TWI408005B - 整體觸媒(bulk catalyst)組合物之製備方法及可得自該方法之整體觸媒組合物 - Google Patents
整體觸媒(bulk catalyst)組合物之製備方法及可得自該方法之整體觸媒組合物 Download PDFInfo
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- TWI408005B TWI408005B TW095139441A TW95139441A TWI408005B TW I408005 B TWI408005 B TW I408005B TW 095139441 A TW095139441 A TW 095139441A TW 95139441 A TW95139441 A TW 95139441A TW I408005 B TWI408005 B TW I408005B
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- Prior art keywords
- catalyst
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- metal
- catalyst composition
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- 239000003054 catalyst Substances 0.000 title claims abstract description 248
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 145
- 229910052751 metal Inorganic materials 0.000 claims abstract description 124
- 239000002184 metal Substances 0.000 claims abstract description 124
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 59
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 59
- -1 VIB metals Chemical class 0.000 claims abstract description 24
- 150000002739 metals Chemical class 0.000 claims abstract description 23
- 238000007493 shaping process Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003294 NiMo Inorganic materials 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 101100255944 Arabidopsis thaliana RWA1 gene Proteins 0.000 description 1
- 101100255945 Arabidopsis thaliana RWA2 gene Proteins 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000002934 lysing effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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Description
本發明係關於一種包含包括一或多種VIII族金屬及兩種或兩種以上VIB族金屬之金屬氧化顆粒之整體觸媒組合物。本發明進一步係關於一種用於製備該整體觸媒組合物之方法;且係關於一種使用該整體觸媒組合物之氫化處理方法。
整體觸媒意謂包含至少60重量%之金屬氧化顆粒(以金屬氧化物相對於整體觸媒之總重量計之重量%)之觸媒,其有別於具有以明顯小於60重量%之量沈積於載體材料上之金屬氧化物的載體觸媒。整體觸媒通常呈例如藉由擠壓包含金屬氧化顆粒及0-40重量%之另外材料(尤其為黏結材料)的組合物而製備之成形顆粒形式。整體觸媒一般在氫化處理中具有極高活性。
本文中之術語"氫化處理(hydroprocessing)或(hydrotreatment)"涵蓋使烴原料與氫在高溫高壓下反應之所有方法,包括諸如氫化、氫化脫硫、氫化脫氮、氫化脫金屬、氫化脫芳構化、氫化異構化、氫化脫蠟、氫化裂解及在緩和壓力條件下之氫化裂解(通常稱為緩和氫化裂解)之方法。此後,當提及根據本發明之整體觸媒之高活性時,除非另外規定,否則尤其意指氫化脫硫活性。
WO 00/41810描述包含包括兩種或兩種以上VIB族金屬及一或多種VIII族金屬之整體觸媒顆粒之整體觸媒(下文亦稱為三金屬整體觸媒),尤其為鎳/鉬/鎢基觸媒。比較實例亦描述包含僅一種VIB族金屬及一或多種VIII族金屬之整體觸媒(下文亦稱為二金屬整體觸媒)。已報導三金屬整體觸媒之催化活性明顯高於二金屬整體觸媒之催化活性。三金屬整體觸媒顆粒以下述方法製備:在質子性液體存在下使金屬化合物組合,且其中一或多種金屬化合物保持至少部分呈固態。其中金屬化合物之一者保持至少部分呈固態且另一種化合物呈溶質狀態之方法稱為固體-溶質方法。其中VIB族金屬化合物及VIII族金屬化合物保持至少部分呈固態之方法稱為固體-固體方法。
WO 00/41811描述一種三金屬整體氫化處理觸媒及其製備方法,該方法包含以下步驟:使溶液狀態之至少一種VIII族金屬化合物與溶液狀態之至少兩種VIB族金屬化合物組合且在反應混合物中反應以獲得沉澱。此方法稱為溶質-溶質方法。比較實例亦描述二金屬整體觸媒。三金屬整體觸媒之催化活性明顯高於二金屬整體觸媒之催化活性。
由於不同氫化處理條件、不同氫化處理原料或不同氫化處理反應器設備限制,可能需要不同組成之三金屬整體觸媒組合物。與所用製備方法之類型無關,就化學觀點而言,與二金屬觸媒相比較,包含兩種或兩種以上VIB族金屬之三金屬整體觸媒組合物明顯更難以製備。所要整體觸媒之組成的改變並非總是直接轉化為起始金屬化合物之組成的改變及/或方法條件的改變。除此之外,在先前技術方法中,當由一種整體觸媒組合物轉換為另一種整體觸媒組合物時,在生產運作之間存在大量停歇時間,從而導致生產能力降低。此外,當由一種整體觸媒組合物轉換為另一種整體觸媒組合物時,與單一生產運作相比較,產生更多廢料,從而導致更多的環境負擔及貴金屬損失。
本發明之目標在於提供一種用於製備不具有上述缺點之包含兩種或兩種以上VIB族金屬及一或多種VIII族金屬之整體觸媒組合物的方法。
根據本發明,提供一種包含包括兩種或兩種以上VIB族金屬及一或多種VIII族金屬之金屬氧化顆粒之整體觸媒組合物,該整體觸媒組合物包含包括一或多種第一VIII族金屬及一或多種第一VIB族金屬之第一金屬氧化顆粒及包含一或多種第二VIII族金屬及一或多種第二VIB族金屬之經獨立製備之第二金屬氧化顆粒,其中第一金屬氧化顆粒與第二金屬氧化顆粒中之VIB族金屬及VIII族金屬之組成不同,其中第一氧化整體顆粒與第二氧化整體顆粒經獨立成形為分開之第一成形整體觸媒顆粒與第二成形整體觸媒顆粒,將第一成形整體觸媒顆粒與第二成形整體觸媒顆粒組合以形成該整體觸媒組合物。在一較佳實施例中,根據本發明之整體觸媒組合物包含第一成形整體觸媒顆粒及第二成形整體觸媒顆粒(較佳為經擠壓之整體觸媒顆粒)之摻合物,較佳為均質摻合物。
發明者已驚奇地發現根據本發明之觸媒組合物之活性與先前技術之三金屬觸媒之活性相當或甚至較其可更佳。尤其令人驚奇的為根據本發明之方法之最佳模式,其中該等第一金屬氧化顆粒與第二金屬氧化顆粒中之一者或較佳兩者均為包含僅一種VIB族金屬之二金屬氧化顆粒(此係由於根據先前技術,二金屬整體觸媒之催化活性明顯較低)。
此發現使得整體觸媒組合物製備方法就化學觀點而言較不複雜且在改變為不同整體觸媒組合物方面具有最佳適應性。第一及第二金屬氧化顆粒在經個別最佳化之標準較長的生產運作中生產,該等生產運作給予所獲得之金屬氧化整體觸媒顆粒之最佳化的高品質及最佳化的高生產能力,而在改變不同組成之整體觸媒組合物時不必產生頻繁的停歇時間及額外的廢料。
此實施例之另一優點在於可能得到第一成形整體觸媒與第二成形整體觸媒的不同物理特性,使得可基於該等不同物理特性而使其彼此分離。不同物理特性可為(例如)不同形狀、尺寸、密度等且可使用彼差異例如藉由篩分進行物理分離。該整體觸媒組合物之其他獨特優點在於VIB族金屬可更易於在再循環中回收。極難以自廢觸媒回收利用VIB族金屬且甚至更難以使一種VIB族金屬與另一種VIB族金屬分離。在該整體觸媒組合物中,可藉由分離包含該等金屬之成形整體觸媒顆粒來使一種VIB族金屬與另一種VIB族金屬分離。
在根據本發明之整體觸媒組合物及其製備方法中,第一氧化整體顆粒與第二氧化整體顆粒經獨立成形以形成獨立的第一成形整體觸媒及第二成形整體觸媒,隨後將獨立的第一成形整體觸媒與第二成形整體觸媒組合以形成整體觸媒組合物,較佳為成形整體觸媒顆粒摻合物組合物。下文描述成形方法之細節。根據本發明之整體觸媒組合物包含組成不同、以達成所要總三金屬組合物之該等相對量組合之第一成形整體觸媒顆粒與第二成形整體觸媒顆粒。第一成形整體觸媒顆粒與第二成形整體觸媒顆粒以基於觸媒之預計應用之相對量組合,整體觸媒組合物中鉬與鎢之莫耳比較佳介於1:9與9:1之間。
第一成形整體觸媒顆粒與第二成形整體觸媒顆粒中之VIB族金屬及VIII族金屬之組成必須不同。較佳地,第一成形整體觸媒顆粒中之VIB族金屬及/或VIII族金屬與第二成形整體觸媒顆粒中之VIB族金屬及/或VIII族金屬不同。較佳地,第一成形整體觸媒顆粒中之VIB族金屬與第二成形整體觸媒顆粒中之VIB族金屬不同。
整體觸媒較佳包含僅一種VIII族金屬,較佳為非貴金屬鈷、鎳或鐵,但視情況可包含另一VIII族金屬。更佳地,第一氧化金屬顆粒中之一或多種VIII族金屬與第二金屬氧化顆粒中之VIII族金屬相同。
較佳地,第一金屬氧化顆粒包含鉬作為主要VIB族金屬且第二金屬氧化顆粒包含鎢作為主要VIB族金屬。最佳地,第一金屬氧化顆粒與第二金屬氧化顆粒中之VIII族金屬相同,較佳為鎳或鈷,且第一氧化整體觸媒中之VIB族金屬大體上僅為鉬且第二氧化整體觸媒中之VIB族金屬大體上僅為鎢。二金屬整體觸媒與三金屬觸媒之區別可在於其包含小於10莫耳%(相對於VIB族金屬之總量),但較佳具有大體上僅一種VIB族金屬。術語"大體上僅"意指該觸媒最佳僅可具有非大量之另一VIB族或VIII族金屬,較佳小於5莫耳%,更佳小於3莫耳%且最佳小於1莫耳%(相對於VIB族或VIII族金屬之總量)。第一金屬氧化顆粒及/或第二金屬氧化顆粒最佳分別大體上為二金屬NiMo及/或NiW氧化顆粒。在一替代性實施例中,第一金屬氧化顆粒包含兩種或兩種以上VIB族金屬及一或多種VIII族金屬且其中第二氧化顆粒包含大體上僅一種VIB族金屬及一或多種VIII族金屬,較佳地,第一金屬氧化顆粒大體上為三金屬NiMoW顆粒且第二金屬氧化顆粒大體上為二金屬NiW及/或NiMo金屬氧化顆粒。
整體觸媒視情況可進一步包含較佳小於10%,更佳小於9%,甚至更佳小於7%且最佳5%以下(相對於VIB族金屬之總量之莫耳%)的另一其他金屬,尤其為V族金屬,較佳為鈮。儘管並非較佳,但該觸媒可含有較少量其他金屬。
在根據本發明之整體觸媒組合物之最重要實施例中,第一氧化整體顆粒與第二氧化整體顆粒均為新鮮製備的。然而,預計本發明可有利地用作改變先前所製備之最終成形整體觸媒之催化特性以根據不同需要改變特性的方法。詳言之,在整體觸媒組合物中,第一氧化整體顆粒可至少部分地以廢、廢棄或再生廢整體觸媒形式提供且第二金屬氧化顆粒為新鮮製備的。廢、廢棄或再生廢整體觸媒可提高等級以滿足用於特定氫化處理條件之要求。
包含第一及第二金屬氧化顆粒之第一及第二成形整體觸媒可以先前技術中所述之各種不同方式製備。本發明亦係關於一種製備根據本發明之整體觸媒組合物之方法,該方法包含:提供第一成形整體顆粒及第二成形整體顆粒,其中第一成形整體顆粒與第二成形整體顆粒中之一者或兩者均已以包含以下步驟之方法來獨立地製備:i)在質子性液體存在下,製備包含一或多種包含一或多種較佳為Ni或Co之VIII族金屬之第一化合物、及一或多種包含一或多種較佳為鉬或鎢之VIB族金屬之第二化合物的反應混合物,ii)使第一化合物與第二化合物反應以形成金屬氧化整體顆粒,iii)使金屬氧化整體顆粒成形為成形整體觸媒顆粒,隨後組合第一成形整體觸媒顆粒與第二成形整體觸媒顆粒以形成整體觸媒組合物。
為了獲得所得觸媒之高催化活性及高產率,在整個反應期間第一及第二金屬化合物較佳至少部分地保持呈固態。
用於製備成形整體觸媒顆粒之方法可進一步包含以下方法步驟的一或多個:i)在使金屬化合物組合及/或反應之前、期間或之後,使金屬氧化顆粒與0至40重量%之一或多種選自黏結劑材料、習知氫化處理觸媒、酸性促進劑或其混合物之群的材料複合,ii)噴霧乾燥、(急驟)乾燥、研磨、捏合、混漿、乾式或濕式混合或其組合,iii)乾燥及/或熱處理,及iv)硫化。
用於製備第一及第二金屬氧化顆粒之方法步驟之細節描述於先前技術中,尤其描述於WO 00/41810或WO 00/41811中,因此該等文獻以引用的方式併入。
儘管熱處理並非必需的,但在熱處理整體觸媒組合物、尤其為整體觸媒組合物中之金屬氧化顆粒期間,溫度必需在發生向非活性結構轉變之溫度以下。此適用於整體觸媒之生產方法中之任何及所有熱處理步驟。技工可確定給定觸媒組合物之最高熱處理溫度。此尤其亦適用於在複合及成形之後對成形整體觸媒顆粒之熱處理。整體觸媒較佳在450℃以下,更佳在400℃以下,甚至更佳在375℃以下,且最佳在350℃以下熱處理。
成形整體觸媒顆粒包含至少60重量%之金屬氧化顆粒(以金屬氧化物相對於整體觸媒之總重量計之重量%),其區別於金屬氧化物以明顯小於60重量%之量沈積於載體材料上的載體觸媒。為了獲得高催化活性,根據本發明之整體觸媒較佳包含至少70重量%,更佳至少75重量%,甚至更佳至少80重量%且最佳至少85重量%之金屬氧化顆粒。其餘0至40重量%可為一或多種選自黏合劑材料、習知氫化處理觸媒、酸性促進劑及裂解組份之群之材料。在成形整體觸媒中,較佳使金屬氧化顆粒與黏合劑材料複合以改良成形顆粒之徑向抗壓碎強度。
金屬氧化顆粒較佳藉由擠壓、製成粒狀或造粒而成形以形成成形整體觸媒顆粒。在此成形方法中,金屬氧化物觸媒顆粒較佳與黏合劑複合。在一替代性實施例中,在根據本發明之整體觸媒組合物中,第一成形整體觸媒顆粒及/或第二成形整體觸媒顆粒可聚結或藉由研磨(直接在反應步驟之後或聚結步驟之後)成形,較佳隨後藉由篩分得窄粒徑分佈。在又一替代性實施例中,第一成形整體觸媒顆粒及第二成形整體觸媒顆粒可藉由視情況與黏合劑一起噴霧乾燥而成形,且視情況隨後藉由篩分得窄粒徑分佈。經研磨或噴霧乾燥之整體觸媒組合物通常具有極小之粒徑且可用於漿料式氫化處理方法中。本發明亦係關於此特定實施例在漿料式氫化處理方法中之用途;且係關於藉由包含在催化轉化條件下在催化有效量之上述整體觸媒組合物存在下使烴原料與氫相接觸之方法對該烴原料的漿料式氫化處理,其中該整體觸媒組合物作為漿料存在於原料中。
第一成形整體觸媒及第二成形整體觸媒較佳藉由摻合顆粒成均質混合物來組合。然而,亦預計將第一成形整體觸媒及第二成形整體觸媒組合在至少兩連續層中,其中該等層具有不同相對量之第一成形整體觸媒與第二成形整體觸媒;或將其組合在一層中,該層在與其垂直之方向上具有第一成形整體觸媒與第二成形整體觸媒之相對量沿其逐漸改變之組成梯度。
本發明進一步係關於根據本發明之整體觸媒或經硫化之整體觸媒組合物,其中該觸媒組合物包含至少50%,較佳大於60%、65%或甚至70%(相對於VIB族金屬之總量之莫耳%)之鎢;係關於該觸媒組合物在氫化處理烴原料中作為氫化脫硫觸媒之用途;且係關於一種使用該觸媒組合物之氫化處理方法。已發現該富含鎢之觸媒在氫化脫硫中尤其具有活性。較佳地,此觸媒組合物在20巴以上,較佳高於40巴,且甚至更佳高於50巴且最佳高於60巴之較高壓力下使用。已發現壓力愈高此觸媒之活性愈高。
或者,本發明係關於成形整體觸媒或經硫化之整體觸媒,其中該觸媒包含至少50%,較佳大於60%、65%或甚至70%之鉬(相對於VIB族金屬之總量之莫耳%);且係關於該觸媒在氫化處理烴原料中作為氫化脫氮觸媒之用途;且係關於一種使用該觸媒組合物之氫化處理方法。已發現該富含鉬之觸媒在氫化脫氮中尤其具有活性。
本發明亦係關於一種包含已經硫化之如上文所述之整體觸媒組合物的經硫化之整體觸媒組合物;且係關於該整體觸媒組合物或經硫化之整體觸媒組合物在氫化處理包含含硫及氮有機化合物之烴原料中之用途。本發明亦係關於藉由包含在催化轉化條件下在催化有效量之根據本發明之整體觸媒組合物存在下使烴原料與氫相接觸之方法來氫化處理該烴原料。此外,本發明係關於整體觸媒組合物中之二金屬鎳-鎢或鎳-鉬成形整體觸媒顆粒在其製備中或在根據本發明之氫化處理方法中之用途。
本發明將藉由下文所述之實例及比較實驗得以進一步說明。
將115.2 g MoO3
(0.8莫耳Mo,ex.Aldrich)及200 g鎢酸H2
WO4
(0.8莫耳W,ex.Aldrich)在6400 ml水中調漿(懸浮液A)且加熱至90℃。將282.4 g羥基碳酸鎳2NiCO3 *
3Ni(OH)2 *
4 H2
O(2.4莫耳Ni,ex.Aldrich)懸浮於1600 ml水中且加熱至90℃(懸浮液B)。此實例及其他實例中所用之羥基碳酸鎳之B.E.T.表面積為239 m2
/g。10分鐘內將懸浮液B添加至懸浮液A中,且在不斷攪拌下,將所得混合物在90℃下保持16小時(隔夜)。此時間結束時,將懸浮液過濾。產率在98%以上(以所計算之已轉化成其氧化物之所有金屬組份之重量計)。將所獲得之濾餅與2.5重量%之黏合劑(以觸媒組合物之總重量計)濕式混合。調整混合物之水含量以獲得可擠壓混合物,且繼而將該混合物擠壓。將所得固體在120℃下乾燥16小時(隔夜)且在300℃下煅燒1小時。將該觸媒硫化且使用來自下文所述之柴油測試程序D1之程序進行測試且轉化結果匯總於表3中。
藉由將未反應之VIB族金屬組份及VIII族金屬組份之氧化物濕式混合製備觸媒:使用185.6 g WO3
(0.8莫耳W,ex.Aldrich)、115.2 g MoO3
(0.8莫耳Mo,ex.Aldrich)及180 g NiO(2.4莫耳Ni,ex.Aldrich)製備觸媒。將濕氧化物混合物與2.5重量%之黏合劑(以觸媒組合物之總重量計)混合。將該等金屬氧化顆粒擠壓、乾燥、煅燒且硫化且繼而使用來自下文所述之柴油測試程序D1之程序進行測試。測試結果匯總於表3中。
除僅使用一種VIB族金屬組份以外,如C1中所述製備濾餅:使用400 g鎢酸(1.6莫耳W,ex.Aldrich)及282.4 g羥基碳酸鎳(2.4莫耳Ni)製備觸媒。產率為約99%。將該等金屬氧化顆粒擠壓、乾燥、煅燒且硫化且繼而使用來自下文所述之柴油測試程序D1之程序進行測試。測試結果匯總於表3中。
除僅應用一種VIB族金屬組份以外,如比較實驗1(C1)中所述製備濾餅:使用230.4 g三氧化鉬(1.6莫耳Mo,ex.Aldrich)及282.4 g羥基碳酸鎳(2.4莫耳Ni)製備觸媒。產率為約85%。將該等金屬氧化顆粒擠壓、乾燥、煅燒且硫化且繼而使用來自下文所述之柴油測試程序D1之程序進行測試。測試結果匯總於表3中。
將C3中所製備之Ni-W成形觸媒與C4中所製備之Ni-Mo成形觸媒摻合以製備成形整體觸媒顆粒摻合物組合物。調整各別觸媒之量以獲得最終顆粒摻合物中Ni:Mo:W莫耳比為1.5:0.5:0.5(對應於341.6 g(乾基)Ni-W餅塊(C3)及256 g Ni-Mo餅塊(乾基,C4)之量)。將由此獲得之成形觸媒顆粒摻合物組合物硫化且使用來自柴油測試程序D1之程序進行測試。測試結果匯總於表3中。實例E5驚奇地展示,與所提及之先前技術之教示相反,三金屬觸媒中不必具有在化合物反應成金屬氧化顆粒期間一起存在之VIB族金屬與VIII族金屬。此外,兩種VIB族金屬甚至不必處於同一觸媒顆粒中。更令人驚奇地,已證明根據本發明之整體觸媒組合物在氫化脫硫(HDS)中與在氫化脫氮(HDN)中均具有甚至較高的活性。
觸媒在降流管狀反應器中進行測試。每一反應器管含有10 ml與等量SiC顆粒混合且夾於SiC顆粒層之間的觸媒。測試之前,使用表1中所述之已經二甲基二硫化物強化至總硫含量為3.7重量%之原料,經由液相預硫化使觸媒預硫化。隨後將經預硫化之觸媒在氫化處理具有表1中所展示之特性之柴油原料中進行測試:
觸媒在表2中所展示之兩種條件下進行測試。
表3中給出柴油氫化處理測試結果,其中RVA及RWA分別為以反應器中所裝載之總觸媒量計之相對體積活性及相對重量活性。HDN為氫化脫氮且HDS為氫化脫硫。CBD意謂觸媒之緊密容積密度。R3指示固體-固體反應方法,其中第一金屬化合物與第二金屬化合物在反應期間至少部分為固體。柴油測試程序D1使用兩種不同溫度及壓力條件1及2進行。後綴1或2(例如如在RWA1及RWA2中)分別係指測試條件1及2。柴油測試程序D1中之參考觸媒C1(表3中之C1)之RWA/RVA值定義為100。所有其他RWA/RVA值均係相對於此參考觸媒計算。
Claims (35)
- 一種包含包括一或多種VIII族金屬及兩種或兩種以上VIB族金屬之金屬氧化顆粒之整體觸媒組合物,該整體觸媒組合物包含i)包含一或多種第一VIII族金屬及一或多種第一VIB族金屬之第一金屬氧化顆粒,ii)包含一或多種第二VIII族金屬及一或多種第二VIB族金屬之經獨立製備之第二金屬氧化顆粒,其中該等第一金屬氧化顆粒與該等第二金屬氧化顆粒中之VIB族金屬及VIII族金屬之組成不同,其中該等第一氧化整體顆粒與該等第二氧化整體顆粒經獨立成形為分開之第一成形觸媒顆粒與第二成形觸媒顆粒,其經組合以形成該整體觸媒組合物。
- 如請求項1之整體觸媒組合物,其中該第一成形觸媒顆粒與該第二成形觸媒顆粒經組合以形成整體觸媒摻合物組合物。
- 如請求項1或2之整體觸媒組合物,其中該等第一成形觸媒顆粒及/或該等第二成形觸媒顆粒已藉由擠壓、製粒或造粒而成形。
- 如請求項1或2之整體觸媒組合物,其中該第一成形觸媒顆粒及/或該第二成形觸媒顆粒已藉由噴霧乾燥或藉由研磨而成形。
- 如請求項4之整體觸媒組合物,其中在噴霧乾燥或研磨後進行篩分。
- 如請求項1或2之整體觸媒組合物,其中該等第一金屬氧化顆粒中之該或該等第一VIB族金屬及/或該或該等第一VIII族金屬與該等第二金屬氧化顆粒中之該或該等第二VIB族金屬及/或該或該等第二VIII族金屬不同。
- 如請求項1或2之整體觸媒組合物,其中該等第一金屬氧化顆粒中之該等VIB族金屬與該等第二金屬氧化顆粒中之該等VIB族金屬不同。
- 如請求項7之整體觸媒組合物,其中該等第一金屬氧化顆粒包含VIB族金屬鉬且該等第二金屬氧化顆粒包含VIB族金屬鎢。
- 如請求項1或2之整體觸媒組合物,其中該等第一金屬氧化顆粒中之該等VIII族金屬與該等第二金屬氧化顆粒中之該等VIII族金屬相同。
- 如請求項9之整體觸媒組合物,其中該等第一金屬氧化顆粒與該等第二金屬氧化顆粒中之該VIII族金屬相同,且該第一氧化整體觸媒中之該VIB族金屬僅為鉬,且在該第二氧化整體觸媒中僅為鎢。
- 如請求項10之整體觸媒組合物,其中該VIII族金屬為鎳或鈷。
- 如請求項10之整體觸媒組合物,其中該等第一金屬氧化顆粒與該等第二金屬氧化顆粒分別為NiMo及/或NiW二金屬氧化顆粒。
- 如請求項1或2之整體觸媒組合物,其中該等第一金屬氧化顆粒包含兩種或兩種以上VIB金屬及一或多種VIII族 金屬且其中該等第二氧化顆粒包含僅一種VIB族金屬及一或多種VIII族金屬。
- 如請求項13之整體觸媒組合物,其中該等第一金屬氧化顆粒為NiMoW氧化顆粒且該等第二金屬氧化顆粒為NiW及/或NiMo氧化顆粒。
- 如請求項1或2之整體觸媒組合物,其中該等第一成形觸媒顆粒與該第二成形觸媒顆粒以使得該整體觸媒組合物中鉬與鎢之莫耳比介於1:9與9:1之間的相對量組合。
- 如請求項1或2之整體觸媒組合物,其中該等第一成形觸媒顆粒與該等第二成形觸媒顆粒均為新鮮製備的。
- 如請求項1或2之整體觸媒組合物,其中該等第一成形觸媒顆粒或該等第二成形觸媒顆粒中之一者為耗廢、廢棄或再生耗廢整體觸媒顆粒且該等第一成形觸媒顆粒或該等第二成形觸媒顆粒中之另一者為新鮮製備的。
- 一種用於製備如請求項1至17之整體觸媒組合物之方法,其提供第一成形觸媒顆粒及第二成形觸媒顆粒,其中該等第一成形觸媒顆粒與該等第二成形觸媒顆粒中之一者或兩者以包含以下步驟之方法來獨立製備:iv)在質子性液體存在下,製備包含一或多種包含一或多種VIII族金屬之第一化合物、及一或多種包含一或多種VIB族金屬之第二化合物的反應混合物,v)使該等第一化合物與該等第二化合物反應以形成金屬氧化整體顆粒,vi)使該等金屬氧化整體顆粒成形為成形整體觸媒顆 粒,隨後組合該等第一成形觸媒顆粒與該等第二成形觸媒顆粒以形成該整體觸媒組合物。
- 如請求項18之方法,其中VIII族金屬為Ni或Co。
- 如請求項18之方法,其中VIB族金屬為鉬或鎢。
- 一種如請求項1至17之整體觸媒組合物用於氫化處理烴原料之用途。
- 一種如請求項4至17之整體觸媒組合物用於漿料式氫化處理烴原料之用途。
- 一種在如請求項1至17之整體觸媒組合物中之鎳-鎢或鎳-鉬二金屬成形整體觸媒顆粒的用途。
- 一種氫化處理烴原料之方法,其包含在催化轉化條件下,在催化有效量之如請求項1至17中任一項之整體觸媒組合物存在下,使該原料與氫相接觸。
- 如請求項24之氫化處理方法,其中如請求項4至17之整體觸媒組合物作為漿料存在於該原料中。
- 如請求項24或25之氫化處理方法,其使用包含至少50%之鎢(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫硫觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於60%之鎢(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫硫觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於65%之鎢(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組 合物作為氫化脫硫觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於70%之鎢(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫硫觸媒。
- 如請求項26之氫化處理方法,其中該氫化處理在至少20巴之壓力下進行。
- 如請求項26之氫化處理方法,其中該氫化處理在至少40巴之壓力下進行。
- 如請求項24或25之氫化處理方法,其使用包含至少50%之鉬(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫氮觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於60%之鉬(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫氮觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於65%之鉬(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫氮觸媒。
- 如請求項24或25之氫化處理方法,其使用包含大於70%之鉬(相對於VIB族金屬之總量之莫耳%)之該整體觸媒組合物作為氫化脫氮觸媒。
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