200417555 玖、發明說明： [發明所屬之技術領域] 本發明係關於一種藉由經固態鋁矽酸鎳觸媒反應而製 備烯烴之寡聚物（特別是二聚物）之方法，此觸媒及製備 此觸媒之方法。 [先前技術] 烯煙之低分子量寡聚物，特別是c 3 - c 5烯烴之二聚物 ，爲用於，例如，醛類、羧酸類與醇類製備之中間產物。 由線形丁烯形成之c8 -烯烴可藉氫甲基化繼而氫化成對應壬 醇而轉化，其依序主要用於塑性劑製備。 在使用藉寡聚合製備之烯烴時，其分支程度經常爲重 要之標準。分支程度之測定爲異構指數。因此，例如，線 形辛烯（正辛烯）具有異構指數0，甲基庚烯具有異構指數 1，及二甲基己烯具有異構指數2。在計算混合物之異構指 數時’需要考量化合物之個別基之質量比例。混合物之異 構指數越小，則平均而言存在於其中之化合物越爲線形。 烯烴混合物之異構指數設定下游產物之最小分支程度 ’因此參與決定其使用性質。 在將c8-烯烴混合物氫甲基化繼而氫化而製備壬醇時 ’混合物之高線形爲有利的，因爲線形烯烴比分支烯烴較 快速地且較選擇性地反應，因此產生較高之產率。使用具 有低異構指數之C8_烯烴混合物產生比使用分支C8-烯烴混 合物時較線形之壬醇混合物。壬醇混合物之低異構指數改 良由其製備之塑性劑之使用性質，特別是其黏度。例如， 在酞酸壬酯混合物之情形，低異構指數造成使用此塑性劑 -5 - 200417555 產生之塑化PVC之有利低揮發性及改良冷破裂溫度。 烯烴之寡聚合，特別是丙烯與丁烯，係在均質相中或 經固態觸媒異質地而工業地進行。 均貝丨隹化步驟欽述於’例如，A . C h a u v e 1與G . L e f e b v r e 之 Petrochemical Processes，第 1 卷，Technip 版（1989) ’第183-187頁。世上廣爲實行之均質催化方法爲使用可 溶性鎳錯合物之寡聚合，其已知爲DIMERS0L法（參考資料200417555 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for preparing oligomers (especially dimers) of olefins through a solid nickel aluminosilicate catalyst reaction. The catalyst and Method for preparing this catalyst. [Prior art] Low molecular weight oligomers of diene, especially dimers of c 3-c 5 olefins, are intermediate products used in, for example, the preparation of aldehydes, carboxylic acids and alcohols. The c8-olefin formed from linear butene can be converted by hydromethylation and then hydrogenated to the corresponding nonanol, which is mainly used in the preparation of plasticizers in sequence. When using olefins prepared by oligomerization, the degree of branching is often an important criterion. The degree of branching is determined as the heterogeneity index. Thus, for example, linear octene (n-octene) has an isomerization index of 0, methylheptene has an isomerization index of 1, and dimethylhexene has an isomerization index of 2. When calculating the isomerization index of a mixture ', it is necessary to consider the mass ratio of the individual groups of the compound. The smaller the mixture's isomorphic index, the more linear the compound present in it, on average. The isomerization index of the olefin mixture sets the minimum degree of branching of the downstream product 'and therefore participates in determining its use properties. The high linearity of the 'mixture is advantageous when the c8-olefin mixture is hydromethylated and then hydrogenated to produce nonanol, because linear olefins react faster and more selectively than branched olefins, resulting in higher yields. The use of a C8-olefin mixture with a low isomerization index results in a nonyl alcohol mixture that is more linear than when a branched C8-olefin mixture is used. The low isomerization index of the nonanol mixture improves the use properties of the plasticizers prepared from it, especially its viscosity. For example, in the case of nonyl phthalate mixtures, the low isomerization index results in the favorable low volatility and improved cold cracking temperature of plasticized PVC produced using this plasticizer. The oligomerization of olefins, especially propylene and butene, is carried out industrially in a homogeneous phase or heterogeneously via a solid catalyst. The homogenization step is described in 'for example, Petrochemical Processes of A. C h a u v e 1 and G. Le f e b v r e, Vol. 1, Technip Edition (1989)', pages 183-187. The homogeneous catalysis method widely practiced in the world is oligomerization using soluble nickel complexes, which is known as the DIMERS0L method (References
Yves Chauvin、Helene Oliviei•之 ’’Applied Homogeneous Catalysis with Organometallic Compounds”，Boy Cor nils · 、Wolfgang A. Herrmann 編著，Ver lag Chemie，1996， 258-268)。 均質催化方法之缺點爲觸媒隨反應產物與未反應原料 離開反應器，而且必須將其分離。如此需要加工步驟且造 成廢液流。由於由觸媒形成之產物無法再生產生活性觸媒 ，產生額外之觸媒成本。 在異質催化烯烴寡聚合方法中不發生這些缺點。長期 已知酸性異質觸媒之寡聚合；工業方法爲，例如，在載體馨 上使用沸石或磷酸而進行。得到之寡聚合產物爲分支烯烴 之異構物混合物。即使是在最適條件下，二甲基己燒在線 形丁細之寡聚合中組成主要產物。嫌烴寡聚合之酸催化之 實例可在W0 92/13818專利中發現。 在高等二聚物選擇性之烯烴之非酸性，異質催化寡聚 合中’在載體材料上之鎳化合物經常用於業界。此外，如 果欲製備具有低異構指數之產物，則鎳化合物之載體材料 必須不過於酸性。此型觸媒爲固定床觸媒，其用於〇χΕΝ〇 200417555Yves Chauvin, Helene Oliviei, "Applied Homogeneous Catalysis with Organometallic Compounds", edited by Boy Cornells, Wolfgang A. Herrmann, Ver lag Chemie, 1996, 258-268). The disadvantage of the homogeneous catalytic method is that the catalyst follows the reaction product. It leaves the reactor with unreacted raw materials and must be separated. This requires processing steps and causes waste liquid flow. Because the products formed by the catalysts cannot be regenerated to produce active catalysts, additional catalyst costs are generated. Oligo-oligomeric catalysts These disadvantages do not occur in the polymerization method. Oligopolymerization of acid heterogeneous catalysts has long been known; industrial methods are, for example, carried out using zeolite or phosphoric acid on a carrier. The resulting oligomerization product is a mixture of isomers of branched olefin. Even under the most optimal conditions, dimethylhexanoate constitutes the main product in linear oligomerization. Examples of acid-catalyzed oligomerization of hydrocarbons can be found in the WO 92/13818 patent. Selectivity in higher dimers Non-acidic, heterogeneously catalyzed oligomerization of olefins' nickel compounds on support materials are often used in the industry Further, if the product is to be prepared having a low index of isomers, the support material of a nickel compound in an acidic, but must This type of catalyst is a fixed bed catalyst, for 〇χΕΝ〇 200417555
Olefinchemie GmbH Z 0CT0L 法（Hydrocarbon Process.， 國際版（1 9 8 6 ) 6 5 ( 2，第 1 節，3 3 3 ))。 用於此應用之受載鎳觸媒爲已知的。因此，W 〇 9 5 / 1 4 6 4 7 專利敘述一種用於烯烴寡聚合之鎳觸媒，其在包括成分鈦 氧化物及/或鉻氧化物、砂氧化物，如果需要及銘氧化物， 及一些鹼金屬氧化物之載體材料上。線形丁烯之混合物經 這些觸媒以少於7 5 %成爲C 8 -烯烴之選擇性寡聚合。C 8部份 之異構指數在0.85至1.1之範圍。 W0 9 9 / 2 5 6 6 8專利揭示藉由稀釋反應器輸入而限制反鲁 應器中之寡聚物含量，經包括Ni、Ti、Zr、A1、與Si之觸 媒可得高碳C8選擇性。依照這此實例，可以80 _81%之選擇 性製備具〇 · 93 - 0 . 95異構指數，或以83%之選擇性製備具1 . 0 異構指數之C8-烯烴。 [發明內容] 由於已知寡聚合方法關於二聚物形成之空間時間產率 及/或選擇性，及關於二聚物部份之分支程度無法令人信服 ，本發明之目的爲發現一種較佳地適合此目的之觸媒或發馨 展改良之方法。 已發現衍生自X -射線非晶性鋁矽酸鹽之鋁矽酸鎳，其 中非常高比例之鍵結至4個氧原子之鋁原子處於四面體環 境（配位數4)，爲特別良好之烯烴用寡聚合觸媒。以此方 式製備之觸媒可得到高空間時間產率及具高二聚物選擇性 與高線性之所形成寡聚物，特別是二聚物。 本發明因而提供一種觸媒，其包括5至6 0重量％之鎳 、5至30重量％之鋁、及1〇至40重量％之矽，其中觸媒中 200417555 10至100%之鋁原子爲四面體地配位。 此型觸媒可特別地用於具有2至1 0個，較佳爲3至5 個碳原子之烯烴之寡聚合，特別是二聚合。 本發明觸媒之優良性質推論歸因於鋁原子整體之配位 幾何。其可藉固態27A1_NMr測定。 至少部份之共價地鍵結至4個氧原子之鋁原子起初在 本發明之觸媒中具有配位數4。此結構單位在以下稱爲「四 面體鋁」，而且可藉27A1-NMR光譜在另一種環境中之鋁原 子存在下（例如，具有配位數5或6之鋁原子）偵測。在 27A1-NMR光譜中，「四面體鋁」產生具有相對Α1(：13·6Η20 爲55 ppm至57 ppm範圍之化學位移之信號。 對於相同實驗式之各種觸媒，烯烴寡聚合之時間空間 產率視鋁矽酸鹽中之「四面體鋁」濃度而定。例如，其受 原料（觸媒先質）影響。觸媒先質中之「四面體鋁」比例 越高’經由其製備之觸魔寡聚合之反應速率越高。相對地 ’在相同轉化率之二聚物選擇性及線性維持實際上固定。 本發明之觸媒較佳爲使用鋁化合物製備，特別是鋁矽 酸鹽’其中10%至1〇〇%，特別是50%至1〇 0%，非常特佳爲70% 至100%之鋁原子爲「四面體」。已可使用觸媒中四面體地 配位鋁之比例在熱處理時改變極小且在相同之範圍內。 此外’本發明之觸媒具有特定之組成物。其含5至6 〇 質量％之鎳，特別是1 〇至3 0質量％。鋁含量爲5至3 0質量 % ’特別是7至20質量％之範圍。矽之質量比例爲10至40% ’特別是20至30%之範圍。至於選用之其他成分，本發明 200417555 之觸媒含0 . 1至1 〇質量％，較佳爲ο . 1至5質量％，特佳爲 0 . 5至2質量％之一或更多種鹼金屬、鹼土金屬、鑭系及/或 稀土族之金屬氧化物。亦可有超過一種之此族氧化物存在 於依照本發明使用之觸媒中。存在於觸媒中之氧化物總和 在上述限制內。較佳鹼金屬氧化物爲氧化鈉與氧化鉀。此 外，此觸媒可進一步包括黏合劑，如黏土。 除了所述之金屬氧化物，依照本發明之觸媒可進一步 包括0.1至50重量％，較佳爲0.5至20重量％，特佳爲1 至10重量％之Ti02&/或Zr〇2。 本發明進一步提供一種製備本發明觸媒之方法。 在一種製備所述組成物之觸媒之方法變化中，其可藉 由混合鎳、矽與鋁化合物，繼而將混合物在3 0 0至8 0 0 °C煅 燒而得，其中鋁化合物中1 0至1 00%之鋁原子爲四面體地配 位。較佳爲使用X -射線非晶性鋁矽酸鹽作爲鋁化合物。 在另一種變化中，矽與鋁化合物係藉由混合及在300 -800°C煅燒而轉化成X-射線非晶性鋁矽酸鹽，其中存在之1〇 至1 00%之鋁原子爲四面體地配位，及繼而藉浸漬及在300 - 800°C煅燒而將鎳化合物應用於所得X-射線非晶性鋁矽酸鹽 〇 在最終產物中，金屬化合物之量對應上述重量比例。 在鋁矽酸鹽製備時或在特別地以鎳浸漬後，可加入選 用之其他組分。 本發明之觸媒較佳爲由其中應用鎳成分之含「四面體 銘」之非晶性鋁砂酸鹽製備。適合用於製備本發明觸媒之 -9- 200417555 商業原料爲，例如，得自Grace以商標名Grace DA VI CAT 銷售之鋁矽酸鹽，高溫鋁矽酸鹽或非晶性沸石（得自Mob i 1 〇 i 1 之 MCM 4 1 )。 至於鎳化合物（例如，應用於非晶性鋁矽酸鹽），可 使用鎳氧化物或在煅燒時排除其他基而轉化成鎳氧化物或 I呂砂酸鎳之含鎳化合物。適當有機鎳化合物之實例爲乙醯 基丙酮I酸鎳、烷氧化鎳、及羧酸（如甲酸或乙酸）之鎳鹽 〇 至於無機化合物，例如，可使用氫氧化鎳、氫氧化鎳 碳酸鹽、碳酸鎳、硝酸鎳、硫酸鎳、及其與水及/或氨之錯 合物。 亦可使用含超過一種用於製備此觸媒之鎳化合物之混 合物或溶液。此外，可將不同之鎳化合物連續地應用於鋁 矽酸鹽。 鎳化合物可藉各種方法引入鋁矽酸鹽中，例如，混合 、沈澱、浸漬、或噴灑。在製備本發明之觸媒前，以鎳化 合物之溶液噴灑或浸漬非晶性鋁矽酸鹽較佳。 如果適當，在預先乾燥後煅燒觸媒，即，非晶性鋁矽 酸鹽與鎳化合物之混合物。如此排除其他基而形成催化活 性鋁矽酸鎳。煅燒較佳爲在3 00至800 °C之溫度範圍，特別 是400至7 00 °C之範圍進行。視溫度而定，煅燒時間爲0 . 5 至6小時。煅燒可在惰性或氧化條件下進行。 觸媒係有利地以提供低流動抗性之形式使用，例如， 顆粒、片、或成形體（如平板、圓柱體、球粒、擠製體、 -10- 200417555 或環）之形式。 成形可在觸媒製程中之各點進行，例如，在鋁矽酸鹽 合成時或之後，在製備鎳化合物與鋁矽酸鹽之混合物之後 ’在煅燒後等。在成形前，如果需要，可將成形助劑加入 觸媒組成物或其先質。 特佳爲首先將觸媒乾燥，粉碎之，及成形而形成具有 0.1至5毫米，較佳爲0.2至2毫米，非常特佳爲0.5至1 毫米之平均直徑之片。適合用於此目的之裝置之實例爲得 自 Gustav Eirich，Hardheim/Baden 之混合器。繼而煅燒 〇 以此方式製備之觸媒具有優良之機械安定性及高體密 度。因爲片之機械磨耗/破壞造成之塵粉形成最少，可快速 地替換消耗或去活化觸媒。 本發明進一步提供一種寡聚合具有2至10個碳原子之 烯烴之方法，其係在20至200°C及超大氣壓力於液相經具 有5至60重量％之鎳、5至20重量％之鋁、及10至40重量 %之矽之固定床觸媒，其中固定床觸媒中10至100%之鋁原 子爲四面體地配位。 比較不含四面體地配位鋁原子或僅具有低比例之觸媒 ，本發明之觸媒在烯烴之寡聚合中產生較高之空間時間產 率。 用於本發明之烯烴寡聚合方法之觸媒可具有全部所提 及之組成物或包括全部所提及之金屬氧化物。 至於用於本發明方法之原料，可使用C2-C1()-烯烴，較 - 1 1 - 200417555 佳爲c3 -c5 -烯烴，或其實際上不含其他不飽和 種不飽和化合物（如二烯或乙炔衍生物）之混 爲使用含以烯烴含量計爲少於5質量％，特別是 %之分支烯烴之烯烴混合物。 丙烯係藉石油精裂煉而工業地製備，而且 本化學物。C5 -烯烴存在於得自精煉物或裂煉物 份。含C4 -烯烴之工業混合物包括得自精煉物之 、得自流體催化裂煉物或蒸氣裂煉物之C4餾份 -闕合成之混合物、得自丁烯脫氫之混合物、 混合物、或得自其他工業方法。 例如，適合用於本發明方法之線形丁烯之 自蒸氣裂煉物之C4餾份。在第一步驟中去除丁 藉丁二烯之萃取或萃取性蒸餾或其選擇性氫化 兩種情形，結果均爲實際上無丁二烯C4餾份， I。在第二步驟中，自C4流去除異丁烯，例如 醇反應而製備甲基第三丁基醚（MTBE)。其他可 物I中之異丁烯與水反應形成第三丁醇，或將 化寡聚合成一·異丁細。現無異丁細之C4飽份， I I，如所需包括線形丁烯，可能及丁院。如果 外藉蒸餾分離1 - 丁烯。兩種餾份，即，包括1 -括2 -丁烯者，均可用於本發明之方法中。 另一種製備適當原料之可能方式爲將萃餘 物I I、或在反應管柱中具有類似組成物之烴混 化。如此特別地可得到含2 - 丁嫌、少量1 - 丁燃 化合物與多 合物。較佳 少於1質量 爲易得之基 之輕汽油餾 輕汽油餾份 、得自費雪 移位形成之 混合物可得 二烯。其係 而完成。在 即，萃餘物 ，藉由與甲 能性爲萃餘 異丁烯酸催 即，萃餘物 需要，可另 丁烯者或包 物I、萃餘 合物氫異構 '可能及正 -12- 200417555 丁烷、及異丁烷與異丁烯之混合物。 本發明之方法係在各種分批或較佳爲 中進行，如在固/液接觸反應中習用者。在 動反應器時，通常但非必然使用固定床。 動反應器時，液體可以向上或向下方向流 向下之液體流動。亦可以產物再循環（循 次操作反應器。 在使用反應器時’觸媒床之長度對直 器之幾何尺寸或經充塡程度而改變。在特 出（LHSV)，以此方式可得到不同之空管速 反應混合物再循環之反應器可在1至5 0 ^ 度操作。在其中使用單次之反應器中，空 至3 0米/小時之範圍。 反應器中觸媒之空間速度（LHSV)爲〇. 鮮進料/觸媒公斤/小時；每次得到之轉化 爲 30-60% 。 由於增加轉化率造成正丁烯濃度之連 釋形成之產物’一種較佳之方法變化包括 環而操作反應器。在此’首先自來自反應 聚物，而且將其餘材料部份地再循環至各 送至後續反應階段。 使用之烯烴流通常含具有相同沸騰範 ，惰性物質，使得增加烯烴轉化率而可得 料流。在此情形，串列地連接多個寡聚合 ~1 3 - 連續操作反應器 使用連續操作流 在使用固定床流 經。通常較佳爲 環模式）或以單 徑比例可經反應 定量之觸媒及輸 度。其中部份之 长/小時之空管速 管速度可爲0.4 8至8公斤之新 率以正丁烯計則 續降低且另外稀 將起始烯烴再循 器之輸出分離寡 反應器之入口或 圍之飽和烴，即 到更多之稀釋進 階段，使得其各 200417555 可在符合降低烯烴濃度之反應條件下操作爲有利的。 寡聚合亦可在多個方法階段中進行。 反應階段數量爲1至10，較佳爲1至4。如果需要， 可進行反應產物之惰性組分及/或未反應烯之中間分離及再 循環。在各階段中，依照本發明之烯烴之寡聚合較佳爲進 行至5至50重量％，較佳爲5-45重量％，特別是5-35重量 %之反應產物中寡聚物含量。以此方式可將存在於工業進料 混合物中超過80%之含約20%惰性組分之烯烴寡聚合。含少 於3 0%之烯烴之殘餘流通常無法經濟地用於此方法中，而且 進一步作爲液化氣體或輕汽油。 這些反應器各可本質上絕熱地、多方地、或本質上恆 溫地操作，即，小於1 (TC之溫度增加。 操作反應器之溫度爲20至200°C，較佳爲70至160 °C ，非常特佳爲70至130°C，特別是80至120°C之範圍。如 果觸媒不含酸內容物，則隨溫度增加觀察到對正辛烯之增 加反應選擇性，因此至少部份地如已知之酸性寡聚合催化 而操作。 反應可在等於或高於烴進料混合物在各反應溫度之蒸 氣壓之壓力，較佳爲在低於40巴之壓力進行。爲了避免反 應器中之蒸發問題，壓力應比反應混合物在反應器中最高 溫度之蒸氣壓高2至4巴。 烯烴之總轉化率視所使用觸媒之型式及量、設定之反 應條件、及反應階段數量而定。爲了經濟之原因，在全部 階段將烯烴轉化率保持在50至100%，較佳爲90至100%之 200417555 範圍。此外，爲了得到局空間時間產率，使用具有不少於6 0 % ，較佳爲不少於8 0%之線形烯烴含量之烴爲有利的。 爲了增加選擇性，藉由將反應產物及/或未反應烯烴中 之惰性組分再循環而將反應產物中寡聚物含量設爲5至4 5 重量％，較佳爲5-35重量％爲有利的。 因此，自未反應烯烴、及反應產物之惰性組分（例如 ’脂族）分離反應產物（寡聚物及其他高沸物）爲必要的 〇 寡聚物含量特別爲1 0至3 0重量％之範圍。寡聚物濃度 限制可藉由選擇如溫度或停留時間之操作參數而達成。另 一種可能性爲藉由加入稀釋劑將反應器入口之起始烯烴濃 度保持低於80%，特別是低於60%。使用存在於原料中，而 且在起始烯烴之部份或實際上完全反應後自反應混合物回 收之稀釋劑爲有利的。在此方法之較佳具體實施例中，離 開反應器之混合物因此分離成含寡聚物之餾份及含稀釋劑 、脂族、可能及未反應烯烴之第二餾份。將一部份稀釋劑 及存在於其中之烯烴再循環至相同反應器或上游反應器， 及將其他部份送至下游反應器或加工。在多個串列連接之 反應器之情形，亦可存在超過一次之寡聚物分離。 在進一步蒸餾中，將已（自一或更多個分離單位）分 離之寡聚物分離成二聚物、三聚物、及高碳寡聚物。 本發明方法製備之寡聚物特別地用於製備醛類、醇類 與殘酸類。因此，例如，可將由線形丁烯得到之二聚物氫 甲基化而產生壬醛混合物。其可藉由氧化成對應之羧酸或 -15- 200417555 藉由氫化成C9 -醇混合物而轉化。q酸混合物可用於製備潤 滑劑或乾燥劑。C9 -醇混合物爲用於製備塑性劑（特別是酞 酸壬酯）之中間產物。 本發明之方法具有以下之優點：在使用本發明之觸媒 時’得到比不含四面體鋁原子或僅低比例之觸媒高之空間 時間產率。 [實施方式] 以下之貫例描述本發明但不限制其由申請專利範圍界 定之範圍。 實例1 (比較例）： 在捏合器中將600克含13重量％之A1203且具有約400 平方米/克之BET表面積之本質上X _射線非晶性鋁矽酸鹽組 合5 3 0克碳酸鎳漿料（檢驗：5 0 · 5 %之N i 0 )、6 5 0克碳酸 六氨鎳溶液（檢驗：14 · 9%之NiO) 、16克乙二醇、與390 克水，產生如濕土之混合均勻組成物。將其擠製形成具2 毫米直徑及3 - 1 0毫米長度之擠製物且乾燥。繼而將此材料 在6 0 0 °C煅燒2小時。將6 0 0毫升擠製物引入具2米長度及 2公分直徑之管反應器中，而且在外部藉水保持恆溫。觸媒 在管反應器中於1 50t在氮流中乾燥。繼而使20%之1 -丁烯 、6 0%之2-丁烯、與20%之正丁烷之混合物以1公斤/小時 之流速及在85°C之管壁溫度通過觸媒。在約40小時之時間 後，輸出之轉化率及組成物不再改變。輸出之組成物爲20% 之正丁烷、2.2%之 1-丁烯、46.2%之 2-丁烯、25.5%之 C8-烯烴、與5 . 1 %之具有1 2、1 6及更多個碳原子之烯烴。正丁 烯之轉化率因此爲3 9 . 5%。藉由蒸發低沸物而將產物餾份自 -16- 200417555 丁烷/ 丁烯餾份分離，及注射至氫化氣相層析中。c8餾份之 組成物如下：29 . 2%之二甲基己烷、61 . 1%之甲基庚烷、9 · 5% 之正辛烷、〇 . 2%之其他辛烷。煅燒後之最終觸媒具有340 平方米/克之BET表面積及1.12毫升/克之擠製物中孔體積 ，其中約0 . 5 3毫升/克具有大於5 0奈米之孔徑。小於5 0 奈米直徑之孔部份具有0.15毫升/克之大於6奈米直徑及 0 . 2毫升/克之4至6奈米直徑範圍。所使用鋁矽酸鹽之 27A1-NMR檢驗顯示，約45%之鋁原子爲四面體地配位。 實___例2 (依照本發明）： 完全依照實例1之步驟，然而，使用依照NMR檢驗含 約8 5%之四面體地配位鋁之鋁矽酸鹽。以相同之方式進行測 試。在 85 °C之壁溫，輸出之組成物爲20%之正丁烷、1 . 8% 之1-丁烯、33.8%之2-丁烯、37.8%之C8-烯烴、與6.7%之 具有1 2、1 6及更多個碳原子之烯烴。正丁烯之轉化率因此 爲5 5 . 6%。藉由蒸發低沸物而將產物餾份自丁烷/ 丁烯餾份 分離，及注射至氫化氣相層析中。C8餾份之組成物如下： 25 . 3%之二甲基己烷、61 . 2%之甲基庚烷、15 . 4%之正辛烯、 0 . 1%之其他辛烷。 爲了得到如比較例（實例1 )之相同條件，將溫度逐 漸降低。在74°C之管反應器壁溫，得到約39 . 7%之正丁烯 轉化率。C8餾份之組成物如下：29 · 0%之二甲基己烷、61 . 4% 之甲基庚烷、9 . 4%之正辛烷、〇 · 2%之其他辛烷。 用於實例2之觸媒因此實質上更爲活性；得到相同之 轉化率需要實質上較低之溫度。另一方面，相同轉化率之Cs -17- 200417555 餾份之組成物實際上相同。 煅燒後之最終觸媒具有3 5 5平方米/克之BET表面積及 1 . 10毫升/克之擠製物中孔體積，其中約0 . 49毫升/克具有 大於5 0奈米之孔徑。小於5 0奈米直徑之孔部份具有0 . 1 3 毫升/克之大於6奈米直徑及0.2毫升/克之4至6奈米直 徑範圍。 實例3 (比較例）： 在捏合器中將1000克含13重量％之A1203且具有約400 平方米/克之BET表面積之本質上X -射線非晶性鋁矽酸鹽組 合200克凝膠，其含30克假水軟鋁石（得自Condea之 Disperal)與170克之10%強度硝酸，加入30克乙二醇與 4 0 0克水，產生如濕土之混合均勻組成物。將其擠製形成具 2毫米直徑及3-10毫米長度之擠製物且在450°C煅燒2小 時。繼而以碳酸六氨鎳溶液（撿驗：1 4 · 9%之N i 0 )浸漬已 以此方式製造之觸媒載體以將孔飽和。將已以此方式浸漬 之載體乾燥及在60CTC煅燒2小時。最終觸媒含9.6%之NiO 。使用20 %之1-丁烯、60 %之2-丁烯、與20 %之正丁烷，如 實例1測試60 0毫升觸媒。在1公斤/小時之流速及85 °C之 管壁溫度，輸出之組成物爲20%之正丁烷、2 . 4%之1 - 丁烯 、49.7%之2-丁烯、24.1%之C8-烯烴、與3.8%之具有12、 1 6及更多個碳原子之烯烴。正丁烯之轉化率因此爲3 4 . 9% 。藉由蒸發低沸物而將產物餾份自丁烷/ 丁烯餾份分離，及 注射至氫化氣相層析中。C8餾份之組成物如下：29 . 8%之二 甲基己烷、60 . 6%之甲基庚烷、9 . 2%之正辛烷、〇 . 4%之其他 200417555 煅燒後之最終觸媒具有3 30平方米/克之BET表面積及 1 . 03毫升/克之擠製物中孔體積，其中約〇 . 45毫升/克具有 大於5 0奈米之孔徑。小於5 0奈米直徑之孔部份具有0 . 1 3 毫升/克之大於6奈米直徑及0.22毫升/克之4至6奈米直 徑範圍。所使用鋁矽酸鹽之27A1-NMR檢驗顯示，約38%之 鋁原子爲四面體地配位。 實例4 (依照本發明）： 完全依照實例3之步驟，然而，使用依照NMR檢驗含 約9 0%之四面體地配位鋁之鋁矽酸鹽。以相同之方式進行測 試。在85 °C之壁溫，輸出之組成物爲 20%之正丁烷、2 . 0% 之1-丁烯、37.8%之2-丁烯、33.8%之C8-烯烴、與6.4%之 具有12、16及更多個碳原子之烯烴。正丁烯之轉化率因此 爲49 . 8%。藉由蒸發低沸物而將產物餾份自丁烷/ 丁烯餾份 分離，及注射至氫化氣相層析中。C8餾份之組成物如下： 26 . 2%之二甲基己烷、61 . 4%之甲基庚烷、12 . 1%之正辛烷、 0 . 3%之其他辛烷。 爲了得到如實例1 (比較例）之相同條件，將溫度逐 漸降低。在7 6 °C之管反應器壁溫，得到約3 4 . 3 %之正丁烯 轉化率。C8餾份之組成物如下：29 · 3%之二甲基己烷、60 . 9% 之甲基庚烷、9 . 4%之正辛烷、〇 · 4%之其他辛烷。 用於實例4之觸媒因此比實例3實質上更爲活性；得 到相同之轉化率需要實質上較低之溫度。另一方面，相同 轉化率之Cs餾份之組成物實際上相同。 [圖式簡單說明]:無 -19"Olefinchemie GmbH Z 0CT0L method (Hydrocarbon Process., International Edition (19 8 6) 6 5 (2, Section 1, 3 3 3)). Supported nickel catalysts for this application are known. Therefore, the W 009 5/1 4 6 4 7 patent describes a nickel catalyst for oligomerization of olefins, which includes the components titanium oxide and / or chromium oxide, sand oxide, if necessary, and oxide, And some alkali metal oxide support materials. The mixture of linear butenes through these catalysts is selectively oligomerized to less than 75% C8-olefins. The C 8 component has a heterogeneity index ranging from 0.85 to 1.1. The W0 9 9/2 5 6 6 8 patent discloses that the oligomer content in the reactor is limited by diluting the reactor input. High-carbon C8 can be obtained by using catalysts including Ni, Ti, Zr, A1, and Si. Selective. According to this example, a C8-olefin with a 0.9 isomerization index with a selectivity of 0.893% to 0.95% can be prepared with a selectivity of 80-81%, or with a selectivity of 1.0% with a selectivity of 83%. [Summary of the Invention] Since the known oligomerization methods are not convincing with respect to the space-time yield and / or selectivity of dimer formation, and the degree of branching of the dimer portion, the object of the present invention is to find a better Locally suitable catalysts for this purpose or methods of fragrant development. It has been found that nickel aluminosilicates derived from X-ray amorphous aluminosilicates in which a very high proportion of aluminum atoms bonded to 4 oxygen atoms are in a tetrahedral environment (coordination number 4) are particularly good. Oligomeric catalysts for olefins. The catalysts prepared in this way can obtain high space-time yields and formed oligomers, especially dimers, with high dimer selectivity and high linearity. The invention thus provides a catalyst comprising 5 to 60% by weight of nickel, 5 to 30% by weight of aluminum, and 10 to 40% by weight of silicon, wherein 200417555 10 to 100% of the aluminum atoms in the catalyst are Tetrahedral coordination. This type of catalyst can be used in particular for oligomerization of olefins having 2 to 10, preferably 3 to 5 carbon atoms, especially dimerization. The superior properties of the catalyst of the present invention are inferred to be due to the coordination geometry of the aluminum atoms as a whole. It can be measured by solid state 27A1_NMr. At least part of the aluminum atoms covalently bonded to 4 oxygen atoms initially have a coordination number of 4 in the catalyst of the present invention. This structural unit is hereinafter referred to as "tetrahedral aluminum" and can be detected by the 27A1-NMR spectrum in the presence of aluminum atoms in another environment (for example, an aluminum atom having a coordination number of 5 or 6). In the 27A1-NMR spectrum, "tetrahedral aluminum" produces a signal with a chemical shift in the range of 55 ppm to 57 ppm relative to A1 (: 13 · 6Η20. For various catalysts of the same experimental formula, the time and space production of olefin oligomerization The rate depends on the concentration of "tetrahedral aluminum" in the aluminosilicate. For example, it is affected by the raw material (catalyst precursor). The higher the proportion of "tetrahedral aluminum" in the catalyst precursor, The reaction rate of magic oligomerization is higher. Relatively, the dimer selectivity and linearity maintenance at the same conversion rate are practically fixed. The catalyst of the present invention is preferably prepared using aluminum compounds, especially aluminosilicates. 10% to 100%, especially 50% to 100%, very particularly preferably 70% to 100% of the aluminum atoms are "tetrahedrons". The proportion of tetrahedral coordination aluminum in the catalyst is already available The change during heat treatment is extremely small and within the same range. In addition, the catalyst of the present invention has a specific composition. It contains 5 to 60% by mass of nickel, especially 10 to 30% by mass. The aluminum content is 5 To 30% by mass' especially in the range of 7 to 20% by mass. Mass ratio of silicon It is in the range of 10 to 40%, especially in the range of 20 to 30%. As for the other ingredients selected, the catalyst of the present invention 200417555 contains 0.1 to 10% by mass, preferably ο. 1 to 5% by mass, particularly preferably 0.5 to 2% by mass of one or more alkali metal, alkaline earth metal, lanthanide and / or rare earth metal oxides. There may also be more than one oxide of this group present in the contact used in accordance with the present invention. The total amount of oxides present in the catalyst is within the above limits. The preferred alkali metal oxides are sodium oxide and potassium oxide. In addition, the catalyst may further include a binder such as clay. In addition to the metal oxidation described The catalyst according to the present invention may further include 0.1 to 50% by weight, preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight of Ti02 & or ZrO2. The present invention further provides a preparation of the present invention. Method for inventing a catalyst. In a variation of a method for preparing the catalyst for the composition, it can be obtained by mixing a nickel, silicon, and aluminum compound, and then calcining the mixture at 300 to 800 ° C. Among them, 10 to 100% of the aluminum atoms in the aluminum compound are tetrahedral X-ray amorphous aluminosilicate is preferably used as the aluminum compound. In another variation, silicon and aluminum compounds are converted to X-ray amorphous by mixing and calcining at 300 -800 ° C. Aluminosilicates in which 10 to 100% of the aluminum atoms present are coordinated in a tetrahedron, and then a nickel compound is applied to the obtained X-ray amorphous aluminum by impregnation and calcination at 300-800 ° C Silicate 〇 In the final product, the amount of metal compound corresponds to the above weight ratio. When preparing aluminosilicate or after impregnating with nickel in particular, other optional components can be added. The catalyst of the present invention is preferably It is prepared from amorphous aluminate containing "tetrahedron inscription" in which nickel is used. -9-200417555 suitable raw materials for preparing the catalyst of the present invention are, for example, aluminosilicates, high temperature aluminosilicates or amorphous zeolites (available from Mob, available from Grace under the trade name Grace DA VI CAT) i 1 〇i 1 MCM 4 1). As for nickel compounds (for example, applied to amorphous aluminosilicates), nickel oxides or nickel-containing compounds that are converted to nickel oxides or nickel lucartrate by excluding other groups during calcination can be used. Examples of suitable organic nickel compounds are nickel acetoacetone I, nickel alkoxide, and nickel salts of carboxylic acids such as formic acid or acetic acid. As for the inorganic compounds, for example, nickel hydroxide, nickel hydroxide carbonate, Nickel carbonate, nickel nitrate, nickel sulfate, and complexes with water and / or ammonia. Mixtures or solutions containing more than one nickel compound used to prepare this catalyst can also be used. In addition, different nickel compounds can be continuously applied to aluminosilicates. Nickel compounds can be incorporated into aluminosilicates by various methods, such as mixing, precipitating, dipping, or spraying. Before preparing the catalyst of the present invention, it is preferred to spray or impregnate the amorphous aluminosilicate with a solution of a nickel compound. If appropriate, the catalyst is calcined after pre-drying, that is, a mixture of an amorphous aluminosilicate and a nickel compound. In this way, other groups are excluded to form a catalytically active nickel aluminosilicate. The calcination is preferably performed at a temperature in the range of 300 to 800 ° C, particularly in the range of 400 to 700 ° C. Depending on the temperature, the calcination time is from 0.5 to 6 hours. Calcination can be performed under inert or oxidizing conditions. The catalyst is advantageously used in a form that provides low flow resistance, for example, in the form of granules, tablets, or shaped bodies (such as flat plates, cylinders, pellets, extruded bodies, -10- 200417555 or rings). The forming can be performed at various points in the catalyst process, for example, during or after the aluminosilicate synthesis, after preparing a mixture of a nickel compound and an aluminosilicate, 'after calcination, and the like. Before forming, if necessary, a forming aid may be added to the catalyst composition or a precursor thereof. It is particularly preferred that the catalyst is first dried, crushed, and shaped to form a sheet having an average diameter of 0.1 to 5 mm, preferably 0.2 to 2 mm, and very particularly preferably 0.5 to 1 mm. An example of a device suitable for this purpose is a mixer available from Gustav Eirich, Hardheim / Baden. Then calcined 〇 The catalyst prepared in this way has excellent mechanical stability and high body density. Due to the least amount of dust formation caused by mechanical abrasion / destruction of the tablet, the catalyst can be quickly replaced or consumed. The present invention further provides a method for oligomerizing an olefin having 2 to 10 carbon atoms, which is performed at 20 to 200 ° C and super atmospheric pressure in a liquid phase through 5 to 60% by weight of nickel and 5 to 20% by weight of nickel. Fixed bed catalysts of aluminum and 10 to 40% by weight of silicon, wherein 10 to 100% of the aluminum atoms in the fixed bed catalysts are tetrahedral coordination. Compared to catalysts that do not contain tetrahedral coordination aluminum atoms or have only a low proportion of catalysts, the catalysts of the present invention produce higher space-time yields in the oligomerization of olefins. The catalyst used in the olefin oligomerization method of the present invention may have all the mentioned compositions or include all the metal oxides mentioned. As for the raw materials used in the method of the present invention, C2-C1 ()-olefins can be used, which is preferably c3-c5-olefins than-1 1-200417555, or it does not actually contain other unsaturated unsaturated compounds such as diene. Or acetylene derivative) is a mixture of olefins containing less than 5% by mass, especially% of branched olefins, based on the olefin content. Propylene is produced industrially by petroleum refining and is also a chemical. C5-olefins are present in fractions derived from refined or cracked products. Industrial mixtures containing C4-olefins include mixtures derived from refined products, C4 fractions-rhenium synthesis obtained from fluid catalytic crackers or steam crackers, mixtures obtained from butene dehydrogenation, mixtures, or obtained from Other industrial methods. For example, the C4 fraction of a linear steam cracker of linear butene suitable for use in the process of the present invention. In the first step, both the extraction or extractive distillation of butadiene butadiene or its selective hydrogenation are removed, and the result is virtually no butadiene C4 fraction, I. In a second step, isobutylene is removed from the C4 stream, such as an alcohol reaction, to produce methyl tertiary butyl ether (MTBE). Isobutylene in other compounds I reacts with water to form a third butanol, or polymerizes the oligo to isobutene. There is no C4 content of Isobutene, I I, including linear butene if necessary, and Ding Yuan. If 1-butene is isolated by distillation. Both fractions, i.e., including 1-butene 2-butene, can be used in the method of the present invention. Another possible way to prepare a suitable raw material is to mix the raffinate II, or a hydrocarbon with a similar composition in the reaction column. In this way, compounds and compounds containing 2-butane and a small amount of 1-butane are obtained. Preferably, less than 1 mass of light gasoline distillate, light gasoline distillate, diene obtained from a mixture formed by Fisher shift. It was completed. Immediately, the raffinate is urged by formate with methacrylic acid, and the raffinate is required. It can be added to the butene or the inclusion I, the hydrogen isomerization of the raffinate, and the Butane, and mixtures of isobutane and isobutene. The method of the present invention is performed in various batches or preferably, such as those used in solid / liquid contact reactions. When moving the reactor, a fixed bed is usually, but not necessarily, used. When the reactor is moved, liquid can flow upward or downward. The product can also be recycled (sequential operation of the reactor. When using the reactor, the length of the catalyst bed varies with the geometry or filling degree of the straightener. In special (LHSV), different methods can be obtained in this way The reactor at which the empty-tube-speed reaction mixture is recycled can be operated at 1 to 50 ^ degrees. In a single-use reactor in which the air is emptied to a range of 30 m / h. The space velocity of the catalyst in the reactor ( LHSV) is 0. Fresh feed / catalyst kg / hour; the conversion obtained each time is 30-60%. The product formed by continuous release of n-butene concentration due to increasing conversion rate. Operate the reactor. Here, 'from the reaction polymer first, and the remaining materials are partially recycled to each of the subsequent reaction stages. The olefin stream used usually contains the same boiling range, inert materials, so that olefin conversion is increased A stream can be obtained. In this case, a plurality of oligomerizations are connected in series ~ 1 3-Continuously operated reactors use continuous operating streams and flow through a fixed bed. Usually a ring mode is preferred) or a single diameter ratio can be used. through The catalyst should proceed quantitatively and lose degrees. Some of the long / hour air tube velocities can be 0.48 to 8 kg. Surrounding saturated hydrocarbons, that is, to more dilution into the stage, so that each of 200417555 can be operated under conditions suitable for reducing olefin concentration is advantageous. Oligomerization can also be performed in multiple method stages. The number of reaction stages is 1 to 10, preferably 1 to 4. If necessary, intermediate separation and recirculation of inert components and / or unreacted olefins of the reaction product can be performed. In each stage, the oligomerization of the olefin according to the present invention is preferably carried out to a content of oligomer in the reaction product of 5 to 50% by weight, preferably 5 to 45% by weight, and especially 5 to 35% by weight. In this way, more than 80% of the olefins containing about 20% inert components present in the industrial feed mixture can be oligomerized. Residual streams containing less than 30% olefins are often not economically used in this process and are further used as liquefied gas or light gasoline. Each of these reactors can be operated essentially adiabatically, multilaterally, or essentially constant temperature, that is, a temperature less than 1 ° C. The temperature at which the reactor is operated is 20 to 200 ° C, preferably 70 to 160 ° C. , Very particularly preferably in the range of 70 to 130 ° C, especially in the range of 80 to 120 ° C. If the catalyst does not contain an acid content, an increase in reaction selectivity to n-octene is observed as the temperature increases, so at least partly It is operated as a known acidic oligomerization catalyst. The reaction can be carried out at a pressure equal to or higher than the vapor pressure of the hydrocarbon feed mixture at each reaction temperature, preferably at a pressure lower than 40 bar. In order to avoid For evaporation problems, the pressure should be 2 to 4 bar higher than the vapor pressure of the highest temperature of the reaction mixture in the reactor. The total conversion of olefins depends on the type and amount of catalyst used, the reaction conditions set, and the number of reaction stages. For economic reasons, the olefin conversion rate is kept in the range of 50 to 100%, preferably 90 to 100% in the range of 200417555 in all stages. In addition, in order to obtain local space time yield, the use of Preferably not less than 80% A hydrocarbon having a linear olefin content is advantageous. In order to increase the selectivity, the oligomer content in the reaction product is set to 5 to 45% by weight by recycling the inert components in the reaction product and / or unreacted olefin. It is preferably 5 to 35% by weight. Therefore, it is necessary to separate the reaction products (oligomers and other high-boiling substances) from unreacted olefins and inert components (such as 'aliphatic') of the reaction products. The oligomer content is particularly in the range of 10 to 30% by weight. Limitation of oligomer concentration can be achieved by selecting operating parameters such as temperature or residence time. Another possibility is to add the reactor inlet by adding a diluent The starting olefin concentration remains below 80%, especially below 60%. It is advantageous to use a diluent which is present in the feedstock and which is recovered from the reaction mixture after the starting olefin is partially or practically completely reacted. In a preferred embodiment of this method, the mixture leaving the reactor is thus separated into a fraction containing oligomers and a second fraction containing diluent, aliphatic, possible and unreacted olefins. A portion of the diluent And exist in The olefins are recycled to the same reactor or upstream reactor, and other parts are sent to downstream reactor or processing. In the case of multiple reactors connected in series, there may be more than one oligomer separation. In further distillation, the oligomers that have been separated (from one or more separation units) are separated into dimers, trimers, and high-carbon oligomers. The oligomers prepared by the method of the present invention are particularly used In the preparation of aldehydes, alcohols and residual acids. Therefore, for example, the dimer obtained from linear butene can be hydromethylated to produce a nonanal mixture. It can be oxidized to the corresponding carboxylic acid or -15-200417555 Conversion by hydrogenation to a C9-alcohol mixture. Q acid mixtures can be used to prepare lubricants or desiccants. C9-alcohol mixtures are intermediate products used to make plasticizers, especially nonyl phthalate. The method of the present invention has the following advantages: When using the catalyst of the present invention, 'a higher space-time yield is obtained than that of a catalyst containing no tetrahedral aluminum atoms or only a low proportion of the catalyst. [Embodiment] The following examples describe the present invention without limiting its scope defined by the scope of patent application. Example 1 (comparative example): In a kneader, 600 grams of A1203 containing 13% by weight and having a BET surface area of about 400 square meters per gram of essentially X-ray amorphous aluminosilicate combination 5 30 grams of nickel carbonate Slurry (inspection: 50.5% Ni 0), 650 grams of nickel hexaammonium carbonate solution (inspection: 14.9% NiO), 16 grams of ethylene glycol, and 390 grams of water, producing as wet A mixture of soil and homogeneous composition. It is extruded to form an extrudate with a diameter of 2 mm and a length of 3-10 mm and dried. This material was then calcined at 600 ° C for 2 hours. 600 ml of the extrudate was introduced into a tube reactor having a length of 2 meters and a diameter of 2 cm, and the temperature was kept constant by external water. The catalyst was dried in a tube reactor at 150 t under a nitrogen stream. Then, a mixture of 20% 1-butene, 60% 2-butene, and 20% n-butane was passed through the catalyst at a flow rate of 1 kg / hour and a wall temperature of 85 ° C. After about 40 hours, the conversion and composition of the output no longer change. The output composition is 20% n-butane, 2.2% 1-butene, 46.2% 2-butene, 25.5% C8-olefin, and 5.1% with 1, 2, 16 and more Olefins of one carbon atom. The conversion of n-butene is therefore 39.5%. The product fraction was separated from the -16-200417555 butane / butene fraction by evaporation of the low boilers and injected into a hydrogenated gas chromatograph. The composition of the c8 fraction is as follows: 29.2% dimethylhexane, 61.1% methylheptane, 9.5% n-octane, 0.2% other octane. The final catalyst after calcination has a BET surface area of 340 m 2 / g and a pore volume in the extruded material of 1.12 ml / g, of which about 0.53 ml / g has a pore size greater than 50 nm. The pore portion having a diameter of less than 50 nanometers has a diameter of more than 6 nanometers per 0.15 ml / g and a diameter range of 4 to 6 nanometers per 0.2 ml / g. A 27A1-NMR examination of the aluminosilicate used showed that approximately 45% of the aluminum atoms were tetrahedrally coordinated. Example 2 (according to the present invention): The procedure of Example 1 was followed exactly, however, an aluminosilicate containing about 85% tetrahedral coordinated aluminum according to NMR was used. Test in the same way. At a wall temperature of 85 ° C, the output composition is 20% n-butane, 1.8% 1-butene, 33.8% 2-butene, 37.8% C8-olefin, and 6.7% having Olefins of 1, 2, 6 and more carbon atoms. The conversion of n-butene is therefore 55.6%. The product fraction was separated from the butane / butene fraction by evaporating the low boilers and injected into a hydrogenated gas chromatograph. The composition of the C8 fraction is as follows: 25.3% dimethylhexane, 61.2% methyl heptane, 15.4% n-octene, 0.1% other octane. In order to obtain the same conditions as in the comparative example (Example 1), the temperature was gradually decreased. At 74 ° C, the wall temperature of the tube reactor gave an n-butene conversion of about 39.7%. The composition of the C8 fraction is as follows: 29.0% dimethylhexane, 61.4% methyl heptane, 9.4% n-octane, and 0.2% other octane. The catalyst used in Example 2 was therefore substantially more active; substantially lower temperatures were required to obtain the same conversion. On the other hand, the composition of the Cs-17-200417555 fraction with the same conversion is practically the same. The final catalyst after calcination had a BET surface area of 355 m2 / g and a pore volume in the extrudate of 1.10 ml / g, of which about 0.49 ml / g had a pore size greater than 50 nm. The pore portion having a diameter of less than 50 nm has a diameter of more than 6 nm and a diameter range of 4 to 6 nm of 0.2 ml / g. Example 3 (comparative example): In a kneader, 1000 g of an essentially X-ray amorphous aluminosilicate containing 13% by weight of A1203 and having a BET surface area of about 400 m2 / g was combined with 200 g of a gel, which Contains 30 grams of boehmite (Disperal from Condea) and 170 grams of 10% strength nitric acid. 30 grams of ethylene glycol and 400 grams of water are added to produce a homogeneous composition such as wet soil. It was extruded to form an extrudate having a diameter of 2 mm and a length of 3-10 mm and calcined at 450 ° C for 2 hours. The catalyst carrier that has been manufactured in this way is then impregnated with a hexaammonium carbonate solution (pickup: 1 4 · 9% Ni0) to saturate the pores. The support impregnated in this way was dried and calcined at 60 CTC for 2 hours. The final catalyst contains 9.6% NiO. A catalyst of 60 ml was tested as in Example 1 using 20% 1-butene, 60% 2-butene, and 20% n-butane. At a flow rate of 1 kg / hour and a wall temperature of 85 ° C, the output composition is 20% n-butane, 2.4% 1-butene, 49.7% 2-butene, 24.1% C8 -Olefins, and 3.8% of olefins having 12, 16 and more carbon atoms. The conversion of n-butene is therefore 34.9%. The product fraction was separated from the butane / butene fraction by evaporation of the low boilers and injected into a hydrogenated gas chromatograph. The composition of the C8 fraction is as follows: 29.8% dimethylhexane, 60.6% methylheptane, 9.2% n-octane, 0.4% other 200417555 calcined final contact The medium has a BET surface area of 3 30 m2 / g and a pore volume in the extrudate of 1.03 ml / g, of which about 0.45 ml / g has a pore size greater than 50 nm. The pore portion having a diameter of less than 50 nanometers has a diameter of more than 6 nanometers and a diameter range of 4 to 6 nanometers of 0.12 milliliter / gram. A 27A1-NMR examination of the aluminosilicate used showed that about 38% of the aluminum atoms were tetrahedrally coordinated. Example 4 (according to the present invention): The procedure of Example 3 was followed exactly, however, an aluminosilicate containing about 90% tetrahedral coordination aluminum was examined by NMR. Test in the same way. At a wall temperature of 85 ° C, the output composition is 20% n-butane, 2.0% 1-butene, 37.8% 2-butene, 33.8% C8-olefin, and 6.4% having Olefins of 12, 16 and more carbon atoms. The conversion of n-butene is therefore 49.8%. The product fraction was separated from the butane / butene fraction by evaporating the low boilers and injected into a hydrogenated gas chromatograph. The composition of the C8 fraction is as follows: 26.2% dimethylhexane, 61.4% methyl heptane, 12.1% n-octane, 0.3% other octane. In order to obtain the same conditions as in Example 1 (comparative example), the temperature was gradually lowered. The tube reactor wall temperature at 76 ° C gave an n-butene conversion of about 34.3%. The composition of the C8 fraction is as follows: 29.3% dimethylhexane, 60.9% methylheptane, 9.4% n-octane, and 0.4% other octane. The catalyst used in Example 4 was therefore substantially more active than Example 3; substantially lower temperatures were required to obtain the same conversion. On the other hand, the composition of the Cs fraction with the same conversion is practically the same. [Schematic description]: None -19 "