TWI324086B - Ni hydrogenation catalysts, manufacture and use - Google Patents

Ni hydrogenation catalysts, manufacture and use Download PDF

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Publication number
TWI324086B
TWI324086B TW093116968A TW93116968A TWI324086B TW I324086 B TWI324086 B TW I324086B TW 093116968 A TW093116968 A TW 093116968A TW 93116968 A TW93116968 A TW 93116968A TW I324086 B TWI324086 B TW I324086B
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TW
Taiwan
Prior art keywords
weight
catalyst
gram
alumina
total nitrogen
Prior art date
Application number
TW093116968A
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English (en)
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TW200513318A (en
Inventor
J Yong Ryu
Hugh M Putman
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Catalytic Distillation Tech
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Publication of TW200513318A publication Critical patent/TW200513318A/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—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
    • B01J23/78—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 alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—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
    • B01J23/80—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 zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—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
    • 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
    • B01J23/843—Arsenic, antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/885—Molybdenum and copper

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

已知之製備活性氧化鋁之技術製備。 此氧化紹可含至多約2重量％之驗金屬，較佳為少於約重 =之驗金屬。本發明揭示之較佳氧化紹之—可藉滴油膠 化技術製備。膠化技術之實例揭示於美國專利第2,62〇314 號⑽2)、及第4,273,735號⑽1)β球形氧化紐可由經基氯 化紹製備，其係藉由使紹金屬在氫氯酸水溶液中浸煮而製 備°滴形式之球形氧化㈣膠材料在㈣液態油相中膠 化，繼而老化、清洗、乾燥，及在商業製造中高溫锻燒而 通常得到γ·氧化紹。或者，較佳之球形氧化紹亦可藉由使 用分散水紹土或假水紹土氧化銘溶夥之滴油膠化技術而製 備。參見美國專利第4,丨79，彻號（丨979)。此氧化㈣勝係 藉由將適當之水紹土、假水紹土、或水铭土與假水紹土氧 化銘之混合物分散於酸性水中而製備。假水銘土或水銘土 原料係藉由將院氧化紹水解，及結晶或反應铭酸納與紹鹽 ⑼硫酸…且結晶而製備。各種水Μ氧化紹或分散水紹土 氧化鋁溶膠為市售。為了製備具有如本發明所揭示之孔結 構之較佳球形氧化铭，可使用Disperal Ηρ 14/2、此〆 11N&-80 . Dispal 23N4-20 ^ Disperal HP 14 ^ Deperal 40 ^ PuM _ ' i 〇〇 ' pural NG等或其混合物。較佳氧化 為在範圍為約750至約1200 °C之高溫煅燒之過渡氧化 鋁而製造δ、κ、0與α結晶形式或其混合物。如果煅燒係 在以上疋義之溫度範圍下限進行，則經煅燒氧化鋁可能含 少量之α氧化鋁。 各種擠製物或錠形式之較佳氧化鋁亦可藉由使用以上討 93707.doc 論之較佳水鋁土或假水鋁土氧化鋁，及在約750至1200°C之 南溫炮燒而製備。由於緩慢結晶而成為較安定之結晶形 式，氧化鋁之表面積因重複暴露於高溫而趨於收縮。此表 面積收縮因在大氣中存在水分或氧化链中有殘量納或兩者 而加速。用於觸媒製儀之先行技藝氧化紹撐體通常因在約 550至700C之溫度锻燒而製成〇1氧化紹。 本發明中較佳氧化紹之實體形狀可為任何形&，如球 形、擠㈣、片、及顆粒，其較佳為具有小於約1/4英忖’ 較佳為1/8英奴直徑，及何約1/2英奴長度，而且㈣ 物或片之長度較佳為小於1/4英时。 錄沈積於撑體上可藉單或多次浸潰而進行。鎳化合物之 溶液係藉由將鎳化合物或有機錦化合物溶於有機溶劑或水 令而製備。鎳化合物之實例為鎳鹽，如硝酸鎳，或有機金 屬鎳化合物’如乙酸鎳、甲酸鎳、乙醯醋酮酸鎳、烷氧化鎳 等。將此浸潰產物乾燥及在2⑼至_1，較佳為250至50(rc 之範圍之溫度煅燒。 除了 Ni，在本氫化觸媒含一或多種元^u、Re、pd、Zn、 1^、]^。心與81時，其較佳為按以下之量使用：〜約〇〇〇5 至約10重1 % ; Re-約〇丨至約5重量％ ; pd_約〇 〇丨至約2重量 %，Zn-約〇.1至約！〇重量％ ; Ca約〇」至約7重量％; Mg·約 〇·1至約7重：g%’ Mo-約（M至約1〇重量％ ;及則·約〇 〇5至約 7重量％。 在製備含①之〜觸媒時，較佳為撐體在沈積錄之前經祕 化合物之溶液浸潰。鉍化合物之實例為硝酸鉍。 93707.doc 1324086 在1備含銀之Νι觸媒時，較佳為撐體經鎳化合物與銀化 合物（如硝酸銀）之混合溶液浸潰。視情況地，可進行一系列 之4序浸潰’其由首先在㈣上浸潰銀化合物開始。 觸媒性能之評估係藉由在特定之乙炔化合物轉化率或在 符合指定之產物定性所需轉化率，比較特定進料之所需產 物回收率而進行。例如，在將粗丁二烯流中之快化合 物選擇性地氫化時，丁二烯為欲自進料流回收之所需產 物，以下數學式定義1，3_BD之回收率。 1，3-BD之回收率（％)=1〇〇_(Nf_Np)x1〇〇/Nf 其中： NF=進料流中之i，3_BD重量％，Np=產物流中之丨，3_bd重量％ 4乙炔（組s之乙稀基乙快與乙基乙块）之回收率係以相 同之方式定義。 完全或接近完全之C4乙炔轉化（殘留少於30 ppm)及高 1，3-丁二烯回收率導致排除兩個萃取蒸餾單位之一，而將 1,3-丁二烯自混合流分離。結果為較低之丨，3_丁二烯製造成 本。 由於各種原因，觸媒之性能隨流中時間而退化。一個原 因為有毒碳質材料在觸媒表面上之缓慢累積。為了延長觸 媒循環或使用壽命，可使用溶劑洗除重聚合物以減緩有毒 碳質材料在觸媒上之累積速率。因此，在選擇性氫化條件 下，重聚合物在溶劑中應為可溶性（至少某些程度）(5此溶劑 之實例為環己烷、甲基環己烷、苯、甲苯、烷基腈、糠醛、 二甲基乙醯胺、二曱基甲醯胺、甲基吡咯啶酮、甲醯基嗎 93707.doc 1324086 啉、及醚類（如四氫呋喃）、或其混合物。將溶劑自反應器流 出液流回收以再循環。視情況地，溶劑可能因將進料之重 成分（其通常為進料之小部份且亦因在催化反應區中選擇 性氫化時之寡聚合與聚合而產生）再循環而在系統中（在單 疋起點處）累積。對於固定床操作，溶劑係隨進料共同進料 至催化反應區》對於催化蒸餾或萃取催化蒸餾操作，溶劑 係在管柱上半部之適當位置引入。另一種替代性操作步驟 為在70Τ至450卞之適當溫度，在〇至500 psig之壓力下，較 佳為在氫存在下，偶而以溶劑清洗觸媒。另一種替代性選 項為，在催化反應區中在大於正常所需之過量氫存在下， 間斷地實行選擇性氩化一段特定時間，例如，數日，即使 在此期間時1，3 - 丁二烯回收率稍低。 對照例1 (習知觸媒） 測試市售Ni觸媒（28重量％之Ni於氧化鋁上）因選擇性氫 化去除粗進料流中C4乙炔雜質。將4〇克之觸媒混合6〇毫升 之3毫米直徑玻璃球，而且裝載於垂直安裝之上流式不銹鋼 固定床反應器（直徑1英吋X長度20英吋）中。此觸媒為直徑 1.2毫米χ2-5毫米三葉擠壓物。在觸媒床各端装設兩個熱偶 以控制反應器溫度。觸媒係由製造商以活化及鈍化形式供 應。此觸媒具有以下之物理性質：113平方米/克之BET表面 積、0.438立方公为/克之總吸附孔體積、及151埃之平均 孔徑》此觸媒在250°F於300 cc/分鐘氣流（33體積％之氫氣於 氮中）中再活化1.5小時，然後在575卞使每分鐘35〇 cc之純 93707.doc - 9 - 1324086 氫氣通過5小時。將反應器冷卻至周溫。以6毫升/分鐘之烴 進料’及在反應開始時為44 seem/分鐘’在1〇8 psig之固定 反應器>1力降至21 seem/分鐘之氫流速，進行粗進料蒸氣中 乙炔雜質之選擇性氫化《此進料包含35〇〇重量ppm2C4乙炔 (2940 ppm之 VA與 56〇 ppm 之 EA)、33〇 ppm之甲基乙炔、 66.60重量％之1，34]0、28〇重量卯〇1重量％之1，2_31)、16〇 重量ppm之丙二烯、21.65重量％之丁二烯等。因為氫化之 放熱，觸媒床終點之溫度高於觸媒床起點。氫化之溫度係 在120°F之固定溫度進行。完全之c：4乙炔轉化需要44 sccm/ 分鐘或更多之氫’在此1，3_BD回收率為96.8%。測試結果描 述於圖中。市售觸媒之物理性質列於表1。 實例2 (本發明） 製備鎳觸媒以證明本發明之催化性能優於實例丨（對照） 之習知Ni觸媒。此觸媒係藉由進行兩次浸潰而製備。用以 製備錄觸媒之γ-氧化紹為藉滴油膠化技術製備之直徑1 6 8 毫米之球。在750°C煅燒3小時之氧化鋁之物理性質歸納於 表1。此氧化鋁中超過約95%之孔直徑大於2〇〇埃。此材料 之X-射線繞射（XRD)顯示為γ氧化鋁。在空氣中於11〇〇它煅 燒又3小時後，氧化鋁球之平均直徑自168毫米收縮至！ 45 毫米。此經煅燒氧化鋁之物理性質列於表！，而且作為州 之撐體《此經般燒氧化鋁之XRD顯示為具一些氧化紹。 藉由將103克之ΝιΝ〇3.6Η2〇溶於285克之水中，而製備第 一次浸潰用之硝酸鎳溶液《將300克之經煅燒氧化鋁置於轉 93707.doc -10- 1324086 動浸潰器中，而且將硝酸鎳溶液倒在轉動浸潰器中之氧化 銘上。在藉由將熱風吹入轉動浸潰器中而使轉動浸潰器中 之内容物在約200°C乾燥後，使乾燥產物在350。(：煅燒2小 時。藉由將56克之NiNOr6H2〇溶於285克之水中，而製備第 二次浸潰用之另一種鎳溶液。第二次浸潰係以如第一次浸 潰之類似方式進行。使乾燥之浸漬產物在3 8〇 t煅燒2小 時。以所使用硝酸鎳之總量計，沈積於氧化鋁撐體上之錦 量為9.67重量％。Ni觸媒之物理性質列於表1。 表1 推體 撐體 1100°C 市售 750C锻燒1100°C锻燒锻燒Ni觸媒Ni觸媒 t為在Ρ/Ρ〇=0·9801半徑 0.62 0.71 0.86 65.6 66.0 113 0.713 0.626 0.438 449 383 151 小於493埃之孔 ABD ’ 克/cc 0 48 BET’平方米/克 145〇 總N2孔體積，（cc/克）t 〇 925 平均孔徑，埃 216 將40克之觸媒混合60毫升之3毫米直徑玻璃球，而且裝載於 垂直女裝之上流式不錄鋼固定床反應器（直徑1英对X長度 20英寸）中。在觸媒床各端裝設兩個熱偶以控制反應器溫 度。此觸媒在250卞於30〇cc/分鐘氣流（33體積％之氫氣於氮 幻中活化1.5小時，及在670然後7卿使每分鐘⑽“之純 氫氣各通過3小時。將反應器冷卻至周溫。以在反應開始時 為6毫升/分鐘之烴進料及31 sccm/分鐘，在1〇8㈣之固定 反應器壓力下降至17 sccm/分鐘之氫流速，及在12打之線 點觸媒床溫度，以用於對照⑷之相同進料進行乙快雜質之 93707.doc 選擇性氫化。因為氫化之放執， 媒床起點。 _床終點之温廑高於觸 完全之C4乙炔轉化需要33 sccm ^3-ΒΟ^^ψΛ 97 7〇Χ , 刀鐘之歲流速，在此 明本發明試結⑽述於圖中。其明確地證 觸媒之性能優於對照例觸媒之性能。 【圖式簡單說明】 氫化觸媒與習知觸媒之HBD回收 圖式為比較本選擇性 率之圖表。
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Claims (1)

  1. .芡)JL本 iiU 〇句4%8號專利申請案 °·中史命^專利範圍替換本('99年2为 請專利範園： 一種用以於粗烯烴與二烯烴流中將乙炔雜質選擇性氫化 之觸媒’其由約9 67至約2〇重量％Ni及一或多種選自約 0.005重量。/。至約丨〇重量。/(>Cu、約〇丨至約丨〇重量％ zn、約 0.1至約1 2 3重量％Mg、約〇.1至約7重量％Ca與約〇.〇5至約7 重量°/〇Bi組成之群組之元素，沈積於具有以下物理性質之 樓體上：30至約100平方米/克之bet表面積，0.4至約〇,9 CC/克之總氮孔體積，及約110至45〇埃之平均孔徑，至少 50%之孔之直徑係大於1〇〇埃，且總氮孔體積係約〇 4 ec/ 克至約〇·9 cc/克且視填積密度（ABD)係約0.35至0.75克 /cc。 2. 根據清求項1之觸媒，其中該氧化鋁在約750至約12001 之溫度範圍煅燒。 3. 根據請求項1之觸媒，其中該氧化鋁含少於約2重量。/〇之驗 金屬。 4. 根據請求項1之觸媒，其中該氧化鋁包含δ、κ、^與^結晶 形式之過渡氧化鋁或其混合物。 1 . 一種選擇性氫化觸媒，其包含約4重量％至約20重量％Ni 及約0.05至約7重量％Bi ’沈積於具有以下物理性質之撐 體上：30至約100平方米/克之bET表面積，〇 4至約〇 9 cc/ 克之總氮孔體積及約110至4 5 0埃之平均孔徑。 2 ' 一種選擇性氫化乙炔化合物之方法，其包含在選擇性氫 匕條件下’以觸媒接觸含乙快化合物與其他不飽和化合 物之進料’此觸媒包含約9.67至約20重量％之Ni及—或多 3 93707-990206.doc 1324086 種選自、約0·1至約10重量％Zn、約0_1至約7重量％]^1§及 . 約〇. 1至約7重量％ Ca組成之群組之元素，在選擇性氫化 條件下沈積於具有以下物理性質之撐體上：3 0至約1 〇〇平 方米/克之BET表面積，0.4至約0.9 cc/克之總氮孔體積， 及約110至450埃之平均孔徑，至少50%之孔之直徑大於 100埃，且總氮孔體積係約0.4 cc/克至約〇.9 cc/克且視填 積密度（ABD)係約〇.3 5至0.75克/cc，而且回收具有較該 進料少之乙炔化合物之產物。 7 ·根據請求項6之選擇性氫化乙炔化合物之方法，其中該氧 化鋁在約750至約120(TC之溫度範圍煅燒。 8. 根據請求項6之選擇性氫化乙快化合物之方法，其中該氧 化鋁含少於約2重量％之鹼金屬。 9. 根據請求項6之選擇性氫化乙炔化合物之方法，其中該氧 化鋁包含δ、κ、Θ與α結晶形式之過渡氧化鋁或其混合物。 1 0.根據請求項6之選擇性氫化乙炔化合物之方法，其中將一 種溶劑隨進料共同進料。 1 1 ·根據請求項1 〇之選擇性氫化乙炔化合物之方法，其中該 溶劑係選自環己烧、甲基環己烧、苯、甲苯、烧基腈、 糠酸、—曱基乙醯胺、二曱基甲醢胺 '曱基。比〇各咬酮、 甲醯基嗎啉、及醚類、及其混合物組成之群組。 12. —種用以於粗烯烴與二烯烴流中將乙炔雜質選擇性氫化 之觸媒，其由約9.67至約20重量％冲組成素，沈積於具有 以下物理性質之撑體上：3〇至約1〇〇平方米/克之ΒΕΤ表面 積’ 〇·4至約〇.9 cc/克之總氮孔體積’及約11〇至45〇埃之 93707-990206.doc 1324086 平均孔徑，至少50%之孔之直徑係大於100埃，且總氮孔 體積係約0.4 cc/克至約0.9 cc/克且視填積密度（ABD)係約 》 0.35 至 0.75 克/cc。 93707-990206.doc
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