592816 A7 ____B7_ 五、發明説明（1 ) 背景 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關觸媒成分和組成物及製造和使用該組成 物的方法，該組成物包括一晶狀多微孔氧化物，其在不增 加該晶狀多微孔氧化物的單位晶胞尺寸之下，另具有一可 促進脫氫反應及增加劉易士酸度之促進劑金屬化合物。 晶狀多微孔氧化物，例如沸石材料，已在多種工業中 付諸商業用途有多年之久。這些材料的特別用處在於彼等 作爲分子篩的流體分離能力，以及彼等作爲觸媒能力。 晶狀多微孔氧化物特別可用爲觸媒，其可將烴混合物 的大鏈烷烴分子轉化成較小較不飽和的分子例如烯烴和芳 族化合物。典型的轉化方法包括流體催化裂解和加氫裂解 。爲了使這種轉化程序最大化，必須將觸媒所具的多種構 造性質予以調合，例如孔徑、孔洞體積劉易士酸度、和布 忍斯特（Brpnsted )酸度。若轉化觸媒的構造性質未經恰當 地調合，則烴混合物變成產物的轉化率會降低，產物品質 可能不良，或轉化觸媒可能快速被抑活化。 經濟部智慧財產局員工消費合作社印製 若能經由調合觸媒所含架構部份和非架構部份的布忍 斯特酸度和劉易士酸度而得到具有高催化活化性的晶狀多 微孔氧化物觸媒將是特別有益者。經由調合結晶構造所含 架構與非架構部份，可以將催化活性有效地最佳化。於裂 解觸媒的情況中，大型鏈烷徑分子的烯烴形成反應可以更 有效率地與隨後形成在最後產物中的更小分子之裂開反應 (scission reactions )相酉己合。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -4 - 592816 A7 B7 五、發明説明（2 ) 發明槪沭 本發明的一具體實例包括一種觸媒其包括（i ) 一基 質材料，和（i i )晶狀多微孔氧化物其係經摻加到該基 質之內及/或與該基質摻加在一起。該晶狀多微孔氧化物 包括一非一架構部份且具有一單位晶胞尺寸。該非一架構 部份一只經摻加到該晶狀多微孔氧化物的非一架構部份內 的促進劑金屬化合物。該促進劑金屬化合物不會實質地增 加該晶狀多微孔氧化物的單位晶胞尺寸。 於該觸媒的另一具體實例中，該晶狀多微孔氧化物包 括一經摻加到該基質材料中的Y沸石。該Y沸石包括一非 --架構部份，具有一大約於2 4 · 3 Ο A的單位晶胞尺寸 ’且包括只經摻加到該晶狀多微孔氧化物的非一架構部份 之內，使該該氧化鋁可增加劉易士酸度但不會實質地增加 該沸石的單位晶胞尺寸。 於該觸媒的另一具體實例中，該晶狀多微孔氧化物包 括一非-架構部份其中括一只經摻加到該晶狀多微孔氧化 物所含非-架構部份中的可增加劉易士酸度之促進劑金屬 化合物，使得該促進劑金屬化合物不會實質地增加該晶狀 多微孔氧化物的單位晶胞尺寸。 該觸媒的該等具體實例可用於F C C單元，異構化單 元，或加氫裂解器之中使該觸媒與適當的進料接觸。 本發明的另一具體實例包括一種製造觸媒之方法。該 方法包括（a )將該晶狀多微孔氧化物與包括一能夠形成 促進劑金屬化合物的促進劑金屬之促進劑前體接觸，該晶 $紙張尺度適用中國國家標準（〇阳）八4規格（210父297公釐） '~ -5- (請先閲讀背面之注意事項再填寫本頁) 訂 争· 經濟部智慧財產局員工消費合作社印製 592816 A7 _____B7 五、發明説明（3 ) 狀多微孔氧化物包括一非-架構部份且具有一單位晶胞尺 寸；及（b )將步驟（a )的混合物加熱到介於1 5〇t： 與5 5 0 °C之間的溫度；其中該包括該促進劑金屬的促進 劑金屬化合物係只經摻加到該晶狀多微孔氧化物所含非一 架構部份中具其中該促進劑金屬化合物不會實質地增加到 該晶狀多微孔氧化物的單位晶胞尺寸。 本發明的另一具體實例包括一種方法其包括（a )將 該晶狀多微孔氧化物與一促進劑前體接觸，該晶狀多微孔 氧化物包括一非-架構部份且具有一單位晶胞尺寸且該促 進劑前體包括一能夠形成促進劑金屬化合物的促進劑金屬 ;及（b )將該促進劑前體分解由是形成包括該促進劑金 屬的氧化物形式之促進劑金屬化合物；（c )將該促進劑 金屬化合物只摻加到該晶狀多微孔氧化物所含非-架構部 份中；其中該促進劑金屬化合物不會實質地增加到該晶狀 多微孔氧化物的單位晶胞尺寸。 本發明的另一具體實例包括一種方法其包括（a )將 一包括一非-架構部份且具有一單位晶胞尺寸的沸石予以 燒；（b )將該沸石與一包括一能夠形成促進劑金屬化合 物的促進劑金屬之促進劑前體接觸，其中該促進劑金屬係 選自下列所構成的組合之中者：鎂、鉻、鐵、鑭、鎵、錳 和鋁且其中該促進劑前體係選自下列所構成的組合之中者 :乙醯基丙酮化鋁、異丙氧化鋁、六氟乙醯基丙酮化鋁、 二氯醇銘（a 1 u m i η u m d i c h 1 〇 r 〇 h y d r ο 1 )、乙氧化銘、三〔2 ，2，6，6 -四甲基一 3，5 —庚烷二酸基〕鋁一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 0 ϋ·* n ialv mmmmu ϋϋ m· a^ni ^ϋ· ml n^i .Hi·— iBi·— ·ϋϋ ιϋ« ϋϋ am·· - 1 n·-— ϋϋ ϋϋ ϋϋ ιϋ·1 ϋϋ ml n I i . -6- 592816 A7 _________B7 五、發明説明（4 ) 1 1 1 〔 A 1 ( Τ Μ H D ) 3〕、乙酸鋁、硝酸鋁、丙氧化 銘、乙醯基丙酮化鎂、乙醯基丙酮化鉻、乙醯基丙酮化鐵 、乙醯基丙酮化鎵、乙醯基丙酮化錳 '和乙醯基丙酮化鑭 ;(c )將步驟（b )的混合物加熱到介於1 5 0 °C與 5 5 〇 C之間的溫度，及（d )將步驟（b )的產物摻加 到一基質材料內，其中該包括該促進劑金屬的促進劑金屬 化合物只經摻加到該沸石所含非一架構部份中且其中該促 進劑金屬化合物不會實質地增加該沸石的單位晶胞尺寸。 本發明的另一具體實例包括一種方法其包括（a )將 經鍛燒過的晶狀多微孔氧化物與包括一能夠形成促進劑金 屬化合物的促進劑金屬之促進劑前體接觸，該晶狀多微孔 氧化物包括一非-架構部份且具有一單位晶胞尺寸；及（ b )將該促進劑金屬化合物活化，其中該促進劑金屬化合 物係只經摻加到該晶狀多微孔氧化物所含非一架構部份中 且其中該促進劑金屬化合物不會實質地增加該晶狀多微孔 氧化物的單位晶胞尺寸。 本發明的另一具體實例包括一種方法其包括（a )鍛 燒一晶狀多微孔氧化物，該晶狀多微孔氧化物包括一非-架構部份且具有一單位晶胞尺寸；（b )與選自下列所構 成的組合之中的烷基鋁接··三甲基鋁、三乙基鋁、三（第 三丁基）鋁、和三（異丁基）鋁；（c )用含氧物質處理 步驟（b )的產物而形成促進劑金屬化合物，其中該促進 劑金屬化合物不會實質地增加該晶狀多微孔氧化物的單位 晶胞尺寸。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) · - * · Γ W----11------^^1. 經濟部智慧財產局員工消費合作社印製 592816 A7 ____ B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) 本發明的其他具體實例包括經由本發明方法製成的產 物。這些產物可以或可以不經摻加到一基質材料之內，不 過較佳者爲置於一程序單元中使用之前經摻加到一基質材 料之內。 詳細說明 晶狀多微孔氧化物，例如，沸石，的催化活性可以經 由有效地摻加可促進脫氫和增加該晶狀多微孔氧化物所具 劉易士酸度而不會增加其單位晶胞尺寸的促進劑金屬化合 物予以改良。雖然該晶狀多微孔氧化物可以單獨地用觸媒 ，不過該晶狀多微孔氧化物最好是經加到一基質材料，較 佳者無機氧化物之內。該基質材料中也可以含有其他催化 性或非-催化性成分。 經濟部智慧財產局員工消費合作社印製 本發明晶狀多微孔氧化物可以用來將來自催化裂解反 應的原產物催化分解成淨產物例如用爲燃料的石油腦油和 用爲化學進料的烯烴。該晶狀多微孔氧化物較佳者係選自 下列所構成的組合：晶狀鋁矽酸沸石（後文稱爲沸石）， 地矽酸鹽（tecto-silicates )，四面體磷酸鹽（A L P〇s )和四面體矽鋁磷酸鹽（S P A〇s )。更佳者，該晶狀 多微孔氧化物爲沸石。 適當的沸石包括天然和合成沸石。適當的天然沸石包 括鈉愛沸石 ’ charbazite，dachiardite，clinoptilolite，八面 沸石’片沸石，菱灰沸石，e i. i ο n i t e，灰霞石，與沸石， offretite ’絲光沸石，和ferrierite。適當的合成沸石爲沸石 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8- 592816 A7 B7 五、發明説明（6 ) (請先閱讀背面之注意事項再填寫本頁) X，Y，L，ZK-4，ZK — 5，E，H，J，M，Q ，T，Z ，α和/3，ZSM —型及Ω。較佳者爲八面沸石 ，特別者爲具有大於或等於2 4 . 3 0 A，更佳者大於或 等於約2 4 . 4 Ο A的單位晶胞尺寸之沸石γ和沸石X。 沸石中的鋁及矽成分可取代其他架構成分。例如，鋁部份 可用硼、鎵、鈦或比鋁更重的三價金屬組成物予以置換。 可以用鍺來置換矽部份。 於觸媒成品中，該晶狀多微孔氧化物較佳者係包括在 一無機氧化物基質材料之內，該無機氧化物基質材料係將 諸觸媒成分黏合在一起使得最後觸媒足夠硬以在粒子間碰 撞與反應壁碰撞之下殘存下來。該無機氧化物基質材料可 以用無機氧化物溶膠或凝膠製成，其經乾燥後可將諸觸媒 成分'\膠合〃在一起。較佳者，該無機氧化物基質材料包 括矽和鋁的氧化物。該無機氧化物基質材料包括更包括一 活性多孔型無機氧化物觸媒成分及一惰性觸媒成分。較佳 者，每一種觸媒成分係經由與一無機氧化物基質材料接觸 而維繫在一起。 經濟部智慧財產局員工消費合作社印製 活性多孔型無機氧化物觸媒成分典型地係催化經由將 太大而不能配合到該晶狀多微孔氧化物內部的烴分子裂解 之原產物形成反應。可摻加到裂解觸媒內的活性多孔型無 機氧化物成分較佳者爲可將相當大量的烴裂解成相對於可 接受的熱空白溫（t h e r m a 1 b 1 a n k )爲較低分子量的烴之多孔 型無機氧化物。一種低表面積氧化矽（如石英）爲一類型 的可接受熱空白品。裂解程度可以用多種A S T Μ檢驗中 Θ氏張尺度適财國國家標準（CNS ) Α4規格（21GX297公釐) --- -9- 592816 A7 B7 五、發明説明（7 ) 的任何一者予以測量，例如M A T (微活性檢驗， ASTM#D3907-8)。合宜者爲例如揭示於 Greensfelder， B. S. et al·，Industrial and Engineering CJiemsitrv, PP · 2 5 7 3 - 8 3，N o v. 1 9 4 9 之中的化合物。較佳者爲 氧化鋁，氧化矽-氧化鋁和氧化矽-氧化鋁-氧化锆等化 合物。 惰性觸媒成分典型地係用來密實化，強化及作爲保護 性熱沼（thermal sink )。可以摻加到本發明裂解觸媒內的 惰性觸媒成分具有不會明顯大於可接受的去熱空白品之裂 解活性。高嶺土和其他黏土以及α -氧化鋁，氧化鈦，氧 化鉻，石英和氧化矽皆爲適當惰性成分之例子。 獨立地氧化鋁相較佳者係經摻加到該無機氧化物基質 材料之內。可以採用氧氫氧化鋁- α -氧化鋁，伯姆石（ boehmite )，水銘石（diaspore )，和過渡型氧化錦例如α 一氧化銘，/3 -氧化銘，r 一氧化銘，3 -氧化銘，ε -氧化銘，/c 一氧化銘，和ρ -氧化錦等物種。較佳者，該 氧化鋁物種爲三氫氧化鋁（例如三水鋁礦，三羥鋁石， hoi.dstrandite，或 doyelite 〇 於本發明一具體實例中，該晶狀多微孔氧化物觸媒成 分包括一促進脫氫及增加劉易士酸度的化合物，於本文中 稱之爲促進劑金屬化合物。該促進劑金屬化合物進入晶狀 多微孔氧化物內的分散不會實質地導致該晶狀多微孔氧化 物所具單位晶胞尺寸的任何增加，且該晶狀多微孔氧化物 材料的單位晶胞尺寸係實質相同者。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210乂297公釐） (請先閲讀背面之注意事項再填寫本頁)592816 A7 ____B7_ V. Description of the invention (1) Background (Please read the precautions on the back before filling out this page) The present invention relates to catalyst components and compositions and methods for making and using the compositions. The composition includes a crystal The microporous oxide, which does not increase the unit cell size of the crystalline microporous oxide, has another accelerator metal compound that can promote dehydrogenation reaction and increase Lewis acidity. Crystalline microporous oxides, such as zeolite materials, have been used commercially for many years in a variety of industries. These materials are particularly useful in their ability to separate fluids as molecular sieves and their ability to act as catalysts. Crystalline microporous oxides are particularly useful as catalysts, which convert large paraffin molecules of a hydrocarbon mixture into smaller, less unsaturated molecules such as alkenes and aromatics. Typical conversion methods include fluid catalytic cracking and hydrocracking. In order to maximize this transformation process, various structural properties of the catalyst must be blended, such as pore size, pore volume Lewis acidity, and Brnsted acidity. If the structural properties of the conversion catalyst are not properly blended, the conversion rate of the hydrocarbon mixture into products will be reduced, the product quality may be poor, or the conversion catalyst may be rapidly inhibited and activated. If printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it is possible to obtain crystalline microporous oxides with high catalytic activation by blending the Bronsted acidity and Lewis acidity of the structural part and the non-structural part of the catalyst. The media will be particularly beneficial. By blending the structural and non-structural parts of the crystal structure, the catalytic activity can be effectively optimized. In the case of a cracking catalyst, the olefin formation reaction of large paraffin-sized molecules can be more efficiently combined with the scission reactions of smaller molecules that are subsequently formed in the final product. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -4-592816 A7 B7 V. Description of the invention (2) Invention 槪 沭 A specific example of the invention includes a catalyst including (i) a The matrix material, and (ii) a crystalline microporous oxide, are incorporated into the matrix and / or blended with the matrix. The crystalline microporous oxide includes a non-framework portion and has a unit cell size. The non-framework portion is a promoter metal compound doped into the non-framework portion of the crystalline microporous oxide. The promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide. In another specific example of the catalyst, the crystalline microporous oxide includes Y zeolite incorporated into the matrix material. The Y zeolite includes a non-structural portion having a unit cell size of about 2 4 · 3 Ο A 'and includes a non-structural portion that is only added to the crystalline microporous oxide. In addition, making the alumina increases Lewis acidity but does not substantially increase the unit cell size of the zeolite. In another specific example of the catalyst, the crystalline microporous oxide includes a non-structural portion including one that is added to the non-structural portion contained in the crystalline microporous oxide A promoter metal compound that can increase Lewis acidity, so that the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide. The specific examples of the catalyst can be used in an F C C unit, an isomerization unit, or a hydrocracker to contact the catalyst with a suitable feed. Another specific example of the present invention includes a method for manufacturing a catalyst. The method includes (a) contacting the crystalline microporous oxide with a promoter precursor including a promoter metal capable of forming a promoter metal compound, and the crystal paper size is in accordance with Chinese National Standard (Oyang) 8 4 Specifications (210 mm 297 mm) '~ -5- (Please read the precautions on the back before filling out this page) Ordering · Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592816 A7 _____B7 V. Description of Invention (3) The microporous oxide includes a non-structural portion and has a unit cell size; and (b) heating the mixture of step (a) to a temperature between 150 ° C and 55 ° C. ; Wherein the accelerator metal compound including the accelerator metal is only added to a non-structural part contained in the crystalline microporous oxide, wherein the accelerator metal compound does not substantially increase to the crystal Unit cell size of the shaped microporous oxide. Another specific example of the present invention includes a method comprising (a) contacting the crystalline microporous oxide with an accelerator precursor, the crystalline microporous oxide including a non-structural portion and having a Unit cell size and the promoter precursor includes a promoter metal capable of forming a promoter metal compound; and (b) the promoter precursor is decomposed to form a promoter metal including an oxide form of the promoter metal Compound; (c) the accelerator metal compound is only added to the non-structural portion of the crystalline microporous oxide; wherein the accelerator metal compound does not substantially increase to the crystalline microporous The unit cell size of the oxide. Another embodiment of the present invention includes a method comprising (a) firing a zeolite including a non-structural portion and having a unit cell size; (b) combining the zeolite with a Promoter contact of a promoter of a metal compound, wherein the promoter metal is selected from the group consisting of magnesium, chromium, iron, lanthanum, gallium, manganese, and aluminum and wherein the promoter precursor system It is selected from the group consisting of aluminum ethylacetonate, isopropyl aluminum oxide, aluminum hexafluoroacetamidoacetone, and dichlorohydrin (a 1 umi η umdich 1 〇r 〇hydr ο 1) , Ethoxylate, tris [2,2,6,6-tetramethyl-1,3,5-heptane diacid] aluminum—this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 ϋ · * n ialv mmmmu ϋϋ m · a ^ ni ^ ϋ · ml n ^ i .Hi · — iBi · — · ϋϋ ιϋ «ϋϋ am ··-1 n · -— ϋϋ ϋϋ ϋ ιϋ · 1 ϋϋ ml n I i. -6- 59281 6 A7 _________B7 V. Description of the invention (4) 1 1 1 [A 1 (T M HD) 3], aluminum acetate, aluminum nitrate, propionate, ethyl ethyl acetonate, ethyl ethyl acetonate, ethyl acetonate Iron acetonate, gallium acetoacetonate, manganese ethionate and lanthanum acetoacetate; (c) heating the mixture in step (b) to between 150 ° C and 55 ° C. The temperature between C, and (d) the product of step (b) is incorporated into a matrix material, wherein the accelerator metal compound including the accelerator metal is only added to the non-a framework part contained in the zeolite And where the promoter metal compound does not substantially increase the unit cell size of the zeolite. Another specific example of the present invention includes a method comprising (a) contacting a calcined crystalline microporous oxide with a promoter precursor including a promoter metal capable of forming a promoter metal compound, the crystal The microporous oxide includes a non-structural portion and has a unit cell size; and (b) activates the promoter metal compound, wherein the promoter metal compound is added only to the crystalline microstructure. The pore oxide is contained in a non-structural part and in which the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide. Another specific example of the present invention includes a method including (a) calcining a crystalline microporous oxide including a non-structural portion and having a unit cell size; ( b) with alkylaluminum selected from the group consisting of: trimethylaluminum, triethylaluminum, tris (thirdbutyl) aluminum, and tris (isobutyl) aluminum; (c) The product of step (b) is treated with an oxygen-containing substance to form a promoter metal compound, wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) ·-* · Γ W ---- 11 ------ ^^ 1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592816 A7 ____ B7 V. Description of the Invention (5) (Please read the notes on the back before filling this page) Other specific examples of the present invention include products made by the method of the present invention . These products may or may not be incorporated into a matrix material, but are preferably incorporated into a matrix material prior to use in a process unit. Describe in detail the catalytic activity of crystalline microporous oxides, such as zeolites, which can effectively promote dehydrogenation and increase the Lewis acidity of the crystalline microporous oxides without increasing their unit cell size through effective addition The accelerator metal compounds are improved. Although the crystalline microporous oxide may be used alone as a catalyst, the crystalline microporous oxide is preferably added to a matrix material, preferably an inorganic oxide. The matrix material may also contain other catalytic or non-catalytic components. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the crystalline microporous oxide of the present invention can be used to catalytically decompose the original product from the catalytic cracking reaction into a net product such as petroleum naphtha for fuel and chemical feedstock. Olefin. The crystalline microporous oxide is preferably selected from the group consisting of: crystalline aluminosilicate zeolite (hereinafter referred to as zeolite), tecto-silicates, tetrahedron phosphate (ALP) 〇s) and tetrahedral silicoaluminophosphate (SPAs). More preferably, the crystalline microporous oxide is a zeolite. Suitable zeolites include natural and synthetic zeolites. Suitable natural zeolites include sodium zeolite ' charbazite, dachiardite, clinoptilolite, faujasite ' flake zeolite, chabazite, e.i.iotonite, wurstite, and zeolite, offretite ' mordenite, and ferrierite. Appropriate synthetic zeolite is zeolite. The size of the paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -8-592816 A7 B7 V. Description of the invention (6) (Please read the precautions on the back before filling this page) X , Y, L, ZK-4, ZK — 5, E, H, J, M, Q, T, Z, α and / 3, ZSM — type and Ω. Preferred are faujasite zeolites, and particularly zeolites γ and zeolites X having a unit cell size of greater than or equal to 2 4.30 A, more preferably about 2 4.4 A. The aluminum and silicon components in zeolite can replace other structural components. For example, the aluminum portion may be replaced with boron, gallium, titanium, or a trivalent metal composition heavier than aluminum. You can replace germanium with germanium. In the finished catalyst product, the crystalline microporous oxide is preferably included in an inorganic oxide matrix material. The inorganic oxide matrix material adheres the catalyst components together so that the final catalyst is sufficiently hard. In order to survive the collision between particles and reaction wall collision. The inorganic oxide matrix material can be made of an inorganic oxide sol or gel, and after drying, the catalyst components can be glued together. Preferably, the inorganic oxide matrix material includes silicon and aluminum oxides. The inorganic oxide matrix material further includes an active porous inorganic oxide catalyst component and an inert catalyst component. Preferably, each catalyst component is held together by contact with an inorganic oxide matrix material. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The active porous inorganic oxide catalyst component typically catalyzes the formation of the original product by cracking hydrocarbon molecules that are too large to fit inside the crystalline microporous oxide. The active porous inorganic oxide component that can be incorporated into the cracking catalyst is preferably one that can crack a considerable amount of hydrocarbons into hydrocarbons of lower molecular weight relative to the acceptable thermal blank temperature (therma 1 b 1 ank). Porous inorganic oxide. A low surface area silicon oxide such as quartz is a type of acceptable thermal blank. The degree of cracking can be measured in various ASTM tests by using the Θ's scale standard (CNS) A4 specification (21GX297 mm) ---- 9- 592816 A7 B7 5. Any of the invention description (7) can be measured , Such as MAT (micro-activity test, ASTM # D3907-8). Suitable are, for example, compounds disclosed in Greensfelder, B.S. et al., Industrial and Engineering CJiemsitrv, PP. 2 5 7 3-8 3, No. 1 9 4 9. Preferred are compounds such as alumina, silica-alumina, and silica-alumina-zirconia. The inert catalyst component is typically used to densify, strengthen, and act as a protective thermal sink. The inert catalyst component that can be incorporated into the cleavage catalyst of the present invention has a cleavage activity that is not significantly greater than the acceptable de-heating blank. Kaolin and other clays, as well as α-alumina, titanium oxide, chromium oxide, quartz and silica are examples of suitable inert ingredients. Independently the alumina phase is preferably incorporated into the inorganic oxide matrix material. Aluminum oxyhydroxide-α-alumina, boehmite, diaspore, and transition oxides such as α-oxide, / 3-oxide, r-oxide, 3- Oxidation inscription, ε-oxidation inscription, / c monoxide inscription, and ρ-oxidation inscription. Preferably, the alumina species is aluminum trihydroxide (eg, gibbsite, bayerite, hoi.dstrandite, or doyelite). In a specific example of the present invention, the crystalline microporous oxide catalyst The composition includes a compound that promotes dehydrogenation and increases Lewis acidity, referred to herein as a promoter metal compound. The dispersion of the promoter metal compound into the crystalline microporous oxide does not substantially cause the crystalline microstructure Any increase in the unit cell size of the pore oxide, and the unit cell size of the crystalline microporous oxide material is substantially the same. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 乂 297 cm) Li) (Please read the notes on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 -10- 592816 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（8 ) 該促進劑金屬化合物較佳者爲處於可以有效地促進將 鏈烷烴和環烷烴化合物氫變成烴進料流以形成烯烴化合物 之化學狀態。例如，鋁的氧化物即爲一此等有效化學狀態 〇 晶狀多微孔氧化物包括一架構部份和一非-架構部份 。該晶狀多微孔氧化物的劉易士酸度係經由將該晶狀多微 孔氧化物的非-架構部份所含有效金屬陽離子部位之數目 增加而不增加單位晶胞尺寸之下予以增高的。典型地，在 物質架構部份內摻加一物質時，其單位晶胞尺寸會增加。 當本發明促進劑金屬化合物係摻加到本發明晶狀多微孔氧 化物材料之內時，，其單位晶胞尺寸係保持實質相同者。 因而，該促進劑物質較佳者係經只摻加到晶狀多微孔氧化 物材料的非架構部份之內。參看，W.〇· Haag， vv Catalysis by Zeolites-Science and Technology" , Zeolites and Related Mlcroporous Materials, edited by J. Weitkamp, H. G. Karge, H. Pfeifer, and W. Holderich, Vol, 84, Elsevier Science B. V., 1994，將其中的pp · 1375 一 1394並於本文作爲 爹考，其中討論劉易士酸部位的相關性。如本文中所用者 ’金屬陽離子指的是金屬離子或金屬離子加上氧化物離子 物種。 本發明一具體實例爲一種製造活化催化性成分之方法 。其他具體實例爲由該方法製成的活性催化性成分及一種 最後觸媒產物，其中包括一基質材料。 本發明方法的一具體實例包括將晶狀多微孔氧化物和 本紙張尺度適财關家標準（CNS ) M規格（210Χ297公菱） -- -11 - (請先閲讀背面之注意事項再填寫本頁) II 一 ----訂-------------------- 592816 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（9 ) 能夠形成促進劑金屬化合物的促進劑前體經由混合或其他 適合方法相接觸。如本文所用者，混合意指將諸成分組合 而不一定需要任何機械攪動。將該促進劑前體與晶狀多微 孔氧化物接觸可促成該促進劑前體分散到該晶狀多微孔氧 化物的非-架構部份之內。爲了增加金屬陽離子非架構酸 性部位的有效數目，要經由液相或氣相反應，例如蒸氣相 轉移吸著到該晶狀多微孔氧化物。 該促進劑前體與該晶狀多微孔氧化物係接觸一段足以 使該晶狀多微孔氧化物保持住4 0至6 0重量％ ’較佳者 約5 0重量％因該促進劑前體分解所致促進劑金屬氧化物 。保持程度可經由在活化/加熱步驟中測量晶狀多微孔氧 化物/促進劑前體混合物的重量而測量。該晶狀多微孔氧 化物和促進劑前體係以1〇0 : 1 5至1 0〇：2 0〇’ 較佳者1 0〇：1 5至1 0 0 : 1 0 0的晶狀多微孔氧化 物··促進劑前體之重量比例混合。例如，於將沸石和乙醯 基丙酮化鋁接觸的具體實例中，在分解/反應之下，該乙 醯基丙酮化會產生約1 5 . 7 %的A 1 2〇3。假設在分解 /反應之後有約5 5重量％來自乙醯基丙酮化的A 1 2〇3 分散到沸石的非-架構部份之內且由沸石所持留住，而得 到在1 00克沸石上有1 5克A 12〇3 (1 5% A 1 2〇3添加率），則要將1 0 0克沸石與約1 7 5克乙 醯基丙酮化鋁混合： (15克Al2〇3/(0.157 Al2〇3/乙醯基丙酮化X 0.55(百分分解 率）））= 1 73.4克乙醯基丙酮化鋁 本紙張尺度適用中國國家標準（CNS ) A4規格i 210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 Γ · -12- 592816 A7 經濟部智慧財產局員工消費合作社印製 B7五、發明説明（10) 殘餘有機部份可經由將其與適當的含氧氣體接觸以燃 燒該有機部份而脫除掉。技藝中已知的其他適當方法也可 以接受。 該促進劑金屬化合物較佳者爲多價金屬化合物。較佳 者，該多價金屬化合物爲含有二-價或三-價金屬，較佳 者選自下列的組合中者·錶、絡、鐵、續、嫁、鐘和銘的 化合物。 較佳者，該促進劑前體在氣相中係穩定者且較佳者具 有低於約5 5 0 °C，更佳者低於約5 0 0 °C之沸點者。較 佳的促進劑前體包括，但不限於：乙醯基丙酮化鋁、異丙 氧化鋁、六氟乙醯基丙酮化鋁、二氯醇鋁（alumnium dichlorohydrol)、乙氧化銘、三〔2 ，2 ，6 ，6 —四甲 基—3 ，5 —庚烷二酸基〕鋁—I I I 〔A1 (TMHD )3 ]、乙酸鋁、硝酸鋁、丙氧化鋁、乙醯基丙酮化鎂、乙 醯基丙酮化鉻、乙醯基丙酮化鐵、乙醯基丙酮化鎵、乙醯 基丙酮化錳、和乙醯基丙酮化鑭。 於一特定具體實例中，將該晶狀多微孔氧化物在與可 包括，但不限於下列於活化下會形成促進劑金屬化合物的 促進劑前體接觸之前，以技藝中已知的方法予以煅燒··乙 醯基丙酮化鋁、異丙氧化鋁、六氟乙醯基丙酮化鋁、二氯 醇金呂（aluminum dichlorohydrol )、乙氧化銘、三〔2 ，2 ，6 ，6 -四甲基一 3，5 —庚烷二酸基〕鋁一 I I I 〔 A 1 ( Τ Μ H D ) 3〕、乙酸鋁、硝酸鋁、丙氧化鋁、乙醯 基丙酮化鎂、乙醯基丙酮化鉻、乙醯基丙酮化鐵、乙醯基 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） '~' -13- (請先閲讀背面之注意事項再填寫本頁) 592816 A7 __ B7 _____ 五、發明説明（Ή) 丙酮化鎵、乙醯基丙酮化錳、和乙醯基丙酮化鑭。 促進劑金屬化合物係經由將該晶狀多微孔氧化物/促 進劑前體混合物加熱到1 5 0 °C與5 5 0 °c之間而活化。 該加熱步驟會將促進劑前體分解成殘餘有機部份和分散在 該晶狀多微孔氧化物非架構部份內的促進劑金屬化合物。 然後可將所得經活化晶狀多微孔氧化物觸媒成分與適當地 基質材料組合且用爲觸媒。於此具體實例中，較佳的促進 劑前體包括。於一具體實例中，該晶狀多微孔氧化物爲沸 石，較佳者爲Y沸石，且該促進劑前體爲乙醯基丙酮化鋁 ，導致氧化鋁的氧化鋁促進劑金屬化合物。 於另一特定具體實例中，該晶狀多微孔氧化物於在與 包括烷基鋁的促進劑前體接觸之前較佳者先以技藝中已知 的方法予以煅燒。適當的烷基鋁包括，但不限於，三甲基 鋁，三乙基鋁，三（第三丁基）鋁和三（異丁基）鋁。於 此具體實例中，該促進劑金屬化合物係經由該晶狀多微孔 氧化物/促進劑金屬化合物混合物與含氧物質接觸而活化 。適當得含氧物質包括，但不限於，空氣、氧氣體、水、 和醇例如甲醇、乙醇、異丙醇、和丁醇。該含氧物質與烷 基鋁反應，由是經由形成氧化鋁和殘留有機部份而將促進 劑金屬化合物活化。該反應步驟將該促進劑前體分解成促 進劑金屬化合物，其係經分散在該晶狀多微孔氧化物的非 -架構部份之內及在殘餘有機部份之內其可於需要時如上 文所述脫除掉。所得經活化晶狀多微孔氧化物觸媒成分即 可與適當的基質材料組合並用爲觸媒，較佳者，該促進劑 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） ' ' -14- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 i^il ^^^1 I— l m m· ^—^1 —^ϋ ml ϋϋ> m —ϋ m· I mi ϋϋ-^-r^J1 i ϋ^— mu ml mi ϋ ϋϋ 1 592816 A7 B7 ----—---—-------— —___ 五、發明説明（12) 金屬包括鋁且該晶狀多微孔氧化物包括沸石。 前段方法所得包括晶狀多微孔氧化物材料及經摻力卩_ 該晶狀多微孔氧化物材料所含非架構部份內的促進劑^ _ 化合物之產物可按上述加到無機氧化物基質材料內而％ $ 觸媒，較佳者形成新鮮未經污染的觸媒。之後可將該觸_ 通到如下所述程序單元內供適當用途所用。 該基質材料可構成最後觸媒組成物的剩餘部份，不@ 也可將其他觸媒成分和物質摻加到觸媒內。較佳者，該g 質材料以總觸媒重計構成該觸媒的約4 0至約9 9重量％ ，更佳者約5 0至約8 0重量％。於本發明範圍內也包括· 於觸媒內摻加其他類別的多微孔氧化物，黏土，和一氧化 碳氧化促進劑。本發明觸媒於通到裂解程序中時較佳者新 鮮者，亦即，其實質地不含在催化裂解程序中可能污染觸 媒的金屬。此等金屬包括，但不限於，鎳、釩、鈉和鐵。 本發明觸媒可用於多種石油和化學程序中，特別是需 要將鏈烷烴脫氫者。例如，彼等可用來催化流體催化裂解 ，加氫裂解，和異構化中的各反應。促進劑金屬化合物係 以可促進鏈烷烴和環烷烴的脫氫化之方式吸著到觸媒所含 晶狀多微孔氧化物部份。較佳者，係將大型鏈烷烴因接觸 到晶狀多微孔氧化物之結果而轉化成烯烴。然後較佳者將 該等烯烴以合乎燃料產品所需的比例較化成更小的鏈烷烴 分子，烯烴分子，和芳族分子。 流體催化裂解係用來將高沸石油轉化成更有價値的低 沸產物，包括汽油和中級餾份，例如媒油，噴射燃料及加 本紙張尺度適用中國國家標準（ CNS )八4規格（210X297公釐） ~ " -15- C請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ϋ— ϋϋ ϋϋ ϋΒϋ ! ^ n ft—·— m· I —ϋ t— i·^— 11 in-— ι^ϋ 1 —^ϋ mV ϋϋ 111 an— 0 w - 592816 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（13) 熱油。送到催化裂解器的典型進料具有高沸點且包括殘油 ，可能爲其本身自有者，或與其高沸餾份混合時而有者。 最常見的進料爲氣體油，其起始沸點通常高於約2 3 0 t ，更常者高於3 5 0 °C，其終點則高達約6 2 0 °C。典型 的氣體油包括直餾（大氣壓）氣體油，真空氣體油，及煉 焦氣體油。如諳於此技者所了解者，此等烴餾份難以由其 起始沸點予以精確地界定，因爲在石油烴餾份中含有太多 不同種類的化合物之故。在此範圍內的烴餾份包括氣體內 ，熱油，殘油，循環油料，蒸餾原油，焦油砂油，真岩油 ，合成燃枓，煉焦過程衍生的重質烴餾份，焦油，瀝青， 地瀝青，和衍生自前述任何一者的經氫化處理之進料。 流體催化裂解單元典型地包含一反應器，於其中該進 料係與在再生器內加熱過的熱粉狀觸媒接觸。有傳送管線 將兩容器連通以將觸媒粒子往返移動。裂解反應係在下列 條件下進行：較佳者在約4 5 0 °C至約6 8 0 t，更佳者 約4 8 0 °C至5 6 0 °C的溫度；約5至6 0 p s i g，更 佳者約5至4 0 p s i g的壓力；約〇 · 5至1 5秒，更 佳者約1至6秒的接觸時間（觸媒與進料接觸）；及約 〇.5至1 0，更佳者約2至8的觸媒對油比例。 於裂解反應中，形成低沸點產物且在觸媒粒子上會沈 積某些烴質物質和不一揮發性焦碳。烴質物質可經由將觸 媒汽滌，較佳者用蒸汽予以移除。不一揮發性焦碳典型地 包括高度縮合的芳族烴。隨著烴質物質和焦碳蓄積在觸媒 上面，觸媒的裂解活性及觸媒對於產生汽油摻合料的選擇 本紙張尺度適用中國國家標準（CNS ) A4規格（210 '乂297公釐） (請先閲讀背面之注意事項再填寫本頁) -16- 經濟部智慧財產局員工消費合作社印製 592816 A7 B7____ 五、發明説明（14) 率部會遞減。觸媒粒子可經由汽滌移除掉大部份的烴質物 質及經由適當的氧化性再生移除焦碳而恢復大部份的原有 活性。因此，觸媒粒子要先送到汽滌器接著到再生器。 觸媒再生係經由將焦碳沈積物用含氧氣體例如空氣燃 燒而從觸媒表面移除掉。再生中的觸媒溫度可爲約5 6 0 °C至約7 0 5 °C。然後可將再生觸媒粒子經由傳送管線傳 回到反應器，且因爲彼等所具熱量之故，能夠將反應器保 持在裂解反應所需的溫度。焦碳燒除爲一種放熱反應；所 以，於一習用的使用傳統進料之傳統催化裂解單元中，不 需要添加額外的燃料。本發明實作中所用的進料，主要因 爲彼等的低芳族化合物水平，以及因爲在反應器或傳送管 線中的相當短接觸時間，可能不會在觸媒粒子上沈積足夠 的焦碳來達到再生器中所需的溫度。所以，可能需要使用 加添的燃料以提供再生器中增加的溫度使得回送到反應的 觸媒粒子熱得足以維持裂解反應。適當的加添燃料之非限 制性粒子包括來自催化裂解程序本身的C 2 -氣體，天然氣 體，及火炬油。較佳者爲C2 -氣體。 異構化爲可以使用本發明觸媒的另一種程序。可以用 本發明方法異構化的烴包括典型地具有4 - 2 0，較佳者 4 - 1 2，更佳者約4 一 6個碳原子的鏈烷烴和烯烴；及 芳族化合物例如二甲苯。較佳的給料包括鏈烷烴，其例子 爲丁烷、戊烷、己烷、庚烷，等。異構化條件包括下列： 約8 0 °C至約3 5 0 °C，較佳者約1 〇 〇 t至2 6 0 °C的 溫度；約〇至1 ，〇〇〇P s i g ，較佳者約〇至3 〇 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）—' " ~ ' -17- (請先閱讀背面之注意事項再填寫本頁)1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-10-592816 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (8) The promoter metal compound is better if it can effectively promote The paraffin and naphthenic compound hydrogen becomes a hydrocarbon feed stream to form a chemical state of the olefinic compound. For example, aluminum oxide is one of these effective chemical states. Crystalline microporous oxide includes a structural part and a non-structural part. The Lewis acidity of the crystalline microporous oxide is increased by increasing the number of effective metal cation sites contained in the non-framework portion of the crystalline microporous oxide without increasing the unit cell size. Typically, when a substance is added to the material structure part, the unit cell size will increase. When the promoter metal compound of the present invention is incorporated into the crystalline microporous oxide material of the present invention, the unit cell size thereof remains substantially the same. Therefore, the accelerator substance is preferably incorporated into only the non-structural portion of the crystalline microporous oxide material. See, W. Haag, vv Catalysis by Zeolites-Science and Technology ", Zeolites and Related Mlcroporous Materials, edited by J. Weitkamp, HG Karge, H. Pfeifer, and W. Holderich, Vol, 84, Elsevier Science BV, In 1994, pp. 1375-1394 was included in this article as a dad test, in which the relevance of Lewis acid sites was discussed. As used herein, ' metal cation refers to a metal ion or metal ion plus an oxide ion species. A specific example of the present invention is a method for manufacturing an activated catalytic component. Other specific examples are active catalytic ingredients made by this method and a final catalyst product, which includes a matrix material. A specific example of the method of the present invention includes the crystalline microporous oxide and the paper standard (CNS) M specification (210 × 297 male diamond)--11-(Please read the precautions on the back before filling (This page) II I ---- Order -------------------- 592816 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (9) Promoter precursors capable of forming a promoter metal compound are contacted via mixing or other suitable methods. As used herein, mixing means combining the ingredients without necessarily requiring any mechanical agitation. Contacting the promoter precursor with the crystalline microporous oxide can facilitate the dispersion of the promoter precursor into the non-structural portion of the crystalline microporous oxide. In order to increase the effective number of non-structural acidic sites of the metal cation, the crystalline microporous oxide is adsorbed via a liquid or gas phase reaction such as vapor phase transfer. The accelerator precursor is in contact with the crystalline microporous oxide for a period of time sufficient to keep the crystalline microporous oxide from 40 to 60% by weight, 'preferably about 50% by weight. Accelerator metal oxide due to bulk decomposition. The degree of retention can be measured by measuring the weight of the crystalline microporous oxide / accelerator precursor mixture in the activation / heating step. The crystalline microporous oxide and accelerator former system has a crystallinity of 100: 15 to 100: 2 00 ', preferably 100: 15 to 100: 100. The weight ratio of the microporous oxide ... accelerator precursor is mixed. For example, in the specific example of contacting zeolite with aluminum acetoacetate, the acetone acetylation under decomposition / reaction will produce about 15.7% A 1 2 03. Assume that after the decomposition / reaction, about 55.5% by weight of A 1 203 from acetamidinate is dispersed into the non-structural part of the zeolite and retained by the zeolite, resulting in 100 g of zeolite. With 15 g of A 12〇3 (15% A 1 2 0 3 addition rate), then 100 g of zeolite is mixed with about 175 g of aluminum ethylacetonate: (15 g of Al2O3 / (0.157 Al2O3 / Ethylacetonate X 0.55 (percent decomposition rate))) = 1 73.4 g aluminum ethionylacetonate This paper is sized to the Chinese National Standard (CNS) A4 size i 210X 297 mm) ( Please read the precautions on the back before filling this page) Order -12-592816 A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (10) Residual organic part can be obtained by combining it with appropriate ingredients. Oxygen gas is contacted to burn off the organic portion and remove it. Other suitable methods known in the art are also acceptable. The accelerator metal compound is preferably a polyvalent metal compound. Preferably, the polyvalent metal compound is a compound containing a di- or tri-valent metal, and is preferably selected from the group consisting of: epi, co, iron, dioxin, dioxin, bell, and inscription. More preferably, the accelerator precursor is stable in the gas phase and more preferably has a boiling point of less than about 5500C, and more preferably a boiling point of less than about 500C. Preferred accelerator precursors include, but are not limited to, aluminum acetonate, isopropyl aluminum oxide, aluminum hexafluoroacetonyl acetonate, aluminum dichlorohydrol, aluminum ethoxylate, , 2,6,6-tetramethyl-3,5-heptanedicarboxylic acid] aluminum-III [A1 (TMHD) 3], aluminum acetate, aluminum nitrate, aluminum propionate, acetamyl magnesium acetonate, ethyl Chromium acetoacetate, iron acetoacetate, gallium acetoacetate, manganese acetate, and lanthanum acetoacetate. In a specific embodiment, the crystalline microporous oxide is applied by a method known in the art before being contacted with an accelerator precursor which may include, but is not limited to, the following which will form an accelerator metal compound upon activation. Calcination ·· Aluminum acetonium acetonate, isopropyl aluminum oxide, aluminum hexafluoroacetonyl acetonate, aluminum dichlorohydrol, ethoxylate, three [2, 2, 6, 6-tetramethyl -3,5-heptane diacid group] aluminum-III [A 1 (TM HD) 3], aluminum acetate, aluminum nitrate, propion alumina, ethionyl magnesium acetonate, ethionyl chromium acetonate, The basic paper size of ethidium iron acetonate and ethidium is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) '~' -13- (Please read the precautions on the back before filling this page) 592816 A7 __ B7 _____ V. Description of the invention (i) Gallium acetonate, manganese acetoacetate, and lanthanum acetoacetate. The accelerator metal compound is activated by heating the crystalline microporous oxide / accelerator precursor mixture to between 150 ° C and 55 ° C. This heating step will decompose the promoter precursor into residual organic moieties and the promoter metal compound dispersed within the non-structural part of the crystalline microporous oxide. The resulting activated crystalline microporous oxide catalyst component can then be combined with a suitable matrix material and used as a catalyst. In this specific example, preferred accelerator precursors include. In a specific example, the crystalline microporous oxide is zeolite, preferably Y zeolite, and the promoter precursor is aluminum ethylacetonate, which results in an alumina promoter metal compound of alumina. In another specific embodiment, the crystalline microporous oxide is preferably calcined by a method known in the art before contacting the crystalline microporous oxide with an accelerator comprising an aluminum alkyl. Suitable aluminum alkyls include, but are not limited to, trimethylaluminum, triethylaluminum, tris (thirdbutyl) aluminum, and tris (isobutyl) aluminum. In this specific example, the promoter metal compound is activated by contacting the crystalline microporous oxide / promoter metal compound with an oxygen-containing substance. Suitable oxygen-containing substances include, but are not limited to, air, oxygen gas, water, and alcohols such as methanol, ethanol, isopropanol, and butanol. The oxygen-containing substance reacts with the aluminum alkyl group to activate the promoter metal compound by forming alumina and a residual organic portion. This reaction step decomposes the promoter precursor into a promoter metal compound, which is dispersed within the non-structural part of the crystalline microporous oxide and within the residual organic part, which can be used when needed Remove as described above. The obtained activated crystalline microporous oxide catalyst component can be combined with an appropriate matrix material and used as a catalyst. Preferably, the paper size of the accelerator is applicable to the Chinese National Standard (CNS) A4 specification (21〇 × 297). ()) '' -14- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i ^ il ^^^ 1 I— lmm · ^ — ^ 1 — ^ ϋ ml ϋϋ > m —ϋ m · I mi ϋϋ-^-r ^ J1 i ϋ ^ — mu ml mi ϋ ϋϋ 1 592816 A7 B7 --------------------------- Explanation (12) The metal includes aluminum and the crystalline microporous oxide includes zeolite. The method obtained in the previous paragraph includes a crystalline microporous oxide material and a mixed force __ The accelerator in the non-structural part of the crystalline microporous oxide material ^ _ The product of the compound can be added to the inorganic oxide as described above Within the matrix material, the catalyst is better, preferably the catalyst is fresh and uncontaminated. This contact can then be routed into a program unit as described below for appropriate use. The matrix material can constitute the remainder of the final catalyst composition, and other catalyst components and substances can also be incorporated into the catalyst. Preferably, the g material constitutes about 40 to about 99% by weight of the catalyst based on the total catalyst weight, and more preferably about 50 to about 80% by weight. It is also within the scope of the present invention to incorporate other types of microporous oxides, clays, and carbon monoxide oxidation promoters into the catalyst. The catalyst of the present invention is better when it is passed into the cracking process, that is, it is substantially free of metals that may contaminate the catalyst in the catalytic cracking process. These metals include, but are not limited to, nickel, vanadium, sodium, and iron. The catalyst of the present invention can be used in a variety of petroleum and chemical processes, especially those requiring dehydrogenation of paraffins. For example, they can be used to catalyze reactions in fluid catalytic cracking, hydrocracking, and isomerization. The accelerator metal compound adsorbs the crystalline microporous oxide portion contained in the catalyst in a manner that promotes the dehydrogenation of paraffins and naphthenes. More preferably, large paraffins are converted into olefins as a result of contact with crystalline microporous oxides. It is then preferred to convert the olefins into smaller paraffin molecules, olefin molecules, and aromatic molecules in a ratio suitable for a fuel product. Fluid catalytic cracking system is used to convert high zeolite oil into more expensive low-boiling products, including gasoline and middle distillates, such as media oil, jet fuel, and paper. Applicable to China National Standard (CNS) 8-4 (210X297) (Mm) ~ " -15- C Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ϋ— ϋϋ ϋϋ ϋΒϋ! ^ N ft— · — m · I —ϋ t — I · ^ — 11 in-— ι ^ ϋ 1 — ^ ϋ mV ϋϋ 111 an— 0 w-592816 Employees' Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 V. Description of the invention (13) Hot oil. A typical feed to a catalytic cracker has a high boiling point and includes residual oil, which may be its own, or sometimes mixed with its high boiling fractions. The most common feed is gas oil, which usually has an initial boiling point above about 230 ° C, more often above 350 ° C, and an end point as high as about 62 ° C. Typical gas oils include straight run (atmospheric) gas oils, vacuum gas oils, and coke gas oils. As understood by those skilled in the art, these hydrocarbon fractions are difficult to define precisely from their initial boiling points because petroleum hydrocarbon fractions contain too many different kinds of compounds. Hydrocarbon fractions in this range include gas, hot oil, residual oil, circulating oil, distilled crude oil, tar sand oil, real rock oil, synthetic fuel, heavy hydrocarbon distillates derived from coking process, tar, asphalt, Bitumen, and a hydrotreated feed derived from any of the foregoing. Fluid catalytic cracking units typically include a reactor in which the feed is contacted with a hot powdered catalyst heated in a regenerator. There is a transfer line that connects the two containers to move the catalyst particles back and forth. The cracking reaction is carried out under the following conditions: preferably at a temperature of about 4 50 ° C to about 680 0 t, more preferably at a temperature of about 4 8 0 ° C to 5 60 ° C; about 5 to 60 psig , More preferably about 5 to 40 psig pressure; about 0.5 to 15 seconds, more preferably about 1 to 6 seconds of contact time (catalyst and feed contact); and about 0.5 to 10 The better is about 2 to 8 catalyst to oil ratio. During the cracking reaction, low-boiling products are formed and certain hydrocarbonaceous materials and non-volatile coke are deposited on the catalyst particles. The hydrocarbonaceous material can be removed by steaming the catalyst, preferably steam. Non-volatile coke typically includes highly condensed aromatic hydrocarbons. With the accumulation of hydrocarbonaceous substances and coke on the catalyst, the catalyst's cracking activity and the choice of the catalyst for the production of gasoline admixture. This paper size applies the Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) (Please read the precautions on the back before filling out this page) -16- Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592816 A7 B7____ 5. Description of the invention (14) The rate department will decrease. The catalyst particles can recover most of the original activity by removing most of the hydrocarbonaceous materials through steam cleaning and removing coke through proper oxidative regeneration. Therefore, the catalyst particles must be sent to the scrubber first and then to the regenerator. The catalyst regeneration is removed from the surface of the catalyst by burning coke deposits with an oxygen-containing gas such as air. The catalyst temperature during regeneration may be about 560 ° C to about 705 ° C. The regenerated catalyst particles can then be transferred back to the reactor via the transfer line, and because of their heat, the reactor can be maintained at the temperature required for the cracking reaction. Coke burning is an exothermic reaction; therefore, no additional fuel is required in a conventional conventional catalytic cracking unit using conventional feeds. The feeds used in the practice of the present invention, mainly because of their low levels of aromatic compounds, and because of the relatively short contact time in the reactor or transfer line, may not deposit sufficient coke on the catalyst particles to Reach the required temperature in the regenerator. Therefore, it may be necessary to use additional fuel to provide increased temperature in the regenerator so that the catalyst particles returned to the reaction are hot enough to maintain the cracking reaction. Suitable fueling non-limiting particles include C2-gas, natural gas, and flare oil from the catalytic cracking process itself. Preferred is C2-gas. Isomerization is another procedure by which the catalyst of the present invention can be used. The hydrocarbons that can be isomerized by the method of the present invention include paraffins and olefins typically having 4 to 20, preferably 4 to 12, and more preferably about 4 to 6 carbon atoms; and aromatic compounds such as xylene . Preferred feedstocks include paraffins, examples of which are butane, pentane, hexane, heptane, and the like. Isomerization conditions include the following: a temperature of about 80 ° C to about 350 ° C, preferably a temperature of about 1000t to 260 ° C; a temperature of about 0 to 1,000 sig, preferably Approx. 0 to 300. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) — '" ~' -17- (Please read the precautions on the back before filling this page)
、1T 592816 A7 __B7_ 五、發明説明（15) p S i g的壓力；約0 . 1至2〇，較佳者約〇· 1至2 的液體每小時空間速度；及約1 ，0 0 0至5 ，0 0〇， (請先閲讀背面之注意事項再填寫本頁) 較佳者約1 ，5 0 0至2，5 0 0的氫氣速率，單位，標 準立尺呎/桶。操作溫度和觸媒活性係與空間速度相關聯 以得到進料在觸媒抑活化速率下的合理快速處理，其中確 保觸媒在諸再生期間之間的最大流線上（on-stream )時間 〇 經濟部智慧財產局員工消費合作社印製 本發明觸媒也可以用於加氫裂解程序中。加熱裂解可 增加品質汽油摻合成分的整體精煉產率。加氫裂解可採用 相當低品質的氣體油進料，否則其會摻合到蒸餾物燃料中 且在氫氣和恰當觸媒存在中於固定床反應器內將其轉化。 典型地，係將進料與氫氣混合，加熱到約1 4 0 t至 4〇0°C ，加壓到約1 ，2〇◦至3 ， 500ps ig ， 及給到一第一段反應器內，於其中有約4 0到5 0 %的進 料會反應以脫除掉會抑制裂解反應且製成較低品質產物之 氮和硫化合物。將得自第一段的物流冷却，液化及流經一 分離器，於其中取出丁烷和更輕質氣體。將底餾份通到一 第二段反應器並在更高溫及壓力下裂解，於其中產生其他 的汽油滲合成分和加氫裂解物。 本發明要參照下而用以闡述本發明具體實例的諸實施 例而進一步了解。 實施例1 在三種分別購自市面上的晶狀多微孔氧化物上進行標 本紙張尺度適用中國國家標準（CNS ) A4規格（2!〇Χ 297公釐） ~ ' -18- ^28161T 592816 A7 __B7_ V. Description of the invention (15) pressure of p S ig; about 0.1 to 20, preferably about 0.1 to 2 space velocity of liquid per hour; and about 1, 0 to 0 to 5,000 (Please read the precautions on the back before filling out this page) The hydrogen rate of about 1,500 to 2,500 is preferred, the unit is standard feet per barrel. The operating temperature and catalyst activity are related to the space velocity to obtain a reasonable and rapid processing of the feed at the catalyst inhibitor activation rate, where the maximum on-stream time of the catalyst between regeneration periods is ensured. The catalyst produced by the employee's consumer cooperative of the Ministry of Intellectual Property Bureau can also be used in the hydrocracking process. Thermal cracking can increase the overall refining yield of quality gasoline blending components. Hydrocracking can use a relatively low-quality gas oil feed that would otherwise be incorporated into the distillate fuel and converted in a fixed bed reactor in the presence of hydrogen and the appropriate catalyst. Typically, the feed is mixed with hydrogen, heated to about 140 to 400 ° C, pressurized to about 1,200 to 3,500 psig, and fed to a first stage reactor. About 40 to 50% of the feed will react to remove nitrogen and sulfur compounds that would inhibit the cracking reaction and make a lower quality product. The stream from the first stage is cooled, liquefied and passed through a separator in which butane and lighter gases are taken out. The bottoms are passed to a second stage reactor and cracked at higher temperatures and pressures, producing other gasoline permeate and hydrocracks. The invention will be further understood with reference to the following embodiments which are used to illustrate specific examples of the invention. Example 1 Specimens were prepared on three types of crystalline microporous oxides that were purchased from the market. The paper size was adapted to Chinese National Standard (CNS) A4 (2! 〇 × 297 mm) ~ '-18- ^ 2816
五、發明説明（16) 準M A T檢驗（如，微活性檢驗，a S Τ Μ # 3 9 0 7 8 ) ，U S Y (得自 w. R. Grace，Davison Division，爲 (請先閲讀背面之注意事項再填寫本頁) Z14USY，或 u〇P ，爲 LZY82 或 LZY84) ;LZ — 21〇 (得自 Katalystlks，Inc·);和煆燒烯土交 換 Y ( C R E Y，可得自 w. R. Grace，Davison Division)。 •於進行M A T檢驗之前，將該等晶狀多微孔氧化物與基質 材料（Ludox，得自DuPont)組合並在1 4 ◦ 0 T蒸汽處理 1 6小時以製成裂解觸媒。每一受檢的觸媒包括2 〇重量 %的沸石及8 〇重量％基質材料。其結果列於下面的表1 之中。 表] mat結果 USY LZ-210 CREY 轉化率（重量％，400°F -) 42.5 47.7 64.1 h2(重量％) 0.0113 0.0186 0.0064 c(重量％) 1.480 1.891 1.760 表面積（平方米/克） 200 189 130 孔隙體積（立方公分/克） 0.439 0.023 0.254 單位晶胞（A ) 24.21 24.24 24.51 經濟部智慧財產局員工消費合作社印製 實施例2 將實施例1的諸晶狀多微孔氧化物根據A_ Dyer，An 本紙張尺度適用中國國家標準（CNS ) A4規格（：^^^公釐） -- -19- 592816 A7 B7 五、發明説明（17)V. Description of the invention (16) Quasi-MAT test (eg, micro-activity test, a S T Μ # 3 9 0 7 8), USY (available from w. R. Grace, Davison Division, please read the note on the back first) Please fill in this page again for the matters) Z14USY, or u〇P, LZY82 or LZY84); LZ — 21〇 (available from Katalystlks, Inc.); and yttriumene exchange Y (CREY, available from w. R. Grace , Davison Division). • Prior to the M A T test, these crystalline microporous oxides were combined with a matrix material (Ludox, available from DuPont) and steam treated at 14 ◦ 0 T for 16 hours to make a cracking catalyst. Each catalyst tested included 20% by weight of zeolite and 80% by weight of matrix material. The results are listed in Table 1 below. Table] Mat results USY LZ-210 CREY conversion (wt%, 400 ° F-) 42.5 47.7 64.1 h2 (wt%) 0.0113 0.0186 0.0064 c (wt%) 1.480 1.891 1.760 surface area (m2 / g) 200 189 130 porosity Volume (cubic cm / g) 0.439 0.023 0.254 Unit cell (A) 24.21 24.24 24.51 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 2 The crystalline microporous oxides of Example 1 were prepared according to A_Dyer, An This paper size applies to China National Standard (CNS) A4 specifications (: ^^^ mm)--19- 592816 A7 B7 V. Description of the invention (17)
Introduction to Zeolite Molecular Sieves, Chapter 6，、' Zeolites as Ion Exchangers" ’ John Wiley & Sons，1988 中所 (請先閲讀背面之注意事項再填寫本頁) 述在沸石中進行陽離子交換的方法予以金屬離子交換，該 章中的內容倂於本文作爲參考。在該等晶狀多微孔氧化物 予以離子交換之後，將彼等與基質材料組合並按實施例1 中所述予以蒸汽處理，且根據標準M A T檢驗操作。其結 果列於表2之中。 表2 MAT 結果 USY + AI2O3 LZ-2IO + AI2Q3 CREY + AI2O3 轉化率（重量％，400 29.8 3 8.5 51.1 T -) H2(重量％) 0.0047 0.0053 0.0056 C(重量％) 1.119 1.737 1.516 表面積（平方米/克 194 172 161 ) 孔隙體積（立方公 0.346 0.314 0.318 分/克） 單位晶胞（A ) 24.25 24.22 24.36 經濟部智慧財產局員工消費合作社印製 結果顯不出經金屬陽離卞父換過的晶狀多微孔氧化物 相對於實施例1未經交換的晶狀多微孔氧化物具有明顯減 低的產物轉化率。此結果指出金屬離子交換程序導致等晶 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' - 20 - 592816 A7 B7 五、發明説明（18) 狀多微孔氧化物的非-架構部份所含有效金屬陽離子部位 之減損’而使布忍斯特部位與劉易士部位之間的平衡不利 於合意的活性。 實施例3 對三種不同的市售晶狀多微孔氧化物進行標準M A T 檢驗，稀土交換C R E Y ( R E C R E Y )，其係用一部 份實施例1的C R E Y與稀土離子溶液以D y e r法交換 而製得；氫氣煅燒烯土交換Y ( H C R E Y )，係將 C R E Y所含約4重量％的N a +與N Η 4 +根據Dyer法交 換而製得；及經超穩定化的锻燒交換稀土 γ (U S C R Ε Υ )，係根據 R. Szostak，、、Modified Zeolites "(Chapter 5)，Introduction to Zeolite Science and Practice· vol. 58, Ed. By H. Van Bekkum, E.M. Flanigan, and J. C. Jansecn，Elsevier，1991，的參考文獻6 - 1 3所述方法煅燒 N Η 4 C R Ε Y而製得。在進行M A T檢驗之前，將沸石與 基質材料組合C 1 0重量％沸石；3 0重量％ S i〇2， 爲得自 Unimin Specialty Minerals，Inc的 I M S I L — A — 8 ;60 重量 ％ Si〇2 — Al2〇3，爲得自 W. R. Grace， Davison Division的凝膠所製成，於乾燥和洗清後得到2 5 重量％ A 12〇3，S i〇2 — A 12〇3)而製得裂解觸 媒。其結果示於表3之中。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製Introduction to Zeolite Molecular Sieves, Chapter 6, "Zeolites as Ion Exchangers" "John Wiley & Sons, 1988 (Please read the precautions on the back before filling this page). Ion exchange, the content of this chapter is incorporated herein by reference. After the crystalline microporous oxides are ion-exchanged, they are combined with a matrix material and steam treated as described in Example 1, and operated according to standard M A T inspection. The results are listed in Table 2. Table 2 MAT results USY + AI2O3 LZ-2IO + AI2Q3 CREY + AI2O3 conversion (wt%, 400 29.8 3 8.5 51.1 T-) H2 (wt%) 0.0047 0.0053 0.0056 C (wt%) 1.119 1.737 1.516 surface area (m2 / G 194 172 161) Pore volume (cubic cubic 0.346 0.314 0.318 cents per gram) Unit cell (A) 24.25 24.22 24.36 The printed results of the employees ’cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs did not show the crystals changed by the metal ionization father Compared with the non-exchanged crystalline microporous oxide of Example 1, the shaped microporous oxide has a significantly reduced product conversion rate. This result indicates that the metal ion exchange procedure has caused the isocrystalline paper size to comply with the Chinese National Standard (CNS) A4 specification (210X297 mm) '-20-592816 A7 B7 V. Description of the invention (18) Non-microporous oxide The depletion of the effective metal cation sites contained in the framework part 'makes the balance between the Bronister site and the Lewis site detrimental to the desired activity. Example 3 A standard MAT test was performed on three different commercially available crystalline microporous oxides. The rare earth exchange CREY (RECREY) was prepared by exchanging CREY with a rare earth ion solution in a portion of the Dyer method. Obtained; hydrogen calcined olefin soil exchange Y (HCREY), which is obtained by exchanging about 4% by weight of Na + and N Η 4 + contained in CREY according to the Dyer method; and super-stable calcined exchange rare earth γ ( USCR Ε Υ), according to R. Szostak, Modified Zeolites " (Chapter 5), Introduction to Zeolite Science and Practice · vol. 58, Ed. By H. Van Bekkum, EM Flanigan, and JC Jansecn, Elsevier, In 1991, reference 6-13 was prepared by calcining NΗ4CREY. Prior to the MAT test, the zeolite was combined with the matrix material as C 10% by weight zeolite; 30% by weight Si02, IMSIL — A — 8; 60% by weight SiO2 — from Unimin Specialty Minerals, Inc. Al2O3 is a gel obtained from WR Grace, Davison Division. After drying and washing, 25% by weight of A12〇3, Sio2—A 12〇3) is obtained to obtain a cracked contact. Media. The results are shown in Table 3. This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
i-ϋ la— ϋϋ IN—>1·— ϋ· ι_ϋ— ϋ^— ·ϋϋ ϋϋ ·ϋϋ n —ϋ I -21 - 592816 A7 B7 五、發明説明（19) 表3 MAT結果 RECREY HCREY USCREY 轉化率（重量％，400°F -) 45.3 50.1 44.0 Η 2 (重量％)) 1.34 1.30 1.33 C(重量％) 32.4 27.4 32.7 表面積（平方米/克） 101 129 113 單位晶胞（A ) 24.49 24.24 _ 實施例4 將實施例3的各晶狀多微孔氧化物與乙醯基丙酮化銘 分別在一容器內摻合（沸石對乙醯基丙酮化鋁的比例約1 :1 · 4 ;乙醯基丙酮化鋁的分解溫度稍大於3 2 0) 。將每一容器置於烘箱內並加熱到1 5 0 °C，保持一小時 ’並一足以沖滌掉該乙醯基丙酮化物分解所得潛在可燃性 分解產物的量之氮氣沖滌該烘箱。於沖滌之後，將烘箱加 熱到5 0 0 °C，保持1小時，並使其冷却。然後在5 0〇 °C空氣中加熱到該烘箱2小時。根據產物重量，計算出約 有4 5重量％來自乙醯基丙酮化鋁的量之氧化鋁會因加成 程序而與沸石保留在一起。然後按實施例3將含有加添的 氧化鋁之沸石製成觸媒，且之後在標準M A T檢驗下操作 。其結果列於表4之中。 本紙張尺度適用中國國家榡準（CNS ) Α4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ---ΊΑ·—·— — IIΤ.II^---Φ — II·---------- -22- 592816 A7 B7 五、發明説明（20) 表4 MAT結果 RECREY HCREY USCREY + AhCh + A 1 2 〇 3 + Al2〇3 轉化率（重量％，400°F -) 55.2 58.2 60.8 H：2(重量％) 1.63 1.57 1.65 C(重量％) 22.6 19.3 17.4 表面積（平方米/克） 118 81 143 單位晶胞（A ) — 24.43 24.46 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 結果顯示出含有爲促進脫氫及劉易士酸度所用的金屬 化合物之晶狀多微孔氧化物顯示出相對於實施例3的未加 金屬之晶狀多微孔氧化物在變成汽油產物的轉化率上有明 顯的增加。此結果指出金屬化合物的添加可增加晶狀多微 孔氧化物所含非-架構部份的有效金屬陽離子部位之數目 。換言之，金屬化合物的添加導致劉易士酸部位的明顯增 加。此點也經由直接測定每克觸媒所含酸性部位的數目而 在下面的表5中顯示。 若在如實施例一般蒸汽處理之後，將吡啶吸附到觸媒 之上，接著在真空下加熱到2 5 0 °C以脫吸掉在非一般性 部位上更弱的酸性部位處之任何吡啶，則可以使用紅外光 譜術來測量以吼啶陽離子形式吸附到布忍斯特酸性部位上 的相對吼陡量，及以配位吼D定形式吸著在強劉易士部位上 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公ϋ -23- 592816 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（21) 的量。在經脫吸的觸媒上完成此步驟時，即觀察吸附在三 種觸媒上的吡啶之下述譜帶強度。 於表5中有三種不同物質：1) RECREY，爲 F A U構造型的稀土交換沸石。此爲該表中下面兩種樣品 的起始枓。2 ) R E C R E Y +加添加氧化鋁一 I ，爲按 本文所述方法添加入氧化鋁而爲有效添加氧化鋁之 RECREY樣品。3) RECREY+加添氧化鋁一 I I ，爲以不是有效的加添劉易士酸之方式加入氧化鋁之 R E C R E Y 樣品。 使用 R. J. Gorte，et al·，[Journal of Catalysis 148, 213-223 ( 1 994)，和其中所引參考文獻]及G. L· Price et al. [Journal of Catalysis 148. 228-236，（ 1 994)]所述方法本定量 地測定總酸度，其經示性爲強酸部位的量（強到足以在熱 脫析時促使正丙胺分解成的丙烯和氨）和弱酸性部位的量 (酸性，因其可在5 0 °C下與正丙胺交互作用而保留住該 胺’但隨著溫度升高，會使正丙胺脫吸掉）兩者之和。此 測定係同時測量布忍斯特酸部位和劉易士酸度部位。酸性 的量度係經表成毫當量的酸每克物質（每一毫莫耳胺係計 算爲與一毫莫耳酸部位反應）。 (請先閲讀背面之注意事項再填寫本頁) • · -I I 丁 、τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） -24- 592816 Α7 Β7 五、發明説明（22) ^5. RECREX RECREY RECREY + Ah〇3 + A 1 2 〇 3 總Al2〇3(重量％) 19.7 30.5 27.0 強酸度，毫當量/克 0.46 0.38 0.40 弱酸度，毫當量/克 2.64 2.99 2.59 總酸度，毫當量/克 3.10 3.37 2.99 (請先閲讀背面之注意事項再填寫本頁) 表5顯示出只有在有效添加氧化鋁（I )的情況中， 其弱酸度才會伴隨著總酸度而增加。另一樣品（I I )顯 示出只單純地增加氧化鋁的量不一定會高酸度。 上述每一種沸石樣品都用來按實施例3所述製備觸媒 ，且接著將這些複合料觸媒在實施例3中所述條件下蒸汽 處理使彼等抑活化。 之後取一部份各觸媒樣品壓成薄圓片。將每一圓片稱 重並測量其直徑和厚度。然後將每一圓片置於一真空室內 並加熱移除任何水分或其他吸著氣體。其後將其冷却到 5 0 °C並暴露於吡啶蒸氣-短時間。然後將該樣品置於真 空中數小時並取得其紅外光譜，特別是在1 4 0 〇 c m ^ 與1 6 Ο 0 c m — 1之間者。再將樣品加熱到2 5 〇 °C並保 持數小時，且再取得光譜。此增高的溫度和高真空可脫除 掉任何經物理吸著的吡啶。 對吡啶吸著之前的物質測量，在1 4 0 0 c m — 1與 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ297公釐） " " -25- - . ---訂----- %1. 經濟部智慧財產局員工消費合作社印製 592816 A 7 _B7 _____ 五、發明説明（23) 1 6 0 0 c m — 1之間的紅外光譜並從含有吼陡的樣品所得 光譜減除。所得光譜爲吡啶與觸媒所含酸性部位交互作用 所致光譜。 於此光譜區中，在1 5 40 cm — 1至1 5 5 0 cm一1 處的譜峰係經指配於經配位到來自布忍斯特酸部位的質子 之吡啶。在1 4 0 0 c m — 1與1 4 6 0 c m — 1之間的譜峰 係經指配於吡啶氮上的電子對係與固體的電子接受部位（ 劉易士酸）交互作用者之吡啶。於此光譜區1 4 0 0 cm — 1 至 1 6 6 0 cm_1 中，在 1 4 8 0 cm_1 與 1 5 0 0 c m一1之間的其他譜峰係來自吸著在布忍斯特部 位和劉易士酸部位兩者之上的吡啶譜帶之組合所促成者。 對於用表5中所示沸石製成的經蒸汽處理之複合料觸 媒，表6列出由布忍斯特部位和劉易士部位存在於觸媒上 所產生的譜帶所具強度。 表6 (請先聞讀背面之注意事項再填寫本頁) •t:# ----、1τ----- 經濟部智慧財產局員工消費合作社印製 帶強度來源： (絕對單位/克） RECCREY RECREY+ADA RECREY+ADA I II 布忍斯特部位 22 33 33 劉易士酸部位 55 104 60 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -26-i-ϋ la— ϋϋ IN— > 1 · — ϋ · ι_ϋ— ϋ ^ — · ϋϋ ϋϋ · ϋϋ n — ϋ I -21-592816 A7 B7 V. Description of the invention (19) Table 3 MAT result RECREY HCREY USCREY transformation Rate (wt%, 400 ° F-) 45.3 50.1 44.0 Η 2 (wt%)) 1.34 1.30 1.33 C (wt%) 32.4 27.4 32.7 Surface area (m2 / g) 101 129 113 Unit cell (A) 24.49 24.24 _ Example 4 Each crystalline microporous oxide of Example 3 and acetoacetone acetonate were blended in a container (the ratio of zeolite to acetoacetone aluminum oxide was about 1: 1; 4; acetone The decomposition temperature of aluminum acetonate is slightly higher than 3 2 0). Each container was placed in an oven and heated to 150 ° C for one hour 'and the oven was flushed with nitrogen in an amount sufficient to flush out the potentially flammable decomposition products obtained from the decomposition of the acetamylacetone. After washing, heat the oven to 500 ° C, hold it for 1 hour, and let it cool. The oven was then heated in air at 500 ° C for 2 hours. Based on the weight of the product, it was calculated that about 45% by weight of the amount of aluminum oxide derived from aluminum ethylacetonate would remain with the zeolite due to the addition procedure. The zeolite containing the added alumina was then made into a catalyst as in Example 3, and then operated under standard M A T inspection. The results are shown in Table 4. This paper size applies to China National Standard (CNS) Α4 (210 X 297 mm) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --- ΊΑ · — · — — IIΤ.II ^ --- Φ — II · ---------- -22- 592816 A7 B7 V. Description of the invention (20) Table 4 MAT result RECREY HCREY USCREY + AhCh + A 1 2 〇 3 + Al2O3 Conversion (wt%, 400 ° F-) 55.2 58.2 60.8 H: 2 (wt%) 1.63 1.57 1.65 C (wt%) 22.6 19.3 17.4 Surface area (m2 / g) 118 81 143 Unit cell (A) — 24.43 24.46 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the results show that there are crystalline micropores containing metal compounds used to promote dehydrogenation and Lewis acidity The oxides showed a significant increase in conversion to gasoline products compared to Example 3 without metal added crystalline microporous oxides. This result indicates that the addition of metal compounds can increase the number of effective metal cation sites in the non-structural portion of the crystalline microporous oxide. In other words, the addition of metal compounds leads to a significant increase in the number of Lewis acid sites. This point is also shown in Table 5 below by directly measuring the number of acidic sites per gram of catalyst. If after the steam treatment as in the example, pyridine is adsorbed on the catalyst, and then heated to 250 ° C under vacuum to desorb any pyridine in the weaker acidic part on the non-general part, Infrared spectroscopy can be used to measure the relative amount of steepness that is adsorbed on the acidic site of Brewster in the form of carbazine cations, and adsorbed on the strong Lewis site in the form of coordination D. This paper applies Chinese national standards ( CNS) A4 specification (210X297 public ϋ -23- 592816 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the amount of invention description (21). When this step is completed on the desorbed catalyst, the adsorption is observed The following band intensities of pyridine on the three catalysts. There are three different substances in Table 5: 1) RECREY, a rare earth exchange zeolite of the FAU structure type. This is the starting point for the following two samples in this table. 2) R E C R E Y + adding alumina-I is a RECREY sample for effectively adding alumina by adding alumina according to the method described herein. 3) RECREY + Adding alumina-I I is a sample of R E C R E Y that adds alumina in a way that is not effective in adding Lewis acid. Using RJ Gorte, et al., [Journal of Catalysis 148, 213-223 (1 994), and references cited therein] and G. L. Price et al. [Journal of Catalysis 148. 228-236, (1 994)] The method described herein quantitatively determines the total acidity, which is shown as the amount of strong acid sites (strong enough to promote the decomposition of n-propylamine to propylene and ammonia during thermal desorption) and the amount of weak acid sites (acid, Because it can interact with n-propylamine at 50 ° C, the amine is retained, but as the temperature increases, it will desorb n-propylamine). This measurement measures both the Brnister acid site and the Lewis acidity site. The measure of acidity is expressed as milli-equivalents of acid per gram of substance (each millimolamine system is calculated to react with one millimolar acid site). (Please read the notes on the back before filling in this page) • · -II D, τ This paper size is applicable to China National Standard (CNS) A4 specification (210 X297 mm) -24- 592816 Α7 Β7 V. Description of the invention (22 ) ^ 5. RECREX RECREY RECREY + Ah〇3 + A 1 2 〇3 Total Al203 (wt%) 19.7 30.5 27.0 Strong acidity, mv / g 0.46 0.38 0.40 Weak acidity, mv / g 2.64 2.99 2.59 Total acidity Milli-equivalent / gram 3.10 3.37 2.99 (Please read the notes on the back before filling this page) Table 5 shows that only in the case of effective addition of alumina (I), its weak acidity will increase with the total acidity. Another sample (I I) shows that simply increasing the amount of alumina does not necessarily result in high acidity. Each of the above zeolite samples was used to prepare catalysts as described in Example 3, and then these composite catalysts were steam treated under the conditions described in Example 3 to activate them. Then take a part of each catalyst sample and press it into a thin disc. Weigh each disc and measure its diameter and thickness. Each disc is then placed in a vacuum chamber and heated to remove any moisture or other sorbent gas. It was then cooled to 50 ° C and exposed to pyridine vapor-for a short time. The sample was then placed in the air for several hours and its infrared spectrum was obtained, especially between 14 0 cm 0 and 16 0 cm 1. The sample was heated to 250 ° C and held for several hours, and a spectrum was taken again. This increased temperature and high vacuum can remove any physically adsorbed pyridine. For the measurement of the substance before pyridine adsorption, the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) is applied at 1 400 cm — 1 and this paper size. &Quot; " -25--. --- Order -----% 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592816 A 7 _B7 _____ V. Description of the invention (23) Infrared spectrum between 1 6 0 0 cm — 1 and obtained from samples containing roar Spectral Subtraction. The spectrum obtained is due to the interaction between pyridine and the acidic site contained in the catalyst. In this spectral region, the peaks at 1540 cm to 1 to 1550 cm-1 are assigned to pyridines coordinated to protons from the Bronsted acid site. The peaks between 140 0 cm-1 and 1460 cm-1 are the pyridines that interact with the electron pair assigned to the pyridine nitrogen and the solid electron accepting site (Lewis acid). In this spectral region 1 4 0 0 cm — 1 to 16 6 0 cm_1, the other spectral peaks between 1 4 0 0 cm_1 and 1 5 0 0 cm-1 are derived from adsorption on the Brewster site and Lewis. The combination of the pyridine bands above the acid sites is facilitated. For steam-treated composite catalysts made from the zeolites shown in Table 5, Table 6 lists the strength of the bands produced by the presence of the Brewster site and the Lewis site on the catalyst. Table 6 (Please read the precautions on the back before filling out this page) • t: # ----, 1τ ----- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Source: (absolute units / gram ) RECCREY RECREY + ADA RECREY + ADA I II Brewster's part 22 33 33 Lewis acid part 55 104 60 This paper size is applicable to China National Standard (CNS) A4 size (210X297 mm) -26-