TW200528189A - Novel zeolite composite, method for making and catalytic application thereof - Google Patents

Novel zeolite composite, method for making and catalytic application thereof Download PDF

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Publication number
TW200528189A
TW200528189A TW93131157A TW93131157A TW200528189A TW 200528189 A TW200528189 A TW 200528189A TW 93131157 A TW93131157 A TW 93131157A TW 93131157 A TW93131157 A TW 93131157A TW 200528189 A TW200528189 A TW 200528189A
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Taiwan
Prior art keywords
zeolite
patent application
item
scope
mixture
Prior art date
Application number
TW93131157A
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English (en)
Inventor
Peter Wilhelm Gerhard Waller
Zhiping Shan
Bowden George Maingay
Philip J Angevine
Jacobus Cornelis Jansen
Chuen Y Yeh
Frits M Dautzenberg
Leonardo Marchese
Heloise De Oliveira Pastore
Thomas Maschmeyer
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Abb Lummus Global Inc
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Publication of TW200528189A publication Critical patent/TW200528189A/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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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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    • B01J29/084—Y-type faujasite
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/7007—Zeolite Beta
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Description

200528189 ⑴ 九、發明說明 本申請案係爲在200 1年1 1月27日提出的U.S.專利 申請案No. 09/995,227的延續部分，該案爲在1999年9 月7日提出的U.S.專利申請案No. 0 9/3 90,2 7 6的延續部分 ，並且如今已申請到優先權且發證爲US ·專利 No· 6,358,486，該二申請案以提及方式倂入本文。 【發明所屬之技術領域】 本揭示係關於一種獨特的、含有在催化劑載體中嵌入 沸石的催化性物質，且特別是關於嵌入中孔隙載體中的微 孔隙沸石。 【先前技術】 現今許多碳氫化物的處理技術係以沸石催化劑爲主。 沸石催化劑在此技藝中相當著名，並擁有具均勻孔徑排列 良好的孔隙系統。然而，這些物質傾向於僅擁有微孔隙或 僅有中孔隙，大多數情況僅有微孔隙。微孔隙的定義爲具 有直徑小於約2 nm的孔隙，中孔隙的定義爲具有直徑在 自約2 nm至約50 nm範圍內的孔隙。小的微孔隙限制了 外部分子進入微孔隙內部的催化性活化位址，或減緩擴散 程序進入催化性活化位址的速度。許多碳氫化物的催化性 反應屬質傳限制，所以降低了催化劑的有效利用。一種解 決的方法爲降低催化劑的粒徑，藉以縮短擴散路徑，並增 加催化劑顆粒的外表面積。 ^5- 200528189 (2) 實際上，並無法直接使用小顆粒的沸石催化劑，因爲 像塵粒的物質是難以操作的，且在固定床反應器中會製造 壓力下降的問題。因此，沸石通常與無機性氧化物混合， 並擠壓成特定的形狀與尺寸。經锻燒、完成的催化劑便具 有良好的物理完整性及孔隙結構。然而因與特殊反應有關 ，黏結劑會對埋在黏結劑內的沸石顆粒帶來質傳限制。若 低孔隙度的黏結劑可被高孔隙度載體所取代，則可增加外 部分子進入沸石中活化位址的可及性。 極希望能有一種具理想孔徑分佈的催化劑，其能促進 反應物傳送進催化劑的活化位址以及讓產物自催化劑中傳 送出來。 【發明內容】 在此提供一種用於碳氫化物的催化性處理之物質。此 物質含有沸石，以及多孔性無機氧化物，其所含中孔隙爲 無機氧化物的微孔隙及中孔隙總計的至少97體積％。沸石 較佳爲微孔隙沸石，諸如例如沸石貝塔、沸石 Y (包括「 超穩定 Y」-U S Y )、絲光沸石、沸石 L、Z S Μ - 5、Z S Μ -11、ZSM-12、ZSM-20、Theta-1、ZSM-23、ZSM-34、 ZSM-35、ZSM-48、SSZ-32、P S H - 3、M C M - 2 2、M C M - 4 9、 MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、 SAPO-ii、SAPO-37、Breck-6、ALP〇4-5 等。在此說明製 造方法及使用此物質的方法。沸石顆粒圍繞著隨機互通的 中孔隙通道，其對沸石提供高度可及性。有些情況中，沸 -6- 200528189 (3) 石顆粒與中孔隙載體之間的作用會達一定程度地改變沸石 及中孔隙載體二者的特性。 在此說明的催化性物質可有利地促使反應物傳送至活 化的催化性位址，視特殊的施用情況而定，活性比單獨使 用沸石約高出2.5倍。 【實施方式】 在此所述的催化劑包含埋在中孔隙載體內的微孔隙沸 石，微孔隙沸石可爲任何類型的微孔隙沸石。一些實例爲 沸石貝塔、沸石Y (包括「超穩定Y」一 U S Y )、絲光沸 石、L 沸石、ZSM-5、ZSM-1 1、ZSM-1 2、ZSM-20、Theta-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3 、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、 ITQ-21 > SAPO-5、SAPO-11、SAPO-37、Breck-6 (也名爲 EMT) 、ALPCU-5等，該沸石皆已著稱於本技藝中，且許 多爲商業上可得。在本發明中，沸石可納入於中孔隙載體 中，或可在催化劑載體內現地的合成。 金屬可以晶格原子的取代物納入沸石的網狀結構中， 且或是配置在沸石的微孔隙內。該金屬例如可包含鋁、鈦 、釩、鍩、鎵、硼、錳、鋅、銅、金、鑭、鉻、鉬、鎳、 鈷、鐵、鎢、鈀及鉑。這些金屬可以組合形式納入，如 NiMo、NiW、PtPd 等。 催化劑載體較佳爲三維的中孔隙無機氧化物物質，所 含的中孔隙以有機氧化物物質（亦即此中不含任何沸石） -7- 200528189 (4) 的微孔隙及中孔隙總計的至少9 7體積百分比（即微孔隙 不超過3體積百分比）’且中孔隙一般至少爲9 8體積百 分比。較佳的含矽多孔隙的催化劑載體之製造方法說明於 U.S·專利No. 6,3 5 8,4 8 6。較佳的催化劑以N2孔隙儀測定 的平均中孔隙大小在自約2 nm至約25 nm的範圍內。 一般而言，中孔隙無機氧化物的製備係對（1 )水中 的無機氧化物的前驅物，及（2 )與氧化物的前驅物或由 前驅物產生的氧化物種進行良好混合的有機模板劑之混合 物加熱，且較佳與其產生氫鍵。起始物質一般爲非定型物 質，且可含有一種或多種無機氧化物，諸如氧化矽或氧化 鋁，含有或不含外加的金屬氧化物。其他金屬原子可局部 地取代矽原子，這些金屬包含、但非限於鋁、鈦、釩、鉻 、鎵、硼、錳、鋅、銅、金、鑭、鉻、鉬、鎳、鈷、鐵、 鎢、鈀及鉑，它們可被納入有機氧化物內部至少一個中孔 隙的牆，及/或至少一個中孔隙的表面。外加的金屬視需 要可在製造含有中孔隙結構體的程序開始之前，納入此物 質中；也可在製備此物質之後，視需要由其他離子取代系 統中的陽離子，諸如那些鹼金屬（如鈉、鉀、鋰等）。 有機模板劑爲製造中孔隙的有機化合物，較佳爲乙二 醇（含有二個或多個羥基官能基的化合物），諸如甘油、 二甘醇、三甘醇、四甘醇、丙二醇、及其類似者，或是組 成三乙醇胺、三異丙醇胺、薩佛蘭（su] folane )、四伸乙 五胺、及二乙基乙二醇二苯甲酸酯（diethylg]yc〇l dibenzoate )的群組者。較佳的是有機模板劑的沸點至少 -8- 200528189 (5) 約 150〇C。 中孔隙催化劑載體爲假結晶物質（亦即以現今可利用 的X射線繞射技術觀察，並無結晶度）。中孔隙的直徑較 佳自約3 nm至約25 nm，催化劑載體以BET ( N2 )測定 的表面積較佳在自約400 m2/g至約1 200 m2/g的範圍，催 化劑的孔隙體積較佳在自約0.3 cm3/g至約2.2 cm3/g的範 圍。 催化劑的沸石含量範圍可自低於約1重量％至高於約 99重量％。然而，較佳自約3重量％至90重量％，且更佳 自約4重量％至約80重量％。帶有沸石的催化劑所含的微 孔隙較佳不超過約1 0體積％。 更特別的是，製造催化劑的方法包含將沸石懸浮在水 中，然後將無機氧化物的前驅物加入水中並混合。無機氧 化物的前驅物可爲含有諸如四乙基正矽酸鹽（TEOS ) 的 矽化物、或諸如異丙氧化鋁的鋁源化合物，其會與水反應 產生無機氧化物。TEOS與異丙氧化鋁已商業化，可取自 已知的供應商。 上述混合物的p Η較佳保持在約7.0。此水性混合物視 需要可含有前面所指的那些其他金屬離子。在攪拌後，加 入有機模板劑，並混合進混合物。有機模板劑在如下討論 的孔隙產生步驟中，幫助中孔隙產生。有機模板劑不應過 於疏水性，導致在混合物中產生分離的相。有機模板劑可 爲上列中之一種或多種化合物。有機模板劑較佳以逐滴加 入攪拌中的無機氧化物水溶液，在一段時間之後（例如自 -9- 200528189 (6) 約1至4小時），混合物產生厚厚的凝膠，在這段期間較 佳要攪拌混合物，以促使成份的混合。此溶液較佳含有醇 ，可直接加入混合物中，且/或經由無機氧化物的前驅物 之分解而現地製造。例如TEOS在加熱時會產生乙醇，藉 由異丙氧化銘的分解則可產生丙醇。 視需要可利用前處理加以改變沸石，例如一種對沸石 前處理的類型爲利用離子交換、浸漬、固定官能基物種及 蒸汽處理以改質。層狀結構的沸石諸如M C Μ - 2 2也可經適 當的處理而剝離成諸如ITQ-2新類型的沸石。特定的處理 諸如夾層或剝層可在鹼的存在下，以陽離子性界面活性劑 將前驅物膨脹（Corna 等人，J. Catal. 191 (1):218- 2 24，2 000 )。膨脹的物質視需要可利用例如具有或不具有 機械攪動的超音波處理而剝層。最後，剝層的物質可自新 類型的沸石分離並煅燒。 本發明提供一種新的方法，將剝層的沸石納入、或穩 定、或承載進孔隙的基質/載體中。膨脹的物質首先懸浮 在水中，其次爲無機氧化物前驅物，或是在水中加入中孔 隙載體，並如上述加以混合。膨脹物質的剝層視需要可在 加入其他成分（如孔隙產生劑）時、及/或在凝膠製造程 序中，利用具有或不具有機械攪動的超音波處理。在凝膠 產生之後，一種與在膨脹之前加入的沸石不同的新類型沸 石可被納入凝膠中。 然後可視需要讓凝膠在溫度自約5 °C至約4 5 °C、較佳 在室溫下陳化，以完成水解及無機氧化物源的聚縮合。陳 -10- 200528189 (7) 化較佳爲進行達約4 8小時，一般自約0小時至 更佳自約2小時至2 0小時。在陳化步驟之後， 9 8 °C至100 °C的空氣下加熱一段足夠長的時間， 水分以乾燥凝膠（如自約6至約4 8小時）。軺 幫助產生中孔隙的有機模板劑在乾燥階段時，應 凝膠中，因此，較佳的模板劑具有的沸點至少約 經乾燥的物質仍然含有有機模板劑，加熱使 產生中孔隙的溫度。孔隙產生步驟是在水的沸點 度下進行，並達至約有機模板劑的沸點。一般而 隙的製造是在溫度自約1 0 〇 °C至約2 5 0 °C、較佳自 至約20(TC下進行。孔隙產生步驟可視需要在密 的自生壓力下水熱地進行。最終產物的中孔隙尺 隙的體積受到水熱步驟的長短與溫度所影響。一 增加溫度及處理延時，會增加最終產物的中孔隙 中孔隙體積的百分比。 在孔隙產生步驟之後’物質在自約300 °C至; 之間煅燒。煅燒溫度較佳自約40〇°C至約7〇〇°C 自約5 0 0 °C至約6 0 0 °C。煅燒溫度維持一段時程 效去除有機模板/孔隙產生劑。煅燒步驟的延時 煅燒的溫度而定，一般在自約2小時至約4 0小 ，較佳自5小時至1 5小時。 爲了避免熱點，溫度應逐漸上升。較佳的是 質的溫度應該以自約〇 · 1 °C /分鐘至約2 5 °C /分鐘 ，更佳爲自約〇 . 5 °C /分鐘至約〗5 °C /分鐘，且最佳 3 0小時， 凝膠在約 藉由驅離 佳的是能 該仍留在 15 0。。。 至可實質 以上的溫 言，中孔 3 約 1 5 0 〇C 閉容器中 寸及中孔 般而言， 直徑以及 灼 1 0 0 0 〇C ，且更佳 ，足以有 一部份視 時的範圍 催化劑物 逐漸上升 :爲自約1 • 11 - 200528189 (8) °C /分鐘至約5 °c /分鐘。 在煅燒的最後會產生催化劑物質的結構，而有機分子^ 會自物質中被排出並分解。 爲去除有機模板劑，可用有機溶劑如乙醇萃取以取代 煅燒程序。在此情況下，模板劑可回收再利用。 而且，本發明的催化劑粉末可與諸如氧化矽及/或氧 化鋁等黏結劑預先混合，然後再以擠壓或其他適當方法製 成想要的形狀（如擠壓物、粒狀、環狀等）。金屬離子^ 如銘、鈦、釩、鉻、鎵、銅、猛、鋅、鎳、鐵、鈷、鍺、 鉻及鉬可藉由浸漬、離子交換、或如G.W_ Skeels及E.m Flanigen in Μ· Occelli 等人編的 A.C.S. Symp0sium Ser· 丄 1 e s , 398 冊，Buttersworth，pp.420-435 ( 1989)中的說明取代 一部份的晶格原子，加入催化劑中。 利用X R D、氣相吸附、2 7 A1 - N M R及N Η 3 -1R (紅外光 )的機構，本發明的組成特徵化。XRD及27A1-NMR顯示 沸石的結構在納入、或承載在砂質中孔隙物質上之後，仍 維持不變。然而，NH^IR顯示在納入沸石貝塔之後，羥 基有改變。該羥基改變的程度也與承載進最終複合物的沸 石有關。並不希望與任何的特別理論連結，相信沸石與中 孔隙基質/載體的作用會導致與將沸石及中孔隙物質簡單 、線性組合結果完全不同的獨特結構。而且，F 丁 I r數據 顯示羥基有頻率偏移，此與酸性改質結果一致。 原則上’在此所述的催化劑可用在一般採用以沸石爲 基礎的催化劑的所有程序中。例如，Z S Μ - 1 1實際上可用 -12- 200528189 (9) 在所有以Z S Μ - 5催化的反應中（如芳族烷化、二甲苯異構 化、脫蠟等）；ZSM-12可用在芳族烷化的程序中（如對-二異丙基苯的製造）、芳香化、異構化、脫躐等；ZSM-20 可用在異構化、烯類製造、氫裂解、及芳香化；ZSM-22 及ZSM-23可用在異構化、烯類製造、氫裂解、及芳香化 ;Z S Μ - 3 4可用以將甲醇催化成烯屬烴；Z S μ - 3 5可用於脫 鱲、異構化、芳香化、裂解及氫化；ZSM-48可用於異構 化；PSH-3及MCM-22對芳族烷化、裂解、異構化、芳香 化等有作用；ITQ-1可用以裂解、氧化等·，ITQ-2對裂解 、水合、烷化等特別有用；ITQ-21對裂解是很好的催化劑 ;SAPO-5可用以異構化、脫水、裂解；SAPO-34可用於 脫氫；SAPO-1 1可用於脫蠟及芳族異構化。 例如，使用在此所述的催化劑行石化原料（如氣油及 真空氣油）的催化裂解，可在FCC或TCC單元中，於溫 度自約4 0 0 °C至約 6 5 下進行，催化劑對進料的重量比 自約3 ·· 1至1 0 : 1。供催化裂解的進料可包含的石化成分其 起始沸點（IBP )自約2 00 °C至約260 °C，且結束沸點（ E B P )自約4 0 0 °C至約4 5 5 °C。進料視需要可包含的石化成 分其組成的沸點在54(TC以上，諸如脫柏油及未脫柏油的 石化殘留物、塔砂油、頁岩油、瀝青、或煤油。 採用在此所述的催化劑進行具烯屬烴的有機化合物的 烷化，可在溫度自約90 °C至約250 °C、壓力自約〇.5 bar 至約35 bar、且空間速度自約1 WHSV至約20 WHS V下 進行。 -13- 200528189 (Ί〇) 採用在此所述的催化劑進行碳氫化合物的氫裂解’可 在反應條件包括溫度自約200 °C至約400 °C、壓力自約1〇 bar至約 70 bar、且空間速度自約 0.4 WHSV至約 50 W H S V下進行。 採用在此所述的催化劑進行碳氫化合物的氫異構化（ hydroisomerization )，可在反應條件包括溫度自約1 5 0 °C 至約5 0 0 °C、壓力自約1 b a r至約2 4 0 b a r、且空間速度自 約0.1 WHSV至約20 WHSV下進行。 採用在此所述的催化劑進行碳氫化合物的催化脫蠟， 可在很寬的反應條件範圍下進行，如溫度自約1 5 0 °C至約 5 00 °C、壓力自約6 bar至約110 bar、且空間速度自約0.1 WHS V 至約 20 WHS V。 採用在此所述的催化劑進行有機化合物（如芳族、烷 基芳族）的醯化，可在反應條件包括溫度自約2 〇。(：至約 3 5 0 °C、壓力自約1 bar至約1 10 bar、且空間速度自約0.1 WHSV至約2 0 WHSV下進行。醯化劑包括例如羧酸酐及 醯基鹵化物。 使用在此所述的催化劑進行輕質碳氫化合物的芳香化 成爲芳族’較佳是在反應條件包括溫度自約6 0 〇 °C至約 8 0 0 °C、壓力低於約1 4 b a r、且空間速度自約〇 · 1 w H S V至 約1 0 WHS V下進行。 在一些特殊的應用中，本發明的組合物甚至比習用的 催化劑表現更多的優點。例如，重質進料的催化裂解理想 上需要中孔隙基質/載體上有一些溫和的酸性，其可達到 -14- 200528189 (11) 讓很大的分子預裂解成中等尺寸的分子，結果並使中等尺 寸的分子進一步裂解成想要的產物。本發明的組合物在中 孔隙基質/載體的網狀結構中可含有金屬（如鋁），提供 溫和的酸性。而且，中孔隙基質/載體所提供的高孔隙體 積及高表面積可增進金屬（如v、N i、F e )對硫、氮及氧 物種的耐受性。再者，本發明的組合物很容易調整，可藉 由改變所採用的沸石類型、沸石的承載量、及中孔隙度， 以符合程序中的一些特別需求。 本發明的組合物含有一些金屬（如Ni、W、Pt、Pd及 其組合），其具有（脫）氫化功能，可作爲供氫裂解的催 化劑。藉由適當地選擇沸石承載、提供酸性的中孔隙基質 /載體中的金屬量、及具氫化功能的金屬量，可簡單地達 成裂解活性與氫化活性之間的平衡。正常而言，沸石物質 具有高的裂解活性，且中孔隙物質具有較低的裂解活性。 因此，可調整沸石與中孔隙物質的組合，以提供想要的裂 解活性。所以，可使產率與選擇性最佳化。例如，可達成 對中間蒸餾物或引擎燃料的高選擇性。在製造以潤滑油爲 主的油品時，本發明的組合物可容許的進料範圍更大，因 爲中孔隙基質/載體提供預裂解活性，它也增進對重金屬 及其他毒化物種的耐受性。 利用以下實例，說明本發明製造催化劑組合物的方法 及催化性組合物的應用，但並不受這些實例所限制。在這 些實例中，組合物的量是以重量的份數表示。 200528189 (12) 實例1 首先，Si/A1莫耳比爲25、平均粒徑爲1 μΐΒ的經煅燒 的沸石1 . 5份在1 6.3份的水中懸浮，並攪拌3 0分鐘。然 後，20.3份四乙基正矽酸鹽（TEOS )在攪拌下加入懸浮 液中。在另外持續攪拌3 0分鐘之後，加入9.3份三乙醇 胺。再次攪拌3 0分鐘後，4.0份四乙基氫氧化銨水溶液（ 取自Aldrich的3 5%溶液）逐滴加入混合物中，以增加PH 。在攪拌約2小時後，混合物成爲厚厚、不流動的凝膠。 此凝膠在靜置狀態下，於室溫中陳化1 7小時。其次，凝 膠在1 〇 〇 °C的空氣中乾燥2 8小時。經乾燥的凝膠轉換至高 壓釜，並於1 7 0 °C水熱處理1 7 · 5小時。最後，以升溫速率 爲1°C /分鐘在6 0 0 °C的空氣中煅燒1 0小時。 最終產物指定爲樣品1，沸石貝塔在樣品1中的理論 含量爲20重量。/〇。樣品1以XRD、TEM、氮氣孔隙法、 氬氣孔隙法、及NH3-溫度程式化脫附（TPD )進行特徵鑑 定。純的沸石貝塔也以XRD進行特徵鑑定，以供比較。 參考圖1，純的沸石貝塔的X R D型態如1 - b之繪圖所 示，掃瞄時間爲3 3分鐘，顯示最明顯的特徵反射在2倍 西塔（Θ )約爲7.70及22 ·2°處。具有沸石貝塔晶體（樣品 1 )的中孔隙無機氧化物載體的XRD型態如卜a之繪圖所 示’可觀察到在低角度處有一強的波峰，指出樣品1爲中 度結構化（m e s 〇 - s t r u c t u r e d )的物質。沸石貝塔的波峰相 當小，因爲最終產物的最大理論沸石含量僅約2 0重量％。 當樣品]的掃瞄時間延長至4 5小時時，沸石貝塔的特徵 -16- 200528189 (13) 波峰變得淸晰可見，如l-c之繪圖所示。 現在參考圖2，說明樣品1的局解析度TEM影像，其 在中孔隙基質1 2中顯示暗灰色區域1 1。插圖” e D，，說明能 確認爲沸石貝塔晶體的暗灰色區域1 1的電子繞射型態。 氮吸附顯示樣品1的中孔隙尺寸分佈很窄，主要集中 在約9.0 nm處，710 m2/g的高表面積，i.oi cm3/g的高總 孔隙體積。氬吸附顯示在約〇 . 6 4 n m附近的微孔隙尺寸分 佈的波峰’相當於在沸石貝ί合中的微孔隙尺寸。孔徑小於 〇·7 nm的微孔隙體積爲0.04 cm3，此大約爲純沸石貝塔的 微孔隙體積之1 6%。未煅燒沸石貝塔的首次添加爲以最終 複合物計的2 0重量％。因爲煅燒時去除了模版，沸石貝塔 的重量減少約2 0重量％。考量沸石在煅燒中的質量損失， 最終複合物中沸石貝塔的預期含量約1 6重量％，其與得自 微孔隙體積的値相符。 參考圖3，樣品1的NH3- TPD測量顯示二個脫附波 峰，指出有與沸石相似的強酸位址。 實例2 首先，Si/A1莫耳比爲1 50、平均粒徑爲0.2 μηι的經 煅燒的沸石3.4份在8 5 · 0份的水中懸浮，並攪拌3 0分鐘 。然後，105.8份TEOS在攪拌下加入懸浮液中。在另外 持續攪拌3 0分鐘之後，加入3 8 . 3份三乙醇胺。再次攪拌 3 〇分鐘’ 2 0 · 9份四乙基氫氧化銨水溶液（3 5 % )逐滴加入 混合物中。在攪拌約2小時後，混合物成爲厚厚、不流動 -17- 200528189 (14) 的凝膠。此凝膠在靜置狀態下，於室溫中陳化24小時。 其次，凝膠在9 8 - 1 0 0 °C的空氣中乾燥2 4小時。經乾燥的 凝膠轉換至高壓釜，並於1 8 0 °C水熱處理4小時。最後， 以升溫速率爲1 °C /分鐘在6 0 0 °C的空氣中煅燒1 0小時。 所得產物指定爲樣品2，其XRD型態如圖5所示。沸石貝 塔在最終複合物中約爲1 0重量％。 實例3 首先，Si/Al莫耳比爲150、平均粒徑爲0.2 μιη的經 锻燒的沸石4.6份在5 1 .0 2份的水中懸浮，並攪拌3 0分鑊 。然後，23.0份三乙醇胺在攪拌下加入懸浮液中。在另外 持續攪拌30分鐘之後，加入63.5份TEOS。再次攪拌30 分鐘，12.6份四乙基氫氧化銨水溶液（35% )逐滴加入混 合物中。在攪拌約2小時後，混合物成爲厚厚、不流動的 凝膠。此凝膠在靜置狀態下，於室溫中陳化24小時。其 次，凝膠在1 〇〇 t的空氣中乾燥24小時。經乾燥的凝膠轉 換至高壓釜，並於1 8 0 °C水熱處理4小時。最後，以升溫 速率爲厂C /分鐘在6 0 0 °C的空氣中煅燒1 〇小時。所得產 物指定爲樣品3 ’其XRD型態如圖5所示，其淸楚顯示沸 石貝塔的二支特徵波峰。沸石貝塔在最終複合物中約爲2 0 重量％。氮吸附顯示其表面積約73 0 m2/g，孔隙體積約 1.08 cm3/g。樣品3的中孔隙尺寸分佈如圖4所示。 實例4 -18- 200528189 (15) 首先，Si/A1莫耳比爲1 50、平均粒徑爲0.2 μηι的經 煅燒的沸石1 2.2份在5 1 . 0份的水中懸浮，並攪拌3 〇分鐘 。然後，2 3.0份三乙醇胺在攪拌下加入懸浮液中。在另外 持續攪拌3 0分鐘之後，加入6 3 . 5份Τ Ε Ο S。再次攪拌3 0 分鐘，1 2 · 7份四乙基氫氧化銨水溶液（3 5 % )逐滴加入混 合物中。在攪拌約2小時後，混合物成爲厚厚、不流動的 凝膠。此凝膠在靜置狀態下，於室溫中陳化2 4小時。其 次，凝膠在1 〇 〇 °C的空氣中乾燥2 4小時。經乾燥的凝膠轉 換至高壓釜，並於180 °C水熱處理4小時。最後，以升溫 速率爲1 °C /分鐘在6 0 0 °C的空氣中煅燒1 〇小時。所得產 物指定爲樣品4，其XRD型態如圖5所示，其淸楚顯示沸 石貝塔的二支特徵波峰。沸石貝塔在最終複合物中約爲4 0 重量％。氮吸附顯示其表面積約63 7 m2/g，孔隙體積約 1 .07 cm3/g。其中孔隙尺寸分佈如圖4所示。 實例5 首先，Si/Al莫耳比爲150、平均粒徑爲ο」μιη的經 煅燒的沸石9 · 2份在1 7 · 0份的水中懸浮，並攪拌3 〇分鐘 。然後，7.6份三乙醇胺在攪拌下加入上述懸浮液中。在 另外持續攪拌3 0分鐘之後，加入2 1 . 2份τ Ε Ο S。再次攪 拌3 0分鐘，4 · 2份四乙基氫氧化銨水溶液（3 5 % )逐滴加 入混合物中。在攪拌約2小時後，混合物成爲厚厚、不流 動的凝膠。此凝膠在靜置狀態下，於室溫中陳化24小時 。其次，凝膠在1 〇 〇 t的空氣中乾燥2 4小時。經乾燥的凝 -19- 200528189 (16) 膠轉換至3個50 ml的高壓釜中，並於180°C水熱處理4 小時。最後，以升溫速率爲1 °C /分鐘在6 0 0 °C的空氣中煅 燒1 〇小時。所得產物指定爲樣品5，其XRD型態如圖5 所示，其淸楚顯示沸石貝塔的二支特徵波峰。沸石貝塔在 最終複合物中約爲60重量％。氮吸附顯示其表面積約639 m 2 / g，孔隙體積約 0.9 7 c m3 / g。其中孑L隙尺寸分佈如圖4 所示。 8份的樣品1與2份萘可（Nyacol )形式的氧化鋁混 合，以提供催化劑。將混合物乾燥並煅燒，條件爲以速率 爲5 °C/分鐘升溫至120 °C、溫度120 °C維持1小時，然後 以速率爲5 °C /分鐘升溫至5 0 0。(：維持5小時，最後以速率 爲5 t： /分鐘降溫至丨5 (TC，再讓催化劑於乾燥器中冷卻至 室溫。然後以手動破碎催化劑，並過1 2/ + 20網目的篩網 ’以供活性測試。此催化劑在中孔隙載體中含有1 6重量％ 的沸石貝塔。循環微分固定床反應器盛裝1 . 〇克催化劑， 循環速率（ 2 00 g/分鐘）約爲進料率（6.1 g/分鐘）的30 倍。承載的反應器開始時有裝苯，當反應器達到1 90 t時 ’以計量栗浦量測進料（含乙烯爲〇 . 3 5重量％的苯）。此 批次進行7小時。反應條件包括溫度爲1 9 0 °C，壓力爲 3 5 0 psig ’及空間速度爲6 WHSV。在批次開始、中間及 結束時’取進料的樣品。每第三分鐘則取產品樣品，並以 E ® t/f丨去分析。以一階速率方程式爲基礎，對含有沸石 貝纟合1 6重4 %的催化劑，獲得苯以乙烯行苯烷化產生乙基 苯的速率常數爲〇·3〇 cm3/g秒。或是，此値等於含沸石貝 •20- 200528189 (17) 塔80重量％的催化劑之1 .50 cm3/g秒。
比較性實例A 除了不加入沸石以外，依據實例1中所述之方法製造 完全矽化的中孔隙載體，所得的載體指定爲比較性樣品A 。比較性樣品A進行N Η 3 - T P D測量，測量結果如圖3所 述。 比較性實例Β 自商業供應商取得的沸石貝塔樣品含有8 0重量％的沸 石貝塔（Si/Al比爲4.9 )及20%的黏結劑，重製尺寸以通 過1 2/ + 20網目的篩網。沸石貝塔的孔隙尺寸分佈說明於 圖4 °此比較性實例的純沸石貝塔的活性使用與上述實例 6相同的方法與裝置，於相同的烷化反應中測試。獲得的 一階速率常數爲〇 . 2 9 c m3 / g秒。 比較實例6與比較性實例B的結果，實例6的催化劑 係依據本發明所製，對於用乙烯將苯烷化而言，所具有的 活性比單獨使用等量的沸石貝塔約大五倍。這些結果指出 在合成樣品1時，仍保持沸石結晶在中孔隙催化劑載體中 的完整性。此結果亦顯示在催化劑合成之後，樣品1的中 孔隙載體中的微孔隙沸石貝塔仍可接近，且載體的中孔隙 促使芳族烷化反應中的質量傳送。 實例7 -21 - 200528189 (18) 本實例說明M C Μ - 2 2的納入。首先，S i / A1莫耳比爲 12.8、平均粒徑爲2.5 μηι的2.4份如所合成的沸石MCM-22在10.5份的水中懸浮，並攪拌30分鐘。然後，9.2份 三乙醇胺在攬拌下加入上述懸浮液中。在另外持續攪拌3 0 分鐘之後，加入1 2.7份Τ Ε Ο S。再次攪拌3 0分鐘，2 · 5 2 份四乙基氫氧化銨水溶液（3 5 % )逐滴加入混合物中。在 攪拌約2小時後，混合物成爲厚厚、不流動的凝膠。此凝 膠在靜置狀態下，於室溫中陳化24小時。其次，凝膠在 9 8 °C的空氣中乾燥24小時。經乾燥的凝膠轉換至高壓釜 中，並於1 8 0 °C水熱處理4小時。最後，以升溫速率爲1 t /分鐘在6001：的空氣中鍛燒10小時。 所得產物指定爲複合物7，其XRD型態如圖6的繪圖 6 - c所示，其淸楚顯示沸石M C Μ - 2 2 (繪圖6 - b )及中孔隙 物質（繪圖6 - a )的特徵波峰。沸石M C Μ - 2 2在複合物7 中約爲40重量％，且元素分析確認此以鋁含量計的數目， 假設鋁非來自矽質的中孔隙物質。氮吸附顯示其表面積約 6 8 6 m2 / g，孔隙體積約0.8 2 c m3 / g，其中孔隙尺寸分佈在 圖7中集中在1 0 nm附近。氬吸附顯示微孔隙集中在〇. 5 nm附近。 實例8 本實例說明MCM-5 6的納入。首先，7·7份的三乙醇 胺與8.5份的水混合半小時。然後，2 〇份來自沸石ΜχΜ_ 56的ΝΗ，（ Si/Al莫耳比爲125)在攪拌下加入上述溶液 -22- 200528189 (19) 中。在另外持續攪拌2小時之後，在攪拌下加入1 0.6份 TEOS。再次攪拌30分鐘後，2. 1份四乙基氫氧化銨水溶 液（3 5 % )逐滴加入混合物中。持續攪拌，直到混合物成 爲厚厚、不流動的凝膠。此凝膠與實例7相同的處理，以 獲得白色粉末。 所得產物指定爲複合物8，其XRD型態如圖8的繪圖 8-c所示，其淸楚顯示沸石MCM-56及中孔隙物質的二支 特徵波峰。繪圖8-b說明MCM-56的XRD型態，繪圖8-a 說明中孔隙物質的XRD型態。元素分析顯示最終複合物 的總Si/A1比爲43，且最終複合物中的沸石承載約33重 量％。氮吸附顯示其表面積約712 m2/g，孔隙體積約0.96 cm3/g，其中孔隙尺寸分佈如圖7所示，集中在2.0 nm附 近。 實例9 本實例說明ITQ-2的納入。首先，15.2份的十六烷基 乙基溴化銨（C T A B ) 連同 3 2.7份的四丙基氫氧化銨， 溶進3 1 . 7份的水中。然後，2 · 7份如合成的M C Μ - 2 2加入 上述溶液中，獲得懸浮液。懸浮液在8 0 °C附迴流冷卻器、 在油浴中的瓶子，攪拌1 8小時，使薄層結構的沸石MCM-2 2膨脹。經膨脹的μ C Μ - 2 2在超音波（1 3 5 W，4 0 Κ Η z ) 浴下，剝層1小時，獲得I T Q - 2沸石。淸洗並離心I T Q - 2 沸石，直到懸浮液的ρ Η降至8。 1TQ-2沸石重新懸浮在1〇.〇份的水中，然後在攪拌下 -23- 200528189 (20) ，加入由9·2份TEA及12.7份TEOS所組成的混合物中 。在大約4 5分鐘後，產生厚的凝膠。凝膠以與實例7相 同方法處理。最終複合物指定爲複合物9，其XRD型態如 圖9的繪圖9 - c所示，其淸楚顯示沸石I T Q - 2及中孔隙物 質的二支特徵波峰。繪圖9_b說明中孔隙物質的XRD型 態，繪圖9 - a說明沸石I T Q - 2的X R D型態。元素分析顯示 最終複合物的總Si/Al比爲36.9，且最終複合物中的沸石 承載約32.3重量％。氮吸附顯示其表面積約6 8 5 m2/g，孔 隙體積約0.40 cm3/g，其中孔隙尺寸分佈集中在2.1 nm。 實例1 〇 本實例說明以「現地」納入IT Q - 2，其中M C Μ - 2 2轉 化成I Τ 0 - 2是在中孔隙產生過程中進彳了。化學品及其化學 品使用量與實例9相同。首先，如合成的M C Μ - 2 2與實例 9相同的方式膨脹。然而，經膨脹的MCM-22不會馬上剝 層。淸洗並隨之離心，直到以硝酸銀溶液偵測無溴離子爲 止。經膨脹的MCM-22再度懸浮於水中。 含有以TEA及TE0S組成的混合物之瓶子置於超音波 浴中，混合物同時以超音波及機械的鐵氟龍攪拌子攪拌， 同時加入經膨脹的M C Μ - 2 2懸浮液。在約1小時的攪拌之 後，加入2.5份ΤΕΑΟΗ ( 35%的四乙基氫氧化銨），最後 產生厚厚的凝膠。凝膠以與實例7相同方法處理。最終複 合物指定爲複合物10，其XRD型態如圖9的繪圖9-d所 示，其淸楚顯示沸石1TQ-2 (繪圖9-a )及中孔隙物質（ -24 - 200528189 (21) 糸曾圖9 - b )的一支特徵波峰。元素分析顯示複合物1 〇的總 S 1 / A1比爲3 2.4，且最終複合物中的沸石承載約$ 〇重量％ 。Μ吸附藏不其表面積約7 2 ό m2 / g，孔隙體積約0.78 c rrr / g ’其中孔隙尺寸分佈如圖7所示，集中在2.2 ^ m。 實例Π 在攪拌的批次反應器中，進行2 -甲氧基萘的醯化，成 爲2 -乙醯基-6-甲氧基萘。反應器有16.5份催化劑，爲實 例1 〇中所製的複合物1 0，在2 4 0 °C、真空下加熱2小時 ，然後塡充乾的氮氣。反應器冷卻至1 2 (TC後，2 5 0份的 十氫萘（作爲溶劑）、3 1 · 6份2 -甲氧基萘、4 0份醋酸酐 及10份正-十四烷（作爲內標準）注入進反應器中。在反 應六小時之後，反應混合物以GC分析，管柱爲WAX 52 CB，且發現2-甲氧基萘的轉化達到56%，對2-乙烯基- 6-甲氧基萘的選擇性爲100%。 實例1 2 使用上述實例中所製的各種催化劑，以進行2 -甲氧基 萘的醯化，成爲2 -乙烯基-6 -甲氧基萘。反應條件與實例 1 1相同。在所有測試中，反應器中的沸石量保持與實例 1 1相同。易言之，催化劑的量會因爲複合物中的沸石承載 的不同而不同。表1顯示在不同催化劑上的反應結果比較 -25- (22) 200528189 表1 2 -甲氧基萘在不同催化劑上的醯化比較 催化劑 催化劑描述 沸石承載％ 沸石中的 轉化 選擇性 Si/Al 比 (%) (%) 複合物 M C Μ - 2 2複合物 40.0 12.8 28.5 96 7 複合物 MCM-56複合物 33.3 12.5 53.4 96 8 複合物 ITQ-2複合物 50.0 12.8 56.2 96 10 實例1 3 在固定床反應室中進行正己烷裂解。約1 g的樣品3 ，以破碎及過篩獲得粒徑爲1 25 -25 0 μιη，導入反應器中。 爲了活化，樣品在5 0 ml/分鐘的空氣流中加熱，以加熱速 率爲1(TC /分鐘自室溫升至600°C，並維持8小時。正己 烷的裂解反應在常壓下且正己烷在氮氣中濃度爲6.6莫耳 %下進行。反應溫度以每步爲l〇°C自5 00 °C變化至5 70 °C 。以催化劑的質量計算調整的接觸時間’保持固定在1.4 g e a t X m i η X ST 1。在所有測量中，正己院的轉化低於15%， 以避免去活化。發現正己烷的裂解可用外觀的一階動力加 以描述，且針對不同的反應溫度，計算以沸石質量爲基礎 計的一階反應速率常數。爲了比較催化劑活性，5 3 8 °C的 反應速率常數則以由四個一階反應速率常數所決定的阿雷 尼烏斯（A r r h e n i u s )方程式計算而得。獲得樣品3的反應 -26- 200528189 (23) 速率爲 0.19 geatxminxl·1。 比較純的沸石貝塔、樣品4及5如下： 具Si/A1比爲1 50的商業沸石貝塔擠壓成顆粒，並過 筛成1 2 5 - 2 5 0 μ m。使用前面實例7中所述的相同方法與裝 置，測試此純的沸石貝塔及樣品4與5的活性。以能將催 化劑的活性特徵化的沸石質量爲基礎計的反應速率常數如 圖1 〇所示。樣品3、4及5的活性約爲純沸石貝塔的二倍 高。經測量得到相當高的活化能150 kJ/mol，指示質量傳 送不會影響相當小的正己烷分子的反應。 實例1 4 以Bruker IFS88光譜儀，於4 cnT1的解析度下，記錄 中孔隙載體及純的沸石貝塔（樣品3、4及5 )的FTIR光 譜。所有樣品皆以KB r壓成錠，並置於永久性連接至真空 管線（最終壓力S1(T5 torr )的石英槽中，供在現地條件下 的熱處理。 參考圖1 1，在3 74 5 cnT1處的強波峰依慣例指定爲矽 醇基，在3 6 1 0 cm_1 (特別是對沸石貝塔）處的很小波峰 可指定爲其布忍氏酸的位址，且在3 72 5 -3 65 0 cnT1區域寬 廣的吸收可指定爲Η鍵結的矽醇類或接近路易士酸中心的 矽醇類。一般而言，本發明的複合物（樣品3、4、5 )比 起個別使用的沸石貝塔及考量的中孔隙載體，顯示在 3 72 5 - 3 6 5 0 crrT1範圍有寬廣的吸收。有趣的是注意到具沸 石貝塔4 0重量％的複合物在3 7 2 5 - 3 6 5 0 cnT 1範圍有最寬廣 -27- 200528189 (24) 的羥基分佈。再者，這些羥基的強度高於其他樣品 。圖Π淸楚顯示具沸石40重量％的複合物明顯與 載體或純沸石貝塔者有差異。 並不希望與任何特別的理論結合，相信萘米尺 石及中孔隙基質之間的作用產生獨特的第三種結構 沸石及中孔隙物質的簡單、線性組合不同。再者， 頻率有偏移，與酸性改變相符合。此可解釋爲何沸 4 0重量％對酸性有顯著的改變。此可能與實例13 己烷裂解相關的催化活性有關聯。 實例1 5 具有Si/Al莫耳比爲14.8且表面積爲606 m2/ 穩定Y ( U S Y )納入含鋁的中孔隙基質中。首先， 的超穩定沸石Y在1 7.0份的水中懸浮，並攪拌3 0 然後，7.7份三乙醇胺在攪拌下加入上述懸浮液中 外持續攬拌3 0分鐘之後，另一含有2 1 . 2份Τ Ε Ο S 份異丙氧化鋁的混合物在攪拌下加入。再次攪拌3 ，4.2份四乙基氫氧化銨水溶液（3 5 % )逐滴加入: 中。在攪拌約2小時後，混合物成爲厚厚、不流動 。此凝膠在靜置狀態下，於室溫中陳化2 4小時。 凝膠在1 〇 〇 °C的空氣中乾燥2 4小時。經乾燥的凝膠 高壓釜，並於1 8 (TC水熱處理2小時。最後，以升 爲1 °C /分鐘在6 0 0 °c的空氣中锻燒]〇小時。最終 定爲複合物1 5。 的羥基 中孔隙 寸的沸 ，苴m 〆、〆、 羥基的 石承載 中的正 g的超 9·2份 分鐘。 。在另 及3.3 〇分鐘 混合物 的凝膠 其次， 轉換至 溫速率 物質指 -28 - 200528189 (25) 複合物1 5的XRD型態如圖12的繪圖12-a所示，其 淸楚顯示沸石Y及中度結構物質的二支特徵波峰。繪圖 1 2 _b說明沸石Y的XRD型態，在最終複合物中約有60重 量％的沸石Y。氮吸附顯示其表面積約6 8 9 m2/g ’孔隙體 積約 0.9 9 c m3 / g。 實例1 6 使用複合物1 5製備催化性裂解之催化劑。利用離子 交換，將一份複合物1 5與十份1 N硝酸銨溶液於6 0 °C、 攪拌之下，混合6小時，獲得複合物的質子形式（H + -) 。過濾固體物質，淸洗並於1 1 〇 °C下乾燥，得到白色粉末 。在第二次離子交換之後，固體物質於5 5 (TC、空氣中煅 燒6小時。
八份H、複合物1 5與二份氧化鋁以萘可形式混合，以 提供催化劑。利用以下步驟將混合物乾燥與煅燒：（a ) 以5°C/分鐘的速率，提升溫度至120t ; (b)溫度120°C 維持1小時；（c )以5 °C /分鐘的速率，提升溫度至5 00 °C，維持5小時；（d )以51： /分鐘的速率，降低溫度至 1 5 (TC ;以及（e )然後讓催化劑在乾燥器中冷卻至室溫。 催化劑含有USY沸石約48%。 然後，於760 °C、蒸汽含量50%之大氣壓下，以蒸汽 處理催化劑1 〇小時。最終的催化劑（含U S Y、中孔隙基 質及氧化鋁黏結劑）指定爲CAT 1 6 A。 爲了比較裂解活性，以與製備C A T 1 6 A相同的離子交 -29- 200528189 (26) 換、擠壓及蒸汽處理方法，製備含4 8 %u s γ及氧化鋁黏結 劑的催化劑，指定爲CAT 16Β。 這二種催化劑每一個皆取一半以含環烷酸釩（ vanadium naphthenate )的甲苯浸漬，在商業化的條件下 產生5 0 0 0 p p m受釩去活化的f C C催化劑。這二種浸瀆後 的催化劑分別指定爲C A T 1 6 A V及C A T 1 6 B V。 實例1 7 使用流體化床FCC單元於40(TC、催化劑/油比例爲2 ，在蒸汽中5分鐘的流體化活性測試（FAI )，評估實例 1 6中所製備的四種催化劑的裂解活性。進料爲輕質東德州 氣油（Light East Texas Gas Oil，LETGO)，其性質如表 2 所示。催化性成效的比較如表3所示。 -30- (27)200528189 表2輕質東德州氣油（LETGO )之性質 API 36.4 蒸餾（D1 160) 積 ％) 2 3 5 °C 10% 2 5 4 〇C 3 0% 26 8 °C 5 0% 2 8 7 〇C 70% 3 0 7 〇C 9 0% 34 1 °C EBP 3 64 〇C 溴數 0.50 KV@1 00〇c，cst 1.30 平均分子量 269 傾注點，t -7 C C R，重量％ 0.02 折射指數@70° 1 .4492 苯胺點，t 76 氫，重量％ 13.3 硫，重量％ 0.13 總氮，ppm 300 驗性氮，ppm 45 鎳，p p m 0. 1 釩，p p m 0. 1 鐵，p p m 0.77 銅，ρ ρ ηι 0.05 石蠟烴，重量％ 44.7 環烷烴 33.2 芳族，重量％ 2 2.1
-31 - 200528189 (28) 表3催化性成效 催化劑 釩含量％ FAI轉化％ 活性滯留％ CAT16A 0 65.6 CAT16AV 0.52 5 1.3 78.7 CAT16B 0 48.3 CAT 16BV 0.53 23.8 49.3 表3中的結果顯示本發明的組合物因爲酸性的中 基質，而增進對重金屬的耐受性。也因爲沸石與酸性 孔隙基質的新型組合而增進裂解的活性。 實例1 8 以與實例1 5中所述的相同方法，合成一種指定 合物18含有USY沸石的複合物。唯一的差異爲化學 使用量：U S Y沸石2 · 9份，異丙氧化鋁2 8份，四乙 磷酸鹽1 7 1 · 4份，四乙基氫氧化銨3 4份，三乙醇胺 份及水138份。複合物18的XRD型態如圖12所示 淸楚顯示沸石Y及中度結構物質的二個特徵波峰。複 含有約5重量％的USY沸石，表面積約694 m2/g，孔 積約 1 . 1 cin3/g。 複合物1 8以離子交換成氫（H')的形式’並以 例1 6所述相同的方法擠壓。最後，複合物1 8製成直 1 . 6 m m的圓柱形，並含有U S Υ約4重量％、含A1的 隙物質7 6重量％及A1 2 Ο 3 2 0重量％。 孔隙 的中 爲複 品的 基正 1 24 ，其 合物 隙體 與實 徑爲 中孔 -32- 200528189 (29) 進一步以Ni及W浸漬，使複合物1 8官能化。五份 硝酸鎳水溶液（1 4重量％的N i )與8 · 4份水合氧化銨鎢（ ammonium metatungstate)溶液（39.8 重量％ 的 W)在攪 拌下混合。然後，混合物在攪拌下以9份水稀釋。1 2 · 5份 的複合物1 8以上述的Ni/W溶液浸漬，於1 1 8 °C下乾燥2 小時，並於5 0 0 °C下煅燒2小時。所得經改質的複合物1 8 指定爲CAT 1 8，含有4.0重量％的Ni及1 8.7重量％的W 。其主要特徵在於具有高含量的弱酸性中孔隙基質。 實例19 本實例說明使用實例1 8的物質，作爲氫裂解催化劑 。評估實例1 8中製備的複合物1 8對於氫裂解的中間蒸餾 物的選擇性。評估係在含有預硫化的複合物1 8的流動反 應器中進行（習用的方法），使用氫處理的重質真空氣油 作爲進料。在LHSV爲1 .5kg/公升小時、總壓力爲140 bar (H2S的分壓爲5.5 bar，且氨的分壓爲0.075 bar)、及 氣體/進料比爲1 5 00 NL/kg的條件下操作。進料的特性如 表4所示。 -33- 200528189 (30)
以組份的淨轉化爲6 5重量％，評估其對中間蒸餾物（ 如沸點範圍自1 75 t至345 t )的選擇性。令人驚訝的是 選擇性達到7 2.6重量％。 上述說明包含許多特性，這些特性不應解釋爲對本發 明的範疇限制，而僅能作爲其較佳具體實例之示範。那些 熟悉本技藝者在如實例所界定的發明範疇與精神中，可以 想像出許多其他的可能性。 【圖式簡單說明】 -34 - 200528189 (31) 參考圖形說明一些具體實例如下，其中： 圖1顯示如下：含有具沸石貝塔的中孔隙無機氧化物 載體的樣品1之X-射線繞射（XRD )型態（圖ι-a )、沸 石貝塔的XRD型態（圖1 -b )、及樣品1的延長掃瞄時間 (EST )的XRD影像。 圖2爲具沸石貝塔的中孔隙無機氧化物載體（樣品1 )之高解析度穿透電子顯微鏡（TEM )影像、及顯示沸石 區域的電子繞射型態的插圖。 圖3顯示具沸石貝塔的中孔隙無機氧化物載體（樣品 !)及不含沸石貝塔的比較樣品以溫度程式控制NH3 ( NH3-TPD )脫附的分析圖。 圖4顯示於本文實例3、4及5所製物質、以及純沸 石貝塔的中孔隙大小分佈圖。 圖5顯示於本文實例2至5所製物質、以及純沸石貝 塔的XRD型態圖。 圖6顯示中孔隙物質（圖6-a) 、MCM-22(圖6-b) 、及實例7的複合物質（圖6-c)的XRD型態。 圖7顯示實例7 ' 8及1 0所製物質的中孔隙大小分佈 〇 圖8顯示中孔隙物質（圖8-a )、純MCM-56 (圖8-b }、及複合物8 (圖8-c )的XRD型態。 圖9顯示純ITQ-2沸石（圖9-a )、中孔隙物質（圖 9_b)、複合物9物質（圖9-c )、及複合物1〇物質（圖 9_d )的XRD型態。 -35- 200528189 (32) 圖1 〇顯示以供樣品3、4、5及純沸石貝塔於5 3 8 °C下 裂解正己烷的沸石質量計的假一階反應速率常數。 圖1 1顯示實例4及5中所製物質的NH3 IR光譜。 圖1 2顯示本文實例1 8中所製物質（圖1 2-a )以及純 USY沸石（圖12-b )的XRD型態。 -36-

Claims (1)

  1. 200528189 (1) 十、申請專利範圍 1 · 一種組合物，含有： (a )至少一種整齊的、結晶的且微孔隙的物質，其 平均孔徑小於1 5埃；及 (b )至少一種非結晶的無機氧化物，該無機氧化物 具有中孔隙或中孔隙及微孔隙，且其中該無機氧化物在χ 射線繞射圖型中具有在2 Θ的0 · 3及3度之間的波峰，且 其中該中孔隙爲相互連接的中孔隙。 2 ·如申請專利範圍第1項之組合物，其中該結晶的 微孔隙物質係選自由沸石貝塔、沸石Υ、U S Υ、絲光沸石 、沸石 L、ZSM-5、ZSM-11、ZSM-12、ZSM-20、Theta-1 、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3 、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、 ITQ-21 、SAPO-5、SAPO-11 、SAPO-37、Breck-6 及 ALP〇4_5所組成的群組。 3 .如申請專利範圍第1項之組合物，其中該至少一 锺無機氧化物具有的中孔隙以該無機氧化物的微孔隙及中 孔隙爲基準計係至少97體積百分比，表面積爲400-1100 m 2 / g，總孔隙體積約0 · 3 - 2.2 c m3 / g。 4 .如申請專利範圍第3項之組合物，其中中孔隙所 鳥有的尺寸範圍係自約2 n m至約2 5 n m。 5 ·如申請專利範圍第3項之組合物，其中多孔性無 _氧化物爲氧化矽。 6.如申請專利範圍第1項之組合物，進一步含有至 -37- 200528189 (2) 少一種金屬。 7.如申請專利範圍第6項之組合物，其中該金屬可 爲晶格原子的取代物納入沸石的網狀結構中，且/或是配 置在沸石的微孔隙內。 8 ·如申請專利範圍第6項之組合物，其中該金屬被 納入無機氧化物內部至少一個中孔隙的牆內，及/或至少 一個中孔隙的表面上。 9 ·如申請專利範圍第6項之組合物，其中該金屬是 至少一種選自由銘、駄、釩、銷、鎵、硼、猛、鋅、銅、 金、鑭、鉻、鉬、鎳、鈷、鐵、鎢、鈀及鉑組成群組之金 屬。 10. 如申請專利範圍第1項之組合物，其中該結晶的 微孔隙物質的組成重量百分比範圍爲自約3%至約90%。 11. 如申請專利範圍第1項之組合物，其中該微孔隙 沸石的組成重量百分比範圍爲自約4%至約80%。 ]2 · —種製造催化性物質之方法，含有以下步驟： (a )將沸石預處理； (b )混合預處理的沸石、水、無機氧化物或無機氧 化物的前驅物、以及至少一種中孔隙產生用的有機化合物 ，產生混合物； (c )乾燥此混合物； (d )將經乾燥的混合物加熱至一溫度及一段時程， 使足以產生中孔隙無機氧化物結構。 13.如申請專利範圍第1 2項之方法，其中該沸石爲 -38- 200528189 (3) 層狀沸石，且預處理包括層狀沸石的剝層及插層。 1 4 ·如申請專利範圍第1 3項之方法，其中該剝層係 將層狀的沸石與陽離子性界面活性劑的鹼性溶液在能使層 狀沸石膨脹並剝層的條件下接觸以完成。 1 5 .如申請專利範圍第1 3項之方法，其中沸石的剝 層包含將沸石進行超音波處理。 1 6 ·如申請專利範圍第1 2項之方法，其中該預處理 包括離子交換、浸漬、官能性物種的固定及/或蒸汽處理 〇 17. 如申請專利範圍第1 2項之方法，其中中孔隙產 生用的有機化合物係選自由甘油、二甘醇、三甘醇、四甘 醇、丙二醇、三乙醇胺、三異丙醇胺、澱粉、薩佛蘭（ sulfolane )、四伸乙五胺、及二甘醇二苯甲酸酯組成的群 組。 18. 如申請專利範圍第1 2項之方法，其中該中孔隙 產生用的有機化合物所具有的沸點爲至少1 5 (TC。 1 9 .如申請專利範圍第1 2項之方法，其中該無機氧 化物係以無機氧化物的前驅物與水反應產生的。 2 〇 ·如申請專利範圍第1 2項之方法，其中該混合物 維持在pH高於約7.0。 2 1·如申請專利範圍第1 4項之方法，其中該混合物 的乾燥係在空氣中加熱一段時間，使足以驅離主要部分的 水分及中孔隙產生用的有機化合物。 2 2.如申請專利範圍第1 2項之方法，其中加熱步驟 -39- 200528189 (4) (d )包含將經乾燥的混合物加熱至溫度 2 5 0 〇C。 2 3 .如申請專利範圍第1 2項之方法 經加熱乾燥的混合物於溫度自約3 0 0 °C至 至少一段足以有效地自中孔隙無機氧化物 隙產生用的有機化合物的時間。 2 4 .如申請專利範圍第1 2項之方法 金屬離子與該混合物混合，該金屬係選自 銷、鎵、硼、錳、鋅、銅、金、鑭、鉻、 、鎢、鈀及鉑組成的群組。 2 5 .如申請專利範圍第1 2項之方法 黏結劑與催化性物質混合及將催化性物質 步驟。 26. —種製造催化性物質之方法，其· (a )將層狀結構的沸石與陽離子性 性溶液在能使層狀沸石膨脹的條件下接觸 (b )混合膨脹的沸石、水、無機氧 物的前驅物、以及至少一種中孔隙產生用 產生混合物； (c )將層狀沸石剝層； (d )乾燥此混合物； (e )將經乾燥的混合物加熱至一溫 使足以產生中孔隙氧化物結構。 2 7.如申請專利範圍第2 6項之方法 自約 1 0 0 °C至約 ，進一步包含將 約1 0 0 0 °c下煅燒 載體中去除中孔 ，進一步包含將 由銘、鈦、釩、 鉬、鎳、鈷、鐵 ，進一步包含將 製成預定形狀的 包含下列步驟： 界面活性劑的鹼 化物或無機氧化 的有機化合物， 度及一段時程， ，其中該中孔隙 -40- 200528189 (5) 產生用的有機化合物係選自由甘油、二甘醇、三甘醇、四 甘醇、丙二醇、三乙醇胺、三異丙醇胺、薩佛蘭、四伸乙 五胺、及二甘醇二苯甲酸酯組成的群組。 2 8.如申請專利範圍第2 6項之方法，其中該中孔隙 產生用的有機化合物所具有的沸點爲至少1 5 0 °C。 29.如申請專利範圍第26項之方法，其中該無機氧 化物係以無機氧化物的前驅物與水反應產生的。 3 0.如申請專利範圍第2 9項之方法，其中該無機氧 化物的前驅物係選自由氧化矽源及氧化鋁源的群組。 3 1 ·如申請專利範圍第2 6項之方法，其中該混合物 維持在pH高於約7.0。 32.如申請專利範圍第26項之方法，其中該混合物 的乾燥係在空氣中加熱一段時間，使足以驅離水分及揮發 性有機化合物。 3 3.如申請專利範圍第26項之方法，其中加熱步驟 (e )包含將經乾燥的混合物加熱至溫度自約丨00 °C至約 2 5 0〇C 〇 34.如申請專利範圍第26項之方法，其中加熱步驟 (e )包含將經乾燥的物質加熱至溫度自約15〇 °C至約200 。。。 3 5 ·如申請專利範圍第26項之方法，進一步包含將 經加熱乾燥的混合物於溫度自約3 00 °C至約lOOOt下煅燒 的步驟。 3 6·如申請專利範圍第26項之方法，進一步包含將 - 41 - 200528189 (6) 經加熱乾燥的混合物於溫度自約4 0 0 °C至約7 0 0 °C下煅燒 約2小時至約40小時的步驟。 37. 如申請專利範圍第26項之方法，進一步包含將 金屬離子與混合物混合，該金屬係選自由鋁、鈦、釩、鍩 、鎵、硼、錳、鋅、銅、金、鑭、鉻、錦、鎳、鈷、鐵、 鎢、銷及鉑組成的群組。 38. 如申請專利範圍第26項之方法，進一步包含將 黏結劑與催化性物質混合及將催化性物質製成預定形狀的 步驟。 3 9 . —種處理碳氫化合物進料的程序，包含： 將含有至少一種碳氫化合物成份的進料與催化性有效 量的催化劑在足以使該碳氫化合物成份有效轉化的反應條 件下接觸，該催化劑含有至少一種承載於多孔性無機氧化 物上的沸石；該多孔性無機氧化物具有的中孔隙以多孔性 無機氧化物的微孔隙及中孔隙爲基準計爲至少97體積百 分比，表面積爲約400-1100 m2/g，且在2Θ的0.3及3度 之間具有至少一個X射線繞射波峰。 4 0.如申請專利範圍第3 9項之程序，其中該碳氫化 合物成份的轉化係利用選自由醯化、烷化、雙聚合、寡聚 合、聚合、脫爐、水合、脫水、岐化（disproportionation )、氫化、脫氫、芳族化、選擇性氧化、異構化、氫處理 、催化性裂解、及氫裂解組成群組中的反應以達成。 4 1.如申請專利範圍第3 9項之程序，其中該進料包 含芳族化合物及醯化劑，且反應爲在足以使芳族化合物與 -42- 200528189 (7) 醯化劑產生醯化的醯化反應條件之下進行的醯化反應。 42.如申請專利範圍第4 1項之程序，其中該醯化劑 包含羧酸酐、醯基鹵化物。 4 3.如申請專利範圍第4 1項之程序，其中醯化的反 應條件包括溫度自約20°C至約35(TC、壓力自約i bar至 約1 10 bar、且空間速度自約〇·1 WHSV至約20 WHSV。 4 4·如申請專利範圍第3 9項之程序，其中該進料包 含石油的餾份，且反應條件爲足以造成該餾分的催化性裂 解。 45. 如申請專利範圍第44項之程序，其中該石油的 餾份包括至少一種成份其具有的起始沸點自約2 0 0 °C至約 2 6(TC，且結束沸點自約400°C至約45 5 °C。 46. 如申請專利範圍第45項之程序，其中該石油的 餾份進一步包含至少一種成份其沸點在約54(TC以上。 47. 如申請專利範圍第4 6項之程序，其中該具有沸 點在5 4 0 °C以上的成份爲未脫柏油的石油殘渣、脫柏油的 石油殘渣、褡砂瀝青、頁岩油、或煤油。 4 8·如申請專利範圍第4 4項之程序，其中該反應條 件包括溫度自4 0 0 °C至約6 5 0 °C，催化劑對進料重量的比 例自約3 : 1至1 〇:]。 49. 如申請專利範圍第3 9項之程序，其中該進料包 括石油的餾份，且反應條件足以造成該餾分的氫裂解，以 製造相對較輕質的碳氫化合物產物。 50. 如申請專利範圍第49項之程序，其中該石油的 -43- 200528189 (8) 餾fe S有至少一種成份其沸點在約2 6 〇它以上。 5 1 .如甲g靑專利$Β圍_ 〇 _之程序，其中該石油的 餾份含有至少一種成份其沸點在約29〇t以上。 52·如申請專利範_第49項之程序，其中該石油的 餾份含有至少一種成份其沸點在約34(rc以上。 5 3·如申請專利範圍第5 〇項之程序，其中該石油的 飽份進一步包含至少一種選自由未脫柏油的石油殘渣、脫 柏油的石油殘渣、褡砂瀝青、頁岩油、及煤油所組成群組 的成份。 5 4·如申請專利範圍第4 9項之程序，其中該相對較 輕質的碳氫化合物產物包括一種選自由沸點範圍自1 5 (TC 至4 0 0 °C的中間蒸餾物成份、柴油燃料及潤滑基底油所組 成群組的成份。 5 5 ·如申請專利範圍第3 9項之程序，其中碳氫化合 物成份的轉化係利用氫異構化而產生，且反應條件包括溫 度自約1 50°C至約5 00 °C、壓力自約I bar至約240 bar、 且W H S V自約〇 · 1至約2 〇。 -44-
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