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TW201700166A - 觸媒組成物以及於重質芳族物轉化方法中的用途 - Google Patents

觸媒組成物以及於重質芳族物轉化方法中的用途 Download PDF

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Publication number
TW201700166A
TW201700166A TW105102873A TW105102873A TW201700166A TW 201700166 A TW201700166 A TW 201700166A TW 105102873 A TW105102873 A TW 105102873A TW 105102873 A TW105102873 A TW 105102873A TW 201700166 A TW201700166 A TW 201700166A
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TW
Taiwan
Prior art keywords
catalyst composition
weight
mordenite
catalyst
metal
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TW105102873A
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English (en)
Inventor
文義 賴
克莉斯汀 艾利亞
繼婭 陳
徐分 廖
哈利 奈爾
約書亞 卡特勒
杜倫 拉分
傳盛 柏
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艾克頌美孚化學專利股份有限公司
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Publication of TW201700166A publication Critical patent/TW201700166A/zh

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    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本發明揭示一種觸媒組成物及其於含有C8+芳烴之原料的轉化以產生包含苯、甲苯及二甲苯之輕質芳族產物的方法中之用途。該觸媒組成物包含從TEA或MTEA合成之絲光沸石、隨意地至少一種IUPAC元素周期表之第10族的第一金屬、及隨意地至少一種IUPAC元素周期表之第11至15族的第二金屬，其中該絲光沸石的中孔表面積大於30m2/g且該絲光沸石包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。

Description

觸媒組成物以及於重質芳族物轉化方法中的用途 相關申請案交互參考
本申請案主張2015年2月4日提出之美國專利申請案第62/111,730號，及2015年9月30日提出之美國專利申請案第14/870,848號之權益及優先權，該等專利案之揭示係以全文引用方式併入。
本發明關於可用於將重質芳族物(尤其是C8+芳族物)轉化較輕質芳族產物(特別是苯、甲苯及二甲苯(下文合稱為BTX))之觸媒組成物、製造該組成物之方法及將該組成物用於重質芳族物轉化方法中之方法。
苯及二甲苯之來源為催化重組油，該催化重組油係藉由使石油腦及氫的混合物與在適度酸性支撐體(諸如經鹵素處理之氧化鋁)上的強氫化/脫氫觸媒(諸如鉑)接觸所製備。通常，C6至C8部分係從該重組油分離出來並以對於芳族物或脂族物具有選擇性的溶劑萃取， 以生產相對不含脂族物之芳族化合物的混合物。該芳族化合物的混合物通常含有BTX以及乙苯。
精煉廠亦著重於藉由以苯或甲苯將較低價值的C9+芳族物轉烷基化以產生二甲苯之苯及二甲苯的生產之日漸重要方法。化學工廠理想上會喜歡儘可能多之重質C9+芳族物同時最小化且可能移除甲苯/苯共進料的方法。轉烷基化活性及脫烷基化活性二者對於成功的觸媒系統均很重要。轉烷基化活性係將甲基轉烷基化以形成二甲苯的能力。脫烷基化活性為將存在於C9+芳族物上之乙基及丙基脫烷基化使能形成較低碳甲基/環物種的能力，該較低碳甲基/環物種可以較高碳甲基/環物種轉烷基化以形成二甲苯。需要金屬官能以飽和在脫烷基化期間所形成的烯烴，同時維持該芳族物飽和的完整性。隨著工廠漸提高進料中之C9+的量，可接受活性及觸媒壽命成為挑戰。
已顯示經由使用堆疊床系統將脫烷基化活性及轉烷基化活性去偶合顯著改善性能。一堆疊床觸媒系統係揭示於美國專利第5,942,651號，且涉及以下步驟：使包含C9+芳烴和甲苯之進料在轉烷基化反應條件下與包含約束指數為0.5至3之沸石(諸如ZSM-12)及氫化組分的第一觸媒組成物接觸。然後使從該第一接觸步驟形成之流出物與包含約束指數為3至12的沸石(諸如ZSM-5)且係在與該第一觸媒組成物分開之床或分開的反應器之第二觸媒組成物接觸，以產生包含苯及二甲苯之轉烷基化反應產物。進料中之乙苯及/或在轉烷基化方法期間所形成 的乙苯係藉由將乙苯脫烷基化成苯及乙烯而部分破壞。
另一堆疊床觸媒系統係揭示於美國專利第5,905,051號，用於將烴物流(諸如例如將C9+芳族化合物)轉化成C6至C8芳烴(諸如二甲苯)之方法，其係藉由使該物流與包含第一觸媒組成物及第二觸媒組成物之觸媒系統接觸，其中該等觸媒組成物存在於分開的階段且非物理性混合或摻合，且其中該第一觸媒為經金屬促進之結合氧化鋁或結合矽石之β沸石，而該第二觸媒組成物為其中併入選自由矽、磷、硫及其組合所組成之群組的活性促進劑之ZSM-5。根據該'051專利，使用分開之催化階段改善C9+芳族化合物及萘成為二甲苯的轉化且減少產物中之不想要的乙苯之量。該'051產物中之乙苯以所得產物之C8芳族物部分的重量計為約3至7重量%之乙苯。
美國專利第8,183,424號、第8,481,443號、及第9,006,125號揭示藉由在有利於使芳烴脫烷基化及飽和所形成之C2+烯烴的條件下，以第一觸媒將與C6及/或C7芳烴和氫接觸的C9+芳烴原料轉烷基化以產生第一流出物來製造二甲苯之方法中使用堆疊床系統的經改良性能，該第一觸媒包含(i)約束指數在3至12之範圍的第一分子篩及(ii)IUPAC元素周期表之6至12族之至少第一及第二不同金屬或其化合物。然後在有利於以該C6/C7芳烴將C9+芳烴轉烷基化之條件下使至少一部分該第一流出物與包含約束指數低於3的第二分子篩之第二觸媒接觸以形成包含二甲苯的第二流出物。
使用至少一種具有MWW架構之沸石的堆疊床係揭示於美國專利第8,163,966號中之用以製造含有二甲苯之產物的方法中，該方法包含使C9+芳族原料、氫及C6-C7芳族原料與包含選自由MCM-22及MCM-49所組成之群組的第一分子篩及0.01至5重量%之第6至10族的第一金屬元素之第一觸媒在第一條件下接觸以形成第一產物，然後使至少一部分該第一產物與包含選自由ZSM-12及絲光沸石所組成之群組的第二分子篩及0至5重量%之第6至10族的第二金屬元素之第二觸媒在第二條件下接觸以形成包含二甲苯的第二產物。
其他者具有所揭示用於單床式系統之觸媒及方法。美國專利第6,867,340號揭示各種烴之歧化/轉烷基化的觸媒，其係由載體及支撐在該載體上之金屬組分組成。該載體包含10至80重量%之矽石/氧化鋁之莫耳比範圍在10至200的絲光沸石及/或β型沸石；0至70重量%之矽石/氧化鋁之莫耳比範圍在30至500的ZSM-5型沸石；及5至90重量%之至少一種由下列所組成之群組的無機黏合劑：γ-氧化鋁、矽石、矽石氧化鋁、膨土、高嶺土、斜髮沸石、及微晶高嶺土。該金屬組分包含鉑和錫或鉛之一。該觸媒使得能從苯、甲苯及C9或更高碳芳族化合物，經由大幅減少芳族物損失之歧化/轉烷基化以明顯高產率製造混合二甲苯。此外，該觸媒可長期維持其催化活性而不會去活化。
美國專利第7,626,064號揭示C7、C9、及C10 芳族物之轉烷基化以獲得高產率之二甲苯的觸媒及方法。該觸媒包含新穎UZM-14催化材料，該UZM-14催化材料包含具有與12環通道之方向平行的平均微晶體長度為約60nm或更小且中孔體積為至少約0.10cc/g之MOR架構型的微晶體之球狀聚集體。該UZM-14觸媒在轉烷基化方法中為特別活性的及安定的。
美國專利第7,553,791號揭示觸媒組成物、用於製造該組成物之方法及用於將含有C9+芳烴的原料轉化以製造含有較輕質芳族產物及以所得產物之C8芳族物部分的重量計少於約0.5重量%之乙苯的所得產物之方法。該C9+芳烴係在轉烷基化反應條件下轉化成含有二甲苯之反應產物。觸媒組成物包含(i)α值為至少300之酸性組分；及(ii)氫化活性為至少300之氫化組分。該組成物可藉由將至少一種氫化組分併入α值為至少300之酸性組分來製造。
即使有此等轉烷基化技術之進展，特別是在用於將C8+芳烴轉化成較輕質芳族產物的方法中仍需要經改善之性能。
已發現包含高活性中孔絲光沸石之單床式觸媒系統相較於其他系統展現經改良之C9+轉化率及降低之芳環損失。較佳地，該觸媒組成物係用於將C8+芳烴轉化成較輕質芳族產物。
本發明關於含有中孔絲光沸石(下文界定)之觸媒組成物。該中孔絲光沸石係從四乙銨陽離子(TEA)或甲基三乙銨陽離子(MTEA)合成。隨意地，該中孔絲光沸石具有至少一種IUPAC元素周期表之第10族的第一金屬。較佳地，根據該觸媒組成物之重量計為0.005重量%至5.0重量%之該至少一種IUPAC元素周期表之第10族的第一金屬。隨意地，該中孔絲光沸石具有至少一種IUPAC元素周期表之第11至15族的第二金屬。較佳地，根據該觸媒組成物之重量計為0.01重量%至5.0重量%之該至少一種IUPAC元素周期表之第11至15族的第二金屬。該中孔絲光沸石之中孔表面積大於30m2/g且該中孔絲光沸石包含由原生微晶體所構成的黏聚物。該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。
此外，本發明關於將包含C8+芳烴之原料轉化成較輕質芳族產物的方法，該方法包含在適當轉化條件將使該原料和隨意的氫在本發明之觸媒組成物任一者存在下接觸以產生該包含苯、甲苯及二甲苯的較輕質芳族產物。
通常，原料中之C8+芳烴包含在大氣壓力下沸點在約135℃至約260℃的範圍，較佳係沸點在約135℃至約230℃的範圍之芳族化合物。通常，該原料另外包含苯或甲苯或其混合物。
圖1顯示對照實例1之TEA-絲光沸石晶體的SEM。
圖2顯示實施例2之中孔絲光沸石晶體的SEM。
圖3顯示實施例3之中孔絲光沸石晶體的SEM。
圖4A、4B及4C顯示將甲苯及模型進料用於實施例7之C9+芳烴的轉化方法之實施例4、5及6的觸媒性能。
圖5A、5B及5C顯示將甲苯及1,3,8-三甲苯模型進料用於實施例10之C9+芳烴的轉化方法之實施例4、5及9的觸媒性能。
圖6A、6B及6C顯示將甲苯及1,3,9-三甲苯模型進料用於實施例13之C9+芳烴的轉化方法之實施例8、9、11及12的觸媒性能。
發明詳細說明 定義
基於本說明書及所附主張權項之目的，界定下列用語。
如本文所使用，用語「Cn芳烴」意指每個分子具有n個碳原子的芳烴，其中n為正整數。用語「Cn+芳烴」意指每個分子具有至少n個碳原子之芳烴。用語 「Cn-芳烴」意指每個分子具有不多於n個碳原子之芳烴。
如本文所使用，用語「芳族」意指經取代及未經取代之單核及多核環化合物。苯系之化合物以及為雜環或含有雜環之芳族特徵的化合物為芳族化合物之實例。然而，該等經取代芳族化合物必須含有至少1個附接至該芳族核的氫。該等芳環可經烷基、芳基、烷芳基、羥基、胺基、烷氧基、芳氧基、環烷基、鹵基、及該等基團之混合物或不妨礙所希望之反應的其他基取代。
用語「烴」意指含有結合至碳之氫的一種類別之化合物，且包含(i)飽和烴化合物，(ii)不飽和烴化合物，及(iii)烴化合物(飽和及/或不飽和)之混合物，包括具有不同n值之烴化合物的混合物。
如本文所使用，用語「較輕質芳族產物」係界定為意指產物中之芳族分子具有的碳原子比原料中之芳族分子的碳原子較少。例如，對二甲苯(以甲苯及/或苯將C9+轉烷基化的所得產物之一)具有8個碳原子，其比C9+芳族分子中之9或更多個碳原子少。
如本文所使用，用語「IUPAC元素周期表」意指國際純化學暨應用化學聯合會(International Union of Pure and Applied Chemistry)日期為2013年5月1日之元素周期表，如同其在The Merck Index(第20版，Merck & Co.,Inc.,1996)內頁出現。
如本文所使用，用語「中孔絲光沸石」意指 從TEA或MTEA合成之絲光沸石，具有之中孔表面積大於30m2/g且該絲光沸石包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2，如美國專利申請案第62/111,730號揭示，該案係引用方式併入本文中。本發明及主張權項中所敘之絲光沸石因其高中孔表面積而稱為中孔絲光沸石。
如本文所使用，用語「TEA」意指四乙銨陽離子。
如本文所使用，用語「MTEA」意指甲基三乙銨陽離子。
如本文所使用，用語「分子篩」係與「沸石」同義使用。
用語「縱橫比」用以指示原生晶體時係界定為微晶體之最長大小除以該微晶體之寬度，其中該微晶體之寬度係界定為在與該最長大小正交之方向中的最長大小中間之微晶體大小，此係以TEM測量，其相對低，例如小於2.0。通常，該原生晶體並非縱橫比大於2.0之長形晶體或小板。
如本文所使用，用語「原生晶體」表示與黏聚物相反之單一個別晶體。原生晶體通常經由弱物理性交互作用(而非化學鍵)黏附在一起以形成黏聚物。本文中字詞「晶體」及「微晶體」係互換使用。
觸媒組成物
本發明方法中所使用之觸媒組成物包含(i)從TEA或MTEA合成之中孔絲光沸石，隨意地(ii)具有至少一種IUPAC元素周期表之第10族的第一金屬，及隨意地(iii)至少一種IUPAC元素周期表之第11至15族的第二金屬，其中該中孔絲光沸石之中孔表面積大於30m2/g且包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。
該中孔絲光沸石具有非常小之晶體大小及高中孔表面積，特別是藉由選擇合成混合物組成獲致。該非常小之原生晶體大小促使反應物化合物達到該中孔絲光沸石的孔內之活性位點，從而提高催化效率。
該中孔絲光沸石係從TEA或MTEA結構導向劑合成且具有大於30m2/g之中孔表面積，且該中孔絲光沸石包含由原生微晶體所構成黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。本發明之絲光沸石亦因其高中孔表面積而稱之為中孔絲光沸石。
該中孔絲光沸石包含黏聚物，通常為不規則黏聚物。該黏聚物係由原生微晶體所構成，該原生微晶體之平均原生晶體大小以TEM測量為小於80nm，較佳係小於70nm，及更佳係小於60nm，例如小於50nm。該原生微晶體之平均原生晶體大小以TEM測量可為例如大 於20nm，隨意地大於30nm。
隨意地，該中孔絲光沸石之原生晶體的平均原生晶體大小為小於80nm，較佳係小於70nm，及在一些情況下為小於60nm，其以X射線繞射測量各在a、b及c晶體向量中。該原生微晶體可隨意地具有大於20nm，隨意地大於30nm之平均原生晶體大小，其以X射線繞射測量各在a、b及c晶體向量中。
該中孔絲光沸石通常包含原生晶體之黏聚物連同一些未黏聚之原生晶體的混合物。大部分中孔絲光沸石，例如，大於80重量%或大於90重量%將作為原生晶體之黏聚物存在。該黏聚物通常為不規則形式。更多關於黏聚物之資訊請見Walter,D.(2013)Primary Particles-Agglomerates-Aggregates,in Nanomaterials(ed.Deutsche Forschungsgemeinschaft(DFG))，Wiley-VCH Verlag GmbH & Co.KGaA，德國Weinheim。doi：10.1002/9783527673919，第1-24頁。有用地，該中孔絲光沸石並非聚集體。
隨意地，該中孔絲光沸石包含至少50重量%，較佳為至少70重量%，有利地為至少80重量%，更佳為至少90重量%及隨意地實質上由該不規則黏聚物組成，該不規則黏聚物係由原生晶體大小為小於80nm，較佳係小於70nm，及更佳係小於60nm，例如小於50nm之原生微晶體所構成。較佳地，本發明之中孔絲光沸石包含少於10重量%之以TEM評估大小為大於80nm的原生 微晶體。較佳地，本發明之中孔絲光沸石係由晶體大小TEM測量為小於80nm之微晶體所構成的該不規則黏聚物所構成。較佳地，以TEM評估，本發明之中孔絲光沸石實質上不含，例如含有少於10%之數目的針狀或小板狀晶體。
較佳地，本發明之中孔絲光沸石的原生微晶體之縱橫比小於3.0，更佳為小於2.0，其中該縱橫比係界定為微晶體之最長大小除以該微晶體之寬度，其中該微晶體之寬度係界定為在與該最長大小正交之方向中的最長大小中間之微晶體大小，此係以TEM測量。
該原生微晶體之黏聚物通常為不規則形式，且因其係由是為「原生」粒子之微晶體的黏聚物所形成，故可稱為「二次」粒子。
該原生微晶體可具有窄粒度分布，使至少90%數目之該原生微晶體的原生晶體大小在20至80nm之範圍，較佳係在20至60nm之範圍，以TEM測量。
該中孔絲光沸石以BET測量之中孔表面積係大於30m2/g，較佳係大於40m2/g，及在一些情況下係大於45m2/g。
該中孔絲光沸石之總表面較佳係大於500m2/g，更佳係大於550m2/g，及在一些情況下係大於600m2/g。該總表面積包括內部孔之表面積(沸石表面積)以及在晶體外部上之表面積(外表面積)。該總表面積係以BET測量。
較佳地，該中孔絲光沸石之中孔表面積對該總表面積的比係大於0.05。
該中孔絲光沸石的中孔體積較佳係大於0.1mL/g，更佳係大於0.12mL/g，及在一些情況下係大於0.15mL/g。
本發明之中孔絲光沸石的Si：Al2比較佳係大於10，及可在例如10至60，較佳為15至40之範圍。經處理後之中孔絲光沸石的Si：Al2比較佳係在40至300之範圍，更佳為60至150。
該中孔絲光沸石可由包含下列步驟之方法製備：
a)提供包含矽源、鋁源、鹼金屬(M)氫氧化物、選自由四乙銨陽離子(TEA)、甲基三乙銨陽離子(MTEA)及其混合物所組成之群組的結構導向劑(SDA)源、隨意的種晶及水之合成混合物，該合成混合物具有包括下列莫耳比的組成：Si：Al2 15-40
OH-：Si0.32
M+：Si0.32
SDA：Si0.10
H2O：Si<20
b)使該合成混合物經歷結晶條件以形成孔內包含結構導向劑(SDA)的中孔絲光沸石之晶體。將該合成混合物之組分組合且維持在結晶條件下。
適用之矽(Si)源包括矽石、矽石之膠態懸浮液、沉澱矽石、鹼金屬矽酸鹽，諸如矽酸鉀及矽酸鈉、正矽酸四烷酯、及焰製矽石，諸如Aerosil及Cabosil。較佳地，Si源為沉澱矽石，諸如Ultrasil(可得自Evonik Degussa)或HiSil(可得自PPG Industries)。
適用之鋁(Al)源包括硫酸鋁、硝酸鋁、氫氧化鋁、水合氧化鋁，諸如軟水鋁石、三水鋁石及/或假軟水鋁石、鋁酸鈉及其混合物。其他鋁源包括但不局限於水溶性鋁鹽、或烷氧化鋁，諸如異丙氧化鋁、或鋁金屬，諸如呈碎片形式之鋁。較佳地，該鋁源為鋁酸鈉，例如濃度在40至45%之範圍的鋁酸鈉的水溶液，或硫酸鋁，例如濃度在45至50範圍的硫酸鋁溶液。
前文提及之Si及Al來源的替代或除該等來源之外，鋁矽酸鹽亦可用作Si及Al二者之來源。
較佳地，合成混合物中之Si：Al2比係在15至40之範圍，更佳為20至30。
該合成混合物亦含有鹼金屬陽離子M+來源。該鹼金屬陽離子M+較佳係選自由下列所組成之群組：鈉、鉀及鈉和鉀陽離子的混合物。以鈉陽離子為佳。適用之鈉源可為例如鈉鹽，諸如NaCl、NaBr或NaNO3、氫氧化鈉或鋁酸鈉，較佳為氫氧化鈉或鋁酸鈉。適用之鋁源可為例如氫氧化鉀或鹵化鉀，諸如KCl或KBr、或硝酸鉀。較佳地，合成混合物中之M+：Si比係在0.15至0.32之範圍，更佳為0.20至0.32。隨意地，M+：Si比小於0.30。
該合成混合物亦含有氫氧離子源，例如鹼金屬氫氧化物，諸如氫氧化鈉或氫氧化鉀。氫氧化物亦可存在作為結構導向劑之相對離子或藉由使用氫氧化鋁作為Al源。較佳地，OH-：Si之範圍大於0.13，及可為例如在0.15至0.32之範圍，較佳為0.20至0.32。隨意地，OH-：Si比小於0.30。
該合成混合物隨意地包含種晶。該種晶可為任何適用之沸石種晶，諸如例如ZSM-5種晶或ZSM-11種晶或絲光沸石種晶。較佳地，該種晶為中孔絲光沸石晶體。該種晶之存在量可為例如該合成混合物的0重量%至10重量%，較佳為0.01重量%至10重量%，諸如0.1重量%至5.0重量%。在較佳實施態樣中，該合成混合物包含種晶。
結構導向劑(亦稱為SDA)為TEA及/或MTEA，較佳為TEA，及可以任何適用形式存在，例如作為鹵化物存在，但較佳係以其氫氧化物形式存在。該結構導向劑之適用來源包括TEABr、TEAOH、MTEACl、MTEABr及MTEAOH。較佳結構導向劑來源為TEABr。較佳地，SDA：Si比係在0.005至0.10之範圍，更佳為0.02至0.10，尤其是0.02至0.05。
該合成混合物中具有相對高固體含量有利於小晶體中孔絲光沸石之合成。較佳地，H2O：Si比不大於20，例如，在5至20之範圍，較佳為5至17，尤其是10至17。該合成混合物可例如具有如下表1中所指示之以 莫耳比表示的組成。
結晶可在靜態或攪拌狀態下在適用反應容器(例如，聚丙烯罐或襯有Teflon®之熱壓器或不鏽鋼熱壓器)中進行。適用之結晶條件包括約100℃至約200℃之溫度，諸如約135℃至約160℃。較佳地，該溫度低於145℃。該合成混合物可保持在高溫下為時足以在所使用溫度下令結晶發生之時間，例如約1天至約100天，隨意的為1至50天，例如約2天至約40天。在一些實例中，該合成混合物可維持在第一溫度為時1小時至10天的第一期間，然後升高至第二較高溫度為時1小時至40天的期間。在結晶步驟之後，從液體分離出合成之晶體並回收之。
中孔絲光沸石之原合成形式通常具有具下列莫耳關係的化學組成：mQ：nSiO2：Al2O3其中0.001m/n0.1，例如，0.001m/n0.05， n為至少10，例如10至60，較佳為15至40，且Q為結構導向劑。
由於原合成中孔絲光沸石在其孔結構內含有結構導向劑，該產物通常在使用前以從該沸石至少部分移除該結構導向劑之有機部分(即，TEA及/或MTEA)的方式活化。
經煅燒之中孔絲光沸石隨意地藉由煅燒該絲光沸石以移除結構導向劑來製備。該中孔絲光沸石亦可經歷離子交換步驟以使用其他陽離子置換存在於原合成產物中的鹼金屬離子或鹼土金屬離子。較佳之置換陽離子包括金屬離子、氫離子、氫前驅物，諸如銨離子及其混合物，更佳為氫離子或氫前驅物。例如，該中孔絲光沸石可經歷離子交換步驟以使用銨陽離子置換鹼金屬離子或鹼土金屬離子，然後煅燒以將呈銨形式之中孔絲光沸石轉化成呈氫形式之中孔絲光沸石。在一實施態樣中，中孔絲光沸石首先經歷煅燒步驟，有時稱為「初步煅燒」以從該中孔絲光沸石之孔移除結構導向劑，接著進行離子交換處理，接著進行進一步煅燒步驟。然而，已發現就本發明之中孔絲光沸石而言，不一定需要初步煅燒步驟。在替代性實施態樣中，因此使該中孔絲光沸石經歷離子交換處理而不經歷先前煅燒步驟(或初步煅燒)，且在該離子交換處理之後，經煅燒以從孔移除結構導向劑，從而提供本發明中所使用之經煅燒中孔絲光沸石。
該離子交換步驟可涉及例如使該中孔絲光沸 石與水性離子交換溶液接觸。此種接觸可進行例如1至5次。與離子交換溶液接觸隨意地在周圍溫度下進行，或者可在高溫下進行。例如，中孔絲光沸石可藉由在室溫下與水性硝酸銨溶液接觸而離子交換，然後乾燥且煅燒。
適用之煅燒條件包括在至少約300℃，較佳為至少約370℃之溫度下加熱至少約1分鐘，且通常不長於20小時，例如1小時至12小時期間。雖然低大氣壓可用於該熱處理，但基於方便性因素，希望其為大氣壓。該熱處理可在至高達約925℃之溫度下進行。例如，該熱處理可在400℃至600℃，例如500℃至550℃之溫度下，於含氧氣體存在下進行。
經煅燒之中孔絲光沸石通常具有以下莫耳關係之化學組成：nSiO2：Al2O3其中n為至少10，例如10至60，更特別為15至40。
本發明之觸媒組成物包含中孔絲光沸石，隨意的至少一種IUPAC元素周期表之第10族的第一金屬，及隨意的至少一種IUPAC元素周期表之第11至15族的第二金屬。通常，中孔絲光沸石以根據該觸媒組成物之重量計為約1至約99重量%之量存在，諸如約20至約80重量%。
除了該中孔絲光沸石之外，該觸媒隨意地包含具有至少一種IUPAC元素周期表之第10族的第一金屬，及隨意地至少一種IUPAC元素周期表之第11至15 族的第二金屬。該第10族金屬之第一金屬包括但不局限於鎳(Ni)、鈀(Pd)、鉑(Pt)、及含有中性金屬或其離子，較佳為鉑或鈀之化合物中的一或更多者。第11至15族之第二金屬包括但不局限於銅(Cu)、銀(Ag)、金(Au)、鋅(Zn)、鎘(Cd)、鎵(Ga)、銦(In)、錫(Sn)、鉍(Bi)、及含有中性金屬或其離子，較佳為銅、鎵或錫的化合物中之一或更多者。
該觸媒組成物包含根據該觸媒組成物之重量計為至少約0.005重量%、或0.01重量%、或0.05重量%、或0.10重量%高達約1.0重量%、2.0重量%、3.0重量%、或4.0重量%、或5.0重量%之IUPAC元素周期表之第10族的第一金屬。該觸媒組成物可包含約0.01重量%之該金屬，諸如大於或等於0.02重量%高達0.5重量%、1.0重量%、2.0重量%、或3.0重量%、或4.0重量%、或5.0重量%之此種第一金屬。在本發明之一或多個實施態樣中，該觸媒組成物具有根據該觸媒組成物之重量計在約0.005重量%至約5.0重量%範圍的第10族之第一金屬。
該觸媒組成物包含根據該觸媒組成物之重量計為至少約0.005重量%、或0.01重量%、或0.05重量%、或0.10重量%高達約0.50重量%、0.75重量%、1.0重量%、或1.25重量%、或1.5重量%、或2.0重量%之IUPAC元素周期表第11至15族的第二金屬。該觸媒組成物可包含根據該觸媒組成物之重量計為約0.005重量%之 該金屬，諸如大於或等於0.01重量%高達0.5重量%、0.75重量%、1.0重量%、或1.25重量%、或1.5重量%、或2.0重量%之此種第二金屬。在本發明之一或多個替代性實施態樣中，該觸媒組成物具有根據該觸媒組成物之重量計在約0.01至約1.5重量%範圍的至少一第11至15族的第二金屬。
熟習本領域之人士將暸解該第一金屬包含一或多種較大催化氫化活性之金屬，例如Pt及/或Pd，則會需要較少量該第一金屬，例如根據該觸媒組成物之重量計在約0.005重量%至約0.1重量%之範圍，諸如例如根據該觸媒組成物之重量計在約0.01重量%至約0.6重量%、或約0.01重量%至約0.05重量%之範圍。
當該金屬組分包含一或多種較低氫化活性之金屬，例如，Ga、In、Zn、Cu、及Sn之一或多者時，會需要較大量該第二金屬，例如根據該觸媒組成物之重量計在約0.005重量%至約5重量%之範圍，諸如根據該觸媒組成物之重量計在約0.01重量%至約1.5重量%、或約0.1重量%至約1重量%之範圍。當該觸媒組成物包含兩種金屬時，例如這兩種金屬可作為不同金屬存在，或作為這兩種金屬之合金存在。當兩種金屬形成合金時，該合金可具有與該等個別金屬之氫化活性不同的氫化活性。
該金屬組分，例如該第一金屬及/或該第二金屬可以任何方式提供在該觸媒組成物上，例如，藉由慣用方法，諸如在形成觸媒粒子之前或之後以相關金屬之化 合物的溶液浸漬該中孔絲光沸石或與該中孔絲光沸石離子交換來進行。
希望將能抗本發明方法中所使用之溫度及其他條件的其他材料併入該觸媒組成物中之中孔絲光沸石。此等材料包括活性與惰性材料與合成或天然沸石，以及無機材料，諸如黏土、矽石及/或金屬氧化物，諸如氧化鋁。該無機材料可為天然或呈凝膠狀沉澱物或包括矽石與金屬氧化物之凝膠的形式。
本發明之觸媒組成物，其另外包含至少一種由下列所組成之群組的黏合劑：氧化鋁、矽石、黏土、氧化鈦、氧化鋯及其二或多者之混合物。合併使用一種本身具有催化活性的材料與該中孔絲光沸石，即與該中孔絲光沸石結合或於該中孔絲光沸石合成期間存在，可改變該轉化作用及/或觸媒組成物之選擇性。不活性材料適於作為稀釋劑以控制轉化的量，因此可以經濟且有序之方式獲得轉烷基化產物，而毋需使用控制反應速率的其他手段。該等催化活性或不活性材料可併入例如天然黏土，例如膨土及高嶺土，來改善在商業操作條件下之觸媒組成物的抗壓碎強度。由於商業用途中希望避免觸媒組成物破裂成粉末狀材料，故希望提供具有良好抗壓碎強度的觸媒組成物。
可與中孔絲光沸石複合作為該觸媒組成物之黏合劑的天然黏土包括微晶高嶺土及高嶺土族，該等族包括變膨潤石，且該等高嶺土慣常稱為Dixie、McNamee、Georgia及Florida黏土，或主要礦物組分為敘永石、高嶺 石、狄克石、珍珠陶土或富矽高嶺石的其他者。此等黏土可以原始開採的原態或初步進行煅燒、酸處理或化學改質之狀態使用。
除了前述材料之外，該中孔絲光沸石可與多孔基質黏合劑材料複合，多孔基質黏合劑材料諸如無機氧化物，其係選自由下列所組成之群組：矽石、氧化鋁、氧化鋯、氧化鈦、氧化釷、氧化鋇、氧化鎂、及其組合，諸如矽石-氧化鋁、矽石-氧化鎂、矽石-氧化鋯、矽石-氧化釷、矽石-氧化鋇、矽石-氧化鈦；以及三元組成物，諸如矽石-氧化鋁-氧化釷、矽石-氧化鋁-氧化鋯、矽石-氧化鋁-氧化鎂及矽石-氧化鎂-氧化鋯。亦可能有利的是提供至少一部分呈膠態形式之前述多孔基質黏合劑材料以促進觸媒組成物擠出。
各沸石通常係與黏合劑或基質材料摻合以使最終觸媒組成物含有根據該觸媒組成物之重量計為5至90重量%，及通常為10至60重量%之量的黏合劑或基質材料。
在使用前，觸媒組成物之蒸汽處理可用以最小化該觸媒組成物的芳族氫化活性。在該蒸汽處理法中，該觸媒組成物通常在至少260℃至650℃之溫度，在100至2590kPA-a之壓力與約0.002hr-1至約20hr-1之WHSV下與5%至100%的蒸汽接觸至少一小時，尤其是1至20小時。
此外，在使該觸媒組成物與該烴床接觸之 前，該氫化組分可經硫化。此藉由使觸媒與硫來源(諸如硫化氫)在約320℃至480℃之溫度下接觸便利地達成。該硫來源可經由載體氣體(諸如氫或氮)而與該觸媒接觸。
在使該觸媒組成物與烴進料接觸之後，該觸媒會因焦化或金屬黏聚而去活化。該去活化之觸媒可藉由使用包含氧或含氧化合物(諸如臭氧、含氧氯化物(oxochlorine)、二氧化碳等)之物流燃燒焦碳、使用氧化-還原循環、氧氯化物(oxochloride)處理等進行金屬再分散、以液態烴或無機及/或有機化學化合物之水溶液(諸如水、乙醇、丙酮等)清洗、或以包含氫之物流復原而便利地再生。再生或復原可在周圍至約600℃之溫度範圍、約100kPa-a至約5000kPa-a之壓力範圍、及約0.2hr-1至約100hr-1之WHSV下進行。
原料
本發明方法中所使用之原料包含一或多種含有至少8個碳原子之芳族化合物，例如C8+芳烴。特別包含之C8+芳烴包括乙苯及二甲苯異構物。通常，此等C8+芳烴包含在大氣壓力下沸點在約135至約230℃之範圍的芳族化合物。
在一或多個實施態樣中，此種原料包含具有9或更多個碳原子之芳族化合物，例如C9+芳烴。典型進料中發現之特別C9+芳族化合物包括(1,3,5-三甲苯)、荰 (1,2,4,5-四甲苯)、半蜜臘質(1,2,3-三甲苯)、假(1,2,4-三甲苯)、乙基甲苯、乙基二甲苯、1,2-甲基乙苯、1,3-甲基乙苯、1,4-甲基乙苯、經丙基取代之苯、經丁基取代之苯、二甲基乙苯、甲基丙苯、甲基丁苯、及其二或多者之混合物。
C9+芳族物的適用來源可為來自富含芳族物之任何精煉法的任何C9+部分。該芳族物部分含有大比例之C9+芳族物，例如，至少80重量%之C9+芳族物，其中較佳係至少80重量%，更佳多於90重量%之烴在C9至C12之範圍。可使用之典型精煉部分包括催化重組油、流體化催化裂解(FCC)石油腦或由此形成之催化裂解(TCC)石油腦。
該原料亦可包含苯或甲苯或苯及甲苯之混合物。因此，在一實務實施態樣中，至轉烷基化之反應器的進料包含乙苯、C9+芳族烴及甲苯。該原料亦可包括再循環/未反應/產生之苯、甲苯、乙苯、及藉由該轉烷基化反應本身之流出物產物蒸餾而獲得的C9+芳族物。通常，甲苯構成該原料的約5重量%至約90重量%且C9+構成約10至約95重量%。在典型輕質原料中，甲苯構成至反應器之整體進料的約40重量%至約90重量%，諸如50重量%至70重量%，然而該C9+芳族物組分構成整體原料的10至60重量%，諸如30至50重量%。在典型重質進料中，甲苯構成至反應器之整體進料的約15重量%至約50重量%，諸如25重量%至40重量%，然而該C9+芳族物組分構 成整體進料的50至85重量%，諸如60至75重量%。
烴轉化法
該將包含C8+芳烴之原料轉化成較輕質芳族產物的方法包含在適當轉化條件將使該原料和隨意的氫在本發明之觸媒組成物任一者存在下接觸以產生該包含苯、甲苯及二甲苯的較輕質芳族產物。
該方法可於任何適當反應器中進行，該反應器包括徑向流、固定床、連續流或流體床。在一替代方案中，用於在適當轉化條件下接觸原料之反應器包含至少一個該觸媒的單一固定觸媒床。在另一替代方案中，用於在適當轉化條件下接觸原料之反應器包含至少一個該觸媒的單一移動觸媒床。
該轉化條件通常包括約340℃至約515℃之溫度，諸如約400℃至約454℃；約380kPa-a至約4240kPa-a之壓力，諸如約1480kPa-a至約3550kPa-a；約1至約5之氫烴莫耳比，諸如約1至約3，及約0.2hr-1至約100hr-1之WHSV，諸如1hr-1至約100hr-1。該等轉化條件足以將重質芳族進料轉化成含有大量C6-C8芳族化合物(諸如苯、甲苯及二甲苯，尤其是苯及二甲苯)之產物。該等轉化條件亦足以將進料中之乙苯轉化成苯及乙烷。
實施例
以下實施例說明本發明。可能有眾多修改及變化，且應暸解在後附主張權項之範圍內，可以本文特別描述以外之方式實施本發明。
實驗 平均一次粒徑及一次粒徑分布之測量
該平均一次粒徑及一次粒徑分布之測量係如下進行。拍攝數張沸石樣本的TEM照片；鑑別及測量一次粒子。就縱橫比大於1之各一次粒子而言，最長大小係藉由在該粒子邊緣分隔得最遠的兩點畫一條線來鑑別。然後一次粒子與該最長大小沿45°對角且通過該最長大小之中點的長度係測量為粒徑。各測量係藉由指派為涵蓋該樣本中所發現之粒徑範圍的約10個粒徑範圍其中之一來分組。測量超過300個一次粒子然後繪製各粒徑範圍中之數目來顯示粒徑分布，例如圖10所示。例如，可使用中間值約187.5、250、312.5、375、437.5、500、562.5及625埃之粒徑範圍。在y軸上之晶體值百分比(%)係從以下計算：各群組中之粒子數/所測量之粒子數乘以100。平均粒徑係計算為根據分組結果的算術平均。
藉由BET測量總表面積及中孔表面積
總BET及t-曲線微孔表面積係使用Micromeritics Tristar II 3020儀器在經煅燒之沸石粉末於350℃除氣4小時之後藉由氮吸附/去吸附測量。中孔表面 積係藉由從總BET表面積扣除t-曲線微孔所獲得。中孔體積係從相同資料組導出。更多關於該方法之資訊可見例如"Characterization of Porous Solids and Powders：Surface Area,Pore Size and Density"，S.Lowell等人，Springer，2004。
X射線繞射圖案
X射線繞射資料(粉末XRD或XRD)係以具有VÅNTEC多通道偵測器之Bruker D4 Endeavor繞射系統使用銅K-α輻射收集。該繞射資料係藉由0.018度2θ之掃描模式(其中θ為Bragg角)，且每一步使用約30秒之有效計數時間記錄。
測量a、b及c向量中之晶體大小
a、b及c晶體向量中之晶體大小係根據X射線繞射圖案中之三個(200)、(020)及(002)峰使用Scherrer等式計算(P.Scherrer、N.G.W.Gottingen,Math-Pys.,2，第96-100頁(1918))。該方法及其於沸石之應用亦描述於A.W.Burton、K.Ong、T.Rea、I.Y.Chan，Microporous and Mesoporous Materials，117，第75-90頁(2009)。就本文所述之測量，使用Materials Data,Inc.之Jade第9.5.1版X射線繞射分析軟體進行該計算。
α值
該α值係觸媒之裂解活性的度量，且係描述於美國專利第3,354,078號及Journal of Catalysis，第4卷，第527頁(1965)；第6卷，第278頁(1966)，及第61卷，第395頁(1980)，各文獻資料係以引用方式併入本文中。此處所使用之試驗的實驗條件包括538℃之恆溫以及Journal of Catalysis第61卷，第395頁(1980)中詳細描述之可變流率。
實施例1-TEA-絲光沸石晶體(對照例)
TEA-絲光沸石晶體係從由水、47%之硫酸鋁溶液、50%之TEABr溶液、UltrasilTM PM經改質之矽石(可得自Evonik Ind.AG)、及50%之氫氧化鈉溶液所製備的混合物合成。該混合物具有以下莫耳組成：SiO2/Al2O3~40
H2O/SiO2~9.33
OH-/SiO2~0.22
Na+/SiO2~0.37
TEA/SiO2~0.31
該混合物係在熱壓器中於300℉(150℃)下反應48小時。該產物係經過濾，以去離子(DI)水清洗，且於250℉(121℃)乾燥。該原合成材料之X射線繞射(XRD)圖案顯示絲光沸石拓樸之典型純相。圖1之原合成材料的掃描式電子顯微鏡影像(SEM)顯示該材料 係由大型微米級(0.2μm至1.0μm)晶體所構成。
該原合成絲光沸石晶體係藉由在室溫下與硝酸銨溶液三次離子交換而轉化成氫形式，然後在250℉(121℃)乾燥，且在1000℉(538℃)煅燒6小時。所得之H-形式絲光沸石晶體的總表面積(SA)(即，微孔SA+中孔SA)為625/(616+9)m2/g，且中孔體積為0.0574cc/g。該SiO2/Al2O3莫耳比為33.4，且α值為610。
實施例2-中孔絲光沸石晶體(NaOH/Si為0.29莫耳)
中孔絲光沸石晶體係從由10,300g之水、670g之TEABr(50%溶液)、2,120g之UltrasilTM PM經改質矽石、487g之鋁酸鈉溶液(45%)、及510g之50%氫氧化鈉溶液所製備之混合物合成。在製備該混合物之後，然後將20g之絲光沸石種晶添加至該混合物。該混合物具有以下莫耳組成：SiO2/Al2O3~26.08
H2O/SiO2~19.48
OH-/SiO2~0.29
Na+/SiO2~0.29
TEA/SiO2~0.05
該混合物在5加崙熱壓器中，在以250RPM攪拌下於300℉(150℃)反應72小時。該產物係經過濾，以去離子(DI)水清洗，且於250℉(121℃)乾 燥。該原合成材料之XRD圖案顯示絲光沸石拓樸之典型純相。圖2之原合成材料的SEM顯示由0.05μm之小型微晶體所構成的不規則形聚集體之形態。從5加崙反應產生更均勻晶體大小及形態。原合成晶體係藉由在室溫下與硝酸銨溶液三次離子交換而轉化成氫形式，然後在250℉(121℃)乾燥，且在1000℉(538℃)煅燒6小時。所得之中孔絲光沸石晶體的SiO2/Al2O3莫耳比為~21，總(微孔+中孔)表面積為624(579+44)m2/g且中孔體積為0.243cc/g。己烷吸附為61.8mg/g，且α值為780。根據該實施例之結果，歸納出具有高中孔體積及表面積之小型中孔絲光沸石晶體可從NaOH/Si為<0.30莫耳之反應混合物合成。
實施例3-中孔絲光沸石晶體(NaOH/Si為0.29莫耳)
中孔絲光沸石晶體係從由9,300g之水、804g之溴化四乙銨(TEABr)(50%溶液)、2,544g之UltrasilTM PM經改質矽石、584g之鋁酸鈉溶液(45%)、及612g之50%氫氧化鈉溶液所製備之混合物合成。然後，將30g之絲光沸石種晶添加至該混合物。該混合物具有以下莫耳組成：SiO2/Al2O3~26.1
H2O/SiO2~15.11
OH-/SiO2~0.29
Na+/SiO2~0.29
TEA/SiO2~0.05
該混合物在5加崙熱壓器中，在以250RPM攪拌下於290℉(143.3℃)反應72小時。該產物係經過濾，以去離子(DI)水清洗，且於250℉(121℃)乾燥。該原合成材料之XRD圖案顯示絲光沸石拓樸之典型純相。圖3之原合成材料的SEM顯示由0.05μm之小型微晶體所構成的不規則形黏聚物之形態。從此經改良合成製造比先前技術較低孔隙度之絲光沸石晶體更小且更均勻之晶體。所得之原合成中孔絲光沸石晶體顯示SiO2/Al2O3莫耳比為約20.7。
該原合成中孔絲光沸石晶體係藉由在室溫下與硝酸銨溶液三次離子交換而轉化成氫形式，然後在250℉(121℃)乾燥，且在1000℉(538℃)煅燒6小時。所得之H-形式、中孔絲光沸石晶體的總(微孔+中孔)表面積為637(580+56)m2/g且中孔體積為0.43cc/g。己烷吸附為53.3mg/g，且α值為1,200。
實施例4-65/35 TEA-絲光沸石/氧化鋁觸媒(對照例)
觸媒係在混練機中從65份(基準：538℃煅燒)來自實施例1之TEA-絲光沸石晶體及35份假軟水鋁石氧化鋁VersalTM 300(可得自UOP LLC；基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機上可擠出之糊劑。TEA-絲光沸石、假軟水鋁石氧化鋁、及水之混合物係擠製成擠出物，然後在121℃乾燥。該經乾燥 擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在116℃乾燥，且在空氣中於534℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α值=640；己烷吸附：62mg/g；BET表面積，總(微孔+中孔)為468/(296+172)m2/g。
實施例5-65/35中孔絲光沸石/氧化鋁觸媒
觸媒係在混練機中從65份(基準：538℃煅燒)來自實施例2之小型中孔絲光沸石晶體及35份假軟水鋁石氧化鋁VersalTM 300(基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機上可擠出之糊劑。中孔絲光沸石、假軟水鋁石氧化鋁、及水之混合物係擠製成擠出物，然後在121℃乾燥。測量所得擠出物之抗壓碎強度且顯示為108lbs/in(19kg/cm)。該經乾燥擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α值=500；己烷吸附：53.8mg/g；BET表面積，總(微孔+中孔)為479/ (312+168)m2/g；且中孔體積=0.427cc/g。
實施例6-65/35中孔絲光沸石/矽石觸媒
觸媒係在混練機中從65份(基準：538℃煅燒)來自實施例2之小型中孔絲光沸石晶體及35份UltrasilTM矽石/膠態矽石(基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機上可擠出之糊劑。中孔絲光沸石、矽石、及水之混合物係擠製成擠出物，然後在121℃乾燥。測量所得擠出物之抗壓碎強度且顯示為73lbs/in(13kg/cm)。該經乾燥擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α值=730；己烷吸附：41.5mg/g；BET表面積，總(微孔+中孔)為446(344+102)m2/g；且中孔體積=0.37cc/g。
實施例7-實施例4至6之性能評估
在C9+芳烴之轉化方法中使用高產出固定床微單元使用甲苯及模型化合物進料以1：1莫耳比同時評估實施例4中所製備之對照TFA-絲光沸石觸媒以及實施例5及6中所製備之中孔絲光沸石。將半(0.5)g經制定大 小以使長度等於擠出物直徑之觸媒裝載至反應器中。將該反應器加壓至300psig且以流動之氮(N2)在250℃下乾燥3小時。在關閉氮(N2)之後，以6WHSV且1：1莫耳比之H2/烴將進料及氫引入該反應器。該反應器溫度係上升至340℃且保持在340℃為時1小時，且藉由線上GC分析總產物。就該實驗其餘部分而言，反應器溫度係以每步提高10℃直到達到450℃，然後進行各步之GC分析。
該性能資料係顯示於圖4A、4B及4C。實施例4中所製備之對照觸媒展現轉化率及二甲苯產率隨著溫度提高而下降；然而實施例5及6之中孔絲光沸石觸媒展現更安定之性能。該中孔絲光沸石/矽石觸媒在受測溫度範圍提供最高轉化率及二甲苯產率。
實施例8-65/35中孔絲光沸石/氧化鋁觸媒
觸媒係在混練機中從65份(基準：538℃煅燒)來自實施例3之小型中孔絲光沸石晶體及35份假軟水鋁石氧化鋁VersalTM 300(可得自UOP LLC；基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機上可擠出之糊劑。中孔絲光沸石、假軟水鋁石氧化鋁、及水之混合物係擠製成擠出物，然後在121℃乾燥。測量所得擠出物之抗壓碎強度且顯示為136lbs/in(24kg/cm)。該經乾燥擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換 之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α值=530；己烷吸附：43.9mg/g；BET表面積，總(微孔+中孔)為504(336+168)m2/g；且中孔體積=0.52cc/g。
實施例9-65/35中孔絲光沸石/矽石觸媒
觸媒係在混練機中從65份(基準：538℃煅燒)來自實施例3之小型中孔絲光沸石晶體及35份UltrasilTM矽石/膠態矽石(基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機上可擠出之糊劑。中孔絲光沸石、矽石、及水之混合物係擠製成擠出物，然後在121℃乾燥。測量所得擠出物之抗壓碎強度且顯示為84lbs/in(15kg/cm)。該經乾燥擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α值=800；己烷吸附：46.8mg/g；BET表面積，總(微孔+中孔)為462(360+102)m2/g；中孔體積=0.53cc/g。
實施例10-實施例6、8及9之性能評估
使用高產出固定床微單元使用與實施例7中所述相同進料及相似製程，但所使用之反應溫度為330至400℃，同時評估實施例4中所製備之對照觸媒及實施例8及9中所製備之中孔絲光沸石觸媒。
該性能資料係顯示於圖5A、5B、及5C。實施例4中所製備之對照觸媒隨著溫度升高展現比實施例8及9之中孔絲光沸石觸媒低的轉化率及二甲苯產率。實施例9之中孔絲光沸石/矽石觸媒在受測溫度範圍提供最高轉化率及二甲苯產率。
實施例11-65/35 ZSM-12氧化鋁觸媒(對照例)
觸媒係在混練機中從65份(基準：538℃煅燒)之高活性ZSM-12晶體(根據美國專利第8,202,506號製成，且稱為「UHA-ZSM-12」)及35份假軟水鋁石氧化鋁VersalTM 300(基準：538℃煅燒)之混合物製成。添加充足的水以製造在擠出機中可擠出之糊劑。該高活性ZSM-12(UHA-ZSM-12)、氧化鋁、及水之混合物係擠出成1/20"四葉形(quadrulobe)然後在121℃下乾燥。該經乾燥擠出物係在氮(N2)中於482℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃ 下煅燒。在空氣煅燒之後，所得之觸媒的性質為α=290。
實施例12-65/35 ZSM-12矽石觸媒(對照例)
觸媒係在混練機中從65份(基準：538℃煅燒)之高活性ZSM-12晶體(根據美國專利第8,202,506號製成，且稱為「UHA-ZSM-12」)及35份Ultrasil矽石/膠態矽石(基準：538℃煅燒)之混合物製成。添加充足的水，然後添加5%氫氧化鈉溶液(目標0.5重量%之NaOH，根據538℃固體基準)以製造在擠出機上可擠出之糊劑。將該高活性ZSM-12、矽石、NaOH、及水之混合物擠出成擠出物，然後在121℃下乾燥。該經乾燥之擠出物係與IN硝酸銨交換以助移除鈉，且在121℃下乾燥。該經乾燥擠出物係在氮(N2)中於538℃下煅燒以分解且移除有機模板。該經N2煅燒之擠出物係以飽和空氣加濕且再次與1N硝酸銨交換以移除鈉。在硝酸銨交換之後，在乾燥之前以去離子水清洗該擠出物以移除殘留的硝酸根離子。該經銨交換之擠出物係在121℃乾燥，且在空氣中於538℃下煅燒。在空氣煅燒之後，所得觸媒之性質為：α=710；己烷吸附：38.6mg/g；BET表面積，總(微孔+中孔)為324/(212+112)m2/g；中孔體積=0.51cc/g。
實施例13-實施例8、9、11、12之性能評估
使用高產出固定床微單元使用與實施例10中 所述相同進料及相似製程同時評估實施例8、9、11、12中所製備之觸媒。
該性能資料係顯示於圖6A、6B、及6C。實施例8及9中所製備之中孔絲光沸石觸媒顯示比實施例11及12但在400℃下之高活性ZSM-12(UHA-ZSM-12)觸媒更高之轉化率及更高之二甲苯產率。兩種類型之觸媒之間的差異在較低溫時更明顯。
實施例14-在65/35 TEA-絲光沸石/氧化鋁上之Pt/Sn觸媒(對照例)
實施例4之擠出物係經由初濕含浸以呈硝酸四銨鉑之0.1重量%的Pt及呈氯化錫(II)鹽之0.24重量%的Sn共浸漬。該觸媒係在空氣中於680℉(360℃)下煅燒3小時。在金屬併入前之擠出物的特性：α=640；己烷吸附：62mg/g。
實施例15-在經蒸汽處理之65/35 ZSM-12/氧化鋁上的Pt/Sn觸媒(對照例)
呈硝酸四銨鉑之0.1重量%的Pt及呈氯化錫(II)鹽之0.24重量%的Sn係經由初濕含浸共浸漬至65/35重量之ZSM-12/氧化鋁的經蒸汽處理擠出物上，其中該ZSM-12係根據美國專利3,832,449號製造且Si/Al2莫耳比為200/1。該擠出物係在金屬添加之前於900℉(482℃)蒸汽處理5小時。該觸媒係在空氣中於680℉ (360℃)下煅燒3小時。在金屬併入前之擠出物的特性：α=100；己烷吸附：37mg/g。
實施例16-在經蒸汽處理之65/35中孔絲光沸石/矽石上的Pt/Sn
來自實施例6之擠出物係在大氣壓力下於800℉(427℃)下充滿蒸汽進行蒸汽處理4小時。該經蒸汽處理之觸媒係經由初濕含浸以呈硝酸四銨鉑之0.1重量%的Pt及呈氯化錫(II)之0.24重量%的Sn共浸漬。該觸媒係在空氣中於680℉(360℃)下煅燒3小時。在金屬併入前之擠出物的特性：α=210；己烷吸附：20mg/g。
實施例17-在65/35中孔絲光沸石/氧化鋁上之Pt/Sn觸媒
實施例8之擠出物係經由初濕含浸以呈硝酸四銨鉑之0.1重量%的Pt及呈氯化錫(II)之0.24重量%的Sn共浸漬。該觸媒係在空氣中於680℉(360℃)下煅燒3小時。在金屬併入前之擠出物的特性：α=530；己烷吸附：43.9mg/g。
實施例18-在65/35中孔絲光沸石/氧化鋁上之Pt/Sn觸媒
實施例9之擠出物係經由初濕含浸以呈硝酸四銨鉑之0.1重量%的Pt及呈氯化錫(II)之0.24重量%的Sn共浸漬。該觸媒係在空氣中於680℉(360℃)下煅燒3小時。在金屬併入前之擠出物的特性：α=800；己烷 吸附：46.8mg/g。
實施例19-實施例14、15、16、18之性能評估
實施例14、15、16、17及18係在單一固定床試驗設備中使用85重量%之C9+作為A100流體及15重量%之甲苯的摻合物予以評估。該進料摻合物係鑑別為「進料摻合物#1」或「進料摻合物#2」。參考觸媒系統的性能視所使用之進料摻合物而偏移。
因此，只能比較在相同進料摻合物上運作的觸媒。二者摻合物之進料資料係提供於下表2。
將3.4克之量的觸媒裝載至該反應器中。該觸媒係在氫中加熱且於752℉(400℃)活化1小時。然後將該溫度提高至806℉(430℃)且引入液態進料12小時之去邊(de-edging)期間。在該去邊期間之後，修改條件以評估觸媒性能。去邊之條件及隨後的反應條件係： 去邊條件：WHSV=4.4hr-1，H2/HC=1，溫度=806℉(430℃)為時12小時，且壓力=350psig(2413kPa)。溫度掃描條件：WHSV=4.4hr-1，H2/HC=2，溫度=734℉(390℃)，且壓力=350psig(2413kPa)。
該產物係藉由線上GC分析。性能比較可見下表3。
使用表3中之進料摻合物#1比較實施例14、17及18之性能展現中孔絲光沸石之性能優於更傳統版之絲光沸石、TEA-絲光沸石的性能之益處。中孔絲光沸石(較高活性絲光沸石)之轉烷基化及脫烷基化活性二者均較高。因此，中孔絲光沸石觸媒之二甲苯產率明顯高於以TEA-絲光沸石為主之觸媒。
使用表3中之進料摻合物#2比較實施例15及16的性能展現中孔絲光沸石優於ZSM-12之益處。由較高二甲苯產率證明，該中孔絲光沸石顯示明顯較高之脫乙基化活性。
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Claims (25)

  1. 一種用於將C8+芳烴轉化成較輕質芳族產物之觸媒組成物，該觸媒組成物包含(i)從四乙銨陽離子(TEA)或甲基三乙銨陽離子(MTEA)合成之絲光沸石，其中該絲光沸石之中孔表面積大於30m2/g且該絲光沸石包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。
  2. 如申請專利範圍第1項之觸媒組成物，該觸媒組成物另外包含根據該觸媒組成物之重量計為0.005至5.0重量%的至少一種第10族之第一金屬。
  3. 如申請專利範圍第1項之觸媒組成物，其中該觸媒組成物具有根據該觸媒組成物之重量計為0.01至5.0重量%的該至少一種第11至15族之第二金屬。
  4. 如申請專利範圍第1項之觸媒組成物，其中該至少一種第10族之第一金屬係選自由下列所組成之群組：鎳、鉑、鈀及其混合物。
  5. 如申請專利範圍第4項之觸媒組成物，其中該第一金屬為鉑。
  6. 如申請專利範圍第3項之觸媒組成物，其中該至少一種第11至15族之第二金屬係選自由下列所組成之群組：銅、鋅、銀、鎵、銦、錫、鉍及其二或多者的混合物。
  7. 如申請專利範圍第6項之觸媒組成物，其中該第二金屬為錫。
  8. 如申請專利範圍第3項之觸媒組成物，其中該第一金屬為鉑而該第二金屬為錫。
  9. 如申請專利範圍第1項之觸媒組成物，其中以X射線繞射測量，該小於80nm之平均原生晶體大小係各在a、b及c晶體向量中。
  10. 如申請專利範圍第1項之觸媒組成物，其中以TEM測量，至少90數量%之該原生微晶體的原生晶體大小小於80nm。
  11. 如申請專利範圍第1項之觸媒組成物，其中該絲光沸石之總表面積大於500m2/g。
  12. 如申請專利範圍第3項之觸媒組成物，其另外包含至少一種由下列所組成之群組的黏合劑：氧化鋁、矽石、黏土、氧化鈦、氧化鋯及其二或多者之混合物。
  13. 一種觸媒組成物，其包含(i)從TEA或MTEA合成之絲光沸石，(ii)根據該觸媒組成物之重量計為0.005至5.0重量%之至少一種IUPAC元素周期表之第10族的第一金屬，及(iii)根據該觸媒組成物之重量計為0.01至5.0重量%之至少一種IUPAC元素周期表之第11至15族的第二金屬，該絲光沸石之中孔表面積大於30m2/g且該絲光沸石包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。
  14. 一種用於將包含C8+芳烴之原料轉化成較輕質芳族產物的方法，該方法包括在適當轉化條件下使該原料與 隨意的氫在觸媒之存在下接觸以產生該較輕質芳族產物的步驟，該觸媒組成物包含(i)從TEA或MTEA合成之絲光沸石，該絲光沸石之中孔表面積大於30m2/g且該絲光沸石包含由原生微晶體所構成的黏聚物，其中該原生微晶體之平均原生晶體大小以TEM測量為小於80nm且縱橫比小於2。
  15. 如申請專利範圍第14項之方法，該觸媒另外包含(ii)根據該觸媒組成物之重量計為0.005至5.0重量%之至少一種IUPAC元素周期表之第10族的第一金屬。
  16. 如申請專利範圍第15項之方法，該觸媒另外包含(iii)根據該觸媒組成物之重量計為0.01至5.0重量%之至少一種IUPAC元素周期表之第11至15族的第二金屬。
  17. 如申請專利範圍第14項之方法，其中該C8+芳烴包含具有九或更多個碳原子之芳族化合物。
  18. 如申請專利範圍第14項之方法，其中該原料另外包含苯。
  19. 如申請專利範圍第14項之方法，其中該原料另外包含甲苯。
  20. 如申請專利範圍第14項之方法，其中該原料另外包含苯與甲苯之混合物。
  21. 如申請專利範圍第14項之方法，其中該C8+芳烴包含在大氣壓力下沸點在135℃至260℃之範圍的芳族化合物。
  22. 如申請專利範圍第14項之方法，其中該較輕質芳族產物包含二甲苯、苯、甲苯及其二或多者的混合物。
  23. 如申請專利範圍第14項之方法，其中該適用之轉化條件至少包括340℃至515℃之溫度、380kPa(55psia)至4240kPa(615psia)之壓力及根據該原料之重量計在1至100hr-1之範圍的每小時之重量空間速度(WHSV)。
  24. 如申請專利範圍第14項之方法，其另外包括用於在該適當轉化條件下接觸該原料之反應器，該反應器包含至少一個該觸媒組成物的單一固定觸媒床。
  25. 如申請專利範圍第14項之方法，其另外包括用於在該適當轉化條件下接觸該原料之反應器，該反應器包含至少一個該觸媒組成物的流體床。
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