TW201609260A - 異構化催化劑 - Google Patents

異構化催化劑 Download PDF

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TW201609260A
TW201609260A TW104121815A TW104121815A TW201609260A TW 201609260 A TW201609260 A TW 201609260A TW 104121815 A TW104121815 A TW 104121815A TW 104121815 A TW104121815 A TW 104121815A TW 201609260 A TW201609260 A TW 201609260A
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zeolite
isomerization catalyst
catalyst according
alumina
beta
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迪 曾 莫尼克 凡
芬森特 羅傑斯
鴻昕 黎
威廉 愛德華 可米爾
伯傑爾 莫登
巴爾特 裴爾格倫
威伯Ｓ 克傑爾斯塔
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蜆殼國際研究公司
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Abstract

本發明描述烷烴異構化催化劑，其在含氧化鋁及二氧化矽與氧化鋁莫耳比(SAR)為5至15之β沸石的載體上包含0.01wt.%至5wt.%第VIII族貴金屬；及使用該催化劑使含具有4至8個碳原子之烷烴之烴饋料異構化的方法。

Description

異構化催化劑
本發明係關於一種烷烴異構化催化劑及一種使烴饋料異構化之方法。
辛烷值為汽油或石油點火性之指示。分支鏈烷烴往往具有比直鏈化合物更高之辛烷值，且從而增加相同沸點範圍之原料之品質。分支可以各種方式獲得，諸如催化重組、異構化及烷基化。異構化涉及在沸點極少改變之情況下將直鏈再配置至其分支鏈異構體。異構化產生至少90wt.%，更具體言之至少95wt.%，最具體言之至少98wt.%在饋料之沸點範圍內沸騰之產物。
Antonio de Lucas e.a.在Ind.Eng.Chem.Res.,2006,45,8852-8859中之文章「Liquid phase hydroisomerization of n-octane over platinum-containing zeolite-based catalysts with and without binder」描述含β沸石催化劑用於正辛烷之液相加氫異構化之用途，該β沸石之矽與鋁比率為13.0，等於26.0之二氧化矽與氧化鋁莫耳比(SAR)。
Trees de Baerdemaeker e.a.在Journal of Catalysis,308(2013),73-81中之文章「Catalytic applications of OSDA-free Beta zeolite」描述在由無模板β沸石組成之催化劑樣本存在下的異構化，催化劑樣本藉由離子交 換，之後用Pt(NH3)4Cl2水溶液處理以NH4+-形式引入。壓縮含鉑β沸石樣本，使其斷裂且篩分以獲得待測試之催化劑粒。由於所研究溫度窗口中正癸烷之高轉化率，在習知異構化條件下預期Si/Al比為4.5及12.4(SAR分別為9及24.8)之含β沸石之催化劑粒的高裂解產率。如應用於Si/Al比為25.2、36及55(SAR分別為50.4、72及110)之催化劑樣本中之蒸汽脫鋁作用之後的酸處理導致酸位點數目減少及較高異構化產率。
現已出人意料地發現，基於β沸石之催化劑在異構化中之效能可藉由使用特定種類之載體，即含氧化鋁及SAR為5至15之β沸石的載體(該β沸石較佳已藉由不使用有機結構導向劑之特定方法製備)改良。出人意料地發現，使用該催化劑載體增加含至少5個碳原子之化合物的產率及/或所獲得產物之研究法辛烷值。不希望受任何理論束縛，認為氧化鋁黏合劑之存在允許相對較高量之鉑沈積於氧化鋁而非沸石上，改良酸位點與金屬位點之間的距離。本發明之催化劑可使用尚未脫鋁之β沸石。
因此，本發明現關於一種在含氧化鋁及具有二氧化矽與氧化鋁莫耳比(SAR)為5至15之β沸石的載體上包含0.01wt.%至5wt.%第VIII族貴金屬之烷烴異構化催化劑。
此外，本發明係關於一種使含具有4至8個碳原子之烷烴之烴饋料異構化的方法，其藉由使該饋料與根據本發明之催化劑在150℃至300℃溫度及0.1絕對巴至30絕對巴壓力下接觸來進行。
異構化催化劑一般使用含4至8(包括值4及8)個碳原子之飽和烴，更具體言之含5或6個碳原子之飽和烴。烴較佳為正烷烴。適合饋料烴之實例包括(但不限於)正丁烷、正戊烷、正己烷、正庚烷、正辛烷、環己烷、甲基環戊烷、環庚烷及甲基環庚烷，一般在氫存在下。
一般而言，烴饋料由40wt.%至100wt.%之具有4至8個碳原子之烷烴，更佳含5或6個碳原子之烷烴組成。較佳地，饋料含有至少50wt.%，更具體言之至少60wt.%，更具體言之至少70wt.%且最具體言之至少80wt.%之此類烷烴。
一般而言，氫與烴饋料混合以形成饋料混合物，其與異構化區域中含有的本發明之異構化催化劑接觸。在此接觸步驟期間，饋料混合物中氫之濃度可廣泛改變。較佳地，氫與烴莫耳比為至少0.01至1，一般在0.01至1與5至1之間，更佳在0.5至1與5至1之間且最佳在0.02至1與2至1之間(mol/mol)。
一般而言，在至少150℃，一般至少200℃，更具體言之至少220℃之反應溫度下使飽和饋料烴及氫與一般存在於固定床中之催化劑接觸。已發現，本發明之催化劑尤其適合於在至多300℃，更具體言之至多290℃，更具體言之至多280℃，更具體言之至多270℃，最具體言之至多260℃之溫度下使用。一般而言，飽和烴饋料流之重量每小時空間速度(亦即，每小時每公克催化劑之液體饋料烴公克數)為0.1至15。異構化區域中反應壓力一般在1絕對巴至25絕對巴，更具體言之5絕對巴至20絕對巴之範圍內。氫饋料流之氣體每小時空間速度為一般每小時每1催化劑10至 2,000 l氫，以便給出上文敍述之氫：烴比。
本發明之異構化催化劑包含二氧化矽與氧化鋁莫耳比(SAR)範圍為5及15，較佳5至12，更具體言之5至11之特定β沸石。
本發明之催化劑無需含有氯化物，更尤其無需含有任何鹵素。因此，本發明之催化劑較佳不含氯化物，更尤其不含鹵素。
用於本發明之催化劑之β沸石較佳不含有機結構導向劑。後者意謂在合成期間已不直接使用有機結構導向劑(SDA)而製造β沸石。然而，應瞭解，當使用接種材料(諸如純β沸石)時，可在具有或不具有SDA下製造接種材料。因此，此術語係指以下事實：所得β產物在任何處理步驟期間從未與有機結構導向劑(SDA)直接接觸，但晶種材料可使用SDA製造，提供至多與孔結構之殘餘或二次接觸。典型地用於製備β沸石之SDA(諸如氫氧化四乙銨及氫氧化二苯甲基-二甲基銨)不僅為昂貴的，而且其不可避免地密封於沸石骨架中，使得需要將其移除之移除步驟，例如熱處理。藉由避免使用有機模板，所得β沸石在結晶材料中不具有非所需有機材料。因此，一或多種合成後處理，諸如自結晶材料移除SDA之煅燒為不必要的。另外，當有機SDA用於製備β沸石時，典型地獲得高二氧化矽產品。舉例而言，藉助於SDA製備之合成β沸石之典型SAR高於20，通常高於40。
本發明較佳包含β沸石，其已藉由包含以下之方法製備：(a)混合及攪拌鹼金屬氧化物源、氧化鋁源、二氧化矽源及水以合成初始鋁矽酸鹽凝膠，其具有以下原料莫耳比：SiO2/Al2O3=15-45，Na2O/SiO2=0.20-0.50，H2O/SiO2=4-50， (b)添加沸石晶體晶種且允許混合物在高溫下結晶以獲得二氧化矽與氧化鋁莫耳比(SAR)為5至15之β沸石晶體。較佳地，允許混合物在100℃至180℃之溫度下在12小時至24小時期間結晶。較佳使用之β沸石已詳細描述於US-A-2011/0286914中。
β沸石定義且描述於「Atlas of Zeolite Framework Types,」Baerlocher等人編，第六修訂版本(Elsevier 2007)中。
在一較佳具體實例中，β沸石之體積平均晶體尺寸如藉由掃描電子顯微法測定為10奈米至1000奈米，更尤其50奈米至500奈米。其表面積如根據ASTM測試D3663-03藉由B.E.T.方法量測較佳為400m2/g至800m2/g，更具體言之550m2/g至750m2/g。微孔體積如藉由ASTM測試D4365-95測定較佳為0.10cc/g至0.40cc/g，更具體言之0.15cc/g至0.30cc/g。
用於本發明之催化劑載體較佳包含50%至98%用於本發明之β沸石。更佳地，載體包含至少60wt.%，更具體言之至少70wt.%該β沸石。載體較佳包含至多95wt.%，更佳至多90wt.%該β沸石。
催化劑載體可含有其他沸石，但較佳由β沸石及氧化鋁黏合劑組成。
氧化鋁黏合劑一般以載體計以2wt.%至50wt.%，更具體言之2wt.%至40wt.%，更具體言之5wt.%至30wt.%，更具體言之10wt.%至30wt.%，最具體言之10wt.%至25wt.%之量存在。黏合劑為氧化鋁視情況與其他化合物，諸如二氧化矽、氧化鋁、二氧化鈦、氧化鋯、二氧化鈰及/或氧化鎵(gallia)之組合。較佳地，無機黏合劑由氧化鋁與至多50wt.%，更具體言之至多20wt.%，更具體言之至多10wt.%，最具體言之至多5wt.% 之其他化合物組成。較佳地，無機黏合劑由氧化鋁組成。
在本發明中，待用作無機黏合劑之氧化鋁可來源於任何來源。較佳地，黏合劑為水鋁礦，諸如購自Sasol之Catapal或Pural系列。
本發明進一步關於一種製備根據本發明之異構化催化劑的方法，該方法包含(a)混合氧化鋁與SAR為5至15之β沸石，擠壓所獲得之混合物且視情況乾燥及煅燒所獲得之擠出物，及(b)用含鉑溶液浸漬步驟(b)中獲得之擠出物，之後乾燥且視情況煅燒該等浸漬擠出物。
方法步驟(b)之浸漬溶液較佳為包含一或多種氯化鉑鹽，更具體言之根據通式XnPtClm之鹽的水溶液，其中X為陽離子，n為1至6之整數，較佳為2至4，最佳為2，且m為4至8之整數，最佳為6。X較佳選自由銨及氫組成之群。最佳地，浸漬溶液包含六氯鉑酸。
典型地，β沸石及黏合劑呈粉末形式且與水混合，且必要或必需時可添加其他化學助劑(諸如膠溶劑、絮凝劑、黏合劑)或其他化合物以形成可形成為聚結物或成形粒子之混合物或糊狀物。可能需要擠壓混合物以形成標稱尺寸為諸如1/16吋、1/8吋及3/16吋之各種形狀(諸如圓柱及三葉狀)中之任一者或多者的擠出物。
聚結物或成形粒子可在標準乾燥條件下經乾燥，該標準乾燥條件可包括在50℃至200℃，較佳75℃至175℃且更佳90℃至150℃範圍內之乾燥溫度。乾燥之後，成形載體粒子一般在標準煅燒條件下經煅燒，該標準煅燒條件包括在250℃至900℃，較佳300℃至800℃且最佳350℃至600℃範圍內之煅燒溫度。
本發明之催化劑包含第VIII族貴金屬。貴金屬較佳為鉑及/ 或鈀，更佳為鉑。第VIII族貴金屬之量較佳為0.1wt.%至3wt.%。
貴金屬較佳藉由浸漬，更具體言之藉由孔隙體積浸漬併入載體中。就此而言，載體較佳浸漬有類似於載體之孔隙體積之含貴金屬溶液，以獲得浸漬催化劑組成物。較佳地，使用含鉑溶液。適合地，含鉑溶液之pH值在0至5範圍內，更佳在0至4範圍內，更佳在0至3範圍內，更佳在0至2範圍內，含有含鉑化合物，諸如六氯鉑酸。適合地，浸漬在5℃至60℃範圍內之溫度下，較佳在15℃至30℃範圍內之溫度下進行。適合地，浸漬進行30分鐘至2小時，較佳45分鐘至1.5小時之時間段，但亦可使用較長時間段。
較佳地，浸漬催化劑組成物隨後經煅燒。煅燒可在進行製造之位置進行，或者浸漬催化劑組成物轉移至將使用其之位置。適合地，浸漬載體之煅燒在300℃至650℃範圍內，較佳在450℃至550℃範圍內之溫度下進行。煅燒進行之時間段將不為重要的。適合地，其可進行30分鐘至3小時，較佳45分鐘至1.5小時之時間段，但亦可使用較長時間段。
催化劑一般在使用之前經還原。此藉由在高溫及壓力(諸如在150℃至700℃範圍內之溫度及在2絕對巴至40絕對巴範圍內之壓力)下使煅燒催化劑與氫接觸來達成。
呈現以下實施例以進一步說明本發明且不應解釋為過度限制本發明之範疇。
實施例1-合成含β沸石之催化劑
將水、NaOH(50%)及鋁酸鈉(23.5% Al2O3、19.6% Na2O)混合在一起。將矽膠(購自PQ公司)添加至溶液中且劇烈混合1小時。最 後，將量為相對於漿料之二氧化矽含量的10wt.%之市售可得β沸石(購自Zeolyst International)添加至混合物中且攪拌24小時。該凝膠具有以下莫耳組成：20.0 SiO2：1.0 Al2O3：6.0 Na2O：400 H2O
將凝膠載入2公升帕爾高壓釜(Parr autoclave)中且加熱至125℃，且在以175rpm攪拌的同時維持在該溫度下48小時。冷卻之後，藉由過濾及沖洗回收產物。為移除殘餘鈉，在3.6M NH4NO3溶液中將固體製成漿液且在90℃下攪拌2小時。重複此NH4NO3交換過程兩次。過濾、沖洗及乾燥之後，最終產物具有9.8之二氧化矽與氧化鋁比(SAR)。產物之BET表面積為668m2/g且微孔體積為0.23cc/g。
以80：20之重量比混合所獲得之β沸石與氧化鋁黏合劑(Sasol Pural SB1)及1.5wt.%硝酸及0.3wt.% Superfloc N。混合物具有53%之燒失量。擠壓此混合物以獲得1.4mm直徑擠出物，在140℃下乾燥2小時且在500℃下煅燒2小時。藉由用六氯鉑酸溶液之孔隙體積浸漬來浸漬該等煅燒擠出物，且隨後在140℃下乾燥且在450℃下煅燒。最終催化劑含有0.3wt.%鉑(以金屬計算)，且具有0.3kg/l之壓實容積密度。
實施例2-異構化方法
此實施例說明如實施例1中所描述製備之催化劑(催化劑1)在正戊烷、正庚烷與環己烷之混合物之異構化中的用途。
出於比較，吾人亦在包含20wt.%氧化鋁黏合劑及SAR為25且壓實容積密度為0.48kg/l之80wt.% β沸石的擠出物(催化劑A)上測試含有0.3wt.%鉑(以金屬計算)之催化劑。
吾人進一步在包含20wt.%氧化鋁黏合劑及SAR為18且表面積為675m2/g之80wt.% β沸石的擠出物(催化劑B)上測試含0.3wt.%鉑(以金屬計算)之比較催化劑。
在200℃下乾燥催化劑中之每一者，且在10絕對巴及300℃下藉由氫還原，且在具有60wt% n-C5、35wt% n-C6及5wt%環-C6之原料上測試。
在1.90cc饋料/cc催化劑/小時之液體每小時空間速度下進行測試，同時維持氫氣流之流動以提供1.2：1之氫與饋料比(體積氫/體積饋料)。藉助於氣相層析分析異構化產物。
辛烷公噸產量為所計算之產物產率乘以所計算之辛烷值。下表1中展示各種溫度下上述催化劑之辛烷公噸產量。

Claims (11)

  1. 一種烷烴異構化催化劑，其在含氧化鋁及具有二氧化矽與氧化鋁莫耳比(SAR)為5至15之β沸石的載體上包含0.01wt.%至5wt.%第VIII族貴金屬。
  2. 如申請專利範圍第1項之烷烴異構化催化劑，其中該第VIII族貴金屬為鉑，其以0.1wt.%至3wt.%之量存在。
  3. 如申請專利範圍第1項或第2項之烷烴異構化催化劑，其中該載體包含60wt.%至95wt.%該β沸石。
  4. 如申請專利範圍第1項至第3項中任一項之烷烴異構化催化劑，其中該β沸石之體積平均晶體尺寸如藉由掃描電子顯微法測定為50奈米至500奈米。
  5. 如申請專利範圍第1項至第4項中任一項之烷烴異構化催化劑，其中該β沸石不含有機結構導向劑。
  6. 如申請專利範圍第1項至第5項中任一項之烷烴異構化催化劑，其中該β沸石藉由包含以下之方法製備：(a)混合及攪拌鹼金屬氧化物源、氧化鋁源、二氧化矽源及水以合成初始鋁矽酸鹽凝膠，其具有以下原料莫耳比：SiO2/Al2O3=15-45，Na2O/SiO2=0.20-0.50，H2O/SiO2=4-50，(b)添加沸石晶體晶種且允許混合物在高溫下結晶以獲得二氧化矽與氧化鋁莫耳比(SAR)為5至15之β沸石晶體。
  7. 如申請專利範圍第6項之烷烴異構化催化劑，其中該方法包含允許該混合物在步驟(b)中在100℃至180℃之溫度下在12小時至24小時期 間結晶。
  8. 如申請專利範圍第1項至第7項中任一項之烷烴異構化催化劑，其中該β沸石之SAR為5至11。
  9. 一種製備如申請專利範圍第1項至第8項中任一項之異構化催化劑之方法，該方法包含(a)混合氧化鋁與SAR為5至15之β沸石，擠壓該步驟(a)中獲得之混合物且視情況乾燥及煅燒該等所獲得之擠出物，及(b)用含鉑溶液浸漬該等在步驟(a)中獲得之擠出物，之後乾燥且視情況煅燒該等浸漬擠出物。
  10. 如申請專利範圍第9項之方法，其中該方法步驟(c)之浸漬溶液為包含六氯鉑酸之水溶液。
  11. 一種用於使含具有4至8個碳原子之烷烴之烴饋料異構化的方法，其藉由使該饋料與如申請專利範圍第1項至第8項中任一項之催化劑或藉由如申請專利範圍第9項或第10項之方法所獲得之催化劑在150℃至300℃之溫度及0.1絕對巴至30絕對巴之壓力下接觸來進行。
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