TW202216293A - 重烴加氫處理催化劑及其製造及使用方法 - Google Patents
重烴加氫處理催化劑及其製造及使用方法 Download PDFInfo
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- TW202216293A TW202216293A TW110132064A TW110132064A TW202216293A TW 202216293 A TW202216293 A TW 202216293A TW 110132064 A TW110132064 A TW 110132064A TW 110132064 A TW110132064 A TW 110132064A TW 202216293 A TW202216293 A TW 202216293A
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- ebullated bed
- catalyst
- range
- bed catalyst
- molybdenum
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Abstract
本說明書揭示一種用於重烴原料之加氫處理及加氫轉化的高度大孔催化劑。高大孔隙率催化劑包含無機氧化物、鉬及鎳組分。其具有如下之孔隙結構:使得其總孔隙體積之至少18%在直徑大於5,000埃之孔隙中,且其總孔隙體積之至少25%在直徑大於1,000埃之孔隙中。較佳地,該孔隙結構為雙峰。該催化劑藉由共研磨催化組分與高分子量聚丙烯醯胺,接著將共研磨混合物形成為粒子或擠出物來製備。該粒子或擠出物經乾燥且在受控煅燒溫度條件下煅燒,以產生高大孔隙率催化劑組合物之煅燒粒子或擠出物。
Description
相關申請案之參考
本申請案主張2020年9月1日申請的名稱為「A HEAVY HYDROCARBON HYDROPROCESSING CATALYST AND METHOD OF MAKING AND USING THEREOF」之美國臨時專利申請案序號63/073015之優先權權益,且該案以全文引用之方式併入本文中。
本發明係關於一種適用於重烴原料之加氫脫硫及重餾份加氫轉化為餾出物的加氫處理催化劑。本發明進一步係關於一種製造加氫處理催化劑之方法。
在精煉廠原油加工中,包含沸點高於約538℃(1,000℉)之重烴的某些餾份經受催化加氫處理以藉由脫硫、脫氮、脫金屬及將重餾份轉化為輕質餾出物餾份來移除諸如硫、氮、金屬及微量碳殘餘物之組分。此等方法使用各種類型的非均相加氫處理催化劑,以藉由使催化劑與原料在高溫及高壓條件下在氫氣存在下接觸來促進反應。用於提供重烴原料之加氫轉化及脫硫的習知催化劑中之多者含有負載於耐火氧化物載體上的VIB族金屬組分(諸如鉬)及VIII族金屬組分(諸如鈷或鎳)。
美國專利第7,820,036號(Bha)揭示發現適用於加氫處理重烴原料之催化劑。此催化劑尤其適用於重烴原料之加氫脫硫及加氫轉化,且即使當在較重烴餾份之高轉化率所需的較高處理溫度條件下使用時亦維持穩定性。催化劑係藉由將三氧化鉬、鎳化合物及無機氧化物材料混合且將混合物形成為經煅燒之粒子來製備。催化劑具有至多12重量%(作為金屬)鉬及至多4重量%(作為金屬)鎳。催化劑之重要特徵為其具有特定窄範圍內之平均孔徑及低大孔隙率。本文所揭示之催化劑之平均孔徑在85 Å至100 Å範圍內。催化劑之大孔隙率小於總孔隙體積之4.5%,該總孔隙體積含於直徑大於350 Å之孔隙中。在製備催化劑中未提及使用高分子量聚丙烯醯胺來製造具有高大孔隙率及增強之催化特性的催化劑。
美國專利第9,114,386號(Bha)揭示一種用於加氫處理重烴原料之催化劑。此催化劑具有獨特自活化特性以使得其活性隨使用而增加。該催化劑具有相對較低濃度之鉬及鎳,其中鎳之比例提供低的鎳:鉬重量比。催化劑含有1至10重量%(作為金屬)鉬及鎳,其量使得鎳:鉬重量比小於0.4。催化劑之特徵為在直徑大於1,000 Å之孔隙中具有其總孔隙體積的至少1%且小於10%。直徑在70 Å至150 Å範圍內之中孔包含催化劑之總孔隙體積的至少40%但小於70%。合乎需要的是,總孔隙體積之至少10%存在於直徑在130 Å至300 Å範圍內的孔隙中。在製備催化劑中未提及使用高分子量聚丙烯醯胺來製造具有高大孔隙率孔隙結構,使得其總孔隙體積之至少20%在直徑大於5,000 Å之孔隙中及增強之催化特性的催化劑。
美國專利第9,879,187號(Bha)揭示具有極佳催化效能特性之另一重烴加氫處理催化劑。此催化劑產生如藉由其P-值反映具有增強之產物穩定性的經處理產物。催化劑進一步具有增強之MCR移除活性及增強之釩移除能力及穩定性。該專利指示催化劑之獨特物理特性提供其極佳催化特性。催化劑之重要特徵在於,其總孔隙體積之至少20%含於孔徑大於5,000 Å之孔隙中,且總孔隙體積之小於70%含於孔徑在70 Å至250 Å範圍內的孔隙中。在製備催化劑中未提及使用高分子量聚丙烯醯胺來製造具有高大孔隙率及增強之催化特性的催化劑。
一直致力於開發用於重烴之加氫處理及加氫轉化以產生加氫處理轉化產物的改良催化劑。此等努力旨在開發具有更高活性且提供重烴物料流之瀝青組分向輕質烴之顯著轉化,同時提供低沈積量的改良催化劑。
因此,提供一種沸騰床催化劑,其包括按沸騰床催化劑之重量計在75至98.5重量%範圍內的氧化鋁、以金屬計算且按沸騰床催化劑之重量計大於5重量%之量的鉬組分、使得沸騰床催化劑之鎳:鉬原子比在0.2至0.9範圍內之量的鎳組分。沸騰床催化劑具有高大孔隙率孔隙結構,使得沸騰床催化劑之總孔隙體積的至少20%在直徑大於5,000 Å之孔隙中,且沸騰床催化劑之總孔隙體積的至少25%在直徑大於1,000 Å之孔隙中。
亦提供一種製備具有高大孔隙率且適用於在最低沈積量下轉化及處理重烴進料之沸騰床催化劑的新穎方法。此方法包含共研磨鉬化合物、催化劑細粒、氧化鋁、高分子量聚丙烯醯胺組分及水以形成能夠擠出之共研磨混合物。共研磨混合物形成為擠出物,其經乾燥以提供乾燥擠出物。在1450℉至1550℉範圍內之煅燒溫度下煅燒乾燥擠出物,由此提供本文所揭示之沸騰床催化劑。沸騰床催化劑具有高大孔隙率孔隙結構,使得沸騰床催化劑之總孔隙體積的至少20%在直徑大於5,000 Å之孔隙中,且沸騰床催化劑之總孔隙體積的至少25%在直徑大於1,000 Å之孔隙中。
藉由本發明方法製得之一或多種所揭示沸騰床加氫轉化催化劑可用於重烴原料之加氫轉化方法中。此方法包括將重烴原料引入至含有催化劑床之沸騰床反應區中,其中該重烴原料在加氫轉化條件下與催化劑接觸。自沸騰床反應區產生重烴轉化產物。
下文將描述本發明的一或多個特定具體實例。此等所描述實施例為本發明所揭示之技術的實例。另外,為致力於將提供對此等實施例之簡明描述,在本說明書中可能不描述實際實施之全部特徵。應瞭解,在任何此類實際實施方案的開發中,如同在任何工程或設計項目中,將制定多個實施特定之決策以達成開發者之特定目標,諸如遵從系統相關及商業相關之約束,該等約束可自一個實施方案至另一實施方案變化。此外,應瞭解,此開發工作可能係複雜且耗時的,但對於受益於本發明之一般技術人員而言,仍可為設計、加工及製造的常規任務。
當介紹本發明之各種實施例的元件時,冠詞「一」及「該」欲意謂存在該等元件中之一或多者。術語「包括」、「包含」及「具有」意欲為包含性的,且意謂除所列元件之外可能存在額外元件。另外,應理解,對本發明之「一個實施例」或「一實施例」的提及並不意欲被解譯為排除亦併有所敍述特徵之額外實施例的存在。
如本文所用之術語「大約」、「約」及「基本上」表示接近於陳述量的量,該量仍執行所要功能或達成所要結果。舉例而言,術語「大約」、「約」及「基本上」可指在陳述量之小於10%內、小於5%內、小於1%內、小於0.1%內及小於0.01%內的量。
本發明之催化劑為一種新穎的高大孔隙率催化劑組合物,其適用於重烴原料之加氫處理(例如加氫脫硫、加氫脫氮及加氫脫金屬)及加氫轉化。此催化劑特別適用於沸騰床製程系統中所用之沸騰床催化劑。
本文所揭示之催化劑能夠提供重烴原料之瀝青部分至較低沸點烴的高轉化率,同時產生少量非所要沈積物。
高分子量聚丙烯醯胺在催化劑製造中之用途及用於製備高大孔隙率催化劑之特殊方法步驟(諸如共研磨及受控煅燒)提供高大孔隙率催化劑之許多特殊特性。
儘管認為催化劑之高大孔隙率及其他孔結構特徵有助於增強催化劑在重質原料處理中之催化特性,但亦認為存在由使得有助於其獨特特性之方式產生之高大孔隙率催化劑的其他物理特性。因此,所揭示之製造高孔隙率催化劑之方法提供具有增強之特性的新穎高大孔隙率催化劑。
本發明之催化劑包含粒子。粒子可為由共研磨混合物形成之擠出物或任何其他粒子或形狀。在受控煅燒溫度條件下煅燒粒子以提供具有獨特孔隙結構之加氫處理催化劑的煅燒粒子。
共研磨混合物包含無機氧化物組分、鉬組分、鎳組分及高分子量聚丙烯醯胺。進一步期望在混合物中包含壓碎的催化劑細粒。此等組分以本發明之最終煅燒粒子及催化劑所需之特定界定濃度及重量比組合在一起。
煅燒粒子進一步具有如本文中詳細描述之特定界定孔隙結構。在共研磨混合物中包含高分子量聚丙烯醯胺提供最終煅燒粒子,且因此提供本發明之沸騰床催化劑,其具有格外高的大孔隙率孔隙結構及有助於增強之催化特性的其他特徵。
高分子量聚丙烯醯胺之應用對於製造具有所述高度大孔的孔隙結構及增強之催化特性的沸騰床催化劑而言重要。控制包含於共研磨混合物中之高分子量聚丙烯醯胺之量以提供具有所需特徵及特性之最終催化劑。共研磨混合物中所包含之高分子量聚丙烯醯胺之量應在共研磨混合物之總重量的約0.1 wt.%至約10 wt.%範圍內。共研磨混合物之高分子量聚丙烯醯胺的濃度較佳在0.2至8 wt.%範圍內,且更佳地,該濃度在0.4至6 wt.%範圍內。
除了無機氧化物組分之外,本文所揭示之煅燒粒子亦包含鉬或鎳,或鉬及鎳兩者。此等金屬在最終催化劑組合物中之濃度對於催化劑之效能以及在催化劑製備中使用高分子量聚丙烯醯胺以產生具有獨特物理特性之催化劑而言重要。因此,煅燒粒子一般包含無機氧化物組分、基本上由其組成或由其組成,該無機氧化物組分為鉬組分或鎳組分,或鉬組分及鎳組分兩者。
煅燒粒子且因此加氫處理催化劑之鉬含量應大於煅燒粒子之總重量的5重量%(wt.%)且小於15 wt.%,以金屬計算,無論其實際形式如何。更期望鉬以在6 wt.%(亦即9 wt.%,以MoO
3計算)至14 wt.%(亦即以MoO
3計算21 wt.%)範圍內的量存在於煅燒粒子中。在一較佳實施例中,煅燒粒子中鉬之濃度在7 wt.%至12 wt.%(亦即以MoO
3計算10.5 wt.%至18 wt.%)範圍內。
當存在時,煅燒粒子之鎳含量應在煅燒粒子之總重量的0.5至5 wt.%範圍內,以金屬計算,無論其實際形式如何(亦即以氧化鎳(NiO)計0.64至6.4 wt.%)。較佳地,鎳含量在0.75至4.5 wt.%(亦即以氧化鎳計1至5.7 wt.%),且更佳1至4 wt.%(亦即以氧化鎳計1.3 wt.%至5.1 wt.%)範圍內。
在所揭示催化劑之一個實施例中,可能期望煅燒粒子具有使得煅燒粒子中之鎳:鉬之重量比在0.2:1至0.9:1範圍內之量的鎳濃度。此重量比係基於元素計算及呈現的。然而,鎳之量應在如上文所表述之濃度範圍內且在某些實施例中可在0.3:1至0.8:1範圍內。鎳:鉬之較佳重量比在0.3:1至0.6:1範圍內。
除鉬、鎳及高分子量聚丙烯醯胺組分之外,共研磨混合物進一步包含無機氧化物材料。將提供催化劑所需之孔隙結構特性之任何適合之多孔無機耐火氧化物可用作混合物之無機氧化物材料組分。可能適合之類型的多孔無機耐火氧化物的實例包含二氧化矽、氧化鋁及二氧化矽-氧化鋁。較佳為氧化鋁或二氧化矽-氧化鋁。最佳為氧化鋁。
混合物中之無機氧化物材料的量係為了在最終煅燒混合物及加氫處理催化劑中提供在70至92.5重量%範圍內之無機氧化物材料的量,其中重量%係以煅燒混合物或加氫處理催化劑之總重量計。較佳地,煅燒混合物中無機氧化物材料之量在72至91重量%,且最佳74至90重量%範圍內。
本文所揭示之催化劑之重要物理特徵為其具有相對較高的大孔隙率,如下文所述。催化劑之總孔隙體積之主要部分包括於其直徑大於5,000 Å之孔隙中。實際上,煅燒粒子或催化劑之總孔隙體積之至少18%應在孔徑大於5,000 Å之孔隙中。然而,較佳地,總孔隙體積之至少20%,且更佳地,總孔隙體積之至少22%包括於直徑大於5,000 Å之孔隙中。
高大孔隙率催化劑具有雙峰孔隙結構。其孔徑分佈使得其具有在40 Å至250 Å之孔徑範圍內的第一孔徑峰及在5,000 Å至11,000 Å之範圍內的第二孔徑峰。高大孔隙率催化劑之雙峰孔隙結構較佳可具有在50 Å至200 Å範圍內之第一孔徑峰及其在5,000 Å至10,000 Å範圍內之第二孔徑峰。更佳地,第一孔徑峰在50 Å至100 Å範圍內且第二孔徑峰在5,000 Å至9,000 Å範圍內。
包括於直徑在40 Å至250 Å範圍內之孔隙中的催化劑之總孔隙體積之百分比在催化劑之總孔隙體積的50%至70%範圍內。較佳地,催化劑之總孔隙體積之45%至65%在其具有40 Å至250 Å範圍內之直徑的孔隙中。更佳地,總孔隙體積之40%至60%%包括於具有40 Å至250 Å範圍內之直徑的孔隙中。
在催化劑之較佳實施例中,催化劑之總孔隙體積之至少18%包括於具有5,000 Å至11,000 Å範圍內之直徑的孔隙中。較佳地,催化劑之總孔隙體積之20%至50%在其具有5,000 Å至11,000 Å範圍內之直徑的孔隙中。更佳地,總孔隙體積之22%至50%包括於具有5,000 Å至11,000 Å範圍內之直徑的孔隙中。
進一步期望催化劑之孔隙結構使得總孔隙體積之至少25%包括於其具有大於1,000埃之直徑的大孔內。更期望總孔隙體積之大於28%包括於具有大於1,000埃之直徑的大孔內,且最期望總孔隙體積之大於30%包括於具有大於1,000埃之直徑的大孔內。
含有直徑大於250 Å之孔隙的催化劑之總孔隙體積百分比為大於30%,較佳大於34%,且更佳大於36%。
在製備本發明之煅燒粒子時,藉由共研磨組分以形成共研磨混合物來混合起始材料。在一個實施例中,製備共研磨混合物之起始材料包含鉬化合物、鎳化合物、無機氧化物材料及高分子量聚丙烯醯胺。
鉬化合物較佳為呈細粉狀粒子形式之三氧化鉬,其可呈乾粉形式或呈懸浮液或漿液中之粒子形式。
無機氧化物材料可選自由氧化鋁、二氧化矽及氧化鋁-二氧化矽組成之群。
鎳組分係選自能夠與成形為粒子之共研磨混合物之其他組分混合的適合鎳化合物之群。
共研磨混合物形成為粒子,其隨後經煅燒以形成本發明之煅燒粒子。鎳組分可為呈氧化物形式之鎳,諸如氧化鎳,或其可為鎳鹽化合物。可適當使用之鎳鹽化合物包含例如鎳之氫氧化物、氯化物、硝酸鹽及乙酸鹽。用於製備共研磨混合物之一種較佳鎳化合物為硝酸鎳。
用於形成共研磨混合物之高分子量聚丙烯醯胺為能夠提供本發明之催化劑的聚合物化合物,該催化劑具有本文所述之高大孔隙率特徵及增強的催化特性。此等增強的催化特性包含提供重烴原料之瀝青組分的顯著轉化以及相關低沈積量。咸信催化劑之獨特、高度大孔的孔隙結構有助於其增強的催化特性。用於形成共研磨混合物之聚合物之分子量及其於共研磨混合物中之濃度對於提供具有其高大孔隙率特性之最終煅燒粒子而言均為重要的。共研磨混合物所需之高分子量聚丙烯醯胺之臨界濃度描述於上文中。
用於製備共研磨混合物之聚丙烯醯胺的分子量與高分子量聚丙烯醯胺化合物中重複單元之數目及聚合物之長度有關。高分子量聚丙烯醯胺應具有在1,000,000 g/mol至25,000,000 g/mol範圍內之分子量。聚丙烯醯胺之較佳分子量在1,000,000 g/mol至20,000,000 g/mol範圍內。
理論上,高分子量聚丙烯醯胺起作用之一個原因為其在共研磨混合物之氧化鋁粒子之間形成橋,其使得共研磨混合物之粒子在混合、粒子或擠出物形成及煅燒以產生具有本文所述之高大孔隙率特徵之催化劑組合物的煅燒粒子期間保持以間隔關係定向。
用於製備組合物之潛在高分子量聚丙烯醯胺化合物包含選自由以下組成之群的分子量在所需範圍內之聚合物:聚(丙烯醯胺)、聚(N-異丙基丙烯醯胺)、聚(N-辛基丙烯醯胺)、聚(N-三級丁基丙烯醯胺、聚(N-苯基丙烯醯胺)及聚(N-二級丁基丙烯醯胺)。其中聚(丙烯醯胺)為較佳的。
共研磨混合物之形成可藉由熟習此項技術者已知之任何方法或手段進行。此等包含使用適合類型之固體混合機,諸如滾揉機、固定殼或槽、碾式混合器(分批型或連續型)及衝擊式混合器,以及使用此類用於混合固體及液體或形成可擠出的糊狀混合物的適合類型之分批式或連續式混合器。適合類型之分批混合器包含但不限於變化罐混合器、固定槽混合器、配備有任何適合之類型的混合刀片的雙臂捏合混合器。適合類型之連續混合器包含單螺桿或雙螺桿擠出機、槽式螺桿混合器及攪拌機。
煅燒粒子之起始材料的混合可進行恰當地均質化共研磨混合物所需的任何適合之時段。一般而言,摻合時間可在向上至2小時或大於3小時範圍內。通常,摻合時間在0.1小時至3小時範圍內。
在本說明書中廣泛地使用術語「共研磨」以意謂至少所述起始材料混合在一起以形成共研磨混合物之個別組分的混合物,該共研磨混合物較佳為此類共研磨混合物之個別組分的基本上均勻或均質混合物。此術語之範疇意欲足夠廣泛以包含混合起始材料以產生糊狀物,該糊狀物展現使其能夠藉由已知擠出方法中之任一者擠出或形成為擠出物粒子的特性。但是,該術語亦意欲涵蓋起始材料之混合以產生較佳基本上均質且能夠聚結為成型粒子的混合物。成型粒子之實例包含球狀體、丸劑或錠劑、圓柱體、不規則擠出物或僅鬆散結合之聚集體或叢集,其藉由熟習此項技術者已知之方法中之任一者,包含但不限於模製、製錠、壓製、造粒、擠出及翻滾。
煅燒粒子之鉬源的主要部分可主要為三氧化鉬。在煅燒粒子之起始材料之混合或共研磨中,較佳地,三氧化鉬呈精細粉碎狀態,呈精細粉末狀固體形式或呈懸浮液或漿液中之細粒形式。最佳地,用於製造催化劑之微粒狀三氧化鉬之粒度具有小於0.5 mm(500微米,μm)之最大尺寸,較佳小於0.15 mm(150 μm)、更佳小於0.1 mm(100 μm)且最佳小於0.075 mm(75 μm)之最大尺寸。
用於製造煅燒粒子之三氧化鉬的粒度一般將對其尺寸具有大於0.2微米之下限。因此,在煅燒粒子之製造中用於形成共研磨混合物之三氧化鉬的粒度較佳在0.2至150 μm、更佳0.3至100 μm且最佳0.5至75 μm範圍內。典型地,無論在乾燥粉末或懸浮液中或以其他方式,三氧化鉬粒子之尺寸分佈使得至少50%之粒子具有在2至15 μm範圍內之最大尺寸。
一旦煅燒粒子之起始材料經恰當混合且形成為成形或成型粒子,乾燥步驟可有利地用於移除包含於共研磨混合物或成型粒子內的一定量之水或揮發物。
對成型粒子進行乾燥可在用於移除過量水或揮發物之任何適合的溫度下進行,但較佳地,乾燥溫度將在約75℃至250℃範圍內。乾燥粒子之時段為在煅燒步驟之前提供所需量之粒子揮發物含量降低所需的任何適合之時段。
乾燥或未乾燥之粒子在含氧流體(諸如空氣)存在下在煅燒溫度下煅燒,該煅燒溫度提供具有本文所述之所需孔隙結構及增強之催化特性的最終煅燒粒子。本發明之乾燥粒子在677℃(1250℉)至843℃(1550℉)範圍內之溫度下煅燒。較佳煅燒溫度在704℃(1300℉)至815℃(1500℉),且更佳746℃(1375℉)至774℃(1425℉)範圍內。
煅燒粒子特別適用作高活性加氫處理催化劑,用於對具有高含量的瀝青、諸如鎳及釩化合物之有機金屬及硫的重質原料流進行加氫處理。在使用之前,煅燒粒子可(但不需要)藉由熟習此項技術者已知之任何方法進行硫化或活化。一般而言,在用於重烴原料之加氫處理中,煅燒粒子含於反應區內,諸如由反應器容器界定之反應區,其中重烴原料與煅燒粒子在適合之加氫處理反應條件下接觸且自其產生經處理之烴或重烴轉化產物。
本文所揭示之方法的重烴原料可源自高沸點溫度石油餾份中之任一者,諸如常壓塔氣油、常壓塔底油、真空塔氣油及真空塔底油或渣油。
本發明方法之特別適用態樣為提供重烴原料之加氫處理,該重烴原料一般定義為具有如藉由使用ASTMD-1160中所述之測試程序所測定,超過300℃(572℉)的在其5%蒸餾點處之沸點溫度,亦即T(5)。本發明更特定而言係關於具有超過315℃(599℉)之T(5)且甚至超過340℃(644℉)之T(5)的重烴原料之加氫處理。
重烴原料進一步可包含沸點溫度高於538℃(1,000℉)之較重烴。此等較重烴在本文中稱為瀝青,且如已提及,應認識到所揭示之催化劑或方法之特定特徵之一為其在重烴原料之瀝青含量的加氫轉化中尤其有效。
重烴原料可包括少至10體積百分比瀝青或多達90體積百分比瀝青,但一般而言,重烴原料中所包含之瀝青的量在20至80體積百分比範圍內。且更典型地,重烴原料中之瀝青含量在30至75體積百分比範圍內。
重烴原料可進一步包含顯著高硫含量。本發明之特殊特徵之一為其提供重烴原料之脫硫及脫金屬。重烴原料之硫含量主要呈有機含硫化合物形式,其可包含例如硫醇、經取代或未經取代之噻吩、雜環化合物或任何其他類型之含硫化合物。
本發明之特徵為其提供具有顯著高硫含量之重質原料的脫硫。此類硫含量通常遠大於1重量%,以便提供具有降低之硫含量,諸如小於1重量%、較佳小於0.75重量%且更佳小於0.5重量%之硫含量的經處理之烴產物或重烴轉化產物。
當在本文中提及重烴原料或經處理之烴或重烴轉化產物的硫含量時,重量百分比係藉由使用測試方法ASTM D-4294測定。
所揭示之方法尤其適用於加工具有超過2重量%之硫含量的重烴原料,且在此類重烴原料之情況下,硫含量可在2至8重量%範圍內。本文所揭示之催化劑及方法尤其適用於加工具有超過3或甚至4重量%,且在3至7重量%或甚至4至6.5重量%範圍內之尤其高硫含量的重烴原料。
該方法在加氫處理重烴原料中利用本文揭示之高大孔隙率催化劑以在降低或低沈積量下提供同時脫硫、脫氮及瀝青轉化。在此方法中,重烴原料與催化劑在適合之加氫脫硫及加氫轉化方法條件下接觸,以產生重烴轉化產物。
重烴原料之鎳含量典型地呈有機鎳化合物形式。重烴原料之鎳濃度可在2 ppmw至250 ppmw範圍內。更典型地,所揭示方法之重烴原料的鎳濃度在5 ppmw至225 ppmw範圍內,且最典型地,鎳濃度在7 ppmw至200 ppmw範圍內。
重烴原料亦可具有典型地在5 ppmw至250 ppmw範圍內之釩濃度。期望重烴原料含有儘可能少的釩,但該組合物提供脫金屬,且因此自重烴原料移除釩。更典型地,重烴原料之釩濃度在10 ppmw至225 ppmw範圍內。
重烴轉化產物應具有降低之硫含量,其低於重烴原料之硫含量。降低之硫含量較佳為小於1重量%之硫濃度。然而,應認識到,所揭示之方法可具有有效地脫硫重烴原料以提供經處理之烴或重烴轉化產物的能力,該經處理之烴或重烴轉化產物之硫含量小於重烴轉化產物之0.5重量%且甚至小於0.4重量%。
如藉由測試方法ASTM-4870所測定,典型地與重烴轉化產物一起產生之沈積物低於0.5 wt%,且其較佳低於0.4 wt.%。本文所揭示之方法在使用高大孔隙率加氫處理催化劑之情況下提供沈積物含量顯著低於比較催化劑提供之沈積物含量的重烴轉化產物。重烴轉化產物之沈積物含量可甚至低於重烴轉化產物之0.35 wt.%或低於0.3 wt.%。
本發明之煅燒粒子(高大孔隙率催化劑)可用作任何適合之反應器系統的一部分,該反應器系統提供催化劑與重烴原料在適合之加氫處理條件下接觸,該等加氫處理條件可包含氫之存在及高總壓力及溫度。此類適合之反應系統可包含固定催化劑床系統、沸騰催化劑床系統、漿化催化劑系統及流體化催化劑床系統。
本發明之催化劑特別適用作沸騰床反應器系統中所用之沸騰床催化劑。參看圖式更詳細地描述沸騰床反應器系統。
另一適合之反應器系統為包含反應器容器內所含之所揭示催化劑之固定床的反應器系統。反應器容器配備有用於將重烴原料引入反應器容器中之反應器進料入口構件,諸如進料噴嘴,及用於自反應器容器排出反應器流出物或重烴轉化產物的反應器流出物出口構件,諸如流出物出口噴嘴。
方法一般在2298 kPa(300 psig)至20,684 kPa(3000 psig),較佳10,342 kPa(1500 psig)至17,237 kPa(2500 psig)且更佳12,411 kPa(1800 psig)至15,513 kPa(2250 psig)範圍內之加氫處理(加氫轉化及加氫脫硫)反應壓力下操作。加氫處理反應溫度一般在340℃(644℉)至480℃(896℉),較佳360℃(680℉)至455℃(851℉)且最佳380℃(716℉)至425℃(797℉)範圍內。
重烴原料饋入方法之反應區中的流動速率一般為使得液體每小時空間速度(LHSV)在0.01 hr
-1至3 hr
-1範圍內。如本文所用,術語「液體每小時空間速度」意謂以體積/小時計之重烴原料饋入方法之反應區的速率除以重烴原料饋入之反應區中所含之催化劑體積的數值比。較佳LHSV在0,05 hr
-1至2 hr
-1,更佳0.1 hr
-1至1.5 hr
-1且最佳0.2 hr
-1至0.7 hr
-1範圍內。
較佳將氫氣與重烴原料一起饋入本文所揭示之方法的反應區。在此情況下,氫氣有時被稱為氫氣處理氣體。氫氣處理氣體速率為相對於饋入反應區中之重烴原料之量的氫氣之量,且一般在向上至1781 m
3/m
3(10,000 SCF/bbl)範圍內。處理氣體速率較佳在89 m
3/m
3(500 SCF/bbl)至1781 m
3/m
3(10,000 SCF/bbl)、更佳178 m
3/m
3(1,000 SCF/bbl)至1602 m
3/m
3(9,000 SCF/bbl)且最佳356 m
3/m
3(2,000 SCF/bbl)至1425 m
3/m
3(8,000 SCF/bbl)範圍內。
圖式呈現其中使用本發明之高大孔隙率催化劑之沸騰床反應器系統10的簡化示意圖。沸騰床反應器系統包括細長容器12,該容器界定若干區,諸如用於使重烴原料在適合之加氫轉化反應條件下與高大孔隙率催化劑接觸之接觸區;及用於使加氫處理重烴產物與高大孔隙率催化劑分離之分離區。
細長容器12內為固定高大孔隙率催化劑床14,其具有固定高大孔隙率催化劑床液位16。包含重烴原料及氫之反應器饋料藉助於管道18引入位於細長容器12內沸騰催化劑床下方的下部區17中。
反應器進料穿過水平分配器板20,其提供用於引導反應器進料向上且穿過固定高大孔隙率催化劑床14之構件。反應器進料穿過固定高大孔隙率催化劑床14用以升高及擴大高大孔隙率催化劑床,從而提供具有擴大之高大孔隙率催化劑床液位24的經擴大之高大孔隙率催化劑床22(沸騰催化劑床)。
在細長容器12之分離區26中,高大孔隙率催化劑自具有液位30之液體烴28及重烴轉化產物分離,該重烴轉化產物藉助於管道32自細長容器12傳出。
細長容器12內之降液管34提供用於將液體烴28再循環至經擴大之高大孔隙率催化劑床22之底部的管道構件。管道36係以操作方式使降液管34與沸騰泵38之間以流體流動連通之形式連接。沸騰泵38提供用於使液體烴28再循環及循環穿過經擴大之加氫轉化催化劑床22之構件。
細長容器12之上端包含催化劑入口管道構件40,其在沸騰床反應器系統10操作時提供新鮮高大孔隙率催化劑的引入。新鮮高大孔隙率催化劑可經由管道構件40,藉助於管道42引入至細長容器12中。細長容器12之下端包含催化劑出口管道構件44,其在沸騰床反應器系統10操作時提供廢高大孔隙率催化劑的移除。廢高大孔隙率催化劑藉助於管道46自細長容器12傳出。
以下實例進一步說明本發明,但不應將其理解為限制本文所揭示之實施例的範疇。
實例 I
此實例I說明所揭示之催化劑及比較催化劑之製備方法及催化劑組成。
本發明催化劑組合物
所揭示之催化劑組合物之實施例係藉由在碾碎機中組合以下各者製備:932.2公克具有23.9%之LOI的氧化鋁粉末與20公克高分子量聚丙烯醯胺組分(Tramfloc
®133 M非離子絮凝劑)、210.7公克催化劑細粒(細粉狀氧化鋁、氧化鉬及氧化鎳粉末)、75.2公克三氧化鉬及78.8公克硝酸鎳。在添加1354.5公克水及29.4公克之68%硝酸之混合物之前,操作碾碎機約一分鐘。將混合物研磨10分鐘,且接著添加20公克低分子量陽離子分散劑,且將混合物再研磨15分鐘。使用螺桿擠出機擠出混合材料以製成圓柱形球粒。將擠出材料在烘箱中在250℉下乾燥1小時。此材料在馬弗爐(muffle furnace)中在1390℉至1415℉溫度下煅燒一小時。最終催化劑之金屬負載包含2.9 wt.%鎳及12.1 wt.%鉬,此等值均以氧化物計。
比較催化劑組合物
如下地製備比較催化劑組合物:藉由在碾式混合器中混合2721.6份(以乾重計2049.4)氧化鋁粉末及594.3份(以乾重計563.5)細粉狀氧化鋁、氧化鉬及氧化鎳粉末與539.1份七鉬酸銨(27% MoO
3)及1406.2份水之鉬組分混合物以及333.3份硝酸鎳溶液、81.1份70%硝酸及1406.2份水之鎳組分混合物。將組分研磨30分鐘,接著添加14.1份絮凝劑(Superfloc LMW 300),接著混合5分鐘。接著將共研磨混合物擠出為在空氣中在大約250℉之溫度下乾燥約1小時的擠出物。此後,將乾燥擠出物在空氣中在1370℉之溫度下煅燒1小時。最終催化劑之金屬負載包含3.0 wt.%鎳及9.0 wt.%鉬,此等值均以氧化物計。
下表1呈現本發明催化劑及比較催化劑之孔隙結構特性。
表1 - 本發明及比較催化劑之孔隙結構特性
*總孔隙體積(TPV)
實例 II
本發明催化劑 | 比較催化劑 | |
> 250 Å | TPV之>35% | TPV之<25% |
> 1,000 Å | TPV之>30% | TPV之<10% |
> 5,000 Å | TPV之>20% | TPV之<5% |
> TPV(cc/g) | > 0.95 | <0.82 |
>氮表面積 | >250 | < 250 |
此實例II描述比較催化劑及本發明催化劑之效能測試條件及效能測試結果。
催化劑係在2級CSTR中試工廠中測試。進料之特性概述於表2中,且方法條件呈現於表3中。
表2 - 用於評估催化劑之進料的特性
表3 - 用於評估催化劑之方法條件
特性 | 值 |
1000 F.+,wt % | 87.7 |
硫,wt % | 5.255 |
MCR,wt % | 20.8 |
鎳,wppm | 43 |
釩,wppm | 130 |
進料密度,g/ml | 1.0347 |
n-C7不溶物,wt % | 12.7 |
n-CS不溶物,wt % | 20.9 |
催化劑LHSV,hr -1 | 0.55 |
總壓力,psia | 2250 |
H2/油比率,scft/bbl | 4090 |
溫度,℉ | 795 |
本發明催化劑之效能相對於比較催化劑(鹼)之效能概述於表4中。
表4 - 催化劑之相對效能
比較催化劑 | 本發明催化劑 | |
硫轉化率,wt.% | 100 | 103 |
968 F+ 轉化 | 100 | 112 |
698 F+餾份沈積物(ASTM D 4870) | 100 | 65 |
對表4中呈現之效能結果的回顧展示本發明催化劑之轉化及脫硫催化效能優於比較催化劑之轉化及脫硫催化效能。相比於比較催化劑,本發明催化劑進一步提供沈積量之巨大改良(亦即沈積量的降低)。本發明催化劑出乎意料地提供比較催化劑所提供之沈積量的65%。因此,與比較催化劑提供之沈積量相比降低了35%。此等結果展示使用高分子量聚丙烯醯胺製備的本發明之催化劑具有其獨特孔隙結構及高大孔隙率,出乎意料地提供低沈積量,同時提供轉化及脫硫之材料改良。
10:沸騰床反應器系統
12:細長容器
14:催化劑床
16:催化劑床液位
17:下部區
18:管道
20:分配器板
22:催化劑床
24:催化劑床液位
26:分離區
28:液體烴
30:液位
32:管道
34:降液管
36:管道
38:沸騰泵
40:管道構件
42:管道
44:管道構件
46:管道
在閱讀以下詳細描述且參看圖式後,本發明之優點可變得顯而易見,其中圖1為本發明之沸騰床反應器系統之某些態樣的簡化示意圖。
10:沸騰床反應器系統
12:細長容器
14:催化劑床
16:催化劑床液位
17:下部區
18:管道
20:分配器板
22:催化劑床
24:催化劑床液位
26:分離區
28:液體烴
30:液位
32:管道
34:降液管
36:管道
38:沸騰泵
40:管道構件
42:管道
44:管道構件
46:管道
Claims (15)
- 一種製備具有高大孔隙率且適用於在最低沈積量下轉化及處理重烴進料之沸騰床催化劑的方法,其中該方法包括: 共研磨鉬化合物、催化劑細粒、氧化鋁、高分子量聚丙烯醯胺組分及水以形成共研磨混合物; 擠出該共研磨混合物以形成擠出物; 乾燥該等擠出物以提供乾燥擠出物; 在1450℉至1550℉範圍內之煅燒溫度下煅燒該等乾燥擠出物,從而提供該沸騰床催化劑,其中該沸騰床催化劑具有高大孔隙率孔隙結構,使得該沸騰床催化劑之總孔隙體積的至少18%在直徑大於5,000 Å之孔隙中且該沸騰床催化劑之總孔隙體積的至少25%在直徑大於1,000 Å之孔隙中。
- 如請求項1之方法,其中該高分子量聚丙烯醯胺之分子量在1,000,000 g/mol至25,000,000 g/mol範圍內。
- 如請求項1之方法,其中該高大孔隙率孔隙結構具有雙峰孔徑分佈,其定義為具有在40 Å至250 Å範圍內之第一孔徑峰及在5,000 Å至11,000 Å範圍內之第二孔徑峰。
- 如請求項1之方法,其中該沸騰床催化劑之總孔隙體積的至少30%在直徑大於250 Å之孔隙中。
- 如請求項4之方法,其中該沸騰床催化劑之總孔隙體積之50至70%在40 Å至250 Å之孔徑範圍內,且該沸騰床催化劑之總孔隙體積之18至60%在5,000 Å至11,000 Å之孔徑範圍內。
- 如請求項1之方法,其包括控制該共研磨混合物之pH,其中該pH控制於4.5至12範圍內。
- 如請求項1之方法,其中催化劑細粒包括壓碎的成品加氫處理催化劑,其包括呈粉末形式之鉬、鎳、磷及氧化鋁,該鉬化合物為呈精細粉碎的粉末狀固體或懸浮液形式之微粒狀三氧化鉬之精細粉碎狀態的二氧化鉬粉末,且其中該微粒狀三氧化鉬具有最大尺寸小於500 μm之粒度。
- 如請求項7之方法,其中該沸騰床催化劑包括以金屬計算且按該沸騰床催化劑之重量計大於5 wt.%且小於15 wt.%之量的鉬。
- 如請求項7之方法,其中該沸騰床催化劑包括鎳,使得鎳:鉬之原子量比在0.2至0.9範圍內。
- 如請求項1之方法,其中該共研磨混合物中該高分子量聚丙烯醯胺之濃度在以該共研磨混合物之乾重計0.1至10 wt.%範圍內。
- 一種沸騰床催化劑,其包括: 氧化鋁,按該沸騰床催化劑之重量計,其在75至98.5 wt.%範圍內; 鉬組分,其量為以金屬計算且按該沸騰床催化劑之重量計大於5 wt.%;及 鎳組分,其量為使得該沸騰床催化劑之鎳:鉬原子比在0.2至0.9範圍內,其中該沸騰床催化劑具有高大孔隙率孔隙結構,使得該沸騰床催化劑之總孔隙體積的至少18%在直徑大於5,000 Å之孔隙中且該沸騰床催化劑之總孔隙體積的至少25%在直徑大於1,000 Å之孔隙中。
- 如請求項11之沸騰床催化劑,其包括雙峰孔徑分佈,該雙峰孔徑分佈定義為具有在40 Å至250 Å範圍內之第一孔徑峰及在5,000 Å至11,000 Å範圍內之第二孔徑峰。
- 如請求項11之沸騰床催化劑,其中該沸騰床催化劑之總孔隙體積的至少30%在直徑大於250 Å之孔隙中。
- 如請求項11之沸騰床催化劑,其中該沸騰床催化劑之總孔隙體積之50至70%在介於50 Å至200 Å之孔徑範圍內的孔隙中,且該沸騰床催化劑之總孔隙體積之18至60%為介於5,000 Å至11,000 Å之孔徑範圍內的孔隙。
- 如請求項11之沸騰床催化劑,其包括以金屬計算且按該沸騰床催化劑之重量計大於5 wt.%且小於15 wt.%之量的鉬,及使得鎳:鉬之原子量比在0.2至0.9範圍內的鎳。
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CN109054894A (zh) * | 2018-08-15 | 2018-12-21 | 黑龙江莱睿普思环境科技发展有限公司 | 一种减压蒸馏-加氢处理废矿物油的方法 |
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2021
- 2021-08-30 TW TW110132064A patent/TW202216293A/zh unknown
- 2021-09-01 KR KR1020237007176A patent/KR20230079012A/ko active Search and Examination
- 2021-09-01 WO PCT/US2021/048625 patent/WO2022051341A1/en active Application Filing
- 2021-09-01 CA CA3190374A patent/CA3190374A1/en active Pending
- 2021-09-01 JP JP2023513978A patent/JP2023539755A/ja active Pending
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- 2021-09-01 US US17/463,887 patent/US12048917B2/en active Active
- 2021-09-01 CN CN202180053747.1A patent/CN115996795A/zh active Pending
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2023
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EP4208287A1 (en) | 2023-07-12 |
US20240157344A1 (en) | 2024-05-16 |
WO2022051341A1 (en) | 2022-03-10 |
US20220062871A1 (en) | 2022-03-03 |
US12048917B2 (en) | 2024-07-30 |
CA3190374A1 (en) | 2022-03-10 |
CN115996795A (zh) | 2023-04-21 |
JP2023539755A (ja) | 2023-09-19 |
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