TW306884B - - Google Patents

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TW306884B
TW306884B TW085107266A TW85107266A TW306884B TW 306884 B TW306884 B TW 306884B TW 085107266 A TW085107266 A TW 085107266A TW 85107266 A TW85107266 A TW 85107266A TW 306884 B TW306884 B TW 306884B
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alumina
zpc
item
pressure
adsorbent
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TW085107266A
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Air Prod & Chem
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40056—Gases other than recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S95/00—Gas separation: processes
    • Y10S95/90—Solid sorbent

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Paper (AREA)

Description

306884 A7 86.1. 9 _B7 ：_ -- _ Z、發明説明（1 ) 發明領域 本發明涉及變壓吸附（PSA)領域，提供使用改良的氧 化鋁吸附劑從一氣體中去除二氧二碳的PSA的方法。 發明背景 在空氣導入到將氮氣和氧氣相互分離的低溫空氣分離 過程中之前，需要去除空氣中存在的低含量如400ppm的 二氧化碳。如果不進行該步驟，則二氧化碳會在空氣分離 裝置中固化。一般用於去除這種二氧化碳的兩種方法是變 溫吸附（TSA)及變壓吸附。 在這兩種技術中，吸附床暴露於原料空氣流中一段時 間以從空氣中吸附二氧化碳。此後，關閉原料空氣流使不 能進入吸附床，並通入沖洗氣流將吸附劑上所吸附的二氧 化碳帶走而將吸附劑再生以備繼續使用。在TSA中，通過 在再生相中加熱吸附劑而將二氧化碳從吸附劑脫附，在 PSA中，沖洗氣的壓力低於原料氣的壓力，壓力上的變化 被利用來從吸附劑中去除二氧化碳。 經濟部中央樣準局員工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁) 通過這些方法還可從原料空氣去除其它組分，包括烴 類和水。這些吸附方法也可應用於非空氣的原料氣體上或 應用到爲用於空氣分離設備以外的目的而純化的空氣上。 利用PSA在低溫空氣分離前從空氣中除去二氧化碳的 文獻有很多，例如美國專利4 2 4 9 9 1 5和美國專利 4477204。最初的方法是採用二張氧化鋁床去除水接著一 張沸石床如13X床去除二氧化碳。此後，已有建議使用全 -3 - 本紙張尺度適用中國國家標準（CNS > A4規格（2丨0>：297公釐） 306884 A7 B7
(1996年1月修正) 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁} 氧化鋁PSA系統，如美國專利5232474中的所述。全氧 化鋁系統的優點包括較低的吸附劑費用、不需要篩來分離 兩種不同的吸附劑的容器設計和在泄料和再加壓時在吸附 容器中更好的熱穩定性。但是需要開發具改良的二氧化碳 吸附量的吸附劑，從而可以達到具較低固定資本的較小床 尺寸及在解壓時較少的空隙氣體損失，於是可獲得較髙的 空氣回收率。 氧化鋁在TSA中也作爲吸附劑作用，爲此已建議將氧 化鋁進行處理以在其上面形成鹼金屬氧化物而提高所述氧 化鋁的吸附能力。例如，美國專利4 4 9 3 7 1 5提出了通過將 原料氣體和一基本包含在氧化鋁上有1一 6%(重量）選自 鈉、鉀和鋰的鹸金屬氧化物的可再生的煆燒吸附劑接觸來 從烯烴流去除C02的方法。所述吸附劑是通過將氧化鋁和 在煆燒時可轉變成金屬氧化物的鹼金屬化合物接觸而製備 的。 經濟部中央樣準局員工消費合作社印製 美國專利4433981描述了一種從氣流中去除C02的方 法，包括所述氣流在高達約3 0 0 °C的溫度下與通過含鈉或 鉀氧化物的多孔氧化鋁的浸潰製備的吸附劑接觸。相應的 氧化物可通過用一種可分解的鹽浸漬並在3 5 0 — 8 5 0 °C的 溫度下煆燒來製備。所述鹽包括鹼金屬碳酸氫鹽。 美國專利3 5 5 7 0 2 5描述了通過選擇性地煆燒氧化鋁並 和一種鹼或碳酸氫銨鹽接觸而形成至少30%(重量）具 MA1(0H)2C03經驗式的鹸化氧化鋁的製備能吸附302的 鹼化氧化鋁的方法。 本紙張尺度適用中國®家標準（CNS ) A4规格（210X25>7公釐） ^06884 A7 B7__ 五、發明説明（） 3 美國專利3 8 6 5 9 2 4插述了細粉狀碳酸鉀和氧化鋁的 混合物作爲二氧化碳的吸附劑的用途，它和碳酸鹽及水反 應形成碳酸氫鹽。所述吸附劑混合物通過適度地加熱如壓 9 3 °C ( 2 0 0 ° F )再生》化學計量量的水的存在是必要的， 所述氧化鋁看來好像基本上只是作爲碳酸鉀的載體。其它 碳酸鹽也可使用。 美國專利5 2 3 2 4 7 4描述了使用佔7 0 — 1 0 0 %床體積 的氧化鋁從空氣除去水和二氧化碳的P S A方法。與大多數 一般只含約1%矽石的氧化鋁相反的含高達10%(重童）矽 石的氧化鋁被認爲是優選的。矽石是酸性材料。因此本文 所提出的使用鹼性化合物提高二氧化碳吸附量的觀點與該 文獻正好相反d 發明要旨 我們已發現用沒有煆燒成鹸金屬氧化物的鹸處理氧化 鋁可極大地提高在PSA條件下可再生的氧化鋁的二氧化碳 吸附量。 因此，本發明提供了從氣體中吸附二氧化碳的變壓吸 附方法，包括在第一種壓力下將氣體暴露到吸附劑上以從 氣體中除去二氧化碳，並通過減壓使吸附劑暴露於低於所 述第一種壓力的壓力下而將所述吸附劑周期性再生，其中 所述吸附劑通過用pH至少爲9的鹼溶液浸漬氧化鋁並將其 乾燥後形成》 本紙張尺度適用中國國家輮準（CNS ) A4规格（2丨0X297公釐） ----------------1T------^ I (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印製
3C ^884 A7 B7 年 月 ί;* , t-y 1' (1996年1月修正) 五、發明説明（4 ) (請先閲讀背面之注項再填寫本頁} 所述氧化鋁用鹸溶液處理的有益效果可能是由於二化 碳和在所述氧化鋁表面的鹼性環境中的氫氧根離子反應形 成碳酸氫根離子，但本申請人並不希望受該理論束縛。 浸漬溶液的p Η較佳的爲至少1 0，更佳的爲1 0至1 2， 已經使用pH約11的浸潰溶液而獲得了最佳效果。 浸潰溶液的pH與所述氧化鋁的零點負荷（ZPC)以下 式相關聯也是較適宜的： PH ^ ZPC - 1 .4 以下式相關聯則更適宜： ZPC + 2^pH^ZPC~1.4 浸溃溶液的p Η最適宜的以下式的形式與氧化鋁的零點 負荷相關聯： ZPC+2^pH^ZPC—1 適合的所述鹸溶液是鹸金屬或銨化合物，例如齡金屬 或銨的氫氧化物、碳酸鹽、碳酸氫鹽、磷酸鹽和有機酸 鹽。可使用之合適鹸化合物包括鈉、鉀或銨的碳酸鹽、氫 氧化物、碳酸氫鹽、硝酸鹽、甲酸鹽、乙酸鹽、苯甲酸鹽 或檸檬酸鹽。 經濟部中央樣準局員工消費合作社印裝 用於本發明之最適宜的鹼性化合物是碳酸鉀。 本發明的PSA方法較適宜的被應用在從低含量例如二 氧化碳含量於吸附前低於1 0 0 0 p p m的氣流中去除二氧化 碳。 發明之詳細說明 本紙張尺度適用中國國家標準（CNS ) A4規格（21 〇 X 297公釐） A7 B7 經濟部中央樣準局員工消費合作社印製 五、發明説明（5 ) (丨996年1月修正) 用於本發明的改性氧化鋁可這樣製備：先配制具上述 適當pH的所選鹼性化合物溶液。然後將體稹正好足夠塡 滿氧化鋁的孔而不產生表面潤濕的所配溶液加到氧化鋁 中》可選擇溶液的濃度和置使氧化鋁上化合物的負載爲1 —1 0 % (以乾重計）。 所處理的氧化鋁應在一定溫度下乾燥，所述溫度下高 到引起所加入化合物的分解而產生通過降低氣壓不能逆轉 而只能像在TSA中通過高溫才能逆轉的和二氧化碳結合的 氧化物。這樣，美國專利4433981公開了用碳酸鈉或其它 化合物的溶液處理氧化鋁、在l〇〇°C下乾燥、然後在5 7 5 °C下進一步熱處理。這裡的第二加熱步驟產生了不適合於 本發明的PSA方法的物質。 用於浸潰用於本發明的氧化鋁的化合物最好不會引起 水和這種吸附劑反應而使它在所用的變壓條件下不被脫 附。水的不可逆吸附會逐漸妨礙二氧化碳的吸附。如果首 先通管一吸附劑將水除去（可逆吸附），那麼這種類型的材 料的使用是可接受的。我們已發現如果浸漬氧化鋁的化合 物是一種磷酸鹽如磷酸鉀那麼就可能遇到水的不可逆吸 附。 因此乾燥較佳地係在2 0 0 °C以下進行，更佳地在1 5 0 °C以下進行。 本發明將通過下列實施例進一步說明。在下列實施例 中，通過將20g氧化鋁置於水中並在24小時後測定PH來 測量氧化鋁的零點負荷。單位爲毫摩爾/克/大氣壓 • m· ^ -{策—I (請先閲讀背面之注意事項再填寫本頁) *ye ,m «^1— 1^1 · 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） A7 £7_ 五、發明説明（6 ) (mmole/g/atm)的作爲初始等溫線斜率的亨利定律常數 ({^)在250 °(：50微米壓力下脫氣16小時並接著在30°(：重 復地定量供給C02和隨後在50微米壓力下抽眞空16小時 後測定。初始的亨利定律常數（K ,)在第一次定量供給 C 0 2時同樣地測定。高的K ,値表示通過變壓不可逆而只 是通過高溫處理才可能可逆的較大的吸附二氧化碳的吸附 能力。高的値指示本發明所需的高的可再生的（通過變 壓）吸附能力。 實施例1 將一種活性氧化鋁用各種不同pH的溶液浸潰。在每 種情況下，加入正好塡滿氧化鋁的孔體積的足童溶液，所 述溶液的濃度是能在120 °C乾燥後的氧化鋁上產生5%(重 量比，溶質/固體物總重量）的溶質負荷的濃度。然後測定 亨利定律常數，其結果列於下面的表1中。 ---------f . II -» j 〆 (請先閱讀背面之注意事項再填¾本頁) 訂 經濟部中央標準局員工消費合作社印製 本紙法尺度適用中國國家揉绛（CMS ) A4規格（210X297公釐） 表1 A7 ____ B7 五、發明説明（7 ) 吸附劑 浸漬溶液的p H (mmole/g/atm) Ki (mmole/g/atm) K2 AlcanAA-300 本 14.8 5.6 5% Fe(N03)3 1 . 2 * 1.3 1.2 5%檸檬酸 1.7* 0.92 0.88 5% Csl 5 . 8 * 2.0 1.6 5% NH4HCO3 7.8* 6.3 4.9 5% (NH4)2C〇3 8 . 9 * 6.6 5.8 5%K2C〇3 114 8 10 2 2.8 5% Na3P04 12,7 12 4 12.2 5% NaOH 13 1 3 4 0 15.1 沒有按照本發明 表1的結果淸楚地表明用酸性溶液浸潰氧化鋁降低了 這種材料的C〇2吸附量》此外，pH9以上的鹼性溶液顯著 提高了對(：02的〖2値，指明使氧化鋁的表面增加鹼性增 大了 C 0 2吸附量》 實施例2 該實施例證明所獲得的吸隊附能力的增加取決於P Η 而不只是所用溶質的本性。爲表明這點，將K2C03浸漬 溶液緩、冲到 13.8 、 1 0 . 4 ( A1 c an AA-300 的 ZPC)f〇4 的 p Η値。這些溶液被用來通過水的早期潤濕技術進行5 % 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -----；--·--i .------IT------1 _ (請先閣讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 經濟部中央標準局貝工消費合作社印装 A7 _______B7 _ 五、發明説明（β ) Ο (重量）的浸漬》然後在3 〇。(：下如上所述的那樣測定C 0 2 等溫線。再用亨利定律常數比較低壓數據。結果列於表2 中。 表2 溶液p Η (mmole /g/ atm) K2CO3 調到 13.8 6.3 Κ 2 C 0 3 調到 1 〇 . 4 1 10.8 K2CO3 調到 4.0 0 . 6 * 沒有按照本發明 明顯酸浸漬的樣品性能下降，但強的驗性溶液和弱鹼 性溶液（p Η = 1 〇 . 4 1 )相比地損失了一些性能。這種出乎 意料的結果表明通過使用等於或稍鹼於吸附劑氧化鋁的自 然零點負荷的浸漬獲得最高的可再生c 0 2吸附量。 實施例3 製備用各種鹽的混合物製備的水溶液而在A 1 c a n A A 一 300氧化鋁上達到5%(重量）浸漬。然後按如上所述在 所述樣品上測量C Ο 2等溫線。測定結果顯示於表3中》 -1 0 - 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） -------^--火------1T------遂 (請先閲讀背面之注意事項再填寫本頁) 五 經濟部中央標準局員工消費合作社印家 〇C^84 a7 一 B7 發明説明（9 ) 表3 樣品（均5重量％) pH (mmole/g/atm) Κι (mmole/g/atm) κ2 碳酸氫銨/甲酸銨 7.78* 2.7 2.1 碳酸氫銨/甲酸鈉 7 8 1 * 16.2 6.0 碳酸氫銨/碳酸鉀 9.0 4 9.2 13.2 NaOH/碳酸氫銨 11.19 2 2 3.5 2 7.3 碳酸鈉 11.4 18 8 12.4 NaOH/碳酸氫鈉 13.34 5 5.4 14.5 NaOH/甲酸鈉 13.58 3 4 9.3 11.1 NaOH/苯甲酸鈉 13.97 2 3 2.7 19.0 沒有按照本發明 表3的結果表明當浸漬溶液的p Η > 9時增強了可再生 的C 0 2吸附。在所述氧化鋁的自然Z P C附近這種增強效果 達到最高，隨著pH再增高這種效果開始下降，在 p Η > 1 3 . 4時則出現明顯下降。在浸漬溶液的這些高p Η 下’初始亨利定律常數是相當高的。但是眞空再生後測得 的亨利定律常數的大的降低表明在第一次操作時吸附的大 量C02被化學吸附而在PSA應用中不可去除。 實施例4 本紙張尺度適用中國國家標準（CNS } A4規格（210X297公釐） I —-1— -----*·ϋι- I I V < - - n ί— In HI I (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印製 A7 B7___ 五、發明説明（1 0 ) 用鹼鹽浸漬的氧化鋁的效用也通過測量C02穿透曲線 來測定。用含400ppm(V)C02的原料空氣流在1〇〇磅/平 方英吋（表壓）（6 8 9 . 5 K P a )的進口壓力和2 2 °C的吸附溫 度下在6英呎XI英吋柱中測量穿透曲線。原料流速是27 lb mol/t2/hr(13 1 Kgmol/m2/hr)。通過在柱上簡間 的質量平衡，測定不同吸附劑的c〇2的吸附量和co2傅質 區長度。穿透測定的結果列於表4中。 表4 吸附劑 (mmole/g)C02 吸附量 英吋（cm)傳統區 AA-300* 0.11 14(35.6) 含 50/〇K2CO3 的 AA-300 0.25 16(40.6) 含5%Na3P〇3 4 的 AA-3 00 0.17 14(35.6) 沒有按照本發明 表4的結果表明用鹼鹽浸漬的氧化鋁對空氣中<：〇2的 吸附童大於未處理的氧化鋁。此外，這種吸附能力的提高 是在沒有增加吸附C 0 2所需的傳質區長度的情況下獲得 的。 實施例5 將實施例4的鹼鹽浸漬的氧化鋁在單柱pSA單元中測 定。所述單元由一個6英吋長1英吋直徑的單柱構成。 所述吸附劑在P S A循環中如下測定： 本紙張尺度適用中國國家橾隼（CNS ) A4说格（210X297公釐） Μ IT------Α’ — (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明说明（H ) (1 )以每分鐘2 8標準升的流速在2 2。〇 1 〇 〇磅/平方英 吋（表壓）（ 6 8 5.5 KPa)下將含4 0 0 ppm C02的空 氣導入， (2)逆流減壓到10磅/平方英吋（表壓）（60KPa)。 (3 )以每分鐘1 5標準升的流速在1 〇磅/平方英吋（表壓） (6 9 K P a )下用N 2沖洗和 (4)用N2再加壓到進料壓力。 總循環時間爲20分鐘，9.8分鐘用於進料，9.8分鐘 用於沖洗。 表5列出了在上述的相同循環下三種表4所列的吸附 劑的吸附量。 表5 吸附劑 (k g處理的空氣吸附劑）吸附量 AΑ- 3 3 0 * 3.54 含 5%K2C〇3 的 AA-300 3.87 含 5%Na3P〇4 的 AA-300 3.99 沒有按照本發明 經濟部中央標準局負工消費合作社印袈 ：--.--ί-- (請先閱禎背面之注意事項再填寫本頁) 表5所示的結果表明用鹼鹽浸漬AA - 300氧化鋁（分 別對K 2 C Ο 3和N a 3 P 〇 4浸漬的吸附劑來說）提高了所述材 料9%和13%的原料空氣處理量。 實施例6 本紙張尺度適用中國國家標率（CNS〉A4規格（210X 297公釐）

Claims (1)

  1. A8 B8 C8 D8
    >06884 —種5%K2C03浸漬的氧化鋁AA — 300樣品在一大 規模PSA中試驗。所述單元含一直徑爲0.21米、長2米的 (請先閲讀背面之注意事項再填寫本頁) 柱。P S A循環仍按上述的循環步驟進行。但是進料時間爲 1 4分鐘，再加壓時間爲2分鐘。該測定結果列於表6中β 表6 進料壓力 淸洗氣/空氣 摩爾比 (kg 空氣/kg/hr) AA-300 (kg 空氣/kg/hr) K2C03 10 0.30 3.1 3.5 6 0.45 2.8 3.3 經濟部中央標準局男工消費合作社印製 表6的結果表明在上述試驗的處理條件下用K 2 C Ο 3浸 漬的氧化鋁可比未處理的氧化鋁處理更大量的空氣。這意 味著和未處理的氧化鋁相比，在進料空氣流速一定時，可 使用較小體積的含經浸漬的氧化鋁的床。在實施例5和該 實施例的條件下，採用經浸漬的氧化鋁比未處理的氧化鋁 需要量減少1 0 - 1 5 %。這種較小的吸附劑物料量和因此 導致的較低的床體積然後就轉換成在泄料時較少的開關損 失，這提高了回收率和降低PSA的操作费用·> 儘管已用優選的實施例描述了本發明的情況，但可以 理解在本發明的範圍內還可進行許多修改和變化。 本紙張尺度逋用中國國家標準（CMS ) Α4規格（210X297公釐） 0884 B8 C8 D8 本 (I 9 9 6年ί月修正） 經濟部中央揉率局貝工消費合作社印製 六、申請專利範圍 — 1. —種從氣體中吸附二氧化碳的變壓吸附方法，包括 在第一壓力下將氣體暴露到一使用pH値介於9至14的鹸溶 液浸漬氧化鋁而形成的吸附劑上，而從該氣體中除去二氧 化碳，並通過減壓使該吸附劑暴露於低於該第一壓力的壓 力下而將該吸附劑周期性再生，其中該鹼性溶液是鹼金屬 或銨的氫氧化物、碳酸鹽、碳酸氫鹽或磷酸鹽的溶液。 2. 如申請專利範圍第1項的方法，其中該浸潰溶液的 pH値介於10至14。 3 ·如申請專利範圍第1項的方法，其中該浸漬溶液的 p Η値爲1 〇至1 2。 4. 如申請專利範圍第1項的方法，其中該浸漬溶液的 ρ Η値是1 1。 5. 如申S靑專利範圍第1項的方法，其中該浸漬溶液的 ρ Η値與氧化鋁的零點負荷（z p c )的關係如下： 14>pH^zpc— 1.4 。 6 ·如申請專利範圍第5項的方法，其中該浸漬溶液的 pH値與氧化銘的零點負荷（zpc)的關係如下： zpc + 2^pH^zpc— 1.4 。 -15- 本紙張又度逍用中國國家棋準（CNS ) A4规格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) J 裝. •IT -M 306884 as ' BB 丨 C8 _ ； _ _ (1996 年 1 月修正） 六、申請專利範圍 7. 如申請專利範圍第1項的方法，其中該浸潰溶液的 pH値與氧化鋁的零點負荷（zpc)的關係如下： zpc + l^pH^zpc — 1 。 8. 如申請專利範圍第1項的方法，其中於吸附處理 前，該氣體含至多lOOOppm的二氧化碳。 ,11„---裝-- (請先閾讀背面之注項再填寫本頁) 訂 線 經濟部中央樣準局員工消費合作枉印製 6 ---- 本紙張尺度逋用中國國家揉準（CNS ) A4規格（210X297公釐）
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US5656064A (en) 1997-08-12
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NO964167L (no) 1997-04-07
CN1076978C (zh) 2002-01-02
CA2186681C (en) 2002-04-23
CN1153077A (zh) 1997-07-02
DE69626913D1 (de) 2003-04-30
EP0766991A1 (en) 1997-04-09
DE69626913T2 (de) 2003-11-13
CA2186681A1 (en) 1997-04-05
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US5917136A (en) 1999-06-29
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