 4、如申請專利範圍第1項所述的方法，其中，還調節 作為進料氣體水含量函數的由被加熱的再生氣體所提供的 熱量。 5、如申請專利範圍第丄項所述的方法，其中，進料氣 體是空氣。 14 1308503 6如申明專利範圍第i項所述的方法’其中，將產品 氣體送入纟溫空氣分離單&，並將其分離成其組成組分。 7、如申請專利範圍第1項所述的方法，其中，水選擇 性吸附劑是活性氧化鋁。 8、 如申請專利範圍第1項所述的方法，其中，水選擇 性吸附劑是矽膠。 、 9、 如申請專利節in筮，π J乾圍第1項所述的方法，其中，C〇選 擇性吸附劑是分子篩。 '、 2 10、如申請專利範圍第 體是天然氣。 項所述的方法，其中，進料氣
    11、如申請專利範圍第i 體是包含一氧化碳及氫氣的 項所述的方法 合成氣。 ’其中，進料氣 12、如申請專利範圍第 <丄項所逑的方法，甘 器是垂直流動容器，進料Q ”中，吸附 ^ Α 位於吸附容器的底邱，日、隹 氣體在到達位於吸附容3| Μ - °卩且進 ΤΓ令态的頂部的產品口 吸附容器。 刖，向上流 13 如申請專利範圍第 1項所述的方法 其中，吸附 1308503 容器是徑向流動容器，進料口將進料氣體分佈於吸附容器 的外部，且進料氣體在到達位於吸附容器外部的產品口之 前，徑向流經吸附容器。
    16
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CN1872388A (zh) 2006-12-06
KR20060107320A (ko) 2006-10-13
SG126836A1 (en) 2006-11-29
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MY140785A (en) 2010-01-15
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US7413595B2 (en) 2008-08-19
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