TW305876B

TW305876B -

Info

Publication number: TW305876B
Application number: TW84110909A
Authority: TW
Original assignee: Asahi Chemical Ind
Priority date: 1994-10-28
Filing date: 1995-10-17
Publication date: 1997-05-21

Description

305876 經濟部中央樣準局員工消费合作社印製 A7 B7五、發明説明（1 ) 本發明係有關轉化烴類之觸媒及使用其接觸轉化之方法。詳言之，即與烴類原料進行/接觸分解之觸媒及使用此觸媒可將石油化學原料中具有價值之乙烯爲主成份的低級烯烴及以苯、甲苯、二甲苯爲主成份單環芳香族烴類以更具效力且安定製得之製法。目前許多烴類原料皆是以與固體酸觸媒，特別是以酸或敍塩脫碱所得酸型（質子型）的沸石接觸，依裂解、異構化、歧化、芳香族化等反應進行轉化。其代表例則如，使用γ型沸石將輕油、重質油等由汽油餾份中轉化，而虞泛實施於石油精製業中。又，質子型 Z SM - 5沸石作爲輕質烴轉化爲芳香族化合物的方法揭示於特開昭4 9 — 4 1 3 2 2號公報（與英國專利 1381427號相對應）、特開昭50 — 49233號公報（與英國專利（1394979號相對應）、特開昭 50-4029號公報（與英國專利1442850號相對應）等。又，特開昭60-222428、特開平3-1 3 0 2 3 6等揭示有以質子型之Z SM — 5沸石將輕質烴類轉化爲低級烯烴與芳香族烴的方法，且美國專利第 4361502號、特開平2-184638號公報亦揭示有使用含有銀之酸型沸石將輕質烴類轉化爲低級烯烴之方法。又，國際申請案號PCT/JP95/01059中揭示，使用特定的沸石系觸媒’於具特定溫度分布之觸媒床中，將輕質烴類製造芳香族烴類的方法。 (請先閲讀背面之注意事項再填寫本頁) 訂卜.305876 Printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1) The present invention relates to a catalyst for converting hydrocarbons and a method of contact conversion using the same. In detail, the catalyst for the decomposition / contact with the hydrocarbon feedstock and the use of this catalyst can reduce the valuable ethylene-based lower olefins in the petrochemical raw materials and the single-rings based on benzene, toluene and xylene Aromatic hydrocarbons are prepared in a more effective and safe way. At present, many hydrocarbon feedstocks are converted by reaction with cracking, isomerization, disproportionation, aromaticization, etc. by contact with solid acid catalysts, especially acid-type (proton-type) zeolites obtained by acid or alkaline debasing . As a representative example, γ-type zeolite is used to convert light oil, heavy oil, etc. from gasoline oil fractions, and Yu Fan is employed in the petroleum refining industry. In addition, a method for converting proton-type Z SM-5 zeolite as a light hydrocarbon to an aromatic compound is disclosed in Japanese Patent Laid-Open No. 4 9-4 1 3 2 2 (corresponding to British Patent No. 1381427) and Japanese Patent Laid-Open No. 50- Gazette No. 49233 (corresponding to British Patent (1394979)), JP-A No. 50-4029 (corresponding to British Patent No. 1442850), etc. Also, JP-A 60-222428, JP-A 3-1 3 0 2 3 6 et al. Disclosed a method for converting light hydrocarbons into lower olefins and aromatic hydrocarbons with proton-type Z SM-5 zeolite, and US Patent No. 4361502 and Japanese Patent Laid-Open No. 2-184638 also disclose the use of silver Acid-type zeolite to convert light hydrocarbons to lower olefins. In addition, International Application No. PCT / JP95 / 01059 discloses that the use of specific zeolite catalysts in a catalyst bed with a specific temperature distribution will Method for manufacturing aromatic hydrocarbons from light hydrocarbons. (Please read the precautions on the back before filling out this page).

J 本紙張尺度適用中國國家標準（CMS ) Α4规格（210Χ297公釐） 305876 A7 B7 五、發明説明（2 ) (請先閱讀背面之注意事項再填寫本頁) 以往由烴類原料製造低級烴類與單環芳香族烴類之方法中’熱分解法受到廣泛的使用，由於係熱分解故必有嚴荷的反應條件’對石油化學原料而言會產生許多不易使用的甲烷副產物。又，分解所得產物中乙烯、丙烯等烯烴、苯、甲苯等單環芳香族烴類的製品產率，約僅在所規定的比例而已，缺乏產率結構上之融通性，又其總產率（有效製品產率）僅達6 0重量％左右等問題。爲解決熱分解法的問題，而對以往使用固體酸觸媒，特別是酸型（質子型）沸石觸媒之烴類的接觸分解法進行檢討。但無論任何一種公知的方法，皆無法將石油化學中以乙烯爲主成份之低級烯烴類（碳數2〜4的烯烴、即乙烯、丙烯、丁烯類）及單環芳香族烴類（碳數6〜9的芳香族之苯、烷基苯）等有用成份同時以有效率、安定，且乙烯爲主成份之低級烯烴較單環芳香族烴爲高產率之方法製得。經濟部中央標準局員工消費合作社印製例如，使用Y型沸石之接觸轉化法雖可生成較多低級輕質的鏈烷烴，但僅生成極少量的芳香族烴類。使用質子型Z SM — 5沸石的方法中，雖芳香族烴類的產率較高，但裂解氣體之，組成以乙烷、丙烷等輕質鏈烷烴爲主，對低級烯烴的選擇性較差。又爲提高低級烯烴的選擇性常有以銅或銀爲載體之方法（特開平2_ 1 4 1 3號公報，特開平2—184638號公報），此方法雖可提高丙烯之產率但卻無法提高乙烯或芳香族烴類的產率。在上述以酸型沸石進行烴類的接觸轉化法中，因觸媒本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 5 305876 A7 A7 __B7 五、發明説明（3 ) 上會產生焦碳沈積，故必須頻繁地進行將焦碳燃燒去除的再生操作，而反覆進行的再生操作將會造成觸媒活性永久劣化等問題。由焦碳燃燒所產生的水蒸氣會使沸石產生力口水分解反應，使鋁自沸石結晶脫離，同時也是引起活性點之質子消失的原因，故於此種反應中爲利質子型沸石所不能避免發生極大問題。因此有將質子型沸石導入銀陽離子，抑制上述活性降低問題的方法（特開昭5 9 -117584號公報（與美國專利第4845063號對應））之提出，但其除抑制效果不充份外，其產率上亦有對低級烯烴之選擇性降低等問題。又，爲抑制焦碳之沈積國際申請公開公報WO 9 5/ 0 9 0 5 0中有揭示將沸石於特定的溫度分佈條件下以水蒸氣接觸的方法。本發明係提供一可同時製得平均且高產率之以乙烯爲主成份之低級烯烴及單環芳香族烴類，且於高溫水蒸氣中不易劣化之安定的轉化烴類之觸媒，及使用上述觸媒之製造方法。經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 本發明者們爲解決上述問題點，對如何將包含1種或 2種以上烴類之原料能有效製造低級烯烴類與單環芳香族烴類，及乙烯爲主成份低級烯烴類其產率能較單環芳香族烴類爲高之方法，經過無數次檢討。發現使用含I b族金屬，且實質上不含質子之中細孔徑沸石時，可極有效且安定地得到低級烯烴及單環芳香族烴類，且以乙烯爲主成份之低級烯烴類其產率能較單環芳香族爲高之事實。本紙張尺度適用中國國家標準（CNS M4规格（210X297公釐）J This paper scale is applicable to the Chinese National Standard (CMS) Α4 specification (210Χ297mm) 305876 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling this page) In the past, low-grade hydrocarbons were manufactured from hydrocarbon raw materials Among the methods with monocyclic aromatic hydrocarbons, the 'thermal decomposition method is widely used, because of the thermal decomposition, there must be strict reaction conditions'. For petrochemical raw materials, many methane by-products that are not easy to use are generated. In addition, the yield of products such as ethylene, propylene and other olefins, benzene, toluene and other monocyclic aromatic hydrocarbons is only about the specified ratio, lacking the structural compatibility of the yield, and its total yield (Effective product yield) only reaches about 60% by weight and other issues. In order to solve the problem of thermal decomposition method, the contact decomposition method of hydrocarbons that used solid acid catalysts, especially acid type (proton type) zeolite catalysts in the past was reviewed. However, no matter what kind of well-known methods, it is impossible to use low-grade olefins (olefins with 2 to 4 carbon atoms, ie ethylene, propylene, butenes) and monocyclic aromatic hydrocarbons (carbon The useful components such as aromatic benzenes and alkyl benzenes in the range of 6 to 9 are produced by the method of higher yield of lower olefins with high efficiency and stability, and ethylene as the main component compared with monocyclic aromatic hydrocarbons. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. For example, the contact conversion method using Y-type zeolite can produce more low-grade light paraffins, but only a very small amount of aromatic hydrocarbons. In the method using the proton type Z SM-5 zeolite, although the yield of aromatic hydrocarbons is high, the composition of the cracking gas is mainly light paraffins such as ethane and propane, and the selectivity to lower olefins is poor. In order to improve the selectivity of lower olefins, there is often a method using copper or silver as a carrier (Japanese Patent Laid-Open No. 2_1 4 1 3, Japanese Patent Laid-Open No. 2-184638), although this method can improve the yield of propylene, it cannot Increase the yield of ethylene or aromatic hydrocarbons. In the above-mentioned contact conversion method of hydrocarbons with acid zeolite, due to the size of the catalyst paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) 5 305876 A7 A7 __B7 V. The invention description (3) will occur Since coke deposits, it is necessary to frequently perform regeneration operations to burn and remove the coke, and repeated regeneration operations will cause problems such as permanent deterioration of catalyst activity. The steam generated by the burning of coke will cause the zeolite to produce a saliva decomposition reaction, which will cause aluminum to detach from the zeolite crystal, and also cause the protons of the active point to disappear. A huge problem occurred. Therefore, there is a method for introducing proton-type zeolite into silver cations to suppress the above-mentioned activity reduction problem (Japanese Patent Laid-Open No. 5-9-117584 (corresponding to U.S. Patent No. 4845063)), but its suppression effect is insufficient, There is also a problem of lower selectivity to lower olefins in its yield. In addition, in order to suppress the deposition of coke, International Application Publication WO 9 5/0 9 0 5 0 discloses a method of contacting zeolite with steam under a specific temperature distribution condition. The present invention provides a stable conversion hydrocarbon catalyst which can simultaneously produce an average and high yield of lower olefins and monocyclic aromatic hydrocarbons mainly composed of ethylene, and is not easily degraded in high temperature water vapor, and uses The manufacturing method of the above catalyst. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back and then fill out this page) The inventors have solved the above problems and are effective on how to use raw materials containing one or more hydrocarbons The method of producing lower olefins and monocyclic aromatic hydrocarbons, and lower olefins with ethylene as the main component, has a higher yield than monocyclic aromatic hydrocarbons, after numerous reviews. It was found that the use of Ib-containing metals and substantially free of proton mesopore zeolites can effectively obtain lower olefins and monocyclic aromatic hydrocarbons, and the production of lower olefins mainly composed of ethylene The fact that the rate can be higher than the monocyclic aromatic. This paper scale is applicable to Chinese national standard (CNS M4 specification (210X297mm)

s〇5876 五、發明説明（4 ) (請先閲讀背面之注意事項再填寫本頁) 即本發明乃提供一種，由s i o2/a52o3莫耳比爲2 0以上，含有1種或2種以上周期表第I b族金屬，實質上不含質子的中細孔徑沸石所形成轉化烴類之觸媒。以下，將詳細說明本發明》本發明所稱ZSM - 5類沸石，係，ZSM—5， ZSM-1 1，及 ZSM— 5/ZSM-1 1 複合體等之 Z S Μ — 5 類沸石，亦含 P. A. Jacobs and J. A. Mart-ens, 「Stud. Surf. Sci.Catal .」33，P. 167-215( 1 987)荷蘭）中所載之類似ZSM— 5，11之沸石。又，本發明的沸石其S i 02/Aj?2〇3莫耳比，爲使觸媒具安定性而必須爲2 0以上。S i 02/Aj?203 莫耳比之上限並無特別的限定，一般S i 02/Α$203 莫耳比爲2 0〜5 0 0左右，較佳則爲2 8〜3 0 0左右〇經濟部中央揉準局員工消费合作社印製本發明的觸媒，Z SM- 5類沸石中實質上須不含質子。此處所述實質上不含質子爲，以液相離子交換一濾液滴定法求得之質子量（酸量）對該沸石1克爲0 . 0 2微莫耳以下，較佳爲0.01微莫耳以下之意。液相離子交換-濾液滴定法所進行的酸量測定法載於 Intrazeolite Chemistry, 「 ACS Symp. Ser·」.218, p 3 6 9 〜 382(1983，美），曰化誌、〔3〕，p521— - 5 2 7 〔 1 9 8 9 )等內 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-7 -s〇5876 V. Description of the invention (4) (Please read the precautions on the back before filling out this page) That is, the present invention provides a kind, with a molar ratio of si o2 / a52o3 of more than 20, containing one or more than two kinds A catalyst for converting hydrocarbons formed by a group Ib metal of the periodic table, which is substantially free of protons and medium-pore zeolites. In the following, the invention will be described in detail. ZSM-5 zeolites referred to in the present invention as ZSM-5, zeolites, ZSM-5, ZSM-1 1, and ZSM-5 / ZSM-1 1 complexes, etc. Contains zeolites similar to ZSM-5, 11 contained in PA Jacobs and JA Mart-ens, "Stud. Surf. Sci. Catal." 33, P. 167-215 (1 987, Netherlands). In addition, the zeolite of the present invention must have a Si02 / Aj? 203 molar ratio of 20 or more in order to stabilize the catalyst. S i 02 / Aj? 203 The upper limit of the molar ratio is not particularly limited. Generally, the S i 02 / Α $ 203 molar ratio is about 2 0 ~ 5 0 0, preferably about 2 8 ~ 3 0 0. Ministry of Economic Affairs The Central Cooperative Bureau ’s employee consumer cooperative printed the catalyst of the present invention, and the Z SM-5 zeolite must be substantially free of protons. The amount of protons described herein is substantially free of protons, and the amount of protons (acid amount) obtained by liquid phase ion exchange-filter titration method is 0.02 micromolar or less, preferably 0.01 micromolar for 1 g of the zeolite. The meaning below the ear. The method for measuring the amount of acid by liquid phase ion exchange-filter titration method is contained in Intrazeolite Chemistry, "ACS Symp. Ser.". 218, p 3 6 9 ~ 382 (1983, United States), Yuehua Zhi, [3], p521—-5 2 7 〔1 9 8 9) etc. _ This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) -7-

五、發明説明（5) 本發明所稱液相離子交換-濂液滴定法，係將於空氣中以400〜600 eC燒成之沸石1 · 5g，於3 . 4莫耳/ 9的N a C $水溶液2 5m5中在水冷下進行1 0分鐘的離子交換’過濾後再以5 0m5純水將沸石洗淨並將濾液全量回收，再將此濾液以〇.1N的NaOH水溶液中和滴定，以中和點求得·沸石的質子置。銨離子型及稀土類金屬離子型等多價金屬陽離子型沸石，經加熱處理可生成質子爲一已知事實，故，在測定質子置時必須使用經上記燒成處理後的樣品進行測定。本發明之實質上不含質子的沸石其較佳態樣爲，碱金牖離子及/或碱土金屬離子型的沸石。而以碱金屬離子型爲佳，以N a及/或K離子型Z SM — 5類沸石爲最佳。又，含有N a及/或K離子及碱土金屬離子之Z SM - 5 類沸石亦適合使用。經濟部中央樣率局貝工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁) 對中細孔徑沸石形成碱金屬離子及/或碱土金雇離子型之方法並無特別限定，可以公知的離子交換法實施，只要實質上須在沸石的酸性側消失爲止可充份進行碱金靥離子及/或碱土金屬離子充份進行交換即可》本發明之實質上不含質子的沸石其較佳態樣爲，經加熱處理，較佳爲與水蒸氣共存下加熱處理的沸石，或經反覆進反應一再生等前處理而得之沸石•加熱處理原則上溫度以500 °C以上爲佳，而以500 °C〜900 °C爲更佳本紙張尺度遑用中國國家標窣（CNS}A4规格U10 X297公釐）-8 -V. Description of the invention (5) The liquid phase ion exchange-Lian titration method referred to in the present invention is a zeolite 1.5 g fired at 400 ~ 600 eC in air at 3.4 moles / 9 N a C $ aqueous solution was subjected to ion exchange for 10 minutes under water cooling in 5m5. After filtering, the zeolite was washed with 50m5 pure water and the filtrate was recovered in full. Then the filtrate was neutralized and titrated with 0.1N NaOH aqueous solution. The proton position of zeolite was determined at the neutralization point. It is a known fact that polyvalent metal cation zeolites such as ammonium ion type and rare earth metal ion type can generate protons by heat treatment. Therefore, when measuring protons, it is necessary to use the sample after the above firing treatment for measurement. The preferred form of the zeolite substantially free of protons according to the present invention is a zeolite of alkali metal ions and / or alkaline earth metal ions. The alkali metal ion type is preferred, and the Na and / or K ion type Z SM-5 type zeolite is most preferred. In addition, Z SM-5 zeolites containing Na and / or K ions and alkaline earth metal ions are also suitable for use. Printed by the Beigong Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page). The method of forming alkali metal ions and / or alkaline earth metal ions for medium and fine pore zeolites is not particularly limited. The well-known ion exchange method can be carried out, as long as the acidic side of the zeolite needs to be substantially eliminated until the alkali gold ions and / or alkaline earth metal ions are sufficiently exchanged. The substantially proton-free zeolite of the present invention is The preferred form is zeolite that has been heat-treated, preferably heat-treated in the presence of water vapor, or zeolite that has been obtained by pre-treatments such as repeated reaction-regeneration. In principle, heat treatment is preferably at least 500 ° C. , And it is better to use 500 ° C ~ 900 ° C. The paper standard is to use the Chinese national standard (CNS} A4 specification U10 X297 mm) -8-

五、發明説明（6) 的實施例溫度。水蒸氣處理以5 0 0°C以上爲佳，而以 500 °C〜900 °C以上爲更佳，水蒸氣分壓在〇 . 〇1 氣壓以上皆可資施·又上記處理可於導入1種或2種以上周期表第I b族金屬實施例也可以，但較好爲導入後實施本發明中，於上記沸为中導入由周期表第I b族金屬中所選出1種或2種以上金屬爲必要工作。周期表第I b 族金屬中以銅、銀爲佳，而以銀爲最佳。導入1種或2種選自周期表第I b族金屬之方法，通常爲離子交換法，含浸法，混練法等等方法，而以離子交換法爲最佳。導入之 I b族金屬以氧化物形式存在也可以，而至少有部份以陽離子形態存於沸石中。可使用之金靥塩，例如硝酸銀、醋酸銀、硫酸銀、氯化銅、硫酸銅、硝酸銅、氣化銅等等。對沸石而言lb族金羼合量以〇 . 1〜10重量％爲佳，而以0 . 2 5重量％爲更佳。lb族金屬含置未達經濟部中央樣準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 0 . 1重量％等其活性並不充份，超過10重量％時既增量也未能提高其性能。將碱金靥離子及/或碱土金屬離子與I .b族金屬導入 z S Μ -5類沸石之順序，次數等並無特別限定，可將沸石形成碱金羼離子及/或碱土金屬離子型後，再導入I b族金屬，或先將I b族金屬導入沸石後，再將沸石形成碱金屬離子及/或碱土金羼離子型也可以*但，經任何方式製得本紙張尺度適用中國國家橾準（CNSM4规格（ 210X297公釐> -9 - 經濟部中央樣準局員工消费合作社印製 305876 at B7 五、發明説明（7 ) 之沸石，應製作爲實質上不含酸性側之物質。又，上述沸石，必要時可使用經燒成之物質。燒成溫度一般爲500〜900 °C。甚至爲製作更適切的使用粒子形狀，可配合例如氧化鋁、二氧化矽、二氧化矽一氧化鋁、氧化鉻、二氧化鈦、矽藻土、粘土等耐火性無機氧化物之多孔性物質以粘結劑或膠粘劑方式配合而成型。本發明中含有1種或2種以上烴類之原料，爲含有碳數2〜約25的，正烷烴、異烷烴、烯烴，碳數4〜約 2 5的環烷烴，具支鏈烷基之環烷基等爲主成份之物質，例如以乙烷、丙烷、丁烷、丁烯等氣體類、戊烷、戊烯、己烷、庚烷、辛烷等單獨或其混合物爲主體之輕質石腦油、重質石腦油、直餾石腦油、主要含01。〜C2。之燈輕油餾份，由C 10〜C 25形成之減壓輕油餾份等等。其中特別以丙烷、丁烷、丁烯、戊烷、戊烯及其混合物、石腦油飽份爲佳。於本發明中，使用上述觸媒進行接觸反應時，即，將上述烴類原料於高溫中接觸本發明的轉化烴類之觸媒時，可製造低級烴類及單環芳香族烴類。本發明接觸分解反應的條件，依烴類原料之不同而有所不同，一般以550〜750。《：，0 · 1〜1〇氣壓的烴類分壓爲佳，而以採用570〜700 °C，0 · 2〜8 氣壓的烴類分壓爲更佳。又，烴類原料與觸媒的接觸時間，在考慮烴類的熱分本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） ---------^ ,4 — (請先閲讀背面之注意事項再填寫本頁) 、115. The temperature of the embodiment of the invention (6). Water vapor treatment is preferably above 500 ° C, and more preferably from 500 ° C to 900 ° C. Water vapor partial pressure can be applied at 〇1 air pressure or more. The above treatment can be introduced in 1 Two or more examples of Group I b metals of the periodic table are possible, but it is preferable to implement the present invention after introduction, and one or two selected from Group I b metals of the periodic table are introduced in the above boiling point. The above metals are necessary work. Among Group I b metals of the periodic table, copper and silver are preferred, and silver is the best. Introduce one or two methods selected from Group I b metals of the periodic table, usually ion exchange method, impregnation method, mixing method, etc., and ion exchange method is the best. The introduced Group Ib metal may exist in the form of oxide, and at least part of it is stored in the zeolite in the form of cation. Usable gold compounds, such as silver nitrate, silver acetate, silver sulfate, copper chloride, copper sulfate, copper nitrate, vaporized copper, etc. For the zeolite, the total amount of the lb group jinyu is preferably 0.1 to 10% by weight, and more preferably 0.25% by weight. The lb group metal is not printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economy (please read the precautions on the back before filling out this page) 0.1% by weight and other activities are not sufficient, when more than 10% by weight The increment also failed to improve its performance. The order and frequency of introduction of alkali gold ions and / or alkaline earth metal ions and Group I.b metals into z S Μ -5 type zeolite are not particularly limited, and the zeolite can be formed into alkali gold ions and / or alkaline earth metal ion types After that, the Group I b metal is introduced, or the Group I b metal is first introduced into the zeolite, and then the zeolite can be formed into an alkali metal ion and / or alkaline earth gold ion type. However, the paper size prepared by any method is applicable to China National Standard (CNSM4 specification (210X297mm > -9-305876 at B7 printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs V. The zeolite of the invention description (7) should be made substantially free of acidic side In addition, the above zeolite can be fired if necessary. The firing temperature is generally 500 ~ 900 ° C. Even to make a more suitable particle shape, it can be mixed with alumina, silica, silica, etc. Porous materials such as alumina, chromium oxide, titanium dioxide, diatomaceous earth, clay and other refractory inorganic oxides are compounded and formed by a binder or an adhesive. The present invention contains one or more types of hydrocarbon raw materials, It is a substance containing n-alkanes, iso-alkanes, olefins with a carbon number of 2 to about 25, cycloalkanes with a carbon number of 4 to about 25, cycloalkyl groups with branched alkyl groups, etc., such as ethane, Gases such as propane, butane, butene, pentane, pentene, hexane, heptane, octane and other light naphtha, heavy naphtha, straight naphtha , Mainly contains 01. ~ C2. Light oil fractions, vacuum light oil fractions formed from C 10 ~ C 25, etc. Among them, propane, butane, butene, pentane, pentene and their In the present invention, when the above catalyst is used for the contact reaction, that is, when the above hydrocarbon raw material is contacted with the catalyst for converting hydrocarbons of the present invention at a high temperature, lower hydrocarbons can be produced And monocyclic aromatic hydrocarbons. The conditions of the contact decomposition reaction of the present invention vary according to the hydrocarbon raw materials, generally 550 ~ 750. ":, 0 · 1 ~ 10 atmospheric pressure hydrocarbon partial pressure is It is better to use hydrocarbon partial pressure of 570 ~ 700 ° C, 0 · 2 ~ 8 air pressure. Furthermore, the contact between hydrocarbon raw materials and catalyst In consideration of the thermal paper size of hydrocarbons, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable --------- ^, 4 — (Please read the precautions on the back before filling in This page), 11

T 10 305876 A7 B7 五、發明説明（8 ) 解性及反應溫度，並防止熱分解的影響過大之情形下，通常以1秒以下爲宜。 (請先閱讀背面之注意事項再填寫本頁) 本發明的接觸分解反應，不論其爲固定床式 '移動床式、流動床式或氣流搬送式等反應式樣，以可連續實施觸媒再生之流動接觸分解（F C C )型或Quick Cntact ( QC)型之反應式樣爲佳。又，Q C型之反應系統則記載於 ^ Q C — A New Reaction System^ ,1 9 8 9 Inter-nat i o-na1 Fluidization Conference, Fluidization VI Proceeding, Banff, Canada, May 7-12內。又，接觸分解反應中接觸的再生方式，通常於空氣中或含氧惰氣中，以4 0 0〜9 0 0°C之溫度將觸媒上的焦碳以燃燒、去除之方式進。使用F C C型反應裝置時，因必須供給反應熱故再生溫度須較反應溫度爲高，本發明的觸媒以其具高水熱安定性，故於如此高溫中再生時觸媒劣化程度較小而呈安定狀態。經濟部中央標準局員工消費合作社印製又，本發明的觸媒若加入加氫/脫氫金靥成份於上記觸媒時，可用於接觸環化反應。特別是添加1種以上由周期表第I lb族、I I lb族及VI I I族之金靥及其化合物所選出之物質時，可使沸石的脫氫環化能量提升，可作爲一種適合由輕質烴類製造單環芳香族烴類時之觸媒。周期表中第I lb族、I I lb族及VI I I族之金屬及其化合物中，較佳者爲鋅、鉀、銦、鎳、鈀、鉑及其氧化物、複合氧化物等，更佳爲鋅及氧化鋅、氧化鋁酸鋅等鋅之複合氧化物。相對沸石周期表第I I b族、I I I b族本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 305876 a? B7 五、發明説明（9 ) 及VIII族之金屬及其化合物的量，以金屬換算爲 0.1〜20重量％爲佳。本發明的接觸環化反應之條件，依烴原料，特別是原料中烯烴與烷烴的量比而變化，以3 0 0〜6 5 0。〇溫度下’大氣壓〜30氣壓的烴類分壓，以0 . 1〜50 h r -1的重量時間空間速度（W H S V )爲佳，更好則爲 400 〜600 °C。本發明的接觸環化反應可適用於固定床式、移動床式、流動床式等任一反應器，反應式樣並不特定，而以構造簡單之斷熱式固定床反應器爲佳。又，接觸環化反應中觸媒的再生方式，通常於空氣中或含氧惰氣中，以4 0 0〜7 0 0°C之溫度將觸媒上的焦碳以燃燒去除之方式進行。 (實施發明的最佳形態）以下將以實施例對本發明作更詳細之說明》經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注^項再填寫本頁) 實施例1 將經水熱合成、濾過、水洗 '乾燥步驟，於空氣中以 5 5 0 °C燒成而得之z SM— 5型沸石（S i 02/ A^2〇3=l 26)以3 . 4N氯化鈉水溶液（1 〇me /g —沸石）中於9 0°C進行3小時離子交換，過濾水洗後以1 1 0°C乾燥製得Na+型Z SM — 5。其次再將此 Na+型ZSM— 5以0 · 02N硝酸銀水溶液（1〇本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） -12 — 305876 A7 B7 五、發明説明（10 ) (請先閲讀背面之注意事項再填寫本頁) —沸石）於室溫進行3小時離子交換。經水洗、乾燥後，於室氣中以5 5 0。(：燒成製得觸媒1 。又，此觸媒之酸量以液相離子交換—濾液滴定法求得之結果爲 0 . 004mmo$/g ^經化學分析結果，此組成之無水基質中氧化物以莫耳比表示則具下式組成。 0 . 49Ag20 . 〇 . 61Na20 > A^203, 126 S i Ο 2 使用觸媒1以下述方法調査烴類轉化性能。於石英反應管（內徑1 中充填8〜1 6網目（mesh )之經濟部中央揉準局員工消費合作社印製整粒觸媒2 g ’於一大氣壓下，氮氣1 〇〇 c c./m i η 流通處所昇溫至所定溫度。其次於氮流通下，將原料之石腦油（比重0 . 684，組成：烷烴79 . 0重量％，環烷1 5 . 0重量％，芳香族烴類5 . 9重量％，烯烴 0.1重量％)以31.3cc/hr供給於反應管。開始供給石腦油後6分鐘之反應生成物直接導入氣相層析儀內分析其組成。6 8 0 °C時反應結果如第1表所示。比較例1 將實施例1所製得之N a+型Z SM — 5不經任何處理直接進行與實施例1相同之石腦油轉化反應。此觸媒之酸量爲0 · 006mmoj?/g。其結果如第1表所示。本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公嫠） 13 - 305876 A7 B7 五、發明説明（11 ) 比較例2 將實施例1所使用之ZSM— 5型沸石（S i 〇2/ A j? 2 0 3= 1 2 6)於IN硝酸水溶液（1 〇m义/ g — 沸石）於室溫下進行3小時離子交換，濾過水洗後以 1 1 0°C乾燥而得H +型Z SM— 5沸石。其後將此H+型 ZSM— 5以0 . 1N硝酸銀水溶液（l〇m5?/g —沸石）於室溫下，進行3小時離子交換處理。水洗、乾燥後 ’於空氣中以5 5 0°C燒成，得含銀之H+型Z SM — 5 觸媒。又，此觸媒之酸量爲0 · O55mm〇i2/g。化學分析結果，此組成之無水基質中氧化物以莫耳比表示貝IJ 具下式組成。 0.48Ag2O，Aj?2O3，126SiO2 使用比較觸媒2，於實施例1相同條件下進行石腦油轉化反應之結果如第1表所示。經濟部中央樣準局員工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 比較例3 除沸石部份以磁器製拉西環（外徑3mm<p，長3 mm)取代充填外，石腦油之熱分解於6 8 0°的條件下實施。其結果如表1所示。實施例2 除0 . 0 2N硝酸銀水溶液以〇 . in氯化銅水溶液本紙張尺度適用中國國家樣準（CNS )八4规格（210X297公釐） 14 - 經濟部中央橾準局員工消費合作社印製 A7 B7 五、發明説明（12 ) 取代外，其他皆與實施例1相同步驟，製得含銅之N a + 型ZSM— 5沸石觸媒。又，此觸媒之酸量爲Ο · 006 mmo j?/g。經化學分析結果，此組成之無水基質中氧化物以莫耳比表示則具下式組成。 0 · 5 0 C u 20，〇 . 4 0 N a 20，Aj?2〇3，126 S i Ο 2 使用此觸媒，於實施例相同條件下進行石腦油轉化反應，其結果如第1表所示。由第1表可得知，N a+型Z SM - 5沸石幾乎不具石腦油之分解活性，若將銀或銅導入時除可使其分解活性大幅升高外，其產率結構亦因酸型的Z SM - 5導入銀或銅而得A gH+型Z SM - 5而顯著不同，使對以乙烯爲主體之低級烯烴的選擇性有顯著升高趨向。實施例3 將硝酸銀水溶液改爲0 . 1N，並進行與實施例1相同之步驟，得含銀之N a +型Z SM - 5沸石觸媒（觸媒 2)。又，此觸媒之酸量爲0 . 004mmoj?/g 化學分析結果，此組成之無水基質中氧化物以莫耳比g示則具下式組成。 0 · 8 8 A g 20 > 0 · 15Na2〇，Aj?203， l 2 q 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、πT 10 305876 A7 B7 V. Description of the invention (8) In the case of decomposability and reaction temperature, and to prevent the effect of thermal decomposition from being too large, it is usually suitable to be less than 1 second. (Please read the precautions on the back before filling in this page) The contact decomposition reaction of the present invention, regardless of whether it is a fixed bed type, moving bed type, fluidized bed type, or air flow conveyance type, can continuously implement catalyst regeneration The reaction pattern of flow contact decomposition (FCC) type or Quick Cntact (QC) type is preferred. In addition, the Q C type reaction system is described in ^ Q C — A New Reaction System ^, 1 9 8 9 Inter-nat i o-na1 Fluidization Conference, Fluidization VI Proceeding, Banff, Canada, May 7-12. In addition, the contact regeneration method in the contact decomposition reaction is usually carried out by burning or removing the coke on the catalyst in the air or in an inert gas containing oxygen at a temperature of 400 to 900 ° C. When using the FCC type reaction device, the regeneration temperature must be higher than the reaction temperature due to the supply of reaction heat. The catalyst of the present invention has high hydrothermal stability, so the degradation of the catalyst during regeneration at such a high temperature is small. In a stable state. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In addition, if the catalyst of the present invention is added with hydrogenation / dehydrogenation element, it can be used for contact cyclization reaction. In particular, when adding more than one substance selected from the group I lb, group II lb, and group VI gold of the periodic table and their compounds, the dehydrocyclization energy of the zeolite can be increased, which can be used as a suitable Catalyst for the production of monocyclic aromatic hydrocarbons from qualitative hydrocarbons. Among metals and compounds of Group I lb, Group II lb, and Group VI II of the periodic table, zinc, potassium, indium, nickel, palladium, platinum and their oxides, composite oxides, etc. are more preferred. Composite oxides of zinc, zinc oxide, zinc aluminate and zinc. Compared with Group II b and Group III b of the zeolite periodic table, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-305876 a? B7 V. Invention description (9) and Group VIII metals and their The amount of the compound is preferably 0.1 to 20% by weight in terms of metal. The conditions of the contact cyclization reaction of the present invention vary according to the hydrocarbon raw material, especially the amount of olefin to alkane in the raw material, and range from 300 to 500. 〇The partial pressure of hydrocarbons at atmospheric pressure to 30 atmospheres at a temperature is preferably 0.1 to 50 h r -1 by weight time space velocity (W H S V), and more preferably 400 to 600 ° C. The contact cyclization reaction of the present invention can be applied to any reactor such as a fixed bed type, a moving bed type, a fluid bed type, etc. The reaction pattern is not specific, and it is preferable to use an adiabatic fixed bed reactor with a simple structure. In addition, the regeneration method of the catalyst in the contact cyclization reaction is usually carried out by burning or removing the coke on the catalyst in the air or in an inert gas containing oxygen at a temperature of 400 to 700 ° C. (The best form for implementing the invention) The following will explain the invention in more detail with examples "Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note ^ on the back and fill in this page) Example 1 Hydrothermal synthesis, filtration, water washing 'drying step, z SM-5 type zeolite (S i 02 / A ^ 2〇3 = l 26) obtained by firing in air at 5 50 ° C with 3.4 N chlorine Sodium ion aqueous solution (10 me / g-zeolite) was ion-exchanged at 90 ° C for 3 hours, filtered, washed with water and dried at 110 ° C to prepare Na + type Z SM-5. Secondly, this Na + type ZSM-5 is used in 0. 02N silver nitrate aqueous solution (10 paper size is suitable for China National Standardization (CNS) A4 specification (210X297 mm) -12 — 305876 A7 B7 V. Description of invention (10) ( Please read the precautions on the back before filling in this page) —zeolite) ion exchange at room temperature for 3 hours. After washing with water and drying, use 5 5 0 in room air. (: The catalyst 1 is prepared by firing. The acid amount of this catalyst is obtained by liquid phase ion exchange-filter titration method. The result is 0. 004mmo $ / g ^ After the chemical analysis result, this composition in the anhydrous matrix The oxide is expressed in molar ratio and has the following composition: 0.49Ag20. 61Na20> A ^ 203, 126 S i Ο 2 The catalyst 1 was used to investigate the hydrocarbon conversion performance by the following method. In the quartz reaction tube (inside The diameter 1 is filled with 8 ~ 16 mesh. The Central Ministry of Economic Affairs, Ministry of Economic Affairs Employee Consumer Cooperative printed a whole-grain catalyst 2 g 'at atmospheric pressure, nitrogen 1 〇〇c c./mi η The circulation space is heated to The temperature is set. Secondly, under the flow of nitrogen, the raw material naphtha (specific gravity 0.684, composition: alkane 79.0% by weight, naphthene 15.0% by weight, aromatic hydrocarbons 5.9% by weight, olefin 0.1% by weight) was supplied to the reaction tube at 31.3cc / hr. The reaction product 6 minutes after the start of the supply of naphtha was directly introduced into the gas chromatograph to analyze its composition. The reaction results at 6 8 0 ° C are shown in Table 1. Comparative Example 1 The Na + ZSM-5 produced in Example 1 was directly carried out and implemented without any treatment 1 The same conversion reaction of naphtha. The acid content of this catalyst is 0.006mmoj? / G. The results are shown in Table 1. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 gong) 13-305876 A7 B7 5. Description of the invention (11) Comparative Example 2 The ZSM-5 type zeolite (S i 〇2 / A j? 2 0 3 = 1 2 6) used in Example 1 was added to IN nitric acid aqueous solution (1 〇m 义 / g — zeolite) Ion exchange at room temperature for 3 hours, filtered and washed with water and dried at 110 ° C to obtain H + type Z SM-5 zeolite. After this H + type ZSM-5 5 0 . 1N silver nitrate aqueous solution (l〇m5? / G-zeolite) at room temperature for 3 hours ion exchange treatment. After washing with water and drying, firing in air at 5 0 0 ° C to obtain silver-containing H + type Z SM — 5 catalyst. The acid content of this catalyst is 0 · O55mm〇i2 / g. As a result of chemical analysis, the oxide in the anhydrous matrix of this composition is expressed by the mole ratio. The IJ has the following composition. 0.48Ag2O, Aj? 2O3, 126SiO2 using Comparative Catalyst 2, the results of the conversion reaction of naphtha under the same conditions as in Example 1 are shown in Table 1. Employee consumption of the Central Bureau of Samples and Statistics of the Ministry of Economic Affairs Zuosha Printing (please read the precautions on the back before filling in this page) Comparative Example 3 Except that the zeolite part is replaced by a magnetized Lasi ring (outer diameter 3mm < p, length 3 mm), the heat of naphtha The decomposition was carried out under the conditions of 680 °. The results are shown in Table 1. Example 2 Except for 0.02N silver nitrate aqueous solution in 0.1% copper chloride aqueous solution. The paper standard is applicable to China National Sample Standard (CNS) 84 specifications (210X297 mm). 14-Printed by the Central Committee of the Ministry of Economic Affairs Employee Consumer Cooperative A7 B7 V. Description of the invention (12) Except for the substitution, the other steps are the same as in Example 1, and a copper-containing Na + type ZSM-5 zeolite catalyst is prepared. In addition, the acid amount of this catalyst is Ο · 006 mmo j · / g. According to the results of chemical analysis, the oxide in the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0 · 5 0 C u 20, 〇. 4 0 N a 20, Aj? 2〇3, 126 S i Ο 2 Using this catalyst, the naphtha conversion reaction was carried out under the same conditions as in the example, the results are as in the first The table shows. It can be seen from Table 1 that Na + type Z SM-5 zeolite has almost no naphtha decomposition activity. If silver or copper is introduced, its decomposition activity can be greatly increased, and its yield structure is also due to acid The type Z SM-5 has silver or copper to obtain A gH + type Z SM -5, which is significantly different, which tends to significantly increase the selectivity to ethylene-based lower olefins. Example 3 The silver nitrate aqueous solution was changed to 0.1N, and the same steps as in Example 1 were carried out to obtain a silver-containing Na + type Z SM-5 zeolite catalyst (catalyst 2). In addition, the acid amount of this catalyst is 0.004 mmoj? / G chemical analysis result. The oxide in the anhydrous matrix of this composition is expressed by the molar ratio g and has the following composition. 0 · 8 8 A g 20 > 0 · 15Na2〇, Aj? 203, l 2 q This paper uses the Chinese National Standard (CNS) A4 specification (210X 297mm) (Please read the precautions on the back before filling in This page), π

I 15 - 經濟部中央樣準局員工消費合作社印製 S05S76 ΑΊ Β7 五、發明説明（13) S i 0 2 使用觸媒2，除將反應溫度變更爲6 6 0 °C以外’依實施例1相同步驟進行石腦油轉化反應。其結果如第2表所示。實施例4 將除反應溫度變更爲6 8 0 °C以外其他皆與實施3相同步驟進行石腦油轉化反應’其結果如第2表所示。實施例5 除氯化鈉以氯化鉀取代，硝酸銀水溶液濃度變更爲 0.1N以外，其他依實施例1相同步驟製作含銀之K+ 型ZSM— 5沸石觸媒（觸媒3)。又，此觸媒之酸量爲 0 . 0 0 2mmoj?/g。經化學分析結果，此組成中無水基質之氧化物以莫耳比表示則具下式組成。 0 · 6 0 A g 2 0，〇 . 4 4 K 2 0、Αβ203’ 1 26 S i 0 2 使用觸媒3 ，除反應溫度變更爲6 6 0°C以外進行與實施例1相同條件之石腦油轉化反應。其結果如表2所示本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)I 15-S05S76 ΑΊ Β7 printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) S i 0 2 Use of catalyst 2, except that the reaction temperature is changed to 6 6 0 ° C 'according to Example 1 The naphtha conversion reaction proceeds in the same step. The results are shown in Table 2. Example 4 The naphtha conversion reaction was carried out in the same procedure as in Example 3 except that the reaction temperature was changed to 680 ° C. The results are shown in Table 2. Example 5 The K + type ZSM-5 zeolite catalyst containing silver (catalyst 3) was prepared according to the same procedure as in Example 1, except that sodium chloride was replaced with potassium chloride and the concentration of the silver nitrate aqueous solution was changed to 0.1N. Moreover, the acid amount of this catalyst is 0.0 2 mmoj? / G. According to the results of chemical analysis, the oxide of anhydrous matrix in this composition is expressed by the molar ratio and has the following composition. 0 · 6 0 A g 2 0, 0. 4 4 K 2 0, Αβ203 '1 26 S i 0 2 Using catalyst 3, except that the reaction temperature was changed to 6 6 0 ° C, the same conditions as in Example 1 were carried out. Naphtha conversion reaction. The results are shown in Table 2. This paper scale uses the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page)

-16 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（14) 實施例6 除觸媒填充量由2 g變更爲3 g，反應溫度變更爲 6 8 0 °C以外’依實施例5相同條件下進行石腦油之轉化反應。其結果如第2表所示。比較例4 除反應溫度變更爲7 9 0 °C外依比較例3相同條件進行石腦油之熱分解。其結果如第2表所示。如第2表所示，依本發明之方法可使低價值之低甲院及重質份C ( C0烴類）之產率較熱分解所得更低，而有效製品產率（乙烯 '丙烯、C6〜C8芳香族烴類之總產率 )較熱分解所得大幅提升，而具優良之選擇性。實施例7 將 Na+型 ZSM-5 沸石（S i 02 / A 3? 2 0 3 = 91)以0 · 05N硝酸銀水溶液—沸石 )於室溫下進行3小時離子交換處理。水洗、乾燥後，於空氣中以5 5 0 °C燒成製得觸媒4。又，此觸媒之酸量爲 0 · 0 0 2mm〇i?/g »經化學分析結果，此組成之無水基質中氧化物以莫耳比表示則具下式組成。 0 · 6 1 A g 2 0，〇 · 2 6 N a 0，A j? 2 Ο 3 1 9 1 S i Ο 2 本紙張尺度適用中國國家標準（CNS Μ4规格（21 ΟΧ 297公釐) ~ -17 - (請先閲讀背面之注意事項再填寫本頁)-16-A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (14) Example 6 Except that the catalyst filling amount was changed from 2 g to 3 g, and the reaction temperature was changed to 6 8 0 ° C. Example 5 The conversion reaction of naphtha was carried out under the same conditions. The results are shown in Table 2. Comparative Example 4 The thermal decomposition of naphtha was carried out under the same conditions as Comparative Example 3 except that the reaction temperature was changed to 790 ° C. The results are shown in Table 2. As shown in Table 2, according to the method of the present invention, the yields of low-value low-A and high-weight C (C0 hydrocarbons) can be lower than those obtained by thermal decomposition, and the effective product yield (ethylene 'propylene, The total yield of aromatic hydrocarbons (C6 ~ C8) is much higher than that obtained by thermal decomposition and has excellent selectivity. Example 7 Na + type ZSM-5 zeolite (S i 02 / A 3? 2 0 3 = 91) was subjected to ion exchange treatment at room temperature for 3 hours at 0. 05N silver nitrate aqueous solution-zeolite. After washing with water and drying, the catalyst 4 was prepared by firing in air at 5 50 ° C. In addition, the acid amount of this catalyst is 0 · 0 0 2mm〇i? / G »After the chemical analysis results, the oxide in the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0 · 6 1 A g 2 0, 〇 · 2 6 N a 0, A j? 2 Ο 3 1 9 1 S i Ο 2 The paper size is applicable to the Chinese national standard (CNS Μ4 specification (21 ΟΧ 297 mm) ~- 17-(Please read the notes on the back before filling this page)

、1T, 1T

J 經濟部中央標準局員工消費合作社印製 305876 at B7 五、發明説明（) 於實施例1所使用之石英管充填2 g觸媒4，於一大氣壓’氮氣1 0 〇 c c/m i η流速下升溫至所定溫度。爲使其在未稀釋的條件下反應而先使氮氣停止流通後，將與實施例2相同之石腦油原料以4 6 . 8 c c / h r供給反應管。開始供給石腦油6分後分析其反應生成物。反應結果如第3表所示。實施例8 將 N a+型 Z SM-5 沸石（S i 02/Aj?203 = 30)以Ο , 〇3N硝酸銀水溶液（l〇m$/g_沸石 )於室溫下進行3小時離子交換處理。水洗，乾燥後，於空氣中以5 5 0 °C燒成製得觸媒5 »又，此觸媒之酸量爲 0 · 002mm〇i/g。經化學分析結果，此組成之無水基質中氧化物以莫耳比表示則具下式組成。 0 . 2 4 A g 2〇 . 〇 · 79Na20，Aj?203，30 S i Ο 2 使用觸媒5 ’於實施例1相同條件下進行石腦油轉化反應。其結果如第3表所示。比較例5 除使用比較例2所使用之Η+型Z SM — 5作爲觸媒 ’及觸媒量爲1 g外其他皆與實施例7相同條件進行石腦本紙張尺度適用中國國家樣準（CNS ) A4规格（210X297公釐） --------^ ^-- (請先閱讀背面之注意事項再填寫本頁)J Printed 305876 at B7 by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention () The quartz tube used in Example 1 was filled with 2 g of catalyst 4 at a pressure of 1 atmosphere of atmospheric pressure 'nitrogen 10 0 cc / mi η Warm up to the set temperature. In order to make it react under undiluted conditions, the flow of nitrogen was first stopped, and then the same naphtha raw material as in Example 2 was supplied to the reaction tube at 46.8 c c / h r. After the naphtha supply started for 6 minutes, the reaction product was analyzed. The reaction results are shown in Table 3. Example 8 Na + type Z SM-5 zeolite (S i 02 / Aj? 203 = 30) was subjected to ion exchange treatment at room temperature for 3 hours at room temperature with 〇, 〇3N silver nitrate aqueous solution (l〇m $ / g_zeolite) . After washing with water, drying, firing in the air at 5 5 0 ° C to prepare the catalyst 5 », the acid amount of this catalyst is 0. 002mm〇i / g. According to the results of chemical analysis, the oxide in the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0.24 Ag 2〇. ○ 79Na20, Aj 203, 30 S i Ο 2 Naphtha conversion reaction was carried out under the same conditions as in Example 1 using the catalyst 5 '. The results are shown in Table 3. Comparative Example 5 Except that the H + type Z SM-5 used in Comparative Example 2 was used as the catalyst 'and the amount of the catalyst was 1 g, all were carried out under the same conditions as in Example 7. CNS) A4 specification (210X297mm) -------- ^ ^-(Please read the precautions on the back before filling this page)

*tT 18 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（16 ) 油之轉化反應。其結果如表3所示。比較例6 使用實施例8所用之N a+型Z SM — 5沸石以1 N 硝酸水溶液（10mP/g -沸石），於室溫下進行3小時離子交換’得H+型ZSM—5沸石。其後以〇·〇3 N硝酸銀水溶液（1 Omj/g 一沸石）於室溫下進行3 小時離子交換’製得比較觸媒3。又，此觸媒之酸量爲 0 . 42mm οβ/g。經化學分析結果，此組成之無水基質的氧化物以莫耳比表示則具下式組成》 0 . 1 6 A g 2 0 ’ A 2 〇 a ' 3 0 S i Ο 2 使用比較觸媒3，除填充量爲1 g以外其他皆與實施例1相同條件下進行，實施轉化反應之結果如第3表所示〇實施例9 將 Na+型 ZSM-5 沸石（SiO 2/ A 又 2〇 3 = 9 1 )以1 N硝酸鎂水溶液（1 〇mj?/g -沸石）於 9 0°C，進行2小時離子交換，過濾水洗後以1 1 燥製得Mg2+Na+型ZSM — 5。再將此Mg2+Na+型 ZSM— 5以0 . 1N硝酸銀水溶液沸石）於室溫下，進3小時離子交換處理。水洗、乾燥後於本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) ,?!* tT 18-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (16) Oil conversion reaction. The results are shown in Table 3. Comparative Example 6 The Na + type Z SM-5 zeolite used in Example 8 was ion exchanged with 1 N nitric acid aqueous solution (10 mP / g -zeolite) at room temperature for 3 hours to obtain H + type ZSM-5 zeolite. Thereafter, a comparative catalyst 3 was prepared by ion exchange with 〇.03N silver nitrate aqueous solution (1 Omj / g-zeolite) at room temperature for 3 hours. Moreover, the acid amount of this catalyst is 0.42 mm οβ / g. According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. "0.16 A g 2 0 'A 2 〇a' 3 0 S i Ο 2 Using the comparison catalyst 3, Except for the filling amount of 1 g, all were carried out under the same conditions as in Example 1. The results of the conversion reaction are shown in Table 3. Example 9 The Na + type ZSM-5 zeolite (SiO 2 / A and 2〇3 = 9 1) Mg2 + Na + type ZSM-5 was prepared by ion exchange with 1 N magnesium nitrate aqueous solution (10 μm · / g -zeolite) at 90 ° C. for 2 hours, filtered and washed with water and dried by 1 1. Then, this Mg2 + Na + type ZSM-5 was boiled with 0.1N silver nitrate aqueous solution) at room temperature for 3 hours of ion exchange treatment. After washing and drying, the Chinese National Standard (CNS) A4 specification (210X297mm) is applicable to this paper standard (please read the precautions on the back before filling in this page),?!

A7 經濟部中央標準局員工消費合作社印製 305876 B7 五、發明説明（17) 空氣中以5 5 0°C燒成，製得含銀之Mg2+N a+型 ZSM—5沸石（觸媒6)。又，此觸媒之酸量爲 0 · 002mm〇$/g。經化學分析結果，此組成之無水基質的氧化物以莫耳比表示則具下式組成。 0 5 8 A g 2 〇 * Ο · 36MgO，Ο . 08Na2O,A7 305876 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (17) Mg2 + N a + ZSM-5 zeolite containing silver (catalyst 6) is fired in air at 5 50 ° C . In addition, the acid amount of this catalyst is 0. 002mm〇 $ / g. According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0 5 8 A g 2 〇 * Ο · 36MgO, Ο. 08Na2O,

AiZ203*91Si02 使用觸媒6，除反應生成物之分析係於供給石腦油後 4分鐘時進行外其他皆與實施例2相同條件進行石腦油轉化反應，其結果如第4表所示。實施例1 0 除硝酸鎂以硝酸鈣代替外其他皆與實施例9相同步驟製作含有銀之C a2+N a+型Z SM - 5沸石。又，此觸媒之酸量爲0 · 003mmojT/g。經化學分析結果’ 此組成之無水基質的氧化物以莫耳比表示則具下式組成。 0 . 6 0 A g 2 Ο > 〇 · 3 2 C a Ο - 〇 · Ο 8 N a 2 Ο *AiZ203 * 91Si02 The catalyst 6 was used. Except that the analysis of the reaction product was conducted 4 minutes after the supply of naphtha, the naphtha conversion reaction was carried out under the same conditions as in Example 2. The results are shown in Table 4. Example 1 0 Except that magnesium nitrate was replaced by calcium nitrate, the same procedure as in Example 9 was carried out. A silver-containing C a2 + N a + type Z SM-5 zeolite was prepared. In addition, the acid amount of this catalyst is 0 · 003mmojT / g. The result of chemical analysis ’The oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0. 6 0 A g 2 Ο > 〇 · 3 2 C a Ο-〇 · Ο 8 N a 2 Ο *

Aj?2〇3，91Si02 使用此觸媒，於實施例9相同條件下進行石腦油轉化反應’其結果如第4表所示。本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Aj? 2〇3, 91Si02 Using this catalyst, the naphtha conversion reaction was carried out under the same conditions as in Example 9. The results are shown in Table 4. The size of this paper is applicable to China National Standard (CNS) A4 (210X297mm) (Please read the precautions on the back before filling this page)

-20 - 經濟部中央標準局員工消費合作社印製 A7 ___B7__ 五、發明説明（18 ) 實施例1 1 除硝酸鎂以醋酸鋇代替外其他與實施例9相同步驟製作含有銀之B a2+N 型z SM — 5沸石。又，此觸媒之酸量爲0 . 002mm〇5/g。經化學分析結果’此組成之無水基質的氧化物以莫耳比表示則具下式組成。 0 . 4 6 A g 20，0 . 6 0 B a Ο，Ο . Ο 4 N a 2 0 ’ A52〇3，91Si02 使用此觸媒，於實施例9相同條件下進行石腦油轉化反應，其結果如第4表所示。實施例1 2 除將 Z SM-5 型沸石（S i 02/A^2〇3=9 1 )以 Z SM— 5 型沸石（S i 02/A 芡 2〇3= 1 7 5 ) 代替外其他與實施例11相同步驟製作含有銀之 B a2+N a+型Z SM— 5沸石。又，此觸媒之酸量爲 0 · O2mm〇i2/g。經化學分析結果，此組成之無水基質的氧化物以莫耳比表示則具下式組成。 0 . 7 8 A g 2 Ο « 〇 · 〇 2 B a Ο，Ο . 2 0 N a 2 Ο * A ^ 2 Ο a > 1 7 5 S i Ο 2 使用此觸媒，於實施例1相同條件下進行石腦油轉化本紙張尺度適用中國國家標準（CNS ) Α4规格（210'Χ297公釐） ---------，二------訂 ——1---、 (請先閲讀背面之注意事項再填寫本頁) -21 - 經濟部中央標準局員工消费合作社印製 3〇5876 at ________ B7 五、發明説明（19) 反應之結果如第4表所示。實施例1 3 將 H+型 Z SM — 5 沸石（S i 〇2/A52〇3 = 126)於Ο . 006N硝酸銀水溶液（l〇m又/g — 沸石）中以室溫狀態’進行3小時離子交換處理。水洗、乾燥後’於空氣中以5 5 0。0燒成，製得含銀0 . 3重量 %之觸媒。其次於一大氣壓、氮氣流量爲485 c c/ m i η下’將觸媒層溫度設定於7 5 0°C。隨後將純水以 1 5 . 6 c c/h r的流量供給4〇分鐘，於750°C，水蒸氣分壓爲0 _ 4a tm的條件下進行40分鐘烘蒸處理。烘蒸處理後的觸媒酸量爲〇 . 〇18mmoj2/g。使用此觸媒’於實施例1相同條件下進行石腦油轉化反應，其結果如第5表所示。實施例1 4 除硝酸銀濃度變爲0·1N外其他與實施例13相同步驟製得含銀1 . 3重量％之觸媒。並與實施例13相同條件進行烘蒸處理，處理後之觸媒的酸量爲〇 · 〇 1 3 m m 〇芡 / g 〇使用此觸媒，於實施例1相同條件下進行石腦油轉化反應，其結果如第5表所示。比較例7 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)-20-Printed A7 ___B7__ by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (18) Example 1 1 Except that magnesium nitrate was replaced with barium acetate, the same procedure as in Example 9 was used to produce B a2 + N type containing silver z SM — 5 zeolite. The acid amount of this catalyst was 0.002 mm〇5 / g. According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0.46 A g 20, 0.6 0 B a Ο, Ο. Ο 4 N a 2 0 'A52〇3, 91Si02 Using this catalyst, the naphtha conversion reaction was carried out under the same conditions as in Example 9, which The results are shown in Table 4. Example 12 Except that the Z SM-5 type zeolite (S i 02 / A ^ 2〇3 = 9 1) is replaced by the Z SM-5 type zeolite (S i 02 / A 芡 2〇3 = 1 7 5) Otherwise, the same procedure as in Example 11 was used to produce silver-containing B a2 + N a + type Z SM-5 zeolite. In addition, the acid amount of this catalyst is 0 · O2mm〇i2 / g. According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0.78 A g 2 Ο «〇. 〇2 B a Ο, Ο. 2 0 N a 2 Ο * A ^ 2 Ο a > 1 7 5 S i Ο 2 Using this catalyst, the same as in Example 1 Conversion of naphtha under different conditions. The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210 '× 297 mm) ---------, two ------ order-1 --- (Please read the precautions on the back before filling out this page) -21-Printed by the Consumer Standardization Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 3〇5876 at ________ B7 5. Description of the invention (19) The results of the response are shown in Table 4. Example 13 H + type Z SM-5 zeolite (S i 〇2 / A52〇3 = 126) in 0.006N silver nitrate aqueous solution (l〇m and / g-zeolite) at room temperature for 3 hours ion Exchange processing. After washing with water and drying, it was fired at 55.0 in air to prepare a catalyst containing 0.3% by weight of silver. Next, set the temperature of the catalyst layer at 7 5 0 ° C at atmospheric pressure and nitrogen flow rate of 485 c c / m i η. Subsequently, pure water was supplied at a flow rate of 15.6 c c / h r for 40 minutes, and was subjected to 40 minutes of steaming treatment at 750 ° C under the condition of a water vapor partial pressure of 0-4 tm. The amount of catalyst acid after baking treatment was 0.018 mmoj2 / g. Using this catalyst ', the naphtha conversion reaction was carried out under the same conditions as in Example 1. The results are shown in Table 5. Example 14 A catalyst containing 1.3% by weight of silver was prepared in the same procedure as in Example 13 except that the concentration of silver nitrate was changed to 0.1N. And the same conditions as in Example 13 were subjected to baking treatment, the acid amount of the catalyst after the treatment was 〇. 〇13 mm 〇芡 / g 〇 Using this catalyst, under the same conditions of Example 1 naphtha conversion reaction , The results are shown in Table 5. Comparative Example 7 This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X297mm) (please read the precautions on the back before filling this page)

-22 --twenty two -

Α7 Β7 經濟部中央樣準局員工消費合作社印装 305876 五、發明説明（2〇 ) 將實施例13所用之沸石在未經烘蒸處理下作觸媒使用’於實施例1相同條件下進行石腦油轉化反應，其結果如第5表所示。又，此觸媒之酸量爲0 · 1 18mmo^ / g。比較例8 將實施例14所用之沸石在未經烘蒸處理下作觸媒使用’於實施例1相同條件下進行石腦油轉化反應，其結果如第5表所示。又，此觸媒之酸量爲〇 . 〇55mm〇i? / g。實施例1 5 爲測試高溫水蒸氣與觸媒劣化之關係而進行以下的實驗。將與實施例3所製得之觸媒2爲相同之觸媒2 g填充入石英反應管內，一大氣壓、氮氣流量爲4 8 5 c c/ m i η下，將觸媒層溫度設定於7 5 0°C。隨後將純水以 1 5 . 6 c c/h r的流量供給2小時，於7 50°C，7_K 蒸氣分壓Ο . 4a tm的條件下進行2小時烘蒸處理。其次爲評估此次觸媒反應之活性，實施例1相同條件下進行石腦油之轉化反應，石腦油中η -戊烷之轉化率可由下式 (1 )計算1次反應速度常數。其結果如第6表所示。又，接觸時間之計算係依進出反應器平均之組成，及以空塔爲基準。本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁)Α7 Β7 The Ministry of Economic Affairs, Central Bureau of Samples and Employee's Consumer Cooperative Printed 305876 V. Description of the Invention (2〇) The zeolite used in Example 13 was used as a catalyst without drying treatment under the same conditions as in Example 1. The results of the naphtha conversion reaction are shown in Table 5. In addition, the acid amount of this catalyst is 0 · 1 18mmo ^ / g. Comparative Example 8 The zeolite used in Example 14 was used as a catalyst without drying treatment. The naphtha conversion reaction was carried out under the same conditions as in Example 1. The results are shown in Table 5. In addition, the acid amount of this catalyst was 0.0555 mm? I / g. Example 15 In order to test the relationship between high-temperature water vapor and catalyst degradation, the following experiment was conducted. Fill the quartz reaction tube with 2 g of the same catalyst as the catalyst 2 prepared in Example 3 under a atmospheric pressure and nitrogen flow rate of 4 8 5 cc / mi η, and set the temperature of the catalyst layer at 7 5 0 ° C. Subsequently, pure water was supplied at a flow rate of 15.6 c c / h r for 2 hours, and was subjected to a 2-hour steaming treatment at a temperature of 7 50 ° C and a vapor partial pressure of 0.75 a tm. Next, to evaluate the activity of the catalyst reaction, the conversion reaction of naphtha was carried out under the same conditions as in Example 1. The conversion rate of η -pentane in naphtha can be calculated by the following equation (1). The results are shown in Table 6. In addition, the calculation of the contact time is based on the average composition of the reactor and the reference to the empty tower. The paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back first and then fill in this page)

-23 - 經濟部中央樣準局員工消费合作社印褽 A7 B7 五、發明説明（21 ) R=(9-1xln {1/ (1 — y) } (1) R :石腦油分解反應速度常數（s e c—” θ :接觸時間（秒） y = (a — b)/a a :石腦油中η —戊院（重量％) b :反應生成物中η_戊烷（重量％) 比較例9 除使用比較例2所用Η+型Z SM — 5沸石爲觸媒，填充量爲4 g，烘蒸處理時間爲4 0分以外其他皆與實施例1 5相同條件下進行試驗。其結果如第6表所示。比較例1 0 除使用比較例2所用之觸媒爲觸媒外其他皆與實施例 1 5相同條件下進行試驗。其結果如第6表所示。如第6表所示，相對於比較例8所使用之酸型沸石與高溫水蒸氣接觸時於短時間內其活性即顯著降低而言，本發明的觸媒活性僅有些微降低而呈安定狀態。又本發明之觸媒較含銀酸型沸石之觸媒（比較觸媒2 )於耐劣化性上有更顯著提升》實施例1 6 除硝酸銀水溶液變更爲〇.1N外其他與實施例7相本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）一 24 — (請先閲讀背面之注意事項再填寫本頁) -* 丁經濟部中央樣準局員工消費合作社印製 A7 B7 五、發明説明（22 ) 同步驟製作含有銀之N a +型Z SM - 5沸石觸媒（觸媒 7)。此觸媒之酸量爲0 · 002mmoJ2/g。經化學分析結果，此組成之無水基質的氧化物以莫耳比表示則具下式組成。 0 · 8 2 A g 20 » 0 . 1 5Na20 · A^203' 9 1 S i Ο 2 使用觸媒7，於實施例1相同條件下進行6分鐘石腦油轉化反應。其次將反應管內滯留之反應氣體以氮氣 100〇〇/1111112分鐘置換後，以100(：<;/ m i η流速之空氣流通1 〇分鐘，由石腦油之轉化反應將觸媒上沈積之焦碳燃燒去除。其次，爲將空氣及焦碳燃燒產生之氣體置換，而將氮氣以1 0 0 c c/m i η流通2 分鐘。將石腦油轉化反應至第2次氮氣流通爲止視爲1次循環，而進行2 6 4次循環。第1次循環及第2 6 4次循環之結果如第7表所示。又，1次反應速度常數係爲式（1 )中η —戊烷值以石腦油中C5〜Ce的烷烴、環烷、烯烴的全體值取代而求得。比較例1 1 使用比較例2所用之H+型Z SM - 5沸石爲觸媒，依實施例1 6相同條件下進行2 3 8次循環操作。第7次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) 訂 -25 - 經濟部中央標準局貝工消費合作社印製 A7 B7_ 五、發明説明（23) 循環及第2 3 8次循環之結果如表7所示。如第7表所示，依本發明方法之石腦油轉化反應，經反覆實施再生操作也未使觸媒劣化情形顯現，且可維持有效製品產率及選擇性。實施例1 7 將 Na+型 ZSM— 5 沸石（Si02 / A 5 2 0 3 = 73)於Ο . 05N硝酸銀水溶液（l〇m$/g —沸石 )中以室溫狀態，進行3小時離子交換處理，水洗、乾燥。於此觸媒3 k g加入日產化學工業社製史諾帝充斯1 〇 k g (二氧化矽3 k g )，經噴霧乾燥而得含二氧化矽 5 0重量％平均直徑6 5mm之觸媒》將此觸媒2 · 5 g填充入反應器內，除採樣時間爲 4 . 5分以外，其他皆與實施例7相同條件進行石腦油轉化反應。其結果如第8表所示。又，此觸媒之沸石1 g中酸量爲0 · 00 5mmoj?/g。經化學分析結果，此組成之無水基質中氧化物以莫耳比表示則具下式組成。 0 . 5 5 A g 20，〇 · 3 3 N a 2 Ο，A^2〇3，15 0 5 i 0 2 實施例1 8 將 N a+型 Z SM — 5 沸石（S i 〇2/Aj?203 = 50) 80重量份與r~鋁2〇重量混練後，經押出成型本紙張尺度逋用中國國家橾準（CNS ) A4規格（210X297公簾) (請先閱讀背面之注意事項再填寫本頁)-23-A7 B7 printed by the Consumer Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy V. Description of the invention (21) R = (9-1xln {1 / (1 — y)} (1) R: Naphtha decomposition reaction rate constant (Sec— ”θ: contact time (seconds) y = (a—b) / aa: η—pentanin (wt%) in naphtha b: η_pentane (wt%) in the reaction product Comparative Example 9 Except that the H + type Z SM-5 zeolite used in Comparative Example 2 was used as a catalyst, the filling amount was 4 g, and the baking treatment time was 40 minutes, the test was conducted under the same conditions as in Example 15. The results are as shown in The results are shown in Table 6. Comparative Example 1 0 Except that the catalyst used in Comparative Example 2 is the catalyst, the tests were conducted under the same conditions as in Example 15. The results are shown in Table 6. As shown in Table 6 Compared with the acid type zeolite used in Comparative Example 8, the activity of the zeolite decreases significantly in a short time when contacted with high-temperature water vapor, the catalyst activity of the present invention is only slightly reduced and is stable. Compared with the catalyst containing silver-acid type zeolite (compared with catalyst 2), the degradation resistance is more significantly improved. For papers other than 0.1N, the paper size is the same as that of Example 7 and the Chinese National Standard (CNS) A4 specification (210X297mm) is one 24 — (please read the precautions on the back before filling in this page)-* Ding The A7 B7 is printed by the Consumer Cooperative of the Bureau of the P.V. 5. Description of the invention (22) In the same step, a Na + type Z SM-5 zeolite catalyst containing silver (catalyst 7) is produced. The acid amount of this catalyst is 0.002mmoJ2 / g. According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0 · 8 2 A g 20 »0. 1 5Na20 · A ^ 203 '9 1 S i Ο 2 Use The catalyst 7 was subjected to a naphtha conversion reaction for 6 minutes under the same conditions as in Example 1. Secondly, the reaction gas retained in the reaction tube was replaced with nitrogen at 100000/1111112 minutes, and then replaced by 100 (: <; / mi η The flow rate of air circulates for 10 minutes, and the coke deposited on the catalyst is burned and removed by the conversion reaction of naphtha. Secondly, in order to replace the gas produced by the combustion of air and coke, the nitrogen is replaced by 100 cc / mi η Circulate for 2 minutes. The naphtha conversion reaction is regarded as one time until the second nitrogen flow Ring, and perform 2 6 4 cycles. The results of the first cycle and the 2 6 4 cycles are shown in Table 7. In addition, the first reaction rate constant is η-pentane value in formula (1). The total value of C5 ~ Ce alkanes, naphthenes, and olefins in naphtha was determined by substitution. Comparative Example 1 1 The H + type Z SM-5 zeolite used in Comparative Example 2 was used as the catalyst, and the same conditions as in Example 16 Perform 2 3 8 cycles. The 7th time this paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling in this page) Order -25-A7 B7_ printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (23) The results of the cycle and the 2 3 8th cycle are shown in Table 7. As shown in Table 7, the naphtha conversion reaction according to the method of the present invention did not cause deterioration of the catalyst by repeatedly performing the regeneration operation, and the effective product yield and selectivity could be maintained. Example 17 Na + type ZSM-5 zeolite (Si02 / A 5 2 0 3 = 73) was subjected to ion exchange treatment at room temperature in a 0.05N silver nitrate aqueous solution (l〇m $ / g — zeolite) at room temperature for 3 hours , Washed and dried. Here, 3 kg of catalyst was added to 10 kg (3 kg of silica) manufactured by Nissan Chemical Industry Co., Ltd., and spray-dried to obtain a catalyst containing 50% by weight of silica with an average diameter of 65 mm. 2.5 g of this catalyst was filled into the reactor, and the naphtha conversion reaction was carried out under the same conditions as in Example 7 except that the sampling time was 4.5 minutes. The results are shown in Table 8. In addition, the amount of acid in 1 g of this catalyst zeolite is 0 · 00 5mmoj · / g. According to the results of chemical analysis, the oxide in the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 0.5 5 A g 20, 〇. 3 3 N a 2 Ο, A ^ 2〇3, 15 0 5 i 0 2 Example 1 8 will be Na + type Z SM-5 zeolite (S i 〇2 / Aj? 203 = 50) After mixing 80 parts by weight with 20 parts by weight of r ~ aluminum, the size of this paper is extruded and extruded to use the Chinese National Standard (CNS) A4 specification (210X297 public curtain) (please read the precautions on the back before filling in this page)

-26 - S〇SS76 Λ7 B7 五、發明説明（24 ) 而得直徑1 . 6mm，長4〜6mm物。隨後，以120 ，4小時乾燥後，以5 0 〇 °C，3小時之燒成’而得Z SM — 5沸石成型觸媒。此觸媒於0 . 1N硝酸銀水溶液 (1 0mj?/g -沸石）中以室溫狀態，進行3小時離子交換，水洗、乾燥。又，此時觸媒之沸石的酸量爲 0 · 005mmo)2/g。將此觸媒浸於3N硝酸鋅水溶液（0 . 沸石）後燒成，得含鋅之ZSM — 5沸石成型觸媒（觸媒8)。經化學分析結果，此組成之無水基質的氧化物以莫耳比表示則具下式組成。 5 · lZnO，〇.4〇Ag20，〇.34Na20， 8.9Aj?203，5〇Si02 將觸媒8，1 0 0 g填充入直徑1寸不銹鋼製成應管，於5 k g/cm2G的加壓下，將觸媒層溫度升至 6 5 0 °C，水蒸氣分壓〇 . 8 a tm的條件下進行5小時的烘蒸處理。隨後，將原料烴類（丙烷0 · 1重量％，丙經濟部中央樣準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 烯0 . 2重量％，丁烷類7 . 7重量％，丁烯類32 . 0 重量％，戊烷類45.7重量％，戊烯類14.3重量％ )以2 8 0 g/h r供給反應管，進行烴類轉化反應。供給原料4小時後，4 0小時後之反應結果如第9表所示。比較例1 2 將 H+型 Z SM - 5 沸石（S i 02/AP203= 5 0 本紙張尺度適用中國國家樣準（CNS ) A4規格（210X297公釐） -27 - 經濟部中央標準局員工消費合作杜印製 Α7 Β7 五、發明説明（25 ) )60重量份，r 一鋁15重量份及硝酸鋅25重量份混練後，進行押出成型而後直徑1.6mm、長4〜6mm 之物。隨後以1 2 0 °C，4小時乾燥後，以5 0 0 °C，3 小時燒成，而得含鋅之Z SM - 5沸石成型觸媒（比較觸媒4)。又，此觸媒之沸石lg中含酸量爲0.24 mm 0又/g。經化學分析結果此組成之無水基質的氧化物以莫耳比表示則具有下式組成。 5 · 2 Ζ η 0 > 8 . 6 Α ^ 2 0 3 ' 5 0 S i Ο 2 使用此觸媒，於實施例1 8相同條件下進行供蒸處理，及烴類之轉化反應。其結果如第9表所示。如表9所示，依本發明之方法可維持長期間之選擇性〇實施例1 9 將觸媒8，4 g填充入石英反應管，於一大氣壓下氮氣流量爲1 4 3 c c/m i η，將觸媒層溫度設定於 650 °C。其次將純水以27 . 6cc/mi η之流量供給5小時，於650 °C，水蒸氣分壓0 · 8a tm的條件下進行5小時烘蒸處理。烘蒸處理完了後，升溫至一定溫度後停止氮氣之流通，並將原料之η -己烷以23 . 4 c c/h r供給反應器。η —己烷供給3 0分鐘後的反應生成物則直接導入氣體層析儀分析其組成》本紙張尺度適用中國國家揉準（CNS ) Α4规格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂-26-S〇SS76 Λ7 B7 V. Description of the invention (24) Obtained a diameter of 1.6 mm and a length of 4 to 6 mm. Subsequently, after drying at 120 ° C for 4 hours, it was fired at 500 ° C for 3 hours to obtain Z SM-5 zeolite molding catalyst. This catalyst was ion-exchanged in 0.1 N silver nitrate aqueous solution (10 mj? / G -zeolite) at room temperature for 3 hours, washed with water, and dried. At this time, the acid amount of the catalyst zeolite was 0. 005 mmo) 2 / g. This catalyst is immersed in a 3N zinc nitrate aqueous solution (zeolite) and fired to obtain a zinc-containing ZSM-5 zeolite molding catalyst (catalyst 8). According to the results of chemical analysis, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 5. lZnO, 0.40Ag20, 0.34Na20, 8.9Aj? 203, 5〇Si02 Catalyst 8, 1 0 0 g is filled into a 1 inch diameter stainless steel to make a tube, pressurized at 5 kg / cm2G Under the condition that the temperature of the catalyst layer was raised to 6 50 ° C, and the partial pressure of water vapor was 0.8 a tm, it was subjected to a baking treatment for 5 hours. Subsequently, the raw material hydrocarbons (propane 0. 1% by weight, printed by the Employee Consumer Cooperative of the Central Prototyping Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) ene 0.2% by weight, butanes 7 7% by weight, butenes 32.0% by weight, pentanes 45.7% by weight, pentenes 14.3% by weight) 280 g / hr is supplied to the reaction tube, and the hydrocarbon conversion reaction proceeds. After supplying the raw materials for 4 hours, the reaction results after 40 hours are shown in Table 9. Comparative Example 1 2 H + type Z SM-5 zeolite (S i 02 / AP203 = 5 0) The paper size is applicable to China National Standards (CNS) A4 specification (210X297 mm) -27-Employee consumption cooperation of the Central Standards Bureau of the Ministry of Economic Affairs A7 Β7 made by Durin V. Description of the invention (25)) 60 parts by weight, 15 parts by weight of aluminum and 25 parts by weight of zinc nitrate are kneaded, and then extruded to form a thing with a diameter of 1.6 mm and a length of 4 to 6 mm. Subsequently, it was dried at 120 ° C for 4 hours, and then fired at 500 ° C for 3 hours to obtain a Z SM-5 zeolite forming catalyst containing zinc (Comparative Catalyst 4). In addition, the acid content of zeolite lg of this catalyst is 0.24 mm 0 g / g. According to the chemical analysis results, the oxide of the anhydrous matrix of this composition is expressed by the molar ratio and has the following composition. 5 · 2 ζ η 0> 8.6 Α ^ 2 0 3 '5 0 S i Ο 2 Using this catalyst, under the same conditions as in Example 18 for steaming treatment, and the conversion reaction of hydrocarbons. The results are shown in Table 9. As shown in Table 9, the method according to the present invention can maintain the selectivity for a long period of time. Example 1 9 Fill catalyst 8, 4 g into a quartz reaction tube, and the nitrogen flow rate is 1 4 3 cc / mi η at atmospheric pressure , Set the temperature of the catalyst layer at 650 ° C. Secondly, the pure water was supplied at a flow rate of 27.6 cc / mi η for 5 hours, and then subjected to a 5-hour baking treatment at 650 ° C and a water vapor partial pressure of 0 · 8 a tm. After the steaming treatment was completed, the temperature of nitrogen was raised to a certain temperature to stop the circulation of nitrogen, and the raw material η-hexane was supplied to the reactor at 23.4 c c / h r. η —The reaction product after 30 minutes from the supply of hexane is directly introduced into the gas chromatograph to analyze its composition》 This paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) (please read the notes on the back first (Fill in this page again)

J -28 - 經濟部中央標準局員工消费合作杜印製 Α7 Β7 五、發明説明（26 ) 將空氣以1 0 0 c c/m i η流通於觸媒上使無碳燃燒，再進行上記烘蒸處理，進行η -己烷轉化反應。其結果如表1 0所示。比較例1 3 除使用比較觸媒4外其他於實施例19相同條件下進行試驗，其結果如第1 0表所示。如第1 0表所示，本發明的觸媒除顯示高活性外，亦可抑制因高溫水蒸氣引起的觸媒劣化。如上所述，依本發明可得到高產率且平均之以乙烯爲主成份之低級烯烴及單環芳香族烴類，及提供一種不易因高溫水蒸氣而引起劣化之烴類轉化觸媒。故本發明可廣泛利用於石油化學工業、石油精製等，特別是對製造乙烯、丙烯等低級烯烴或芳香族化合物、高辛烷值汽油等可有效利用》本紙張尺度適用中國國家橾牟（CNS ) Α4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁)J -28-Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs du printed Α7 Β7 V. Description of the invention (26) Circulate air at 100 cc / mi η on the catalyst to burn carbon-free, then perform the above-mentioned baking treatment To perform η-hexane conversion reaction. The results are shown in Table 10. Comparative Example 1 3 The test was carried out under the same conditions as in Example 19 except that Comparative Catalyst 4 was used. The results are shown in Table 10. As shown in Table 10, in addition to showing high activity, the catalyst of the present invention can suppress the deterioration of the catalyst due to high-temperature steam. As described above, according to the present invention, it is possible to obtain low yield olefins and monocyclic aromatic hydrocarbons with ethylene as a main component in high yield and on average, and to provide a hydrocarbon conversion catalyst that is not easily deteriorated by high-temperature water vapor. Therefore, the present invention can be widely used in the petrochemical industry, petroleum refining, etc., especially for the production of ethylene, propylene and other lower olefins or aromatic compounds, high octane gasoline, etc. "This paper size is applicable to the Chinese national ) Α4 specification (210X297mm) (Please read the notes on the back before filling this page)

29 - Ϊ0587629-Ϊ05876

A7 B7 五、發明説明（）實施例2 0，2 1爲碳數大的烴類（減壓輕油： 1 9〜2 5餾分）及ZSM - 1 1之實施例·A7 B7 Fifth, the description of the invention () Example 2 0, 2 1 is a hydrocarbon with a large carbon number (pressure-reduced light oil: 1 9 ~ 25 5 fraction) and ZSM-1 1 Example ·

C 經濟部中央揉隼局貝工消費合作杜印11 實施例2 0 將資施例7所用之4 g觸媒4充填於實施例1所用之石英反應管，在大氣壓下淳氮在3 3 3 c c/m i η流通 ’並升溫至所定溫度。其次在氮流通下將原料之減壓輕油 (比重0 . 895、氫含有率12 · 98重邏：％，容積平均沸點，403 °C)於31 . 3cc,/ hr供給於反應管。全量捕集原料供給5分後〜1 0分後之反應生成物，藉氣體層析分別對生成氣體及生成液體進行組成分析。在 6 8 5°C之反應結果如第1 1表所示。比較例1 4 與實施例2 0同樣，但以磁器製拉西環（Rasching ring)替代沸石充填•在在7 9 6 °C之條件下實施減壓輕油之熱分解。結果如第1 1表所示。實施例2 1 將溶解矽酸鈉（◦品牌）60g，NaOH 0 . 54g · n-C7F15C00H 2g 於蒸餾水 60 g之A液，其他爲溶解硫酸鋁18水合鹽4g，1 * 8_ 二氨基辛烷4g，20%硫酸20g於蒸餾水76g之B 液。其次，使用勻化器之A液在強攪拌下添加B液，得到 (請先閲讀背面之注意事項再填寫本頁) 訂l· 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） 29—1 — it ib 經濟部中央樣準局貝工消费合作社印裝 A7 B7 五、發明説明（）均質凝膝組成物。將其裝入2 0 〇 c c之內塗鐵氟龍高壓鍋’保持於1 8 〇°C 5天，進行水熱合成。反應後將固形物過滅’水洗，脫水，乾燥，使其在5 5 0 °C於空氣中燒成三小時。確認所得白色粉末之X線繞射圖案時則顯示 ZSM—11之圖案。其次’在1 N硝酸鈉夺溶液（1 Om^/g —沸石）中於8 0°C使該z SM — 1 1離子交換2小時，過濾水洗後以1 l〇°C乾燥並調製Na+型ZSM — 1 1。其次使用〇 · 02N硝酸銀水溶液（l〇mj?/g —沸石）在室溫對此N a +型z SM — 1 1進行2小時之離子交換處理。在水洗’乾燥後，在空氣中以5 5 〇«c燒成並調製含有 Ag之Na+型zsM— 1 1沸石。又，此觸媒之酸量爲〇 . Olmmop/g。又，其組成在無水狀態下，以氧化物之莫耳比表示則具有下列組成^ °-17 A g 20 - 〇 . 4 2 N a 2 Ο · Α ^ 2 Ο 3 ’30 S i 〇 2 使用此觸媒，除了將觸媒充填量變成2 . 5 g，石腦油改爲5 5 . 3 c c/h r以外，其他與實施例7同樣條件’進行石腦油之轉化反應β結果如第1 1表所示。實施例2 2 依曰本特開昭5 2 -4 3 8 0 0號公報之實施例1及本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X 297公釐）_ 29-2 - (請先閲讀背面之注意事項再填寫本頁) 訂 \VS- Jz.C The Ministry of Economic Affairs, Central Falcon Bureau, Shell Industry Consumer Cooperation Du Yin 11 Example 2 0 The 4 g catalyst 4 used in Example 7 was filled in the quartz reaction tube used in Example 1, and the nitrogen was 3 3 3 at atmospheric pressure. cc / mi η circulates' and heats up to the specified temperature. Secondly, under the flow of nitrogen, the reduced-pressure light oil of the raw material (specific gravity 0.895, hydrogen content rate 12.98 heavy logic:%, volume average boiling point, 403 ° C) was supplied to the reaction tube at 31.3 cc, / hr. After collecting all the raw materials and supplying the reaction products after 5 minutes to 10 minutes, the composition of the generated gas and the generated liquid were analyzed by gas chromatography. The reaction results at 685 ° C are shown in Table 11. Comparative Example 14 is the same as Example 20, except that a magnetic device made of Rasching ring is used instead of zeolite filling. • The thermal decomposition of reduced-pressure light oil is carried out at 796 ° C. The results are shown in Table 11. Example 2 1 Dissolve 60g of sodium silicate (brand name), NaOH 0.54g · n-C7F15C00H 2g in A solution of 60g of distilled water, the other is dissolved 4g of aluminum sulfate 18 hydrated salt, 4g of 1 * 8_diaminooctane , 20% sulfuric acid 20g in distilled water 76g of B liquid. Secondly, use liquid A of the homogenizer to add liquid B under strong stirring to obtain (please read the precautions on the back and then fill out this page). Order l · This paper size is applicable to China National Standard (CNS) A4 specification (210X297 ) 29-1 — it ib A7 B7 printed by the Beigong Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economy V. Description of the invention () Homogeneous condensate composition. This was put into a Teflon-coated autoclave within 200 ° C and kept at 180 ° C for 5 days to perform hydrothermal synthesis. After the reaction, the solid matter was washed with water, dehydrated, and dried, and it was fired in air at 5 50 ° C for three hours. When the X-ray diffraction pattern of the obtained white powder is confirmed, the pattern of ZSM-11 is displayed. Secondly, in a 1 N sodium nitrate solution (1 Om ^ / g — zeolite), the z SM — 11 ion exchange was carried out at 80 ° C for 2 hours. After filtering and washing with water, it was dried at 110 ° C and the Na + type was prepared. ZSM — 1 1. Next, this Na + type z SM-11 was subjected to ion exchange treatment for 2 hours at room temperature with a 0.02 N silver nitrate aqueous solution (10 mol / g-zeolite). After washing with water and drying, it is calcined in air at 5 5 〇c and the Na + type zsM-11 zeolite containing Ag is prepared. Also, the acid amount of this catalyst is 0.01 Olmmop / g. In addition, the composition in the anhydrous state, expressed as the molar ratio of oxides, has the following composition ^ ° -17 A g 20-〇. 4 2 N a 2 Ο · Α ^ 2 Ο 3 '30 S i 〇2 Use This catalyst, except that the catalyst filling amount was changed to 2.5 g and the naphtha was changed to 55.3 cc / hr, the same conditions as in Example 7 were performed. 1 shown in the table. Example 2 2 According to Example 1 of Japanese Patent Publication No. 5 2 -4 3 8 0 0 and the paper size, the Chinese National Standardization (CNS) Α4 specification (210X 297 mm) _ 29-2-( Please read the precautions on the back before filling in this page) Order \ VS- Jz.

^ ilnJ A7 B7 經濟部中央標準局貝工消費合作社印«. 五、發明説明 ( ) I 2 » 使用酒精之乙酵 » 合成她石 • Z E T A 3 〇 1 1 | 接著 > 將此 Z E T A 3 水洗 » 乾燥後 ♦ 在空氣中 1 1 f 5 5 0 °c 燒成 5 小時接著在 3 N 硝酸鈉水溶液 (10 1 I 請 1 I m / g — Λ4Ι, 沸石 ) 中 » 進行 2 次 8 0 °C * 1 小時之離子交先閲 1 | 讀 1 1 換處理 9 過濾水洗後在 1 1 0 °C 乾燥調製 N a + 型 Z E T 背 1 1 之 1 A 3 〇其次使用 0 0 3 N 硝酸銀水溶液 ( 1 0 m β / g 注意畫 1 | — 沸石 ) 在室溫離子交換處理此 N a + 型 Z E T A 3 ，2 Ψ 項再 1 小填時〇水洗後在 1 2 0 °C 乾燥調製含有 A g 之 N a +型寫本頁 1 Z E T A 3 她石 β 又此觸媒之酸置爲 0 0 0 1 1 I m m 0 9. / g 〇又其組成係以 4nr. 水狀態下氧化物之莫耳 1 1 比表示具有下列組成〇 1 I 訂 0 5 7 A g 2〇 0 8 4 N a 2 0 A 2 〇 3 1 1 ， 8 5 S i 0 2 1 1 I 將此觸媒 3 S 充填於實施例 1 所用之石英反應管，在 1 後、 1 I 大氣壓下使氮在 7 5 C C / m 1 η 流通並升溫至 7 3 0 °C 1 1 〇其次將石腦油在 1 1 0 • 5 C c / h r 供給於反應管， 1 1 將石腦油供給開始 5 秒後之反應生成物直接導入氣體層析 1 1 » 分析組成 t 得到以下結果 0 1 | 氫 1 0 重優甲烷 6 • 5 重量 % » 乙烯 1 9 . 7重 1 I 量 % 丙烯 2 1 • 5 重量 % I 丁院 6 * 1 重量 % ，C β - 8 1 1 | 芳香族烴 1 6 * 8 重量 % » C 6 - 8芳香族烴] 8 . 3重量 1 1 | % t C 2 — 4烯烴4 7 - 2 1重量& 3。 1 本紙伕尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）_ 經濟部中央標準局員工消費合作社印裝 ^05876 ΑΊ Β7 五、發明説明（27 ) 第1表實施例1 比較例1 比較例2 比較例3 實施例2 沸石 AgNa 型 N a型 Ag i 1型熱分解 CuN a型酸量（mm 〇 ) 0.004 0.006 0.055 - 0.006 麵原料石腦油石腦油石腦油石腦油石腦油反應溫度ΓΟ 680 680 6 8 0 680 6 8 0 產率（軍最％) 氫 1.2 0.2 4.3 0 1 1 . 6 甲烷 9.3 3.2 8 · 4 2 6 8 5 乙烯 2 2-8 6.1 14.6 5 1 17. 8 丙烯 19-5 6 5 8.9 5 6 1 6 . 1 丁烯 5 . 4 4.6 1 . 5 4 1 4 . 0 Ce—8芳香族烴類 19-8 9.7 45-0 8 9 2 8 4 ce+烴類 1 . 5 1 . 4 5 · 5 1 3 1 9 Ce—β芳香族烴類 20.5 11.0 4 5-9 10.1 29 . 3 C 2—4嫌煙 47.7 17.2 2 5-0 14 8 3 7 · 9 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)^ ilnJ A7 B7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs «V. Description of the Invention () I 2» Using Alcoholic Yeast »Synthesizing Her Stone • ZETA 3 〇1 1 | Next> Wash this ZETA 3» After drying ♦ Bake in air at 1 1 f 5 5 0 ° c for 5 hours and then in a 3 N aqueous solution of sodium nitrate (10 1 I please 1 I m / g — Λ4Ι, zeolite) »2 times 8 0 ° C * 1 hour of ion exchange first read 1 | read 1 1 change treatment 9 filter water wash and dry at 1 1 0 ° C to prepare N a + type ZET back 1 1 of 1 A 3 〇 followed by 0 0 3 N silver nitrate aqueous solution (1 0 m β / g Note 1 | — zeolite) This N a + type ZETA 3 is ion-exchanged at room temperature, and the 2 Ψ term is then 1 small filling time. After washing with water, it is dried at 1 2 0 ° C to prepare Na containing A g + Type to write this page 1 ZETA 3 She stone β and the acidity of this catalyst It is 0 0 0 1 1 I mm 0 9. / g 〇 and its composition is 4nr. Mole of oxide in water state 1 1 ratio means that it has the following composition 〇1 I set 0 5 7 A g 2〇0 8 4 N a 2 0 A 2 〇3 1 1, 8 5 S i 0 2 1 1 I This catalyst 3 S was filled in the quartz reaction tube used in Example 1, after 1, at 1 I atmospheric pressure, nitrogen was 7 5 CC / m 1 η Circulate and heat up to 7 3 0 ° C 1 1 〇 Secondly, supply naphtha to the reaction tube at 1 1 0 • 5 C c / hr, 1 1 5 seconds after the start of the supply of naphtha The product was directly introduced into gas chromatography 1 1 »The composition t was analyzed and the following result was obtained. 0 1 | Hydrogen 1 0 Heavy Methane 6 • 5 wt%» Ethylene 1 9 .7 Weight 1 I amount% Propylene 2 1 • 5 wt% I D 6 * 1% by weight, C β-8 1 1 | Aromatic hydrocarbons 1 6 * 8% by weight »C 6-8 aromatic hydrocarbons] 8.3% by weight 1 1 |% t C 2 — 4 olefins 4 7-2 1 weight & 3. 1 The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) _ Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 05876 ΑΊ Β7 5. Description of the invention (27) Table 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 2 Zeolite AgNa type Na type Ag i Type 1 thermal decomposition CuN a type acid amount (mm) 0.004 0.006 0.055-0.006 surface raw material naphtha naphtha naphtha naphtha naphtha naphtha reaction Temperature ΓΟ 680 680 6 8 0 680 6 8 0 Yield (Most military%) Hydrogen 1.2 0.2 4.3 0 1 1. 6 Methane 9.3 3.2 8 · 4 2 6 8 5 Ethylene 2 2-8 6.1 14.6 5 1 17. 8 Propylene 19-5 6 5 8.9 5 6 1 6. 1 butene 5. 4 4.6 1. 5 4 1 4. 0 Ce-8 aromatic hydrocarbons 19-8 9.7 45-0 8 9 2 8 4 ce + hydrocarbons 1. 5 1. 4 5 · 5 1 3 1 9 Ce-β aromatic hydrocarbons 20.5 11.0 4 5-9 10.1 29. 3 C 2-4 smoke 47.7 17.2 2 5-0 14 8 3 7 · 9 This paper size is suitable for China National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page)

-30 - 305876 A7 B7 五、發明説明（28 )第2表經濟部中央揉準局員工消費合作社印製實施例3 比較例4 實施例5 賨施例6 比較例4 沸石 AgNa 型 AgNa 型 AgK型 AgK型熱分解酸量（mm 〇 ) 0.004 0 . 004 0.002 0. 002 — 烴類原料石腦油石腦油石腦油石腦油石腦油反應溫度rc) 6 6 0 6 8 0 6 6 0 680 790 觸媒填充量U) 2.0 2 .0 2.0 3.0 — 產率（重量％) 氫 1 · 5 1 • 2 1 · 2 1 · 5 0 . 8 甲烷 9.5 9 .4 7 . 4 9.5 13. 5 乙烯 2 2.8 24 .1 2 1-3 24.9 24 · 6 丙烯 17.2 18 .1 20.3 17.4 1 6 · 7 丁烯 4.4 4 .9 6.2 4 · 0 6 · 2 Ce—8芳香族烴類 2 3.9 2 1 .2 18.4 2 2.7 1 2 . 1 c9+讎 1.7 1 .4 1 · 5 2 1 2 · 7 C2—3烯烴 ce—β芳香族麵 6 3.9 6 3 .4 6 0.0 6 5.0 5 3 · 4 (請先閲讀背面之注意事項再填寫本頁)-30-305876 A7 B7 V. Description of the invention (28) Table 2 Printed by the Ministry of Economic Affairs, Central Bureau of Accreditation and Employee Consumer Cooperative of Example 3 Comparative Example 4 Example 5 Example 5 Comparative Example 4 Comparative Example 4 Zeolite AgNa Type AgNa Type AgK Type AgK type thermal decomposition acid amount (mm 〇) 0.004 0. 004 0.002 0. 002 — hydrocarbon raw material naphtha naphtha naphtha naphtha naphtha naphtha reaction temperature rc) 6 6 0 6 8 0 6 6 0 680 790 catalyst Filling amount U) 2.0 2 .0 2.0 3.0 — Yield (% by weight) Hydrogen 1 · 5 1 • 2 1 · 2 1 · 5 0. 8 Methane 9.5 9 .4 7. 4 9.5 13. 5 Ethylene 2 2.8 24. 1 2 1-3 24.9 24 · 6 Propylene 17.2 18 .1 20.3 17.4 1 6 · 7 Butene 4.4 4 .9 6.2 4 · 0 6 · 2 Ce—8 aromatic hydrocarbons 2 3.9 2 1 .2 18.4 2 2.7 1 2. 1 c9 + 雠 1.7 1 .4 1 · 5 2 1 2 · 7 C2-3 olefin ce-β aromatic surface 6 3.9 6 3 .4 6 0.0 6 5.0 5 3 · 4 (Please read the notes on the back first Fill in this page)

本紙張尺度適用中國國家橾準（CNS ) A4规格（210X 297公釐） 31 A7 B7五、發明説明（29 ) 經濟部中央標準局員工消費合作社印製第3表實施例7 實施例8 比較例5 比較例6 沸石 A g N a 型 A g N a 型 Η 型 A g Η型烴類原料石腦油石腦油石腦油石腦油酸量（m m 〇 j? / g ) 0.002 0.002 0-096 0.42 反應溫度（°C ) 6 8 0 6 8 0 6 8 0 6 8 0 觸媒填充量（g ) 2 · 0 2.0 1.0 1 · 0 產率（重量％) 氫 1 · 0 1 3 1 5 3 1 甲烷 10.3 11.4 10.3 11.8 乙烯 2 5.2 2 0-8 2 0.1 12.8 丙烯 17.9 17.1 14.8 9 5 丁烯 2.2 4 5 3 · 4 2 6 ce_8芳香族烴類 2 4.5 2 3-7 3 0.4 3 5.1 c0+烴類 2 8 2.9 3.6 6 9 ce_e芳香族烴類 2 6-7 2 4.4 3 2-7 3 6.4 c2-4烯烴 4 5-2 4 2.4 3 8.2 2 5.0 (請先閱讀背面之注意事項再填寫本頁)This paper scale is applicable to China National Standard (CNS) A4 (210X 297mm) 31 A7 B7 V. Description of invention (29) Printed by the Ministry of Economy Central Standards Bureau Employee Consumer Cooperatives Table 3 Example 7 Example 8 Comparative Example 5 Comparative Example 6 Zeolite A g N a type A g N a type H type A g H type hydrocarbon raw material naphtha naphtha naphtha naphtha naphtha acid content (mm 〇j? / G) 0.002 0.002 0-096 0.42 reaction Temperature (° C) 6 8 0 6 8 0 6 8 0 6 8 0 Catalyst loading (g) 2 · 0 2.0 1.0 1 · 0 Yield (% by weight) Hydrogen 1 · 0 1 3 1 5 3 1 Methane 10.3 11.4 10.3 11.8 Ethylene 2 5.2 2 0-8 2 0.1 12.8 Propylene 17.9 17.1 14.8 9 5 Butene 2.2 4 5 3 · 4 2 6 ce_8 Aromatic hydrocarbons 2 4.5 2 3-7 3 0.4 3 5.1 c0 + hydrocarbons 2 8 2.9 3.6 6 9 ce_e aromatic hydrocarbons 2 6-7 2 4.4 3 2-7 3 6.4 c2-4 olefins 4 5-2 4 2.4 3 8.2 2 5.0 (please read the notes on the back before filling this page)

本紙張尺度適用中國國家梂準（CNS〉A4规格（210X297公釐） -32 - 經濟部中央樣準局員工消費合作社印製 J05876 A7 B7 五、發明説明（3〇 ) 第4表實施例9 實施例10 實施例11 實施例12 沸石 AgMgNa 型 AgCaNa 型 AgBaNa 型 AgBaNa型酸量（m m 〇又/g ) 0. 002 0. 003 0. 002 0. 002 烴類原料石腦油石腦油石腦油石腦油反應溫度（°C ) 6 8 0 6 8 0 6 8 0 6 8 0 觸媒填充量（g ) 2 • 0 2.0 2 · 0 2 0 產率（重量％) 氫 1 · 1 1.2 1.0 1 . 3 甲烷 7 · 0 7 . 3 6.9 8 · 1 乙烯 2 1 . 9 2 2.4 2 2-1 2 1. 1 丙烯 2 1 . 0 2 0.6 2 2-6 2 0 . 1 丁烯 5 7 5 4 6 · 3 5 5 Ce_8芳香族烴類 2 1 . 7 2 1.9 18-4 2 2 0 ce+烴類 2 · 2 2 2 1.9 1 . 3 Ce-9芳香族烴類 2 3 1 2 3.2 19-7 2 2 · 7 <:2-4烯烴 4 8 6 4 8.4 5 0.9 4 6.7 (請先閱讀背面之注意事項再填寫本頁)This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X297mm) -32-Printed by the Ministry of Economic Affairs, Central Bureau of Standards and Employee Consumer Cooperatives J05876 A7 B7 V. Description of the invention (3〇) Table 4 Example 9 Example 10 Example 11 Example 12 Zeolite AgMgNa-type AgCaNa-type AgBaNa-type AgBaNa-type acid amount (mm 〇 //) 0. 002 0. 003 0. 002 0. 002 hydrocarbon raw materials naphtha naphtha naphtha naphtha naphtha naphtha Reaction temperature (° C) 6 8 0 6 8 0 6 8 0 6 8 0 Catalyst loading (g) 2 • 0 2.0 2 · 0 2 0 Yield (% by weight) Hydrogen 1.11 1.2 1.0 1.3 Methane 7 · 0 7. 3 6.9 8 · 1 Ethylene 2 1. 9 2 2.4 2 2-1 2 1. 1 Propylene 2 1. 0 2 0.6 2 2-6 2 0. 1 Butene 5 7 5 4 6 · 3 5 5 Ce_8 aromatic hydrocarbons 2 1. 7 2 1.9 18-4 2 2 0 ce + hydrocarbons 2 · 2 2 2 1.9 1. 3 Ce-9 aromatic hydrocarbons 2 3 1 2 3.2 19-7 2 2 · 7 <: 2-4 olefin 4 8 6 4 8.4 5 0.9 4 6.7 (please read the notes on the back before filling this page)

J 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） -33 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（si ) 第5表實施例13 實施例14 比較例7 比較例8 銀含量（重量％) 0. 3 1.3 0. 3 1. 3 酸量（m m 〇 5/g ) 0. 018 0. 013 0. 118 0. 055 烴類原料石腦油石腦油石腦油石腦油反應溫度（°C ) 6 8 0 6 8 0 6 8 0 6 8 0 產率（重量％) 氫 1 · 8 2.1 4 1 4 · 3 甲烷 10-1 12-5 10.2 8.4 乙烯 2 2.3 2 3.5 16.7 14.6 丙烯 18-1 13-3 8 · 2 8.9 丁烯 4.5 2.5 1 · 0 1 · 5 Ce 8芳香族烴類 2 7.4 3 2.7 4 2.9 4 5.0 ce+烴類 1.0 1 3 5.8 5.5 Ce β芳香族烴類 2 7.9 3 3-2 4 3-8 4 5-9 C2M烯烴 4 4.9 3 9.3 2 5-9 2 5.0 (請先閱讀背面之注意事項再填寫本頁) 訂丨. 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -34 - 經濟部中央標準局員工消費合作社印製 S05876 A7 A7 B7 五、發明説明（32 ) 第6表實施例1 5 比較例9 比較例1 0 觸媒 AgNaZSM-5 HZSM-5 AgHZSM-5 烘蒸條件溫度(。〇 750 750 750 水蒸氣分壓(氣壓） 0.4 0.4 0.4 處理時間(分） 120 40 120 反應條件處理前處理後處理前處理後處理前處理後觸媒量(g) 2.0 2.0 2.0 4.0 2.0 2.0 溫獻。C) 685 677 682 672 683 692 接觸時間(秒） 0. 24 0. 24 0. 24 0.49 0. 24 0. 24 η-戊烷轉化率(%) 97.5 95.5 98.6 81.2 96.0 91.9 反應速度常數*(秒” 14.6 13.2 17.6 3.7 13.2 9.1 (相對值） (100) (90) (100) (21) (100) (69) * 6 8 CTC溫度修正值（活化能量：2 2 k c a 1 /m ο 1 ) (請先閱讀背面之注意事項再填寫本頁) 訂丨· 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） 35 五、發明説明（33 ) A7 B7 經濟部中央標準局員工消費合作社印製第7表實施例1 6 比較例1 1 觸媒 A g N a 型 Η型酸量（mm 〇 j? / g ) 0. 002 0. 096 循環數 1 264 7 238 烴類原料石腦油石腦油石腦油石腦油反應溫度（°c) 679 685 674 687 收率（重量％) 氫 1.3 1.5 1.3 1. 2 甲烷 9. 4 9. 8 10. 1 9. 3 乙烯 21. 6 21.4 20. 7 19.4 丙烯 18. 3 18. 5 16. 2 20. 3 丁烯 4. 8 4. 9 4. 3 6. 4 Ce_8芳香族烴類 26. 7 29. 3 28. 8 24. 5 C 9+烴類 2. 3 1. 9 2. 2 1.5 C 2-4晞煙+ c6_9芳香族烴類 66. 6 69. 2 65. 7 64. 2 C5-8PN0 轉化率（％) 94. 9 95. 9 94. 9 91. 0 反應速度常數$ 12. 4 12. 5 13. 2 9. 2 (秒-1)(相對值） (100) (100) (100) (70) (請先閱讀背面之注意事項再填寫本頁)J This paper scale uses the Chinese National Standard (CNS) A4 specification (210X297mm) -33-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of invention (si) Table 5 Example 13 Example 14 Comparative Example 7 Comparative Example 8 Silver content (% by weight) 0. 3 1.3 0. 3 1. 3 Acid amount (mm 〇5 / g) 0. 018 0. 013 0. 118 0. 055 Hydrocarbon raw material naphtha naphtha Naphtha naphtha reaction temperature (° C) 6 8 0 6 8 0 6 8 0 6 8 0 yield (wt%) hydrogen 1 · 8 2.1 4 1 4 · 3 methane 10-1 12-5 10.2 8.4 ethylene 2 2.3 2 3.5 16.7 14.6 Propylene 18-1 13-3 8 · 2 8.9 Butene 4.5 2.5 1 · 0 1 · 5 Ce 8 Aromatic hydrocarbons 2 7.4 3 2.7 4 2.9 4 5.0 ce + hydrocarbons 1.0 1 3 5.8 5.5 Ce β Aromatic hydrocarbons 2 7.9 3 3-2 4 3-8 4 5-9 C2M olefins 4 4.9 3 9.3 2 5-9 2 5.0 (Please read the precautions on the back before filling out this page) Order 丨. This paper size is applicable China National Standards (CNS) A4 Specification (210X297mm) -34-S05876 A7 A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of invention (32) Table 6 Example 15 ratio Example 9 Comparative Example 1 0 Catalyst AgNaZSM-5 HZSM-5 AgHZSM-5 Steaming condition temperature (. 750 750 750 water vapor partial pressure (atmospheric pressure) 0.4 0.4 0.4 treatment time (min) 120 40 120 reaction conditions before treatment Post-treatment pre-treatment post-treatment pre-treatment after catalyst amount (g) 2.0 2.0 2.0 4.0 2.0 2.0 Warm offer. C) 685 677 682 672 683 692 Contact time (seconds) 0. 24 0. 24 0. 24 0.49 0. 24 0.24 η-pentane conversion rate (%) 97.5 95.5 98.6 81.2 96.0 91.9 Reaction rate constant * (seconds) 14.6 13.2 17.6 3.7 13.2 9.1 (relative value) (100) (90) (100) (21) (100) (69) * 6 8 CTC temperature correction value (activation energy: 2 2 kca 1 / m ο 1) (please read the precautions on the back before filling in this page) Order 丨 · The paper size is applicable to Chinese National Standard (CNS) A4 Specifications (210X297 mm) 35 V. Description of invention (33) A7 B7 Printed by the Consumer Standardization Bureau of the Ministry of Economic Affairs Central Standards Table 7 Example 1 6 Comparative Example 1 1 Catalyst A g N a type H type acid amount (mm 〇j? / G) 0. 002 0. 096 cycle number 1 264 7 238 hydrocarbon raw material naphtha naphtha naphtha naphtha Naphtha reaction temperature (° c) 679 685 674 687 Yield (wt%) Hydrogen 1.3 1.5 1.3 1. 2 Methane 9. 4 9. 8 10. 1 9. 3 Ethylene 21. 6 21.4 20. 7 19.4 Propylene 18 . 3 18. 5 16. 2 20. 3 Butene 4. 8 4. 9 4. 3 6. 4 Ce_8 aromatic hydrocarbons 26. 7 29. 3 28. 8 24. 5 C 9+ hydrocarbons 2. 3 1. 9 2. 2 1.5 C 2-4 Xi Yan + c6_9 aromatic hydrocarbons 66. 6 69. 2 65. 7 64. 2 C5-8PN0 conversion rate (%) 94.9 9 95. 9 94. 9 91. 0 Response rate constant $ 12. 4 12. 5 13. 2 9. 2 (sec-1) (relative value) (100) (100) (100) (70) (Please read the notes on the back before filling this page )

X * 6 8 0°C溫度修正值（活化能量：2 2 k c a 1 /m ο 1 ) C 5 —8 PNO C 5_8 的、烷烴、環烷、烯烴_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -36 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（34 ) 第8表實施例1 7 沸石 A g N a型Z SM— 5/S i 02 酸量（mm 〇 i? / g ) 0 . 0 0 5 烴類原料石腦油反應溫度（°C) 6 7 5 觸媒填充量（g) 2.5 收率（重量％) 氫 0 8 甲烷 8 6 乙烯 2 2 6 丙烯 18 2 丁烯 5 2 C 6-8芳香族烴類 2 3 5 c9+烴類 2 9 c6_9芳香族烴類 2 5-1 C 2 —4晞烴 4 6 · 0 (請先閱讀背面之注意事項再填寫本頁)X * 6 8 0 ° C temperature correction value (activation energy: 2 2 kca 1 / m ο 1) C 5 —8 PNO C 5_8, alkanes, naphthenes, alkenes _ This paper scale is applicable to China National Standard (CNS) A4 Specifications (210X297 mm) -36-A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (34) Table 8 Example 1 7 Zeolite A g N a type Z SM— 5 / S i 02 acid Amount (mm 〇i? / G) 0. 0 0 5 Hydrocarbon feedstock naphtha reaction temperature (° C) 6 7 5 Catalyst loading (g) 2.5 Yield (wt%) Hydrogen 0 8 Methane 8 6 Ethylene 2 2 6 Propylene 18 2 Butene 5 2 C 6-8 Aromatic Hydrocarbons 2 3 5 c9 + Hydrocarbons 2 9 c6_9 Aromatic Hydrocarbons 2 5-1 C 2 —4 Hydrocarbon 4 6 0 (Please read the back first (Notes to fill out this page)

、1T 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -37 - A7 經濟部中央標準局員工消費合作社印製 305876 B7 五、發明説明（35 ) 第9表實施例1 8 比較例1 2 酸量（m m 〇 j? / g ) 0 . 0 0 5 0.2^ 1 反應時間（h r .) 4 4 0 4 4 1 反應溫度（°C ) 517 517 517 517 反應壓力（kg/cm2G) 5. 0 5. 0 5. 0 5. 0 WHSV(hr_l) 2.81 2.81 2.81 2. 81 收率（重量％) 氫 1. 7 1.5 1.3 1.4 非芳香族烴類 45.4 46. 2 53. 6 54. 7 C β_8芳香族烴類 46.9 43.8 38. 5 37. 9 c9+芳香族烴類 6.0 6.9 6. 6 6. 0 芳香族烴類產率 52. 9 50. 7 45. 1 44. 0 (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標準（CNS ) A4规格（210X297公釐） -38 - 經濟部中央標準局員工消費合作社印製 S05876 A7 B7 五、發明説明（36 ) 第1 0表實施例1 9 比較例1 3 酸量（m m 〇 j? / g ) 0. 005 0. 24 烘蒸處理時間（hr) 5 10 5 10 反應溫度（°C ) 528 528 531 530 η-戊烷轉化率（％) 82. 2 77. 7 57. 2 41.4 收率（重量％) C β_β芳香族烴類 33. 8 30. 9 17. 0 11. 1 反應速度常數$ (秒—Μ(相對值） 0.86 (100) 0. 77 (90) 0.40 (100) 0. 24 (60 * 530°C溫度修正值（活化能量：22kcal/mol) (請先閱讀背面之注意事項再填寫本頁)、 1T The size of this paper is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) -37-A7 Printed by employee consumer cooperative of Central Bureau of Standards of Ministry of Economic Affairs 305876 B7 5. Description of invention (35) Table 9 Example 1 8 Comparison Example 1 2 Acidity (mm 〇j? / G) 0. 0 0 5 0.2 ^ 1 Reaction time (hr.) 4 4 0 4 4 1 Reaction temperature (° C) 517 517 517 517 Reaction pressure (kg / cm2G) 5. 0 5. 0 5. 0 5. 0 WHSV (hr_l) 2.81 2.81 2.81 2. 81 Yield (wt%) Hydrogen 1. 7 1.5 1.3 1.4 Non-aromatic hydrocarbons 45.4 46. 2 53. 6 54. 7 C β_8 aromatic hydrocarbons 46.9 43.8 38. 5 37. 9 c9 + aromatic hydrocarbons 6.0 6.9 6. 6 6. 0 aromatic hydrocarbon yield 52. 9 50. 7 45. 1 44. 0 (please read the back first Please pay attention to this page and then fill out this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -38-Printed by S05876 A7 B7, Employee Cooperative of Central Bureau of Standards, Ministry of Economic Affairs V. Description of Invention (36) Article 1 0 Table Example 1 9 Comparative Example 1 3 Acid amount (mm 〇j? / G) 0. 005 0. 24 Steaming treatment time (hr) 5 10 5 10 Reaction temperature (° C) 528 528 531 53 0 η-pentane conversion rate (%) 82. 2 77. 7 57. 2 41.4 yield (% by weight) C β_β aromatic hydrocarbons 33.8 8 30. 9 17. 0 11. 1 Reaction rate constant $ (second —Μ (relative value) 0.86 (100) 0. 77 (90) 0.40 (100) 0. 24 (60 * 530 ° C temperature correction value (activation energy: 22kcal / mol) (please read the notes on the back before filling in (This page)

、1T 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） -39 - S0S876、 1T The size of this paper is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) -39-S0S876

1/ At B 五、發明説明（經濟部中央樣準局員工消費合作社印製第1 1表實施例20 比較例14 實施例2 1 沸石 AgNa型 ZSM-5 熱分解 AgNa型ZSM-11 酸量（mnio 1 /g) 0. 002 - 0. 01 烴原料減壓輕油減壓輕油石油腦反應溫度（°C ) 685 796 680 收率（重量％ ) 氫 0.8 0. 5 1.4 甲烷 5. 3 11.0 8.9 乙烷 19. 9 25. 0 17.4 丙烷 17. 3 11.1 18.8 丁烷 3.4 1.3 5.7 C 5_8芳香族烴 13.2 3.6 24. 2 C 5-9芳香族烴 14. 3 4. 5 25.5 C 2-4烯烴 40. 6 37. 4 41. 9 ---------^------iTk——一---Μ. (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標準（CNS ) A4规格（210X297公釐） 1.1 / At B V. Description of the invention (printed by the Central Sample Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperative, No. 1 1 Table Example 20 Comparative Example 14 Example 2 1 Zeolite AgNa ZSM-5 Thermal decomposition AgNa ZSM-11 Acid content ( mnio 1 / g) 0. 002-0. 01 Hydrocarbon feedstock vacuum light oil vacuum light oil naphtha reaction temperature (° C) 685 796 680 yield (wt%) hydrogen 0.8 0. 5 1.4 methane 5. 3 11.0 8.9 Ethane 19.9 25.0 17.4 Propane 17.3 11.1 18.8 Butane 3.4 1.3 5.7 C 5_8 aromatic hydrocarbon 13.2 3.6 24.2 C 5-9 aromatic hydrocarbon 14. 3 4. 5 25.5 C 2-4 olefin 40. 6 37. 4 41. 9 --------- ^ ------ iTk—— 一 --- Μ. (Please read the precautions on the back before filling out this page) This paper size Applicable to China National Standard (CNS) A4 specification (210X297mm) 1.

r I 申請曰期 84年10月17日案號 84110909 類別 ci〇^^/〇,· (以上各糊由本局填柱）公告本r I Date of application October 17, 84 Case No. 84110909 Category ci〇 ^^ / 〇, (The above pastes are filled in by the Bureau) Announcement

補充 Α-Γ C4Supplement Α-Γ C4

30537G 305876 备—專利説明書經濟部中央標準局貝工消费合作社印 % 發明 =名稱中文轉化烴類之触媒及使用其接触轉化之方法英文 A catalyst to convort hydrocarbons and a catalytic conversion method using it 姓名 ⑴角田隆 (2)閎口光弘 (3 金島節陲國籍 ⑴日本（25日本（3) 日本二、發明人創作 ⑴曰本國岡山縣會敷市西鑫并一〇八六一二九住、居所 (2) 日本國岡山縣倉敷市堀南九八0_三 (3) 日本國岡山縣會敷市冲新町三七_四姓名 (名稱）國籍 (1)旭化成工業股份有限公司旭化成工業株式会社 (1)日本 (1)日本國大阪府大阪市北匾堂島浜一丁目二番六三、申請人住、居所 (事務所）代表人號姓名 (1)弓會礼一本紙張尺度逋用中國國家標準（CNS)八4规格（2丨OX297公釐} 裝訂線30537G 305876 Preparation—Patent Specification Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Invention = Name Chinese name: catalyst for convort hydrocarbons and a catalytic conversion method using it Long (2) Hongkou Guanghong (3 Golden Island Festival Nationality ⑴ Japan (25 Japan (3) Japan II, inventor creation ⑴ Japanese hometown, Xixin, Okiyama, Okayama Prefecture, 10, 229, residence and residence ( 2) Nine Eight, Horie, Kurashiki City, Okayama Prefecture, Japan 0_three (3) Sanqi_4, Okshincho, Hokkaido City, Okayama Prefecture, Japan Japan (1) Japan, Osaka City, Osaka City, Beibantang Island, Hama-chome, two and three, three, applicant's residence, residence (office) Representative number name (1) Bow meeting ceremony a paper standard using the Chinese National Standard (CNS ) Eight 4 specifications (2 丨 OX297mm) binding line

Claims

修羹補充經濟部中央棵準局員工消費合作社印笨六、申請專利範圍 - 1 . 一種轉化烴類之觸媒，其係由s i 〇2/ A^20 3莫耳比2 0〜5 0 0，且含有1種或2種以上靥於週期表’第I b族之金屬，實質上不含質子之z SM -5類沸石所組成’該轉化烴類之烴爲碳數2〜2 5者。 2 ·如申請專利範圍第1項之觸媒，中細孔徑沸石爲金屬離子型及/土金靥離子型。 3.如申請專利範圍第1項之觸媒，其靥於周期表第 I b族之金靥爲銀。 4 .如申請專利範圍第2項之觸媒，其靥於周期表第 Ib族之金屬爲銀。 5 .如申請專利範圍第1項之觸媒，其中，沸石爲 Z S Μ — 5。 6 .如申請專利範圍第2項之觸媒，其中，沸石爲 Z S Μ - 5。 7 .如申請專利範圍第3項之觸媒，其中，沸石爲 Z S Μ - 5。 8 .如申請專利範圍第4項之觸媒，其中，沸石爲 Z S Μ - 5。 9 . 一種低級烯烴及單環芳香族烴類之製造方法，其係將申請專利範圍第1〜8項中任一項之觸媒，與碳數2 〜2 5之烴類之原料於5 5 0〜7 5 0 °C間接觸。 1 0 .如申請專利範圍第1〜8項中任一項之觸媒，其至少含有一個由周期表第I I b族、I I I b族及 VI I I族所屬金饜及其化合物組成群中所選出之物質。 I _-i.-----一— 裝------訂^------、* I (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规格（210 X 297公釐） 305876 修正木济年"+ A8 B8 蝻充丨 C8 D8 1 1 . 一種芳香族烴類之製造方法，其係將申請專利六、申請專利範圍範圍第1 0項所述之觸媒與含有1種或2種以上烴類之原媒 1 觸 . 之 ο 項爲一量任有中含項屬。8 金觸-之接 1 族度第 b 溫圍 I 下範第以利靥 P 專’ ο 請言 5 申而 6 如石。相.沸% 氣 2 對量於 1 ，重 , 中 ο 料其 1 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製本紙張尺度適用中國國家搞準（CNS ) A4規格（210X297公釐）-ZXiujian supplemented the Ministry of Economic Affairs, Central Kezhun Bureau Employee Consumer Cooperative Yinben VI. Patent application scope-1. A catalyst for converting hydrocarbons, which is composed of si 〇2 / A ^ 20 3 molar ratio 2 0 ~ 5 0 0 , And contains 1 or more than 2 metals in Group I b of the periodic table, which is substantially free of protons and composed of z SM -5 type zeolites. The hydrocarbons of the converted hydrocarbons have a carbon number of 2 to 2 5. . 2 · As for the catalyst in item 1 of the patent application, the medium and fine pore size zeolites are of metal ion type and / or alkaloid ion type. 3. If the catalyst applied for in item 1 of the patent scope, the gold in the group Ib of the periodic table is silver. 4. If the catalyst applied for in item 2 of the patent scope, the metal in Group Ib of the periodic table is silver. 5. The catalyst as claimed in item 1 of the patent scope, in which the zeolite is Z S M-5. 6. The catalyst as claimed in item 2 of the patent scope, wherein the zeolite is Z S Μ -5. 7. The catalyst as claimed in item 3 of the patent application, wherein the zeolite is Z S Μ -5. 8. The catalyst as claimed in item 4 of the patent application, in which the zeolite is Z S Μ -5. 9. A method for the production of lower olefins and monocyclic aromatic hydrocarbons, which is based on the application of the catalyst of any one of the items 1 to 8 of the patent scope, and the raw materials of hydrocarbons with a carbon number of 2 to 2 5 in 5 5 Contact between 0 ~ 7 5 0 ° C. 1 0. The catalyst according to any one of the items 1 to 8 of the patent application scope, which contains at least one selected from the group consisting of the Golden Barley and its compounds belonging to Groups II b, III b and VI II of the periodic table Substance. I _-i .----- 一 — 装 ------ 定 ^ ------ 、 * I (please read the precautions on the back and then fill out this page) ”This paper size is applicable to Chinese countries Standard (CNS) A4 specification (210 X 297 mm) 305876 Amendment Muji Year " + A8 B8 蝻充丨 C8 D8 1 1. A method of manufacturing aromatic hydrocarbons, which will apply for a patent The catalyst described in item 10 of the scope range is in contact with the original medium containing one or more than two hydrocarbons. Item ο is a quantity with any contained items. 8 Golden Touch-Connect 1 b Wenwei I Xianfandi Yili P Pian 'ο Please say 5 and 6 like stone. Phase. Boiling% gas 2 Contrast to 1, heavy, medium ο expected 1 (please read the precautions on the back first (Fill in this page) The paper standard printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is applicable to the Chinese National Accreditation (CNS) A4 specification (210X297mm) -Z