Α2282δ 經濟部中央樣隼局員工消費合作社印製 Α7 Β7_^_五、發明説明（1 ) 【發明說明】 本發明係關於烴之處理，尤其是烯烴之處理，以完成 低聚合作用，及關於用於該斑理中的觸媒。 烯烴係用於氫甲基化作用或羰氧化法中當作起始物質 以用於許多有價値產品的最後製造，例如酵類、酯類、及 衍生自其的醚類、醛類及酸類。在許多這些最終用途中， 線型及輕度分枝的烴鍵優於較重度分枝的鏈。 再者，羰氧化法本身中，具有重度分枝的鏈的反應性 係比具有線型或輕度分枝結構者低，且就所給定的分枝程 度而言，有些異構物的反應性係比其它者低。 烯類原料，特別是（：4至（：2〇者，且更尤其是c6至 C 15範圍者，常常由低分子量原始起始物質之低聚合作用 所製得，其爲一種方法，因爲反應期間中發生重排，而可 能產生非所欲高比例之多重分枝烯類，即使原始物質爲線 型也一樣。而且，分枝的位置，在烴鏈上互相接近處，或 在鏈之中央部位，或兩者處，低聚合作用會更進一步減少 羰氧化法中分子的反應性。 有其它區域，其中較不高度分枝的烴係佔儍勢的；此 些包含於製造界面活性劑及聚烯安定劑中藉與烯類反應使 芳烴之烷化。 美國專利第5,284,989號（亞培林<丨卩611&11>等人，轉 讓給美孚石油公司）敘述使用中度孔隙大小形狀的選擇酸 結晶沸石於烯烴之催化低聚合作用中，及討論影響產物之 線性或分枝程度的因素。沸石粒子表面處的酸活性據說有 本紙張尺度適用中國國家標準{ CNS ) A4規格（210X297公釐）-4 - I 1. —^^1 I I- - ι^ϋ I— 1 in - -I 1 S' (請九聞讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印裝 ’ 4228 2 c at __B7_：_五、發明説明（2 ) 利於分枝產物的製造*且提及沸石表面之去鋁化作用以減 少表面酸度，或表面酸度對晶內酸部位活性的比率。此專 利的廣泛先前技藝評論中所提及的其它減少方法係包括使 用廉大的胺來使酸部位去活化；此專利所針對的發明係使 用二羧酸來使表面酸部位去活化。 美國專利第5,250 ,484(貝克<Back>等人，亦轉讓給美 孚公司）中，藉氨-甲硼烷溶液與觸媒之接觸，及煅燒以在 表面上形成不活性之陶瓷層，而減少表面酸度。美國專利 第4,788,374號中（邱<Chu>等人，亦轉讓給美孚）中，於氟 化物之存在下，在核心表面上結晶矽石，使得金靥矽酸鹽 表面上形成矽石殻，而減少表面酸度。 本發明提供一種用於烯之低聚合作用的方法，其包括 於低聚合作用條件下，使含有至少一種烯的進料與烯低聚 合作用觸媒接觸，該觸媒包括粒狀分子篩，各分子篩粒子 包括一上沈積有表面層的核心，核心包含一種沸石，含有 矽及至少一選自鋁、鎵及锇的元素，表面層之沸石係與核 心者屬相同之晶體結構，且具有比核心者高的矽：所選元 素的比率。 本發明亦提供之一種粒狀分子篩，其可以催化烯之低 聚合作用，各分子篩粒子包括一上沈積有表面層的核心， 核心包含一種沸石，含有矽及至少一選自鋁、鎵及鐵的元 素，而表面層之沸石係與核心者屬相同之晶體結構，且矽 :所選元素的比率係高於核心者。 本發明更提供粒狀分子篩之用途，各分子篩粒子包括 本紙張尺度適用中國國家標準（CNS>A4規格（210X297公釐）_ 5 _ I. m I i I - — —--I Ϊ- ' I -1 I— I , - · i L) - t (請先間讀背面之注$項再填寫本頁) ' 4228 2 8 at B7 經濟部中央榡準局負工消費合作社印» 五、發明説明（3 ) —上沈稹有表面層的核心，核心包含一種沸石，含有矽及 至少一選自鋁、鎵及鐵的元素，而表面層之沸石係與核心 者屬相同之晶體結構，且矽：所選元素的比率係高於核心 者，當作烯低聚合作用之觸媒以減少低聚物產物的分枝程 度0 本發明猶更提供一種用於製造粒狀分子篩的方法，其 包括加熱一水性合成混合物，此混合物包括矽源，選自鋁 、鎵及鐵的元素源，及單價無機陽離子源，且若希望或需 要時選用有機結構指引劑，該合成混合物具有分子篩晶體 分散在其中，該分子篩含有矽及一選自鋁、鎵及截的元素 ，晶體中矽對所選元素的莫耳比率係低於它們在合成混合 物中的各個來源者，以使得分子篩層由合成混合物結晶到 晶體之表面上。 在本發明上述各觀點中，所選之元素較佳係鋁。所選 之元素對核心及外層係有利的，但是不蘅要相同。例如含 鎵的外層可包繞在含鋁的核心上。 有利上，所得的結晶產品可與銨離子或質子作離子交 換，且經烺燒以產生分子篩之酸形式。有利上，煅燒係溫 度至多爲600 °C，較要至多爲500 °C時發生。 用於製造本發明的分子篩之方法的某些特徵係與一般 此藝實施所熟知方法或文獻中所述者共有分享。 該些者可簡單說明如下： 矽源係必要的：此例如可爲一種膠髏矽石懸浮液，例 如，以Ludox商品名稱所販售者，可爲精細分割之固髖， 裝-- (請先閲讀背面之注$項再填寫本頁) 本紙張尺度適用中國國家梯準（CNS ) Α4規格（210X297公缝） 經濟部中夬標準局員工消费合作杜印裝 422828_；； 卞_五、發明説明（4 ) 例如，以Aerosil商品名稱所販者。 適當的鋁源可爲一種引入合成混合物中的氧化鋁，例 如Α12〇3· 3H2〇先溶於鹸或鋁鹽中，例如Ai2(S〇4)3· 18H0 ，溶於鹼溶液中。適當的鎵源例如是Ga2〇3，亦於鹼溶液 中*而Fe(N〇3)3係較宜的。以下說明中，爲了清晰起見， 將僅提及鋁。 合成混合物含有單價陽離子源，例如鹺金屬，例如鈉 、鉀或鈣，或銨離子源。其有利上可以提供爲氫氧化物之 形式，藉此而提供一種可加有氧化鋁的鹼性溶液。 有機結構指引劑若存在的話則藉所謂的樣板效應而指 引所給分子篩之形成。有機分子在分子篩合成中的角色係 爲周知的，且例如討論於洛克（Lok)等人的沸石1983,第3 冊，第282至291頁，及馬瑞提（Moretti)等人，Chim, Ind.( 米蘭）67, No. 1至2, 21至34 (1 985 )。有機結構指引劑 的效果係在於晶體骨架之製作中，有機化合物當作一種樣 板，而晶體圍繞其上生長，或是其指引結晶作用形成特殊 晶體骨架。用於製造ZSM-22篩的較宜試劑係具有高至12個 碳原子的單·及二-胺基烷，特別是4,6,8,10或12個碳者， 例如1,6 -二胺基己烷（其係較佳的）、二乙胺、；[-胺基丁烷 或2,. 2’-二胺基二乙胺：含有高至8個碳原子的芳胺，雜 環有機化合物，例如N -乙基吡啶：聚伸烷基聚胺，例如三 伸乙四胺或四伸乙五胺，及烷醇胺，例如乙醇胺或二乙醇 胺。 基於較佳之1,6-二胺基己烷樣板，較佳的樣板R之量 ί紙張尺度適用中囱國家標準（CNS ) A4規格（210父29?公釐）-7二 ' {請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消资合作社印裝 ^^^4228 2 8 A7 - B7 ^ 五、發明説明（5 ) 係爲使得合成混合物中R/SiOs之莫耳比率爲0()25至〇.4。 合成混合物中的Si〇2 /A丨2〇3莫耳比率一般係至少150 :1，較佳至少250:1，且可能高至1500:1。介於3〇〇:1與 900 : 1間的比率，尤其是介於300: 1與600 : 1，係特別佳的 0 結晶後沸石餍中的Si〇2/Al2〇3莫耳比率可能比合成混 合物中的莫耳比率低至於達及30%:此減少可當作爲選擇 合成混合物的成分比例之參考，以確保核心與外靥比率間 的必要關係。分散於合成混合物中的核心晶體內的Si〇2/ A丨2〇3莫耳比率有利上係爲至多120 : 1，更有利上係在範圍 40:1至120:1，且較宜在範圍60至100:1內。 合成混合物中的反應物比例一般係低於正常之合成混 合物中者，即是，除了較低的鋁含量外，合成混合物應被 高度稀釋，例如用水稀釋。含有核心物質的合成混合物可 含有，例如，高至85重量％，有利上50至80重置％的稀釋劑 ，尤其是水。 有利上，結晶作用係在120至180°C完成，較隹140至 1 7 0 °C。結晶時間可爲1 0至7 2小時，典型上1 5至4 8小時。 結晶作用後，可用去離子水或酸化之水來洗沸石，然 後視需要在乾燥或煅燒步驟後，離子交換以產生酸形式。 沸石較佳係與銨離子交換，且經過銨離子分解的條件 ，形成氨及質子，因此產生沸石之酸形式。另可選擇的是 ，可藉與（例如）鹽酸作酸交換而得酸形式。 可由任何逋合之方法來進行與銨離子之交換，例如用 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ! J. ! I - - m n |=1 ί -I i I ί - I - If In ΙΊΙ 1Γ - - (請先w讀背面之注$項再填寫本頁) 422328 經濟部中央標隼局貝工消费合作杜印製 A7 B7 二_五、發明説明（6 ) 氯化銨、硝酸銨或氫氧化銨的水溶液來處理晶體。有利上 使晶體與稀酸溶液例如HC1接觸而進行與質子之交換。 與銨離子或質子交換後，晶體可經烺燒，有利上在溫 度120β至600°(：，較佳150β至500。(：。適當的煅燒時間範 圍係1小時至數天，規定溫度範圍之上段中的溫度係對應 較短之加熱時間，而規定溫度範圍之下段中的溫度係對應 於較長之加熱時間。 因此，例如，晶體可在溫度4 00°C烺燒1至20小時。在 1 2 0°C時，通常需至少兩天較長的烺燒時間，且較宜爲3至 5天，以達成適當的孔隙空間。 篩可經後處理，如汽蒸，或可在製備期間藉混入或藉 離子交換而使其含有它陽離子，適合之陽離子的例子係鎳 '鎘、銅、鋅、鈀、鈣、硼及鈦和稀土金靥。 有利上，本發明之分子篩具有精煉拘束指數（如以下 所定義）大於2,且有利上大於10。 精煉拘束指數（r e f i n e d c ο n s t r a i π t i π d e X ) C I β 係定 義於 J . A · ίί a r t e π s , Μ . T i e [ e η , P . A , J a c 〇 b s 及 J. We i t ka m p ,沸石，1 9 84 , 98頁，及 P . A . J a c o bs & J . A . Martens,純及應用化學，1 986, 58冊，1 3 2 9頁中，其爲 在正癸烷之氫-異構作用中5¾轉化率時，所產生的2 -甲基 壬烷對產生的5-甲基壬烷之比率。 具有CP介於2與10間的分子篩之例子包括ZSM-5、11 、12、35、38、48 及 57、SAP0-11、MCM-22 及毛沸石，具 有CT介於5與10閫者係較佳的。具有CT大於10的分子 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐） 經濟部中央楳準局貝工消費合作社印製 422828 A7 _B7_ __五、發明説明（7 ) 篩之例子係最佳的，其包括ZSM-22、ZSM-23及某些弗利提 (furrierites) 0 .使用含有兩種或多種分子篩的混合物係在本發明之低 聚合方法的範圍內。 分子篩或沸石有利上係爲美國專利第45564 77號及1ίΟ 93/25475中所述的ZSM-22，其之揭示併於本文中作參考。 可用的分子篩之晶髏大小有利上係高至5微米，較佳 在範圍0.05至5微米內，更佳在0.0 5至2微米，且最佳在0. 1至1. 0微米。 表面層所代表的重置比率（佔本發明分子篩的總重）係 可爲例如在範園5¾至20¾內，方便上8¾至15Μ炮燒後）。 分子篩之可用形式爲顆粒、粉髏或其它形狀，例如爲 擠出物。擠出物有利上係含有分子篩及一黏合劑，例如氧 化鋁、矽石、矽酸鋁、或黏土，有利上重量比例爲10:90 至90:10，較佳20:80至80:20，的分子筛對黏合劑。篩及 黏合劑之組合如可經由：例如，於水之存在中使它們緊密 混合一起，及擠壓或者其它成形，例如藉壓丸。 進料烯有利上含有2至12個碳原子，且較佳2至6個碳 原子：更佳爲烯進料有利上含有丙烯、丁烯及/或戊烯。 本發明之低聚合方法的反應條件，除了使用新穎觸媒 外，其它可依照先前技藝對相同之烯作低聚合反應所用的 操作條件。 烯例如可送入混有鈍性稀釋劑的觸媒中，該稀釋劑例 如是飽和烴，爲液相，較佳爲氣相。就含有丙烯的進料而 本紙張尺度通用t國國家標準（CNS ) A4規格（210X297公釐)~~ ' -iu - n. 1·- I -I I - ii m n^v i 4 !. I - . I I!!— I I-. (請先聞讀背面之注意事項再填寫本頁) 經濟部t夬梯準局員x消費合作社印製 4228 2 6 at __ __B7_—五、發明説明（8 ) 言，適合的稀釋劑是丙烷，有利上丙烯：丙烷之重量比例 爲 90 : 10至 10 : 90，較隹 10 : 90至 60 : 40，尤其是約 50 : 50。 相應地，就丁烯進料而言，逋合的稀釋劑是丁烷，有利上 重S比例爲90 : 10至10 : 90，較佳75 : 25至50 : 50 ,尤其是 約2:1的烯：飽和物。進料有利上係水合的：較佳爲其拾 有0.05重置％至2重:1:¾的水。在逋當的溫度，例如25至60 °C，使進料飽和，或經由泵注入水，而可併有所欲比例的 水。 低聚合作用有利上可發生在160eC至300°C的溫度範圍 ，較佳17CTC至260°C，且最佳180至260°C，在5至lOMPa之 壓力範困，較佳6至8M Pa，及在0.1至20之烯每小時空間速 度範圍，較佳0.5至10,且最佳0.75至3.5。 在使用正常先前技藝觸媒如ZSM-22的烯低聚合作用中 ，茲發現轉化率減少，對二聚物的選擇性，例如由丁烯至 辛烯，增加，但是分枝程度亦增加。然而使用本發明的觸 媒，已驚異地發現在較低的轉化率時，對二聚物的選擇性 被保持著，且伴隨著減少之分枝程度。因此，低聚合作用 可在較低之轉化率時進行，未反應的單體由低聚物分離出 及循環，而產生高的二聚物選擇性，沒有損失產品的線性 度。 再者，本發明之觸媒另有優於先前技藝之經巨大-胺 處理的物質之優點，其易於再生，例如經由煅燒，而不寄 要後績之胺處理作業。對於將烯低聚合成較不高度分枝產 物的能力而言，本發明之觸媒再生後者與其原始製備的觸 本紙張又度通用t國國家標隼（CNS> A4規格（210'乂297公釐）_ __ -I nn I...... - - I Ji --1 ^ni I _f— 一aJ - t (請先閱讀背面之注意事項再填寫本莧) 4228 2 8 A7 B7 五、發明説明（9 ) 媒之能力並無不同。 以下用於說明本發明的實例中，除非另有指明，份及 百分率係以重量計： 實例1 - 3 觸媒之製備 實例1 合成混合物之製備： 溶液A : 成分 份 h2〇 229.4 A 1 2(S〇3 )318H2〇 0.6538 NaOH(98.4¾) 2.11 1，6-二胺基已烷 12.85 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印^ 將成分依所示順序溶於水中。 溶液B : 成分 份 Ludox(路多克斯）AS-40 (膠體矽石） 54.81 本紙張尺度通用中國國家標隼（CNS>A4規格（ 210X297公釐）· π _ 42282 8 Α7 Β7 五、發明说明（10 ) 溶液A與B混合約3分鐘，而產生匀和稍白色凝膝（合成 混合物） 混合物C : 成分 份 ZSM-22(H 0含量 1 . 18¾) 50.00 Si〇2/A丨2〇3莫耳比率73:1 h2〇 50 _ 09 (請先W讀背面之注意事項再填寫本頁) 經濟部中夾橾準局员工消費合作社印裝 ZSM-22之粒子大小芸1微米。 將混合物之成分混合5分鐘，而產生非常黏稠之糊。 將72.54份的合成混合物（溶液ΑδΒ)加入及混合15分鐘。得 到易傾注性及均匀性的質髏。 最終合成混合物（晶饈除外）的莫耳組成是： 26.4 Na2〇/112.6 R/Al2〇3/372 Si〇2/26580 H2〇 其中R係1 ,6-二胺基己烷。 此混合物含有28. 7¾預形成之ZSM-22晶體。 將80.87份的合成混合物移送到不銹鋼高壓釜內，及 加熱至160°C歷經2小時，並保持在此溫度48小時。 將產物過濾及用500份水來洗三次而至ρΗ9.4，隨後於 本紙張尺度適用令國國家標準（CNS)A4说格（210X297公釐）_ _ 422828 經濟部令央揉隼扃員工消費合作社印装 A7 B7 _ ~r五、發明説明（11 ) 125°C乾燥；25.88份乾燥之產物被回收得。乾燥後之產物 具有强烈之帶黄色外觀，顯示核心晶饅覆羞有富矽的ZSM -22外層或殻。般對核心的重量比係如下計算： 合成混合物X部分預形成之晶體的部分 (80.87X0.287) 23.21 乾燥產物部分 25.88 獲得* 2.67 般/未經烺燒之核心的比率 2.67/23.21 即 0 . 1 2 假定烺燒下重S損失約12¾，煅燒過之殼對核心的預 期重量比係約0.10:1。 乾燥過產物之X-射線繞射顯示ZSN-22之結構稍微被白 矽石所污染。 實例2 依照實例1之程序，得到莫耳組成之最終合成混合物 53.0 Na20/226 R/Al2〇3/746 Si〇2/61Q45 H2〇 其中R係1,6-二胺己烷，含有29.32¾預形成之ZSM-22晶體 〇 將111 . 24份的含微晶體之合成混合物移送到不銹鋼高 壓釜內，其置於室溫的烘箱內。烘箱加熱至15 8°C歷經2小 時及保持在該溫度24小。 本紙張尺度適用中闺國家標準（€邓）八4規格（210><297公釐）_ ^ . 二请先W讀背面之注意事項再填寫本頁)Α2282δ Printed by the Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs Α7 B7 _ ^ _ V. Description of the Invention (1) [Invention Description] The present invention relates to the treatment of hydrocarbons, especially the treatment of olefins, in order to complete the oligomerization, and The catalyst in this patch. Olefins are used as starting materials in hydromethylation or carbonyl oxidation processes for the final manufacture of many valuable europium products, such as fermentations, esters, and ethers, aldehydes, and acids derived from them. In many of these end uses, linear and lightly branched hydrocarbon bonds are superior to heavier branched chains. Furthermore, in the carbonyl oxidation method itself, the reactivity of a chain with a severe branch is lower than that of a linear or lightly branched structure, and for a given degree of branching, the reactivity of some isomers Department is lower than others. The olefinic raw materials, especially those in the range of (: 4 to (: 20), and more particularly in the range of c6 to C15, are often prepared by the low polymerization of low molecular weight original starting materials, which is a method because the reaction Rearrangement occurs during the period, and an undesirably high proportion of multiple branched olefins may be produced, even if the original substance is linear. Moreover, the branching positions are close to each other on the hydrocarbon chain, or in the center of the chain , Or both, oligomerization will further reduce the reactivity of the molecules in the carbonyl oxidation process. There are other areas where the less highly branched hydrocarbons are silly; these are included in the manufacture of surfactants and polymers In alkylene stabilizers, alkylation of aromatic hydrocarbons by reaction with olefins. U.S. Patent No. 5,284,989 (Apelin < 丨 卩 611 & 11 > et al., Assigned to Mobil Petroleum Corporation) describes the choice of using moderate pore size shapes Acid crystalline zeolite in the catalytic oligomerization of olefins, and discuss the factors that affect the linearity or degree of branching of the product. The acid activity at the surface of the zeolite particles is said to have the paper size applicable to Chinese national standards {CNS ) A4 specification (210X297 mm) -4-I 1. — ^^ 1 I I--ι ^ ϋ I— 1 in--I 1 S '(Please read the notes on the back of Jiuwen before filling this page) Economy Printed by the Consumer Procurement Cooperative of the Ministry of Central Standards Bureau '4228 2 c at __B7_: _ V. Description of the invention (2) Conducive to the production of branch products * and mentioning the de-alumination of zeolite surface to reduce surface acidity, or surface acidity Ratio of activity to intragranular acid sites. Other reduction methods mentioned in this patent's extensive prior art review include the use of inexpensive amines to deactivate acid sites; the invention targeted by this patent uses dicarboxylic acids to Deactivate the acid sites on the surface. In U.S. Patent No. 5,250,484 (Baker < Back > et al., Also assigned to Mobil Corporation), the ammonia-methane solution is contacted with the catalyst and calcined to form on the surface Inactive ceramic layer, reducing surface acidity. In US Patent No. 4,788,374 (Qiu < Chu > et al., Also assigned to Mobil), the silica is crystallized on the core surface in the presence of fluoride, making gold矽 Silica shells are formed on the surface of silicates while reducing the surface The present invention provides a method for oligomerization of olefins, which comprises contacting a feed containing at least one olefin with an olefin oligomerization catalyst under oligomerization conditions, the catalyst including granular molecular sieve, Each molecular sieve particle includes a core on which a surface layer is deposited. The core includes a zeolite containing silicon and at least one element selected from aluminum, gallium, and gadolinium. The zeolite on the surface layer has the same crystal structure as the core, and has a specific ratio. The core is high silicon: the ratio of selected elements. The invention also provides a granular molecular sieve, which can catalyze the oligomerization of olefins. Each molecular sieve particle includes a core with a surface layer deposited on it. The core contains a zeolite containing Silicon and at least one element selected from aluminum, gallium, and iron, and the zeolite of the surface layer has the same crystal structure as the core, and the ratio of silicon: selected element is higher than that of the core. The invention further provides the use of granular molecular sieves, each molecular sieve particle including the paper size is applicable to the Chinese national standard (CNS > A4 specification (210X297 mm) _ 5 _ I. m I i I-— --- I Ϊ- 'I -1 I— I,-· i L)-t (please read the note on the back before filling in this page) '4228 2 8 at B7 Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and Consumer Cooperatives »V. Description of the invention (3) — A core with a surface layer on the top, the core contains a zeolite, containing silicon and at least one element selected from aluminum, gallium and iron, and the zeolite on the surface layer has the same crystal structure as the core, and the silicon : The ratio of the selected element is higher than the core, which is used as a catalyst for the oligomerization of olefins to reduce the degree of branching of the oligomer product. The present invention further provides a method for manufacturing a granular molecular sieve, which includes heating An aqueous synthesis mixture including a silicon source, an element source selected from aluminum, gallium, and iron, and a monovalent inorganic cation source, and if desired, an organic structure directing agent is selected, and the synthesis mixture has molecular sieve crystals dispersed therein, The molecular sieve contains silicon and An element selected from the group consisting of aluminum, gallium, and truncation. The molar ratio of silicon to the selected element in the crystal is lower than that of each source in the synthesis mixture, so that the molecular sieve layer is crystallized from the synthesis mixture to the surface of the crystal. In the above aspects of the present invention, the selected element is preferably aluminum. The selected elements are good for the core and outer layers, but they need not be the same. For example, a gallium-containing outer layer may be wrapped around an aluminum-containing core. Advantageously, the resulting crystalline product can be exchanged with ammonium ions or protons and sintered to produce the acid form of the molecular sieve. Advantageously, the temperature of the calcination system is at most 600 ° C, and more than 500 ° C. Certain features of the methods used to make the molecular sieves of the present invention are shared with those generally known in the art or methods described in the literature. These can be briefly explained as follows: Silicon source is necessary: this can be, for example, a colloidal silica suspension, for example, sold under the Ludox trade name, can be a finely divided solid hip, loaded-(Please First read the note on the back and fill in this page.) This paper size is applicable to China National Standard for Ladder (CNS) Α4 (210X297 cm). Employees ’cooperation with the China Standards Bureau of the Ministry of Economic Affairs. Du printed 422828_; 卞 _V. Invention Explanation (4) For example, a trader under the Aerosil trade name. A suitable aluminum source may be an alumina introduced into the synthesis mixture, such as A1203 · 3H2O first dissolved in rhenium or an aluminum salt, such as Ai2 (S04) 3 · 18H0, dissolved in an alkaline solution. A suitable source of gallium is, for example, Ga203, also in an alkaline solution *, and Fe (N03) 3 is more suitable. In the following description, for clarity, only aluminum will be mentioned. The synthesis mixture contains a source of monovalent cations, such as a rhenium metal, such as sodium, potassium, or calcium, or a source of ammonium ions. It can advantageously be provided in the form of a hydroxide, whereby an alkaline solution to which alumina can be added is provided. Organic structure directing agents, if present, guide the formation of the given molecular sieve by the so-called template effect. The role of organic molecules in the synthesis of molecular sieves is well known and is discussed, for example, in Zeolite 1983, Vol. 3, pp. 282-291, and Moretti et al., Chim, Ind. . (Milan) 67, No. 1 to 2, 21 to 34 (1 985). The effect of the organic structure directing agent is that in the production of the crystal skeleton, an organic compound is used as a template, and the crystal grows around it, or it directs the crystallization to form a special crystal skeleton. The preferred reagents for making ZSM-22 sieve are mono- and di-aminoalkanes with up to 12 carbon atoms, especially those with 4, 6, 8, 10 or 12 carbons, such as 1, 6-2 Aminohexane (which is preferred), diethylamine, [-aminobutane or 2 ,. 2'-diaminodiethylamine: aromatic amines containing up to 8 carbon atoms, heterocyclic Organic compounds, such as N-ethylpyridine: polyalkylene polyamines, such as triethylenetetraamine or tetraethylenepentamine, and alkanolamines, such as ethanolamine or diethanolamine. Based on the better 1,6-diaminohexane sample, the better quantity of the template R, the paper size is applicable to the National Standard (CNS) A4 specification (210 father 29? Mm) -7 2 '{Please read first Note on the back, please fill out this page again) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives ^^^ 4228 2 8 A7-B7 ^ V. Description of the invention (5) is to make the R / SiOs in the synthetic mixture The ear ratio is from 0 () 25 to 0.4. The SiO2 / A2203 molar ratio in the synthesis mixture is generally at least 150: 1, preferably at least 250: 1, and may be as high as 1500: 1. The ratio between 300: 1 and 900: 1, especially between 300: 1 and 600: 1, is a particularly good 0 Moore ratio of Si〇2 / Al203 in zeolite after crystallization may be smaller than The mole ratio in the synthetic mixture is as low as 30%: this reduction can be used as a reference for selecting the proportion of the ingredients in the synthetic mixture to ensure the necessary relationship between the core and the outer ratio. The molar ratio of Si〇2 / A 丨 203 in the core crystals dispersed in the synthetic mixture is advantageously at most 120: 1, more preferably in the range of 40: 1 to 120: 1, and more preferably in the range Within 60 to 100: 1. The proportion of reactants in the synthesis mixture is generally lower than in normal synthesis mixtures, that is, in addition to the lower aluminum content, the synthesis mixture should be highly diluted, for example with water. Synthetic mixtures containing core substances may contain, for example, up to 85% by weight, advantageously 50 to 80% by weight of diluent, especially water. Advantageously, the crystallization is completed at 120 to 180 ° C, which is lower than 隹 140 to 170 ° C. The crystallization time can be from 10 to 72 hours, typically from 15 to 48 hours. After crystallization, the zeolite can be washed with deionized water or acidified water, and then after the drying or calcining step, if necessary, ion exchanged to produce the acid form. The zeolite is preferably exchanged with ammonium ions and undergoes the conditions of ammonium ion decomposition to form ammonia and protons, thus generating the acid form of the zeolite. Alternatively, the acid form can be obtained by acid exchange with, for example, hydrochloric acid. The exchange with ammonium ions can be carried out by any combination of methods, for example, the Chinese paper standard (CNS) A4 (210X 297 mm) is used for this paper size! J.! I--mn | = 1 ί -I i I ί-I-If In ΙΊΙ 1Γ--(please read the note on the back and fill in this page first) 422328 Printed A7 B7 by the Shellfish Consumer Cooperation Department of the Central Bureau of Standards of the Ministry of Economic Affairs II_V. Description of Invention (6) An aqueous solution of ammonium chloride, ammonium nitrate or ammonium hydroxide is used to treat the crystals. Advantageously, the crystals are contacted with a dilute acid solution such as HC1 for exchange with protons. After exchange with ammonium ions or protons, the crystals can be calcined, advantageously at a temperature of 120β to 600 ° (:, preferably 150β to 500. (:. The appropriate calcination time range is 1 hour to several days, within the specified temperature range). The temperature in the upper section corresponds to a shorter heating time, while the temperature in the lower section of the specified temperature range corresponds to a longer heating time. Therefore, for example, the crystal can be burned at a temperature of 400 ° C for 1 to 20 hours. At 120 ° C, it usually takes at least two days for longer scorch time, and more preferably 3 to 5 days to achieve proper pore space. The sieve can be post-treated, such as steaming, or can be used during preparation Examples of suitable cations include nickel, cadmium, copper, zinc, palladium, calcium, boron, titanium, and rare-earth gold rhenium. Advantageously, the molecular sieve of the present invention has a refinement constraint index. (As defined below) is greater than 2, and advantageously greater than 10. The refinement constraint index (refinedc ο nstrai π ti π de X) CI β is defined in J. A · ί arte π s, Μ. T ie [e η, P. A, J ac bs and J. We it ka mp, Zeolite, 1984, p. 98, and P. A. Jaco bs & J. A. Martens, Pure and Applied Chemistry, 1 986, 58 vol., 1 3 2 9 p. The ratio of 2-methylnonane to 5-methylnonane produced at a 5¾ conversion in the hydrogen-isomerization of n-decane. Examples of molecular sieves with CP between 2 and 10 include ZSM -5, 11, 12, 35, 38, 48 and 57, SAP0-11, MCM-22 and erionite, those with CT between 5 and 10 are preferred. Molecules with CT greater than 10 (please read first Note on the back, please fill out this page again) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Printed by the Shellfish Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs 422828 A7 _B7_ __ V. Description of the invention (7 Examples of sieves are the best, which include ZSM-22, ZSM-23 and certain furrierites. The use of a mixture containing two or more molecular sieves is within the scope of the oligomerization process of the present invention. The molecular sieve or zeolite is advantageously ZSM-22 as described in U.S. Patent Nos. 45564 77 and 1/93/25475, the disclosure of which is incorporated herein by reference. The zeolite crystal size of the skull on the system advantageously up to 5 microns, preferably in the range of 0.05 to 5 microns, more preferably from 0.0 to 5 2 microns, and most preferably at 0.1 to 1.0 microns. The replacement ratio represented by the surface layer (accounting for the total weight of the molecular sieve of the present invention) can be, for example, within 5¾ to 20¾ of Fan Yuan, after being easily fired at 8¾ to 15M). Molecular sieves may be used in the form of granules, crossbones, or other shapes, such as extrudates. The extrudate advantageously contains a molecular sieve and a binder, such as alumina, silica, aluminum silicate, or clay. The weight ratio is advantageously 10:90 to 90:10, preferably 20:80 to 80:20. Molecular sieve on the binder. The combination of the sieve and the binder can be, for example, intimately mixed together in the presence of water, and extruded or otherwise shaped, such as by pellets. The olefin feed advantageously contains 2 to 12 carbon atoms, and preferably 2 to 6 carbon atoms: more preferably the olefin feed advantageously contains propylene, butene and / or pentene. In addition to the reaction conditions of the oligomerization method of the present invention, in addition to the use of novel catalysts, other operating conditions for oligomerization of the same olefin according to the prior art can be used. The olefin can be fed, for example, into a catalyst mixed with a passive diluent, such as a saturated hydrocarbon, which is a liquid phase, preferably a gas phase. For the feed containing propylene, the paper size is in accordance with the national standard (CNS) A4 specification (210X297 mm) ~~ '-iu-n. 1 ·-I -II-ii mn ^ vi 4!. I-. II !! — I I-. (Please read the precautions on the back before filling out this page) t 准 ladder prospective member of the Ministry of Economy x printed by Consumer Cooperatives 4228 2 6 at __ __B7_—V. Description of the invention (8) A suitable diluent is propane, which advantageously has a weight ratio of propylene: propane of 90:10 to 10:90, more than 10:90 to 60:40, especially about 50:50. Correspondingly, as far as the butene feed is concerned, the combined diluent is butane, with an advantageous weight S ratio of 90:10 to 10:90, preferably 75:25 to 50:50, especially about 2: 1. Olefin: saturates. The feed is favorable for hydration: it is preferred to pick up water from 0.05% reset to 2 weight: 1: ¾. Saturate the feed at a convenient temperature, such as 25 to 60 ° C, or inject water through the pump, but mix the desired proportion of water. The low polymerization can advantageously occur in a temperature range of 160eC to 300 ° C, preferably 17CTC to 260 ° C, and most preferably 180 to 260 ° C, in the pressure range of 5 to 10MPa, preferably 6 to 8M Pa, And in the range of space velocity per hour from 0.1 to 20, preferably 0.5 to 10, and most preferably 0.75 to 3.5. In the oligomerization of olefins using normal prior art catalysts such as ZSM-22, it is found that the conversion is reduced and the selectivity to dimers, such as from butene to octene, is increased, but the degree of branching is also increased. However, using the catalyst of the present invention, it has been surprisingly found that at lower conversions, the selectivity to dimers is maintained, with a reduced degree of branching. Therefore, low polymerization can be performed at a lower conversion rate, and unreacted monomers are separated and recycled from the oligomer, resulting in high dimer selectivity without loss of product linearity. Furthermore, the catalyst of the present invention has another advantage over the mega-amine treated materials of the prior art, which are easy to regenerate, such as by calcination, without post-treatment amine treatment operations. For the ability to oligomerize olefins into less highly branched products, the catalyst regeneration method of the present invention and the original contact paper produced by the catalyst are generally in accordance with the national standard (CNS > A4 specification (210 '乂 297)). (Centi) _ __ -I nn I ......--I Ji --1 ^ ni I _f— a a-t (Please read the notes on the back before filling in this card) 4228 2 8 A7 B7 V. Description of the invention (9) The ability of the medium is not different. In the examples used to illustrate the present invention, parts and percentages are by weight unless otherwise specified: Examples 1-3 Preparation of catalysts Example 1 Preparation of synthetic mixtures: Solution A: Ingredients h2〇229.4 A 1 2 (S〇3) 318H2〇0.6538 NaOH (98.4¾) 2.11 1,6-diaminohexane 12.85 (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Central Consumer Bureau of Consumers' Cooperative ^ Dissolve the ingredients in the order shown. Solution B: Ingredients Ludox AS-40 (colloidal silica) 54.81 This paper is in accordance with the Chinese National Standard (CNS >); A4 specification (210X297 mm) · π _ 42282 8 Α7 Β7 V. Description of the invention (10) Solution A and B is mixed for about 3 minutes to produce a homogeneous and slightly white gel (synthetic mixture) Mixture C: Ingredients ZSM-22 (H 0 content 1. 18¾) 50.00 Si〇2 / A 丨 203 Molar ratio 73: 1 h2〇50 _ 09 (please read the precautions on the reverse side before filling out this page) The particle size of the printed ZSM-22 printed by the Consumers' Cooperatives in the Ministry of Economy is 1 micron. Mix the ingredients for 5 minutes, and A very viscous paste was produced. 72.54 parts of the synthetic mixture (solution AδB) was added and mixed for 15 minutes. An easily pourable and homogeneous skeletal skeleton was obtained. The molar composition of the final synthetic mixture (except crystal urn) was: 26.4 Na2. /112.6 R / Al2〇3 / 372 Si〇2 / 26580 H2〇 where R is 1,6-diaminohexane. This mixture contains 28. 7¾ preformed ZSM-22 crystals. 80.87 parts of the synthetic mixture is transferred Into a stainless steel autoclave, and heated to 160 ° C for 2 hours, and maintained at this temperature for 48 hours. The product was filtered and washed three times with 500 parts of water to ρΗ9.4, and then applied to this country Standard (CNS) A4 grid (210X297 mm) _ 422828 Ministry of Economy Ling Yang Co-op employees shut printing equipment A7 B7 _ ~ r V. Description of the Invention (11) 125 ° C dry; 25.88 parts of dried product was recovered too. The dried product has a strong yellowish appearance, showing that the core crystal is covered with a silicon-rich ZSM-22 outer layer or shell. The ratio of the general weight to the core is calculated as follows: The pre-formed crystal portion of the X part of the synthesis mixture (80.87X0.287) 23.21 The dried product portion 25.88 is obtained * 2.67 The ratio of the normal / unfired core is 2.67 / 23.21, which is 0. 1 2 Assuming a weight loss of about 12¾ under calcination, the expected weight ratio of the calcined shell to the core is about 0.10: 1. X-ray diffraction of the dried product showed that the structure of ZSN-22 was slightly contaminated with white silica. Example 2 According to the procedure of Example 1, a final synthetic mixture of 53.0 Na20 / 226 R / Al2 03/746 Si 2 / 61Q45 H2 was obtained, in which R is 1,6-diamine hexane, containing 29.32¾ The formed ZSM-22 crystals. 111. 24 parts of the microcrystal-containing synthetic mixture was transferred to a stainless steel autoclave and placed in an oven at room temperature. The oven was heated to 15 8 ° C for 2 hours and kept at this temperature for 24 hours. The size of this paper is applicable to China National Standard (€ Deng) 8 4 specifications (210 > < 297 mm) _ ^. 2. Please read the precautions on the back before filling this page)
42282S B7 一 _ 五 '發明説明（12 ) 所得之晶髏產物經水重覆洗及在125eC乾燥40小時。 35. 8份的乾燥產物被回收得。經由實例1中所述的煅燒， 發現未經烺燒的般：核心之重量比爲0.10:1，而預期之煅 燒過的般：核心比係常約0.09:1。义110顯示純晶體23!^22結 構。 實例3 合成混合物之製備： 溶液A : I 1.1 I I II -I I I - -- I I - - I - — I I - - 1 -1 4H V* {請先閱讀背面之注意事項再填寫本頁) 成分 份 A]2(S〇4) I8H2O 0.2193 NaOH(98.4%) 2.10 1 , 6-二胺基已烷 12.87 HaO . . 175.00 經濟部中央橾隼局貞工消費合作社印装 將最初三個成分依所示順序加到175份水中/將54 .82 份的膠體矽石（Udox AS40)溶液B置於一混合器中，將溶 液A到混合器的內含物上，及用54 . 6 7份的水來沖洗溶液A 之製備所用的容器，然後將沖洗之水倒進混合器內。然後 將內含物攪拌3分鐘以提供混合物C。 於40.4 6份的水中， 加入44.13份的混合物C， 然後將此稀释物質與35.02份的 ZSM-22晶體混合。混合5分鏟後，得到黏稠但可傾注的質 本紙張尺度逍用中國國家梯準（CNS ) A4規格（21〇ί 297公釐）_ — 經濟部中央標隼局負工消费合作社印製 4 22828, A7 _ B7 v五 '發明説明（13 ) 體D，具有莫耳組成爲： 78,9 Na2〇/336 R/Al2〇3/1112 Si〇2/85320 H20 其中K係1，6-二胺基己烷：具有29 . 0¾乾重含量的ZSM-22晶 種。 將110.05份的質嫌D移送至一不銹鋼高壓釜中，高壓 釜係置於室溫的烘箱內。烘箱加熱至150eC歷經3小時，及 保持在此溫度24小時。在分離出之晶體產物被洗三次而達 到pH(最後清洗之水）9.4後，於120°C將其乾燥過夜，產生 35.75份的乾燥產物。如實例1所述作烺燒，顯示未經煅燒 之殼：核心的重量比爲0.12:1，且預測的經煅燒之般：核心 爲 0. 10 : 1。 實例1至3中，產物各小心地與0.5N NH C1溶液交換、 清洗及在400°C煅燒16小時。 實例4及5 及比較例A、B及C 烯低聚合作用 完成以下實例以證明依本發明所製造的觸媒在烯之低 聚合作用中的功效。各案例中，進料係爲一混合之丁烯進 料，被丁烷所稀釋，約65¾烯及35¾飽和物之比例，於40°C 被水蒸氣所飽和。反應器之溫度保持在205至235°C之範圍 ，天數隨各案例增加。反應器壓力保持在約7MPa。 所用的先前技藝觸媒係（a) ZSM-22，被用當作上述實 本紙張尺度適用中國國家標準（CNS > A4規格（2ί〇Χ297公* )_ μ _ ' (請先.閱讀背面之注意Ϋ項再填寫本頁) 422828 A7 B7 五、發明説明（l4 ) 例1至3中的核心晶體（在以下表1及2中稱爲"專利1及（b) 柯林羧（collidine)處理過之ZSM-22:觸媒（a)及（b)皆 被形成爲5毫米直徑的擠出物：本發明的觸媒及觸媒（a)以 粉末被使用。表1顯示根據205eC 丁烯轉化率的觸媒活性， 及1 . 3克烯/克觸媒/小時.的重置每小時空間速度。 表1 實例號數 觸媒 轉化率，％ 比較例A (a )專利，粉末 97.0 比較例B (a )專利，擠出物 80.3 比較例C (b)柯林羧處理過 8.1 之擠出物 4 賨例1 *粉末 91.3 5 實例2 *粉末 84.9 n. 1— I I — i— I -I - I- ί Ji I l 1 -I - m n^i «1 · a (請免聞讀背面之注意事項再填寫本頁) > ‘ 經濟部中央樣準扃男工消費合作社印製 實例6至13 及比較例D至Η 道些實例中，實例1及2以及比較例Β及C的觸媒被用在 丁烯二聚合作用中，並比較所得之辛烯的分枝程度。所用 的進料及條件係參考上述實例4及5所述者，但是進料速率 及空間速度係不同，以便得到不同的轉化率。結果摘述於 以下表2中。 本紙張尺度適用中國國家標準（€奶）六4規/格（210/ 297公釐）_17_ 42282 8 A7 B7 五、發明説明（15 ) -* w >-* u) ro (0-SCJ 墓B t^B kf 慕4 3 ΊΛ 84 00 , 96 73 73 . 79 . _ s Ί2 ai, 91 , 95 , TMiritx 請 —先 閲 讀 背 面 之. 注 3 广2 3.9 Γ 3 麥 裝 s s 56 办5 么7 58 56 52 s s ,<s 39 ’ 3 12.2 04 49 23 35 37 2 厶6 33 35 么0 27 5? 2 52 1% 4>s i¥wlitellgl 訂 5.0 5 經濟部中夾標準局員工消费合作社印袈 一 1: 5 6 1‘57 5 3 s 18 3厶 37 SO 56 3、t 3S 3山 25 厶5 J 1 58 503 57 s 56 61 56 厶9 - 5 s -42282S B7 One_five 'Explanation of the invention (12) The crystal skull product obtained was repeatedly washed with water and dried at 125eC for 40 hours. 35. 8 parts of the dried product were recovered. Through the calcination described in Example 1, it was found that the ratio of the weight of the core without calcination: 0.10: 1, and the ratio of the expected calcined ratio: the core was usually about 0.09: 1. Yi 110 shows the structure of pure crystal 23! ^ 22. Example 3 Preparation of Synthetic Mixture: Solution A: I 1.1 II II -III--II--I--II--1 -1 4H V * (Please read the precautions on the back before filling this page) Ingredient A ] 2 (S〇4) I8H2O 0.2193 NaOH (98.4%) 2.10 1, 6-Diaminohexane 12.87 HaO.. 175.00 The first three ingredients are printed in the order shown by the Central Government Bureau of Zhengong Consumer Cooperative, Ministry of Economic Affairs Add to 175 parts of water / 54.82 parts of colloidal silica (Udox AS40) solution B in a mixer, place solution A on the contents of the mixer, and use 54.6 parts of water to Rinse the container used for the preparation of solution A, then pour the rinsed water into the mixer. The contents were then stirred for 3 minutes to provide mixture C. In 40.4 6 parts of water, 44.13 parts of mixture C was added, and then this diluted substance was mixed with 35.02 parts of ZSM-22 crystals. After mixing 5 minutes of shovel, a thick but pourable quality paper size was obtained using the Chinese National Standard (CNS) A4 specification (21〇ί 297 mm) _ — Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives 4 22828, A7 _ B7 v Five 'Description of the Invention (13) The body D has a moire composition of 78,9 Na2〇 / 336 R / Al2〇3 / 1112 Si〇2 / 85320 H20 where K is 1,6-di Amine hexane: ZSM-22 seed with a dry weight content of 29.02. 110.05 parts of mass D were transferred to a stainless steel autoclave, and the autoclave was placed in an oven at room temperature. The oven was heated to 150 eC for 3 hours and maintained at this temperature for 24 hours. After the separated crystalline product was washed three times to reach pH 9.4 (the last washing water), it was dried overnight at 120 ° C to produce 35.75 parts of a dried product. 10: 1。 As sintered as described in Example 1, showing the uncalcined shell: the weight ratio of the core is 0.12: 1, and the predicted calcined like: the core is 0.10: 1. In Examples 1 to 3, the products were each carefully exchanged with 0.5N NH C1 solution, washed and calcined at 400 ° C for 16 hours. Examples 4 and 5 and Comparative Examples A, B, and C. Olefene oligomerization The following examples were completed to demonstrate the effectiveness of the catalysts produced according to the present invention in the oligomerization of olefins. In each case, the feed was a mixed butene feed, which was diluted with butane. The ratio of approximately 65¾ene and 35¾ saturates was saturated with water vapor at 40 ° C. The temperature of the reactor was maintained in the range of 205 to 235 ° C, and the number of days increased with each case. The reactor pressure was maintained at about 7 MPa. The previous technology catalyst system (a) ZSM-22 was used as the above-mentioned actual paper size. Applicable to the Chinese national standard (CNS > A4 specification (2ί〇Χ297 公 *) _ μ _ '(Please first. Read the back Note the item (please fill in this page again) 422828 A7 B7 V. Description of the invention (l4) The core crystals in Examples 1 to 3 (referred to as " Patents 1 and (b) in Tables 1 and 2 below) ) Treated ZSM-22: Catalysts (a) and (b) were both formed into 5 mm diameter extrudate: The catalyst and catalyst (a) of the present invention were used as powder. Table 1 shows that according to 205eC Catalytic activity of butene conversion rate and resetting hourly space velocity of 1.3 grams of olefin per gram of catalyst per hour. Table 1 Example No. Catalyst conversion rate,% Comparative example A (a) patent, powder 97.0 Comparative example B (a) Patent, extrudate 80.3 Comparative example C (b) Colin carboxyl-treated 8.1 extrudate 4 Example 1 * Powder 91.3 5 Example 2 * Powder 84.9 n. 1— II — i— I -I-I- ί Ji I l 1 -I-mn ^ i «1 · a (Please read the precautions on the reverse side and fill out this page) > '' Printed by the Central Ministry of Economic Affairs, the Ministry of Economy Examples 6 to 13 and Comparative Examples D to Η Among the examples, the catalysts of Examples 1 and 2 and Comparative Examples B and C were used in the dimerization of butene, and the degree of branching of the octene obtained was compared. The feed and conditions are based on those described in Examples 4 and 5 above, but the feed rate and space velocity are different in order to obtain different conversion rates. The results are summarized in Table 2 below. This paper scale applies Chinese national standards ( € milk) 6 rules / block (210/297 mm) _17_ 42282 8 A7 B7 V. Description of invention (15)-* w >-* u) ro (0-SCJ Tomb B t ^ B kf Mu 4 3 ΊΛ 84 00, 96 73 73. 79. _ S 2 ai, 91, 95, TMiritx Please-read the back first. Note 3 Canton 2 3.9 Γ 3 Wheat ss 56 Office 5 5 7 58 56 52 ss, < s 39 '3 12.2 04 49 23 35 37 2 厶 6 33 35 0 0 27 5? 2 52 1% 4 > si ¥ wlitellgl Order 5.0 5 Employees' Cooperatives of the China National Standards Bureau, Ministry of Economic Affairs, India 1: 5 6 1'57 5 3 s 18 3 厶 37 SO 56 3, t 3S 3 Shan 25 厶 5 J 1 58 503 57 s 56 61 56 厶 9-5 s-
本紙張尺度適用中國國家標準（CNS ) A4说格（210X297公釐）-18This paper size applies Chinese National Standard (CNS) A4 scale (210X297 mm) -18