TW304170B - - Google Patents

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TW304170B
TW304170B TW084101472A TW84101472A TW304170B TW 304170 B TW304170 B TW 304170B TW 084101472 A TW084101472 A TW 084101472A TW 84101472 A TW84101472 A TW 84101472A TW 304170 B TW304170 B TW 304170B
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particles
alumina
sodium
weight
sodium carbonate
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TW084101472A
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Ici Plc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/68Halogens or halogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041Oxides or hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06Solid 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
    • B01J20/08Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004Sorbent size or size distribution, e.g. particle size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3028Granulating, agglomerating or aggregating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Paper (AREA)
  • Gas Separation By Absorption (AREA)

Description

經濟部中央橾準局貝工消費合作社印製 病84101472¾專利由諝案 -------- 中文銳明寄修正頁(86年1月)A7 % , 0 _____B7 丨。υ .. ’五、發明説明(/ ) 本發明係有鼷一棰吸收劑及其製法•特別是有W—檯遘 用於自氣賴流中移除污染物氯化氫之吸收劑。 此種吸收劑一般係使用作為欲虔理氣《溁連鑛通遇之床 :污染物氯化氫被該吸收劑吸收因此流出物氣體具有相當 低的氣化氫含量。一段時間後,吸收劑麥得被所吸收之氯 化氫所負載直至吸收劑床無法減少氛化氯含量至可接受之 量:一般期望流出物氣賴所含氛化氫之體積少於一特定董 ppm 。當流出物氣體含有無法接受之比例之氯化氫 時,將發生”轉折(break-through)” ;通常發現當發生轉 祈時·床之氡化物含最多少會少於理論之最大值•·因而當 自床入口區域取出之樣品具有氯化物含鼉等於或接近理論 之昜大值時,自床出口取出之樣品所具有之氯化物含量明 顯地低於理諂之最大值。 已知一種自氣體流移除污染物氣化氫之吸收劑包括已Μ 氳舊,化納或碳酸納浸潤且接著在高溫如高於500 1C下煆燒 之氧化IS顆粒。在此種溫度之烜燒會引起至少某些氫氧化 纳或碳酸納與氧化鋁反懕而形成鋁酸納。 其中某些納係W碳酸钠與氧化鋁間反懕所得之鋁酸納存 在之此種吸收劑顆粒一般具有總納含鼉(以氧化納Na2〇表 示)在12-14重量!S内(K樣品在900C燃燒後所測得者)。 這些吸收劑在高溫例如350 C 下顯現吸收氯化簋之可接受 活性,及當吸收劑具有約15-17重量Ji之總氣化物含量時一 般會發生”轉析”(得到含有大於0.1 PPB1氯化氳體積之產物 氣鵂)。然而此穐吸收劑在低溫如低於約150=0時之活性受
---------^-- {請先閲讀背面之注意事項'寫本頁) 訂 線 -4 - 本紙張尺度適用中國國家標率(CMS ) A4規格(2I0X297公釐) 第ΟI4"?2號專利申請累 書修正頁(86年1月) A7 B7 Q 1 ιϊΙα sc 經濟部中央標準局員工消費合作社印製 五、發明説明(7) 到限制,且當發生轉折時床之氯化物含量相當低。例如在 常溫下,當庆之平均氯化物含最僅約8-9重最X時會發生 轉祈(0 · 1 Ρ Ρ η H· C 丨)。 在fiB 1433762中提出使用已Μ碳酸納溶液浸潤接著蒸發 水及在120C 加熱之高表面播之活化氧化鋁顆粒作為酸性 氣髑之吸收劑。在P C Τ公報W 0 9 3 / 2 2 0 4 9中,提出以有楗 酸如乙酸之驗金賵锂浸潤氧化鋁,接著乾燥並在300-550 C下鹣博而製成類似吸收劑。後者之參考文歙建議吸收劑 .顆粒可W包含將氧化鋁粉末飼入旋轉盤上,並將鹼金鼷化 合物之水溶液晡佈至旋轉盤中之氣化鋁粉末上之聚结技術 製得。此技術建議可併入之鹼之鼉以鹼金鼷氧化物表示時 ,吸收_之鹼金厲含量為達氧化鋁之15重量X 。蘋此棰浸 潤方法,無法產生含有多於約15重最鹸(Μ驗金屬氧化物 表示)之吸收劑。 藉由使用另一種製造方法,發現可能可達到具有更高鹸 性含最之吸收劑巨因而具有更大之氛化物容最。此種吸收 劑具有明顯改良之低溫性能。 依搏本發明提供一榫吸收劑顆粒,其包括選自氣化鋁及 /或水含氧化鋁之氧化鋁成份,選自碳酸納及/或碳酸氫 納之鹸性成份(其重鼉比例為每份該氧化鋁成份為0.5至2 份之該鹼性成份)及作為黏合劑之水合水泥或黏土的緊密 潖合物;該顆粒含有自5至20重黃%之該黏合劑巨具有樣 品顆粒在90〇r·燃焴後樣品之氧化納Na20含量至少為20重 最5:之鹼性成份含鼉。 本紙伕尺度適用中國國家標準(CNS ) A4規格(210X297公康) ---------^-- 請先閲讀背面之注意事項fv.寫本頁) -訂 線 1'$·正 補充| €84101 472號專利$謫冪 A7 甲文銳明寒络正百u 6年1月)B7 五、發明説明(i) 此吸收謂顆粒較好具有平均大小至少約2 «米,且較好 至少約3骛米,較小顆粒之床易於產生對氣體流之無法接 受之抗性。因而當氣體流经較小顆粒床時會產生無法令人 接受之高壓降。 此顆粒較好具有至少10米2/克之BET表面橫。 黏合劑可為水合水泥,如鋁酸鈣水泥。或者,且較佳乃 黏合劑*其包括鈷土,例如針狀鈷土如美國活性白土或海 泡石。 龙發明之吸收劑之製造,係將氧化鋁或水合氧化鋁(如 S化铝三水合物),碳酸納或較好為碳_每納及黏合劑之 必要比例之混合物粒化,且使所得混合物在遘宜溫度如低 於約350 t且較好在105-300 t:之範圍内烺燒。在此溫度 下,咸信氣化IS三水合物有鲜少或無任何分解之情況發生 ,但碳酸氣納會轔化成碳酸納。X -射埭繞射檢視顯示納僅 W碳酸納相存在:不形成或很少量之IS酸钠形成。 粒化意指使粉末吠成份亦即氧化鋁及/或水合氧化鋁· 硝酸納及/或碳酸《納,及黏合劑與足κ形成漿液之少量 潭潤劑(如水)混合,並使所得混合物形成約為球形構造之 聚结物;此種粒化技術為太技藝中眾所週知者》 較好使用氧化IS三水合物而非氧化鋁,係由於含有高比 例之碳酸納或碳酸S納及氧化鋁之组合物之粒化較有困難 之故。使用W酸納取代碳_氮納可導致較低表面棟之吸收 劑,因此較偏好使用重量比例在1:2至2:1範圊之氧化铝三 本紙張尺度適用中國國家標準(CNS ) M規格(2丨0X297公釐) (請先閱讀背面之注意事項再填寫本頁)
*tT 經濟部中央標準局黃工消资合作社印製 A7 B7 經濟部+央標準局員工消費合作社印^ 五、發明説明() 水合物及碳酸氫納之混合物: ‘為了使顆粒具有適當強度,較好使用呈细粒狀之成份* 典型上諸成份具有平均粒徑在;1 - 2 0微米之範圍,較好在 5 - 1 0微米之範圍: 本發明Μ下列實洌加以說明。 蓄例1 碳酸氫納(8公斤)氧化鋁三水合物U公斤)及美國活性白 土( 1 . 6公斤)(各均呈具有平均粒徑在5 - 1 0激米範圍之妞粒 μ 粉末狀)進行乾混合,混合物之一部份(約2公斤)饋刀2 5升 容積之Η 〇 b a r t混合器中並以約6 0 r ρ m ( 1 Η 2 )之速度於其内 攪拌,在撹拌下緩慢添加水直至混合物黏结形成小球或顆 粒。並逐漸添加其他量之粉末混合物及水直至所有粉末混 合物形成顆粒。接著’顆粒過篩捨去小於約3毫米或大於約 5毫米大.小之顆粒。 刺餘顆粒在1 1 5 °C烘箱中於空氣中乾燥4 小時,乾燥顆 粒之樣品(樣品A )如下述般測試。接著烘箱溫度Μ 1 0 °C / 分鐘之速率升至2 0 0 °C並在2 0 (TC维持3小時以進行煆燒, 接著亦測試煆燒顆粒之樣品(樣品B )。 兩種顆粒樣品之整體密度約0 . 8克/毫升及B E T表面積約 1 4米2 /克。在9 0 0 :C 燃燒後顆粒樣品之分析顯示氧化納 Na20含量超過30重量%。 接著使含約1體積$氯化氫之甲烷在大氣壓及約2 0C下 Μ約7 0 0小時—1之空間速度,向下通過高1 2公分且高度對 直徑比例為5之顆粒垂直床,而測試樣品Α及Β之氯化氫 (請先閱讀背面之注意事項再塡寫本頁) 裝 *νδ 線 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 83.3.10,000 304170 五、發明説明() A7 B7 經濟部中央標準局S工消費合作社印^ 吸 收 特 性 。測定 流 出 氣 體 中 氯 化 氫 量達 1 P P Witt m m 積 之前 之 時 間 並於下 表 中 表 示 為 ’至1 P P m HC 1 之 轉 折時 間 接 著 此 顆 粒小心 地 白 床 中 排 出 並 分 成 6個 部 份 ,各 相 當於 床 深 度 之 2公分 帶 分 析 各 部 份 之 氮 化物 含 量 ,结 果 示於 下 表 中 ;) 樣品 A 樣品B 至 1 P P m H C 1之轉折時間( 小 時 ) 6 13 氯 化 物 含 量(重量5Π 部 份 1 ( 頂端) 19 . 8 23 . 1 0 部 份 2 15 . 2 24 . 3 部 份 3 9 . 1 24 . 3 部 份 4 2 . 9 23 . 7 部 份 5 0 . 5 1 6 . 7 部 份 6 ( 底部) 0 . 1 4 . 9 筲 例 2 對 下 列 吸收物 質 進 行 類 似 於 實 例 1之測試步驟(但 空 間速 度 約 750 小時-1 且 當, 出 Ρ 氣 體 之 氯 化 氫含 量 達 10 ρ pm 體積 時 發 生 ”轉折”) C . 使 用50重 量 份 碳 、酸 氫 納 50 重 量份 氧 化 鋁三 水 合物 及 10重量 份 美 國 活 性 白 土 t 以 實例 1 之 步驟 在 145 ec 之旋轉乾燥器内進行單- -階段之乾燥及锻燒所 製 得之具 有 粒 徑 在 3 至 5 毫 米 ,整 體 密 度約 0 . 9克 /毫升及BET 表 面 積 約 16米 2 /克之顆粒 此顆粒在 9 0 0 °C 燃 燒 後 之 樣 品 分 析 顯 示氧 化 納 Na20 含 量約 (請先閲讀背面之注意事項再塡寫私頁) 裝
-1T 線 本紙張又度適用甲國國家標準(CNS)A4規格(210 X 297公釐) 83.3.10,000 經濟部中处標準局員工消費合作社印¾ A7 B7 五、發明説明() 為30重量:¾。 D. 約3毫米大小之市害氧化|g顆粒K碳酸納浸潤且在 高於500 C鍛燒而得整體密度約0.75克/毫升及 Β Ε Τ表面積約1 1 3米2 /克之顆粒*在9 0 0 C燃燒後, 具有氧化納H a 2 0含量約1 4重量%。 E . 具有整體密度為0.83克/毫升及BET表面積約300米 2 /克之顆粒大小約3毫米之市售活化氧化鋁顆粒。 下表中係表示各吸收物質之”轉折時間”(:至1 0 P P nu H C 1 )及各部份之氛化物含量。此外,由於重要判斷d準為 可被既定體積之吸收劑床吸收之氯化氫量,因此在表中, 係計算每立方米吸收劑之氯化物重童(C 1 -公斤)。
吸 收 劑 C 0 E 至1 0 P P m H C 1之轉折時間(小時)1 1 4 2 氯化物含量(重量ί:) 部 份 1 ( 頂 端 ) 23 .9 10 . 5 4 . 5 部 份 2 24 .8 9 . 3 5 . 8 部 份 3 24 .9 8 · 5 5 . 1 部 份 4 21 .9 7 . 5 3 . 4 部 份 5 13 .1 4 . 2 2 . 9 部 份 6 (底 部 ) 2 .4 0 . 9 1 . 0 收 之 氯 化 物 (公斤每立方米) 1 73 .5 5 5 . 2 32 . 1 由 此 可 見 本 發 明 之吸 收 劑顆 粒 C 比吸 收劑 D或E 有 更 氯 化 物 吸 收 容 積 ,而 與 吸收 劑 顆 粒C 之較 低BET 表 面 -9-
本紙張尺廋適用中國國家標準(CNS)A4規格(210 X 297公釐J 83.3.10,000 ----------裝----— — — — — .π------線 (請先閱讀背面之注意事項再塡寫本頁) 經濟部_央標準局員工消費合作社印製 3q^17〇 A7 B7 五、發明説明() 無關。 (請先閲讀背面之注意事項再填寫本頁) 裝 線 -1 ο - 本紙張& t適用中國國家標準(CNS)A4規格(210 X 297公釐、 83.3.10,000

Claims (1)

  1. 么、 Γ ^ 中文由請 72¾ 專利 7〇 _利碎鼷修IE太(86年ΐ月) Α8 Β8 C8 D8 年月 86. 1. 修正丨 六、申請專利範圍 - 1. —種吸收劑顆粒,包括選自氧化鋁及/或水合氧化鋁之 氲化18成份,碳酸納《其重量比例為每份該氧化鋁成份 含0.5至2份的碳酸納)及作為黏合劑之水合水泥或黏 土之緊密琨合物;該顆粒含5至20重最之該黏合劑並 且具有碳酸钠之含最係使顆粒樣品在9〇〇t:下燃燒後, 樣品之氣化納Na2〇含量為至少20重量Si *該顆粒係將氧 化鋁或水合氧化鋁粒子、碳酸納、或碳酸氫納粒子及黏合 劑粒子的混合物粒化,並&在3 5 0 t Μ下之溫度烺燒該 所得羥粒化渴合物而得。 2. 根搏申請專利範圍第1項之吸收劑顆粒,其BET表面檟 至Φ為1 0米2 /克。 3. 一薄製造根棟申請專利範匾第1項之吸收劑顆粒之方法 ,包栝使氧化鋁三水合物粒子,碳酸納或碳酸氫納、及 作為黏合劑之水合水泥或黏土的混合物粒化,並在低於 3 5 之溫度下埠燒所得經粒化混合物。 4. —種自氣賴流中移除氣化氫之方法,包括在低於150 C 溫度下,令氣雅流通過根據申謫專利範圍第1項之吸收 劑雜粒之床。 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央揉準局貝工消費合作杜印裂 本紙張尺度逋用中國國家揉準(CNS )戍^说格(210 X 297公釐)
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