TWI233837B - Titania catalyst and catalyst support composition and Fischer-Tropsch process using the same - Google Patents

Titania catalyst and catalyst support composition and Fischer-Tropsch process using the same Download PDF

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TWI233837B
TWI233837B TW088102097A TW88102097A TWI233837B TW I233837 B TWI233837 B TW I233837B TW 088102097 A TW088102097 A TW 088102097A TW 88102097 A TW88102097 A TW 88102097A TW I233837 B TWI233837 B TW I233837B
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item
weight
catalyst carrier
metal
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Stanislaw Plecha
Charles Harrison Mauldin
Larry Esteen Pedrick
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Exxon Research Engineering Co
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

1233837 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1 ) 發明 本發明係關於含有二氧化鈦的載體，其製法及（.和添 加的i屬）在費雪措希（Fischei-Tropsch )煙合成法中 作爲觸媒之用途。更特別地，本發明係關於能夠忍受在烴 合成法（如：以漿狀物爲基礎的方法）中常遇到的高水分 壓之材料。 發明背景_ 美國專利案第5 ，140，050號描述製備費雪一措 希觸媒中所用之載體之改良，及藉由將這些觸媒用於費雪一 措希法中而得到之令人意外的結果。使用這些經改良的觸 媒和載體時，費雪一措希合成法的操作條件（特別是因爲費 雪一措希反應而造成之相當高的水分壓）會導至觸媒變弱及 在反應混合物中形成過多的細碎物。這些細碎物有數個不 良效果，包括阻塞管線、降低觸媒效率和觸媒通過濾器之 耗損及阻塞濾器。因此，有必要發展出在通蒸汽的條件（ 如：費雪一措希法遭遇的情況）下，可以維持其完整性並因 此維持其效能的觸媒。特別地，漿狀物操作及通蒸汽條件 的嚴格要求，須要高度耐耗損的觸媒。 發明槪述 根據本發明，二氧化矽和氧化鋁作爲含有二氧化鈦的 載體之黏合劑，以獲致費雪一措希合成法中所用觸媒所須的 整體性。藉由將用於費雪一措希合成法的一或多種金屬活性 (請先閱讀背面之注意事填寫本頁) —# 丨裝 * 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4 -
1233837 五、發明說明（2 ) 物（如：第V I I I族金屬，如鈷或釕）分散於載體表面 上而形成此觸媒。因此，形成局強度（依抗耗損性測定） 觸媒，其在用於費雪一措希法中時，於水分壓相當高、高溫 (如：1 7 5 — 4 0 0 °C )的條件下仍維持其完整性。 美國專利案第5 ，140 ，〇5〇和 4，992，406號提出藉由使用氧化鋁或氧化鉻或二 氧化矽黏合材料（依喜用程度排列）來改良含有二氧化鈦 的載體之孔隙度。但此處所述的本發明提出使用二氧化矽 (比氧化錕較不受喜愛的材料）和氧化鋁一起作爲黏合劑 ’製造出無論是在乾燥狀態或在通蒸汽條件下，耐耗損性 都比僅使用氧化鋁或二氧化矽來得好之含二氧化鈦的材料 。因此，就在含有一氧化欽和氧化鋁的組合物中添加較不 受喜愛的材料竟得到更強的載體材料方面來看，似乎有違 常理。 與製造出含有一氧化鈦之高強度材料有關之氧化鋁和 一氧化砂的合作效應未明。但是，在不希望受限於任何特 別的機構同時，吾等推論：最終、經鍛燒的載體中，小的 一氧化砂顆粒佔據較大的氧化鋁顆粒和更大的二氧化鈦顆 粒之間的空隙’並作爲化學結合劑。因此，二氧化矽微晶 可以部分沒入氧化銘和二氧化鈦微晶中而形成基本上連續 的結晶相。此二氧化矽作爲氧化鋁和二氧化鈦之間的黏合 劑，在鍛燒或費雪一措希合成法期間內所通的蒸汽進一步形 成一氧化矽和氧化鋁及二氧化矽和二氧化鈦的這些混合的 周圍相。此外，氧化鋁本身無法與二氧化鈦良好混合，僅 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事！^填寫本頁) -裝 訂· 經濟部智慧財產局員工消費合作社印製 -5 - 1233837 經濟部智慧財產局員工消費合作社印制衣 A7 B7____ 五、發明說明（3 ) 依賴物理力來結合顆粒。通蒸汽可能會瓦解這些物理力， 可能會因爲燒結氧化鋁及形成較大的氧化鋁顆粒而比較無 法提供結合量。二氧化矽因爲與二氧化鈦之間的親和力會 使得二氧化矽損失大部分的獨立性，所以其本身不是良好 的黏合劑。附圖描述 附圖1是多個樣品的音波耗損圖，其中，縱座標代表 < 2 5微米細粒的重量％，而橫座標代表在超音波浴中的 時間（分鐘）。曲線A、B、C和D分別代表含有通過蒸 汽之氧化鋁、新製氧化鋁、通過蒸汽的二氧化矽一氧化鋁和 新製二氧化矽一氧化鋁黏合劑之二氧化鈦載體。 較佳實施例之描述 含有二氧化鈦的載體是一種細粒材料，其以含有至少 約5 0重量％二氧化鈦爲佳，含有至少約§ 〇重量％二氧 化欽更佳，金紅石：銳鈦比例以至少約1 ·· 9爲佳。此材 料與適當量的二氧化矽和氧化鋁摻合作爲黏合劑材料，其 中’黏合劑佔載體總重的不到約3 〇重量％，以低於約 20重量％爲佳，約3一 2〇重量％較佳，約4〜丄5重 量％更佳，5 - 1 〇重量％又更佳。二氧化矽和氧化鋁黏 合劑混合物可含有5 〇重量％或以下的二氧化矽，二氧化 5夕s里以約3 - 5 0重量％爲佳5 — 3 5重量％更佳。 利用習知壓出、造粒、成錠、噴霧乾燥· ·等方法， 將載體基本上作成基本上爲球形或圓柱形的多孔顆粒。較 佳方法是噴霧乾燥法，其中，二氧化鈦和黏合劑材料之適 (請先M讀背面之注意事:填寫本頁) •裝 訂： 本紙張尺中國國家標準（CNi)A4 規格（2】0 X 297公爱） 6 1233837 A7 B7 五、發明說明（4 ) 當的水性發狀物被霧化進入通有熱空氣的槽中。噴霧乾燥 法製造出尺寸約2 0至約1 2 〇微米的球形載體，其非常 適合用於漿狀費雪一措希法中。 爲了要獲致多孔和強度的優點，黏合劑組份與二氧化 鈦起始材料於成形操作之前混合。它們可以多種形式（鹽 或膠態懸浮液或溶膠形式，以後兩者爲佳）添加。例如， 由氯化鋁、醋酸鋁或硝酸鋁製得的鋁溶膠是氧化鋁組份的 車父丨土來源。易於取侍的一與化砂溶膠是二氧化砂組份的較 佳來源。各個情況中，必須要小心避免這些黏合劑溶膠被 對於活化費雪一措希金屬有害的元素所污染。例如，在費雪 一措希條件下，鹼和鹼土金屬陽離子和含硫的陰離子（如： 硫酸鹽）是鈷的潛在鈍化劑，因此在製備鈷觸媒的載體時 必須儘可能減少它們的量。 二氧化鈦載體基本上於成形之後鍛燒·，以防黏合劑脆 化並視情況地將二氧化鈦的銳鈦相轉變成金紅石枏。此鍛 燒基本上於5 0 0至1 0 0 0 °C的溫度於空氣中進行。 由此載體製備費雪—措希觸媒時，用於費雪——措希合成 法的金屬催化活性物與載體複合。較佳金屬是那些得自元 素週期表第V I I I族者，特別是鐵、鈷和釕，以鈷和釘 爲佳，最佳者是銘。也可以使用促進劑，如：鉻、鈦、銶 、鈴、铈、钍和鈾及他種嫻於此技術者習知者。一或多種 金屬的存在量是對於費雪一措希合成法具催化活性的量，此 量將視所選用的金屬而定。例如，釘在此環境下活性比鈷 大得多，因此用量是約0 · 5 — 3 · 〇重量％，而銘的用 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事填寫本頁) 裝 訂· 經濟部智慧財產局員工消費合作社印製 1233837 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（5 ) 量以約2 一 4 〇重量％爲佳，5 - 3 0重量％較佳，1 〇 一 2 5皇量％更佳。 使用促進劑日守，其用量比活性催化金屬量得來少，如 •與活I生走屬的重里比約；[/ 2 〇至1 2 〇。（本發明 亦含括使用釘作爲促進劑，與作爲主要活性催化金屬的鈷 倂用）。最佳觸媒是那些含有鈷和銶、鈷和釕及鈷和钍者 ，特別是含有銘和鍊者。 觸媒可箱嫻於此技術考習知的多種技巧製備，這些技 巧包括k泡（與促進劑一起浸泡或多次浸泡一乾式浸泡或初 步潤濕技巧）。因爲用於固定床費雪一措希法的較佳觸媒中 ’催化性金屬存在於觸媒顆粒外部（即，在不超過 2 5 0微米深的層中，以在不超過2 〇 〇微米深的層中爲 佳）’所以製備觸媒的較佳方法是噴霧法，其述於美國專 利案第5 ’ 1 4 0，0 5 〇號（茲將其中所述者倂入本文 中以資參考）或EP 0，266，898 (茲將其中所述 者倂入本文中以資參考）。用於漿狀費雪一措希法中時，觸 媒以藉由噴霧乾燥的載體之初步潤濕浸泡法製得者爲佳。 因爲細粒耗損產物有黏合在原顆粒上的趨勢而無法以 慣用的方法（如：習知的D a v 1 s ο η耗損試驗、M i c r ο n· a c或 Malvern光繞射設備）測定，所以測定含二氧化鈦顆粒的強 度並不容易。因此，發展出新穎的加速耗損試驗，其結果 有再現性，其基於在類似於大型漿狀物、氣泡管柱單元的 環境中之浸触或硏磨環境中操作之經耗損產物的S E Μ光 顯微圖。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 . 8 - " (請先閲讀背面之注意事'填寫本頁) 馨 -裝 訂： 1233837 A7 ^____B7_ 五、發明說明（6 ) 此試驗包括.處理懸浮於丙酮中的觸媒或載體小樣品 (如：約0 . 5至約3兄），於超音波浴中達一段預定時 間’之後過濾、以疋出装得之細碎物（即，平均直徑低於 2 5微米的顆粒）的量。因此’ 2 · 5克樣品篩經+ 4 5 微米尺寸餘網’懸浮於1 2毫升丙酮中之後，引至〇 . 5 盘司瓶中。在Bianson Model 2 2 〇 〇超音波槽中以超音 波振動基本上3 0分鐘或以上之後，混合物濾經5 〇 〇 m e s h篩網（2 5微米開口）落在〇 · 〇 2微米濾膜上 (Whatman Anodise )。之後，固體以丙酮淸洗，乾燥， 稱重，以定出<25微米的重量百分比（重量％)。 費雪一措希合成法是習知的方法，其反應條件可見於容 易得到的文獻中。例如，溫度範圍由約1 7 5艺至約 4 0 0 °C ’以約1 8 0 — 2 5 0 °C爲佳，壓力範圍可由約 1 — 1〇〇巴，以約1 5至4〇巴爲佳。氫/ c〇比例可 .由〇· 5 / 1至約4 / 1 ，以約1 · 7 / 1至2 · 5 / 1 爲佳，以化學計量土約3 %最佳。由本發明之黏合劑製得 的觸媒以用於漿狀物（如：漿狀物氣泡管柱）反應器爲佳 ，其中，氣體每小時的空間速度範圍可由約4 0 0 0至 2 0 0 〇 〇。較佳的漿狀物氣泡管柱操作述於美國專利案 第5 ，3 4 8，9 8 2號，茲將其中所述者倂於本文中以 資參考。 實例 將多種黏合劑和De.fussa P - 2 5 Τ ι〇2之混合物 本紙張尺度適用中國國家標準（CNtS)a4規格（210 x 297公釐） 0 (請先閱讀背面之注意事 填寫本頁)
I -裝
經濟部智慧財產局員工消費合作社印M 1233837 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 加以噴霧乾燥，製得1 2種二氧化鈦載體。經乾燥的載體 在迴轉式鍛燒機中於介於7 〇 〇 °c和1 0 〇 〇 °c之間的溫 度鍛燒。這1 2種載體中的每一者所用的氧化鋁黏合劑和 二氧化矽黏合劑的量和來源，噴霧乾燥機進料中的固體含 量（重量％)及最終鍛溫度列於附表1。氧化銘氯醇溶 膠製自 GRACE Davison，名稱爲CX — 1〇〇 ，其含有約 2 3 . 5重量％ A 1 2〇3。分析結果亦列於附表1 ，其中 包括由3 0分鐘音波耗損試驗的數據。金紅石含量代表二 氧化鈦中的金紅石相的重量百分比，餘者是銳鈦相，此以 X —射線繞射（A S 丁 M D 3 7 2〇一7 8 )測定。 S Α代表Β Ε Τ表面積，Ρ V代表直徑低於約5 〇 〇 〇埃 的孔隙之孔隙體積，此以汞孔隙計（使用的汞接觸角度是 1 2 5度）測定。 實例1和2代表使用氧化鋁黏合劑的基本情況，其具 有良好的強度，但如下文中所示者，在通蒸汽之後會損失 強度。實例3 - 5使用得自不同供應商的二氧化矽溶膠， 製得的顆粒非常弱，鍛燒之後有高比例的細碎物存在，顯 示僅使用二氧化矽黏合劑並非可實行的選擇。實例6代表 本發明，其摻有含括氧化鋁和二氧化矽溶膠（9 : 1 )之 混合物的黏合劑。此載體所顯現的耗損値最低，因此在這 些未通以蒸汽的樣品中，是強度最佳者。 附表1中的實例7 — 1 2於7 0 0 °C鍛燒，因此，相 較於實例1 - 6 ，此處的二氧化鈦中的金紅石含量較低， 表面積較高’孔隙體積較高。較高的孔隙體積是特別重要 (請先閱讀背面之注意 事 裝--- 填寫本頁) . ί·^, 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 1233837 A7 B7 五、發明說明（8 ) 的特徵，因爲在這樣的情況中，每次初步潤濕浸泡時，隨 著孔隙體積的提高，會有更多活性金屬附著。實例7，使 用與實例6相同的氧化鋁和二氧化矽之混合物作爲黏合劑 ’顯示於較低鍛燒溫度亦能明顯改善所得孔隙體積，僅略 爲損失顆粒強度而已。比較實例8和7，顯示氧化鋁與二 氧化砂之比例由9 : 1改爲2 : 1 ，皆佔黏合劑組成物總 重之6重量％時，形成良好的孔隙體積。但是，如實例8 、9和1 2中所示者，總黏合劑濃度越高（1 2重量％相 對於6重量％ )，孔隙體積越小。實例1 1和1 2說明使 用硝酸鋁代替氧化鋁氯醇溶膠作爲氧化鋁黏合劑來源，會 得到非常類似的結果。 附表2列出噴霧乾燥之後，在與氧化鋁結合的載體中 添加二氧化·矽所得的較差結果。二氧化矽的添加方式是： 以四乙基矽酸鹽的甲醇溶液浸泡，乾燥並於實驗規模的爐 中於8 0 0 C鍛燒3小時。如附表中所示者，所加入的大 部分矽酸鹽因爲乾燥或鍛燒期間內的蒸發作用而耗損，此 對於此方法造成嚴重的問題。更重要的，留在載體上的二 氧化矽無法改善顆粒強度。實例1 3中，在實例1的載體 中添加一氧化砂’無法有效地改善強度。實例1 4使用與 貫例1相同的組成物，但因爲於靜態爐中於8 5 〇它鍛燒 而形成弱得多的起始材料。實例1 5使用非常弱的載體， 此載體由噴霧乾燥二氧化鈦的實驗、沉澱形式代替Degussa P - 2 5而得。貫例1 4和1 5中，添加二氧化砂之後， 載體變得更弱’此反映出氧化鋁黏合劑在鍛燒步驟中通以 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公餐） (請先閱讀背面之注意事填寫本頁) -裝 訂· 經濟部智慧財產局員工消費合作社印製 -11 - 1233837 A7 B7 經濟部智慧財產局員Η消費合作社印製 五、發明說明（9 ) .蒸汽之後可能會進一步變弱。由這些實例可以淸楚得知： 二氧化矽與氧化鋁一起作爲改善用的黏合劑時，兩者必須 存在於初噴霧步驟中。 爲進一步確定出新S 1〇2 — A 1 2〇3黏合劑的效果 ，製備兩種C 〇 - R e觸媒：一般的二氧化鈦載體含有6 % A 1 2〇3黏合劑，而本發明的實例中，二氧化鈦載體中 含有6 % 9 : 1的A 1 2〇3 — S 1〇2黏合劑。經噴霧乾 燥的載體以與實例1和6相同的方式製得，但大規模製造 。之後，各觸媒製自：初步潤濕浸泡於硝酸鈷和高銶酸的 水溶液中，繼而在迴轉式鍛燒機中於空氣中於約4 0 0 °C 鍛·繞。藉由雙重浸泡/鍛燒來達到最終金屬載量。此載體 在小型固定床反應器中以2 / 1 H 2 / C〇合成氣體測試 ’測試之前先於3 7 5 °C還原。如附表3中所示者，這兩 1重觸媒對於烴類形成都具有高度活性和選擇性。 於如同烴合成所生成的高蒸汽分壓、一般溫度條件下 進行最終最嚴格的強度試驗。爲了要模擬此環境，將一部 分的各個觸媒引至流化床反應器中，並以純蒸汽於約 2 5 0 °c、6 · 8大氣壓條件下處理六天。使用音波耗損 言式驗以不同的音波振動時間評估新製和通過蒸汽之.後的變 化。其結果列於附表4的實例1 6 - 1 9並繪於附圖1中 ° %附圖1 ，淸楚得知耗損試驗所製得的細碎物量隨著 所有材料的音波振動時間增加而提高。如數據的曲線A所 $ ^ ’通以蒸汽使得氧化鋁黏合劑變弱。本發明的二氧化 石夕一氧化鋁黏合劑’（曲線C )在通蒸汽之後僅略爲變弱。此 (請先閱讀背面之注意事填寫本頁) -裝 · 本纸張尺度適用中國國家標準（CNS)A4規格（2】〇 X 297公釐） -12 - 1233837 A7 __B7___ 五、發明說明（10 ) 改良的黏合劑顯著改善初強度和通以蒸汽後的安定性。 (請先閱讀背面之注意事^f填寫本頁) -裝 .. 經濟部智慧財產局員工消費合作社印製 -13 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1233837 A7B7 五、發明說明（11 ) 經濟部智慧財產局員工消費合作社印製
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^ :PTM iu 沴Jor®〇 3 ASHOΦ ^ 承 W II € 虔 ¥ II 03 g<nis，p00N 丨裝--- 填寫本頁) · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16 - 1233837 A7 B7 五、發明説明（/今） 附表4 :通以蒸汽對於觸媒耗損之影翠 經濟部智慧財產局員工消費合作社印製 實例 黏合劑 處理 音 波耗損試驗 分鐘 <25微米 16 A1203 新型 0 0.2 10 0.4 20 0.7 20 0.9 30 3.6 40 3.8 60 8.5 90 7.0 90 6.3 Π A1203 通以蒸汽6天 0 0.7 10 5.0 20 5.4 20 6.2 30 7.4 30 12.0 40 11.6 60 18.5 90 22.1 120 28.4 18 SiO2-A1203 新型 30 0.4 30 0.5 60 1.3 120 1.1 120 1.9 19 Si〇2-A1203 通以蒸汽6天 30 1.1 30 1.4 30 2.3 60 2.7 60 4.5 120 6.6 120 8.8 (請先閱讀背面之注意事項再填寫本頁) 辞 •項再填 裝·
、1T 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）

Claims (1)

1233837 A8 B8 C8 D8 六、申請專利範圍 附件一（A):第88102097號專利申請案 中文申請專利範圍修正本 民國8 9年4月修正 1 . 一種二氧化鈦觸媒載體組成物，其中摻有其量低 於載體之約3 0重量％的黏合劑，該黏合劑包含二氧化砍 及氧化鋁，且二氧化矽量低於黏合劑之約5 0重量％。 2 ·如申請專利範圍第1項之觸媒載體組成物，其中 載體含至少約8 0重量％之二氧化鈦。 3 .如申請專利範圍第1項之觸媒載體組成物，其中 黏合劑佔載體之約3 - 2 0重量％，二氧化矽佔黏合劑之 約3-50重量％。 4 ·如申請專利範圍第1項之觸媒載體組成物，其中 具有促進費雪—措希（Fischer-Tropsch)反應活性的金屬 分散於載體上。 5 ·如申請專利範圍第4項之觸媒載體組成物，其中 該金屬是第VIII族金屬。 6 ·如申請專利範圍第5項之觸媒載體組成物，其中 該金屬選自鈷、釕及它們的混合物。 7 ·如申請專利範圍第5項之觸媒載體組成物，其中 該金屬係以選自銶、鈴、鍩、鈽、钍和鈾的金屬來促進效 果。 8 . —種費雪-措希法，其特徵爲其包含使氫和一氧化 碳於如申請專利範圍第4項之組成物上反應並回收C 5 +烴類 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公嫠） -------------------#! (請先聞讀背面之注意事項存填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1233837 §s8 C8 D8 六、申請專利範圍 〇 9 .如申請專利範圍第8項之方法，其係於如申請專 利範圍第6項之組成物上進行。 1〇.如申請專利範圍第8項之方法，其係於漿狀物 中進行。 ------^---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -2-
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