572897 A7 ____ 五、發明說明（1 ) [發明背景] 本發明係有關一種藉由在觸媒存在下，於氣相中使脂 族藤、脂族酮或其混合物與氨反應之製造D比咬驗之方法。 藉由在觸媒存在下於氣相中使脂捧路、準族酮或其混 合物與氨反應製造吡啶鹼之方法為已知。已報導各種方 法’例如’使用非晶形氧化矽-氧化鋁作為觸媒之方法，使 用沸石如銘矽酸鹽等之方法，以及其他方法。觸媒中，沸 石適合作為在高溫條件下進行氣相反應製造吡啶鹼的觸 媒，此乃由於其優異耐熱性之故。 可使用作為製造卩比唆驗之觸媒的彿石，除了銘梦酸鹽 外’已知有例如雜矽酸鹽如鐵矽酸鹽、硼矽酸鹽及旋石夕酸 鹽。該等沸石係單獨使用作為觸媒。或者，這些沸石可含 有各種元素的離子及/或化合物，如銅、辞、鑛、紐、路、 鉬、鎢、鈷、鎳、釕、铑、鈀、銥等，以獲致欲使用之觸 哦咬驗的製造中，已知主成分，吡啶鹼，係由原料， 脂族醛及脂族酮的組合決定之，其典型實例示於表〖 II--I--II--I -裝 ------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產咼員Η消費^咋吐巾挺 適 度 尺 張 紙 本 準 標 家 釐 公 97 58: 572897 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（2 ) 表1 原料（脂族醛、脂族酮） 主產物（哦啶鹼） 乙醛 α -甲基吡啶 + r -甲基吡啶 乙醛+甲醛 吡啶+点-甲基吡啶 丙烯醛 ys -甲基吡啶 丙稀駿+乙搭 吡啶 丙稀搭+丙媒 召-甲基啦咬 丙醛+甲醛 3,5-二甲基吡啶 丁烯醛+丙醛 3,4-二甲基吡啶 丁烯醛+丙酮 2,4-二甲基吡啶 甲路+丙嗣 2,6-二甲基吡啶 丙_ 2,4,6-二甲基吡啶 甲基丙烯醛+甲基乙基酮 3,5-二甲基吡啶 + 2,3,5-三甲基吡啶 如上所述，藉由在作為觸媒的沸石存在下於氣相中使 脂族路、脂族酮或其混合物與氨反應可製得各種吡啶鹼。 然而，由傳統方法製得之吡啶鹼的產率依然低。 例如，由本發明人所進行，係依據上述傳統方法，亦 即’使用鋁矽酸鹽、鐵矽酸鹽等作為觸媒，使乙醛與氨反 應以製造α -甲基吡啶及r -甲基吡啶之下述比較例中，使 用銘矽酸鹽時，甲基吡啶及7-甲基吡啶的產率分別為 17.60/〇及18.50/〇，使用鐵矽酸鹽時，分別為18.6%及17.50/〇, 以及使用鎵矽酸鹽時，分別為17 3〇/0及H3%。 因此，利用傳統方法之所欲吡啶鹼產率尚未令人滿 意，故希望在產率上有進一步的改良。 本發明人深入研究以發現一種可以較高產率製造吡啶 ------ ----— II - I I----I ^» — — — — — 1 — ΙΜ (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規格（210 X 297公爱） 2 311582 經濟部智慧財產局員工消費合作社印製 572897 A7 ______ B7 五、發明說明（3 ) 鹼的方法。結果，本發明人發現當在含有鈦及/或鈷及矽作 為沸石構成元素（其中矽對鈦及/或鈷的原子比為約5至約 1，000)的沸石存在下，於氣相中使脂族醛、脂族酮或其混 合物與氨反應製造吡啶鹼時，能以比使用沸石如鋁矽酸 鹽、鐵矽酸鹽等作為觸媒的傳統方法獲得更高的產率。因 此完成本發明。 [發明概述] 本發明提供一種製造吡啶鹼之方法，包括在含有鈦及/ 或鈷及矽作為沸石構成元素（其中矽對鈦及/或鈷的原子比 為約5至約1，〇〇〇)的沸石存在下，於氣相中使脂族醛、脂 族酮或其混合物與氨反應。 [較佳具體實例的說明] 本發明吡啶絵:之製法係藉由使用對應於所欲吡啶鹼之 脂族醛、脂族酮或其混合物，使其在上述特定沸石的存在 下於氣相中與氨反應而進行之。 月曰族酸較佳為具有1至5個竣原子之脂族酸。其實例 包含飽和脂族醛如甲醛、乙醛、丙醛、丁醛等，及不飽和 脂族醛如丙烯醛、甲基丙烯醛、丁烯醛等。脂族酮較佳為 具有3至5個碳原子之脂族酮，其實例包含丙酮、甲基乙 基嗣、二乙基酮等。產生脂族路或脂族酮之二聚物、二聚 物、其他寡聚物及聚合物亦可使用作為原料。原料（亦即脂 族醛與脂族酮的組合）與主產物（亦即吡啶驗）間之關係示 例於上表1。 如上所述’本發明反應中使用含有鈦及/或鈷及矽作為 ------------裝-------訂---------線 (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規格（210 X 297公釐） 3 311582 572897572897 A7 ____ V. Description of the invention (1) [Background of the invention] The present invention relates to a method for producing D ratio bite by reacting aliphatic rattan, aliphatic ketone or mixture thereof with ammonia in the gas phase in the presence of a catalyst. Experience. A method for producing a pyridine base by reacting a lipid group, a quasi-ketone or a mixture thereof with ammonia in the gas phase in the presence of a catalyst is known. Various methods have been reported, such as a method using an amorphous silica-alumina as a catalyst, a method using a zeolite such as aluminosilicate, and others. Among the catalysts, zeolite is suitable as a catalyst for producing a pyridine base by carrying out a gas phase reaction under high temperature conditions, because of its excellent heat resistance. As a catalyst for the production of tritium, Buddhist stones can be used. In addition to mingmeng salt, for example, heterosilicates such as iron silicate, borosilicate, and rotolinate are known. These zeolites are used alone as a catalyst. Alternatively, these zeolites can contain ions and / or compounds of various elements, such as copper, iron, ore, neutron, road, molybdenum, tungsten, cobalt, nickel, ruthenium, rhodium, palladium, iridium, etc., to obtain the desired touch. In the manufacture of the bite test, the main component, pyridine base, is known to be determined by the combination of raw materials, aliphatic aldehydes and aliphatic ketones, and typical examples are shown in Table 〖II--I--II--I-装- ----- Order --------- line (please read the notes on the back before filling out this page) Intellectual Property of the Ministry of Economic Affairs, Staff, Consumption, ^, Spit towel, Moderate paper, Prospective bidder Centimeter 97 58: 572897 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (2) Table 1 Raw materials (aliphatic aldehydes, aliphatic ketones) Main product (Ohidine base) Acetaldehyde α-methyl Pyridine + r-methylpyridine acetaldehyde + formaldehyde pyridine + dot-methylpyridine acrolein ys-methylpyridine propionate + acetaminopyridine propionate + propionate-methylparaben + formaldehyde 3, 5-dimethylpyridinal + propionaldehyde 3,4-dimethylpyridinal + acetone 2,4-dimethylpyridine methyl chloride + propanyl 2,6-dimethylpyridinepropan-2 4,6-two Pyridylmethacryl + methyl ethyl ketone 3,5-dimethylpyridine + 2,3,5-trimethylpyridine is prepared in the gas phase in the presence of zeolite as a catalyst as described above. A variety of pyridine bases can be prepared by reacting aliphatic pathways, aliphatic ketones, or mixtures thereof with ammonia. However, the yield of pyridine bases produced by conventional methods is still low. For example, it was performed by the present inventors according to the above-mentioned traditional method, that is, 'using aluminosilicate, ferrosilicate, etc. as a catalyst, reacting acetaldehyde with ammonia to produce α-methylpyridine and r-methyl In the following comparative examples of pyridine, the yields of methylpyridine and 7-methylpyridine are 17.60 / 〇 and 18.50 / 〇 when using aluminosilicate, and 18.6% and 17.50 when using iron silicate, respectively. / 〇, and when using gallium silicate, 17 3 0/0 and H3%. Therefore, the desired yield of pyridine base using the conventional method has not been satisfactory, and further improvement in the yield is desired. The inventors have conducted intensive research to find a pyridine that can be produced at a higher yield ------ ------ II-I I ---- I ^ »— — — — — 1 — ΙΜ (Please read the Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love). 2 311582 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 572897 A7 ______ B7. Methods. As a result, the present inventors have found that in the presence of zeolite containing titanium and / or cobalt and silicon as zeolite constituent elements (wherein the atomic ratio of silicon to titanium and / or cobalt is about 5 to about 1,000) in the gas phase When producing a pyridine base by reacting an aliphatic aldehyde, an aliphatic ketone, or a mixture thereof with ammonia, a higher yield can be obtained than a conventional method using a zeolite such as aluminosilicate, iron silicate, etc. as a catalyst. Thus, the present invention has been completed. [Summary of the Invention] The present invention provides a method for manufacturing a pyridine base, which comprises titanium and / or cobalt and silicon as zeolite constituent elements (wherein the atomic ratio of silicon to titanium and / or cobalt is about 5 to about 1,000). In the presence of zeolite), an aliphatic aldehyde, an aliphatic ketone or a mixture thereof is reacted with ammonia in the gas phase. [Explanation of a preferred specific example] The method for preparing pyridine of the present invention is to use an aliphatic aldehyde, an aliphatic ketone or a mixture thereof corresponding to a desired pyridine base in the gas phase in the presence of the above-mentioned specific zeolite. It is carried out by reacting with ammonia. The Yue acid is preferably an aliphatic acid having 1 to 5 atoms. Examples thereof include saturated aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and the like, and unsaturated aliphatic aldehydes such as acrolein, methacryl, butenal, and the like. The aliphatic ketone is preferably an aliphatic ketone having 3 to 5 carbon atoms, and examples thereof include acetone, methyl ethyl fluorene, diethyl ketone and the like. Dimers, dimers, other oligomers and polymers which produce aliphatic or aliphatic ketones can also be used as raw materials. The relationship between the raw materials (ie, the combination of aliphatic aldehydes and aliphatic ketones) and the main product (ie, pyridine test) is shown in Table 1 above. As described above, 'In the reaction of the present invention, titanium and / or cobalt and silicon are used as the ------------ equipment ------- order --------- wire ( Please read the notes on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 3 311582 572897
五、發明說明（4 ) • ^ ί 裝--- (請先閱讀背面之注意事項再填寫本頁) 沸石構成元素（其申矽對鈦及/或鈷的原子比為約5至約 1，000及約束指數為約〇 8至約12)的沸石作為觸媒。後文， 使用作為本發明觸媒的上述沸石稱為鈦及/或鈷矽酸鹽沸 石。鈦及/或鈷矽酸鹽沸石的實例包含含有鈦及矽作為沸石 構成元素之鈦矽酸鹽；含有鈷及矽作為沸石構成元素之鈷 矽酸鹽，以及含有鈦、鈷及矽作為沸石構成元素之沸石。 可使用其中之一種或多種作為本發明反應中之觸媒。使用 於本發明中之鈦及/或鈷矽酸鹽沸石中之矽對鈦及/或鈷的 原子比較佳為約10至約500。 使用於本發明之觸媒可藉由習知方法製備。能輕易地 獲得矽對鈦及/或鈷的原子比，晶體結構等彼此不同的各種 鈦及/或鈷矽酸鹽沸石。例如，可以日本專利申請案公開 (JP-A)第 63-54358、60-12135、56-96720 及 55-7598 號; 乍用期刊，130’440 (1991)，_^^催化作用八:一般， 126，51 (1995);速^，17 (4) ’ 354 (1996)等所述之相同 方式予以製備。 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 使用於本發明觸媒的晶體結構並無特別限制，但較佳 為具有五矽（pentasil)型晶體結構者。其中，更佳為具有 MFI型或MEL型晶體結構者。 本發明中，鈦及/或鈷矽酸鹽沸石可就此使用，但較好 使敛及/或銘石夕酸鹽彿石進一步含有選自I至xvii族元素 之一種或多種元素的離子及/或化合物，此乃因使用其時， 吡啶鹼的產率增加。 I至XVII族元素為元素週期表第族型元素，其特V. Description of the invention (4) • ^ Packing-(Please read the notes on the back before filling this page) Zeolite constituent elements (the atomic ratio of silicon to titanium and / or cobalt is about 5 to about 1, Zeolite with a restriction index of about 0,000 to about 12). Hereinafter, the zeolite used as the catalyst of the present invention is referred to as titanium and / or cobalt silicate zeolite. Examples of titanium and / or cobalt silicate zeolites include titanium silicate containing titanium and silicon as zeolite constituent elements; cobalt silicate containing cobalt and silicon as zeolite constituent elements, and titanium, cobalt and silicon as zeolite constituents Elemental zeolite. One or more of them can be used as a catalyst in the reaction of the present invention. The silicon to titanium and / or cobalt atom used in the titanium and / or cobalt silicate zeolite used in the present invention is preferably about 10 to about 500. The catalyst used in the present invention can be prepared by a conventional method. Various titanium and / or cobalt silicate zeolites having different atomic ratios, crystal structures, and the like of silicon to titanium and / or cobalt can be easily obtained. For example, Japanese Patent Application Laid-Open (JP-A) Nos. 63-54358, 60-12135, 56-96720, and 55-7598; Journal of the First Use, 130'440 (1991), _ ^^ Catalysis 8: General , 126, 51 (1995); Su ^, 17 (4) '354 (1996) and other methods were prepared in the same manner. The crystal structure of the catalyst used in the present invention is not limited to the one printed by the Consumer Affairs Agency of the Intellectual Property Office of the Ministry of Economic Affairs, but it is preferably one having a pentasil type crystal structure. Among them, those having a MFI-type or MEL-type crystal structure are more preferred. In the present invention, titanium and / or cobalt silicate zeolite may be used for this purpose, but it is preferred that the agglomerate and / or the aragonite buddite further contain an ion of one or more elements selected from the elements of the group I to xvii and / Or compounds, because when it is used, the yield of pyridine base is increased. The elements of groups I to XVII are elements of group type of the periodic table,
572897 A7 五、發明說明（5 y 定實例包含I族元素如Li、K、Rb及Cs，II族元素如Mg、 Ca、Cr及Ba，III族元素如Sc、Y及鑭系元素、La、Ce、 Pr、Nd、Er及Yb ’ IV族元素如Ti、Zr及Hf、γ族元素 如V、Nb及Ta，VI族元素如Cr、Mo及W，VII族元素如 Mn、Tc及Re ’ VIII族元素如pe、ru及〇s，jx族元素如 Co、Rh及Ir，X族元素如Ni、pd及pt , χι族元素如 及Ag，XII族元素如Zn及Cd , XIII族元素如a/、Ca、In 及T/，XIV族元素如Ge、Sn及Pb’XV族元素如Sb及Bi， XVI族元素如p〇，及X Vn族元素如ρ及c/。其中，較佳 為Τ/及Pb。 至於I至XVII族元素的離子及/或化合物，其離子可 例不如其氧化物、鹵化物、硫酸鹽、磷酸鹽、硝酸鹽、氫 氧化物、硫化物、矽酸鹽、鈦酸鹽、硼酸鹽及碳酸鹽。鈦 及/或鈷矽酸鹽沸石中可含有一種或多種此等離子及/或化 合物。使鈦及/或鈷矽酸鹽沸石含有這些離子及/或化合物 之方法實例包含離子交換法、混鍊法、浸滲法、浸潰法、 沈積法、蒸發乾燥法等，但方法並不限於這些實例。其特 定實例說明如下。 ①雜子交換法實你丨 使上述元素之水可溶鹽，如氣化物、硝酸鹽、醋酸鹽 等以0.01至2g離子/升的濃度溶於水。 然後：添加驗離子態、銨離子（NH4+)態或質子態鈦 及/或姑梦酸鹽沸石，較佳為ΝΗ4+態鈦及/或鈷矽酸鹽沸石 至上述得到之水溶液中，於既定溫度攪拌，然後過濾，重 尽紙诋尺度過用中國國家標準（CNS)A4規格（21〇 X 297公釐） 311582 -------------裝i I C請先Μ讀背面之注意事項再填寫本頁) 訂- --線· 572897 A7 Β7 五、發明說明（6 ) 複此程序。 之後’以水沖洗最終所得之過濾殘留物。乾燥由此獲 得之含有上述7〇素離子的鈦及/或鈷矽酸鹽沸石，若需要則 予以锻燒。 (2)混鋏法實例 混鍊上述元素的化合物與H+或NH/態鈦及/或鈷矽酸 鹽沸石，若需要，與水一起混鍊。然後，乾燥混鍊產物， 若需要則予以锻燒。 ③ 浸潰法實例 使上述元素的水可溶鹽溶於水。 然後’使NH4+態或h+態鈦及/或鈷矽酸鹽沸石，較佳 為NH/態鈦及/或鈷矽酸鹽沸石浸潰於此溶液中。之後， 乾燥浸潰的沸石，及若需要則予以煅燒。 ④ 沈積法膏你丨 使NH/態或H+態鈦及/或鈷矽酸鹽沸石分散於上述元 素之水可溶鹽的水溶液中。 添加氨水溶液至此混合物中以使上述元素的氫氧化物 沈積在NH/態或H+態鈦及/或鈷矽酸鹽沸石表面上，然後 過濾。 之後’以水沖洗過濾的殘留物再乾燥，及若需要則予 以煅燒。 ⑤ 蒸發乾燥法實你丨 於水中攪拌上述元素的化合物與NH4+態或H+態鈦及/ 或鈷矽酸鹽沸石以使之混合。 ---------------裝--- (請先閲讀背面之注意事項再填寫本頁) 訂· -•鲜- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 6 311582 572897 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（7 ) 之後，進行蒸發乾燥，然後，若需要則進行锻燒。 於上述任一方法中，通常係在空氣、氮氣及/或二氧化 碳的氣氛下於350至800°C進行锻燒數小時。然而，由於 觸媒在氣相接觸媒反應期間於反應器中加熱，故觸媒未必 需要煅燒。 選自I至XVII族元素之一種或多種元素之離子及/或 化合物之含量較佳範圍視鈦及/或鈷矽酸鹽沸石的種類或 含於其中之元素種類或形式而變。通常，較佳範圍係每lg 含有鈦及/或鈷和矽作為沸石構成元素的沸石，含〇 〇〇〇5 至10毫克當量，更佳為0.01至5毫克當量。 使用於本發明之鈦及/或鈷矽酸鹽沸石可就此使用或 添加黏合劑如二氧化矽、矽藻土、高嶺土、膨潤土、氧化 鋁、氧化矽-氧化鋁等，及水，聚乙烯醇以及醋酸乙烯酯後， 藉由壓片機或擠壓機模製成所需形狀如實心圓柱體、中空 圓柱體等。使用此模製物作為固定床觸媒。 或者，使鈦及/或鈷矽酸鹽沸石與黏合劑如氧化矽、矽 藻土、高嶺土、膨潤土、氧化鋁、氧化矽-氧化鋁等，及水 混合以得到隸，然後喷霧乾燥此漿、液以形成球形微球 珠，其係使用作為流化床觸媒。為了製造含有選自〗至 族元素之一種或多種元素之離子及/或化合物的鈦及/或鈷 石夕酸鹽沸石，可使上述已模製成所需形狀的鈦及/或始石夕酸 鹽滞石藉由上述之離子交換法、浸渗法、浸潰法等而含有 離子及/或化合物。上述任一方法中，可在空氣、氮氣、二 氧化碳等氣氛下於350至800t煅燒所獲得之觸媒數小時 ‘紙張尺度適用中國國家標準（CNS)A4規格（21Q x 297公爱）- 1 311582 --------------裝—— (請先閱讀背面之注意事項再填寫本頁) -線· 572897 A7 B7 五、發明說明（8 ) 以賦與模製物強度並移除含於黏合劑等中之揮發性成分， 但由於在氣相接觸反應期間觸媒於反應器中加熱，因而觸 媒未必需要煅燒。 本發明之吡啶鹼的製造能於固定床反應器、流化床反 應器或移動床反應器中進行。 使用固定床反應器之本發明方法的實例將說明如下。 將本發明之觸媒填充在反應管令。將脂族醛及/或脂族 酿I和氨的混合氣體導入此反應管中，再施加氣相反應。脂 族酸及/或知族_和氨的混合氣體亦可與水、惰性氣體如氮 氣及/或甲醇一起饋入。 脂族链及/或脂族酮的組合和脂族醛及/或脂族明對氨 的適合使用比率視所欲之吡啶鹼而變。例如，為了製造哦 咬及石-甲基吡啶作為主成分，使用乙醛及甲醛作為脂族醛 及/或脂族酮的組合，且乙醛··甲醛··氨的莫耳比較佳為i ·· 0.3-3 : 0·5_5。於此情形令，當額外使用甲醇時，較佳係每 1 mol乙酿，甲醇的用量為〇 5 mol或更少。甲搭可使福馬 林（甲醛水）形式。為了製造α -甲基吡啶及曱基吡啶作為 主成分，使用乙醛作為脂族醛及/或脂族酮的組合，且乙 搭·氣的莫耳比較佳為1 : 0.8-3。當乙趁與氨依據本發明 方法反應時，可改良α -甲基吡啶的選擇性。 使脂族醛、脂族酮及氨及若需要之水、惰性氣體如氮 氣及/或甲醇的混合氣體以100至10,000 hr·1，較佳為3〇〇 至3,000 hr·1的空間速度（sv)通過觸媒。反應溫度為3〇〇 至7〇〇°C，較佳為350至600°C。反應壓力可為低於大氣壓 (請先閲讀背面之注意事項再填寫本頁) 裝 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） 8 311582 572897 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 印 製 A7 B7 五、發明說明（9 ) 至數大氣壓，但反應壓力通常較佳為大氣壓至2大氣壓。 如上述般進行反應後，可冷凝流出反應管之含於反應 氣體中之吡啶鹼。或者，藉由使溶劑與含有吡啶鹼之反應 氣體接觸而使其溶於適合溶劑中。所得之冷凝物或溶液可 蒸餾回收吡啶。 當觸媒在長期反應期間劣化時，可依據傳統觸媒再生 法予以再生。亦即，使空氣於不超過觸媒之耐熱溫度的高 溫，較佳為350至800°C之溫度通過觸媒層，以燃燒沈積 在觸媒上的碳。若需要，空氣可藉水蒸氣、氮氣、二氧化 碳等予以稀釋。 [實施例] 下列實施例更明確地進一步說明本發明，但不偈限本 發明的範圍。 觸媒Μ備例1 依據iikiLSJOL，130，440 (1991)所述之方法如下 合成鈦矽酸鹽。 將566g氫氧化四正丁基銨（〇 436 m〇1)之2〇重量％曱 醇浴液與455g(2· 18 mol)原矽酸四乙酯的混合物置入備有 攪拌器及滴液漏斗的派勒斯反應容器中。在同時攪拌下將 2,300g鈦酸四丁酯（〇 〇33冚〇1)之〇 5重量％異丙醇溶液自 滴液漏斗滴加至其中，然後持績攪拌約30分鐘。添加79〇g 蒸销水至所得混合物中同時攪拌，使反應持續2小時同時 於75至80 C移除醇類。冷卻所得之反應混合物，再轉移 至南壓蚤中，於170°C保持2天同時挽拌。然後，冷卻高 了―、㈣屮_本標準（CNS)A4規格咖χ 9 311582 - - - - - - - ------^ i — — — — — — ^----! !線 (請先閲讀背面之注意事項再填寫本頁) 572897 A7 ___________ B7 五、發明說明（1G ) 壓釜，過濾内容物以獲得晶體。以離子交換水沖洗所獲得 之晶體，於100°C乾燥8小時，然後在空氣流動中於550 t煅燒16小時。分析所得之煅燒物質，分析結果顯示其係 Si/Ti(原子比）為50之具有MEL型晶體結構之鈦矽酸鹽。 將所得之鈦矽酸鹽添加至1升之5%氣化銨水溶液 中，然後於50至60°C攪拌1小時，接著過濾，以進行離 子交換。依據如上述之相同方式對藉由過濾所獲得之殘留 物進行離子交換三次。以水沖洗最終所得之殘留物直至洗 液中C/·離子的濃度變成1 ppm或更低，然後於not乾燥 16小時以獲得]^114+態鈦矽酸鹽。在空氣中於550。(：進一步 煅燒6小時以獲得H+態鈦矽酸鹽。 觸媒製備例2 依據JP-A-63-543 5 8所述之方法如下合成鈷矽酸鹽。 於高壓釜中混合100g原矽酸四乙酯（0.48 mol)及 217.5g氫氧化四正丙基按（0.96 mol)之10重量％水溶液。 於所得混合物中添加5.7g乙醯基醋酮酸鈷（Πΐ)(〇 β〇ι 6 mol) 與乙二醇的混合溶液同時攪拌，然後持續攪拌約30分鐘。 之後，將所得之混合物加熱至105°C，在相同溫度攪拌120 小時以進行水熱合成。冷卻高壓釜，再過濾内容物以獲得 晶體。以離子交換水沖洗晶體直至洗液的pH達7.3。於1 20 °C乾燥所得之產物16小時，然後在空氣流動中於550°C锻 燒4小時。分析锻燒物質，分析結果顯示其係si/c〇(原子 比）為25之具有MFI型晶體結構之鈷矽酸鹽。 依據與觸媒製備例1相同之方式對所得之始梦酸鹽施 -II I — 1 — — — — — — I — · I I (請先閱讀背面之注意事項再填寫本頁) lrj· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 10 311582 572897 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（11 加離子父換、水沖洗、乾燥及煅燒獲得NH/態鈷矽酸鹽及 H+態鈷矽酸鹽。 觸媒製備例3 依據JP-A_2-209867所述之方法如下合成鋁矽酸鹽。 /¾¾ 433.4g蒸餘水、硫酸銘、558g溴化四正丙 基銨及40g硫酸以得到溶液A。混合32〇g蒸餾水及453g 3 號矽酸鈉以得到溶液B。混合754g蒸餾水及i89g氣化鈉 以得到溶液C。將溶液c置入不銹鋼高壓釜中，再於其中 滴加溶液A及B兩者同時激烈攪拌。控制此混合物使pH 保持於9.5至11的範圍。密封高壓釜再使溫度上升至ι6〇 C，然後持績攪拌以進行水熱合成2()小時。此時，錶壓顯 不0.5至0.6Mpa (5至6 kg/cm2)。反應完成後，混合物冷 部至室溫，過濾高壓釜中的内容物獲得反應產生之晶體。 添加此晶體至蒸餾水令，再攪拌及沖洗，然後過濾。重複 上述沖洗及過濾直至濾液中離子濃度變成！ ppm或更低。 之後’於110 C乾燥晶體16小時，然後在空氣流動中於530 C煅燒4小時。分析鍛燒物質，分析結果顯示其係Si/A/(原 子比）為100之具有MFI型晶體結構之Na+態铭♦酸鹽。 以與觸媒製備例1相同的方式對所得之Na+態鋁矽酸 鹽施加離子交換、水沖洗、乾燥及煅燒，獲得NH/態鋁矽 酸鹽及N+態鋁矽酸鹽。 盤媒製備例4 依據JP-A-2-2 098 67所述之方法如下合成鐵矽酸鹽。 由19g硝酸鐵（111)9水合物、34g氣化四正丙基銨及蒸 ---I--— — — — —--^---I----^--I--I---線 <請先閲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規格（210 X 297公釐） 11 311582 572897 A7 五、發明說明（12 ) 德水所組成之水溶液稱為溶液A。由7〇g發煙二氧化石夕及 蒸餾水所組成之懸浮液稱為溶液m4g氫氧化納及心 蒸傑水所組成之溶液稱為溶液c。將溶液c置入不錄鋼高 壓釜中’再於其十添加溶液AAB兩者同時攪拌混合。密 封高壓爸再使溫度上升至160t ,然後持續搜掉進行水熱 合成60小時。1)11由12·4變成過濾高磨釜中的内容 物以獲得固體。以蒸餾水沖洗此固體直至洗液的{)11達 7.3。分析所得固鱧’分析結果顯示其係3服(原子比）為 25之具有MFI型晶體結構之Na\態鐵矽酸鹽。 以與觸媒製備例1相同的方式對所得之Na+態鐵矽酸 鹽施加離子交換、水沖洗、乾燥及煅燒，獲得nh4+態鐵矽 酸鹽及H+態鐵矽酸鹽。 觸媒製備例5 依據觸媒製備例4相同的方式獲得Na+態鎵矽酸鹽， NH/態鎵矽酸鹽及H+態鎵矽酸鹽，但使用i9g硝酸鎵（111)8 水合物取代觸媒製備例4中所使用之硝酸鐵（ΙΠ)9水合 物。分析Na+態鎵矽酸鹽，分析結果顯示其具有MFI型晶 體結構且Si/Ga(原子比）為25。 實施例1 以39 Mpa之壓力壓縮觸媒製備例1所獲得之H+態鈦 矽酸鹽（H+態Ti/Si)，然後，研磨獲得具有1.0至1.7mm(10 至16網目）之均勻顆粒大小的顆粒。依據下列方式使用這 些顆粒作為觸媒進行吡啶鹼的製造。 將6g上述獲得之觸媒填充在内徑20mm之玻璃反應管 頁 訂 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐 12 311582 經濟部智慧財產局員X消費合昨 572897572897 A7 V. Description of the invention (5y examples include group I elements such as Li, K, Rb and Cs, group II elements such as Mg, Ca, Cr and Ba, and group III elements such as Sc, Y and lanthanides, La, Ce, Pr, Nd, Er and Yb 'group IV elements such as Ti, Zr and Hf, γ group elements such as V, Nb and Ta, group VI elements such as Cr, Mo and W, and group VII elements such as Mn, Tc and Re' Group VIII elements such as pe, ru and 0s, group jx elements such as Co, Rh and Ir, group X elements such as Ni, pd and pt, group X elements such as Ag, group XII elements such as Zn and Cd, and group XIII elements such as a /, Ca, In and T /, XIV group elements such as Ge, Sn and Pb 'XV group elements such as Sb and Bi, XVI group elements such as p0, and X Vn group elements such as ρ and c /. Among them, preferred It is T / and Pb. As for the ions and / or compounds of Group I to XVII elements, the ions may be inferior to its oxides, halides, sulfates, phosphates, nitrates, hydroxides, sulfides, and silicates. , Titanate, borate and carbonate. Titanium and / or cobalt silicate zeolites may contain one or more of these ions and / or compounds. Titanium and / or cobalt silicate zeolites contain these ions and / or compounds Method Examples include ion exchange method, mixed chain method, infiltration method, impregnation method, deposition method, evaporative drying method, etc., but the methods are not limited to these examples. The specific examples are described below. ① The heterodyne exchange method does the above Water-soluble salts of elements, such as gaseous, nitrate, acetate, etc., are dissolved in water at a concentration of 0.01 to 2 g ions / liter. Then: add test ion state, ammonium ion (NH4 +) state or proton state titanium and / or Gumenite zeolite, preferably NΗ4 + -state titanium and / or cobalt silicate zeolite, is stirred at a predetermined temperature, and then filtered, and the paper is re-scaled to the Chinese National Standard (CNS) A4 specifications. (21〇X 297 mm) 311582 ------------- Please install the IC, please read the precautions on the back, and then fill out this page) Order --- line · 572897 A7 Β7 V. Invention Explanation (6) Repeat this procedure. After that, the resulting filtration residue was rinsed with water. The titanium and / or cobalt silicate zeolite thus obtained containing the above 70 element ions is dried and calcined if necessary. (2) Example of mixing method The compound of the above-mentioned element is mixed with H + or NH / state titanium and / or cobalt silicate zeolite, and if necessary, mixed with water. The mixed product is then dried and calcined if necessary. ③ Example of impregnation method Water-soluble salts of the above elements are dissolved in water. Then, NH4 + or h + titanium and / or cobalt silicate zeolite, preferably NH / state titanium and / or cobalt silicate zeolite, is impregnated in this solution. Thereafter, the impregnated zeolite is dried and, if necessary, calcined. ④ Deposition method 丨 Disperse NH / state or H + state titanium and / or cobalt silicate zeolite in an aqueous solution of a water-soluble salt of the above elements. An aqueous ammonia solution is added to this mixture to cause hydroxides of the above elements to be deposited on the surface of titanium and / or cobalt silicate zeolites in the NH / state or H + state, and then filtered. Thereafter, the filtered residue is rinsed with water and dried, and calcined if necessary. ⑤ Evaporation drying method 丨 stir the compound of the above elements in water with NH4 + or H + titanium and / or cobalt silicate zeolite to mix them. --------------- Packing --- (Please read the notes on the back before filling out this page) Order ·-· Fresh-Printed on paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 6 311582 572897 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 5. After the description of the invention (7), evaporate to dry, and then, if necessary calcination. In any of the above methods, calcination is usually performed at 350 to 800 ° C for several hours in an atmosphere of air, nitrogen, and / or carbon dioxide. However, since the catalyst is heated in the reactor during the reaction of the gas-phase contact catalyst, the catalyst does not necessarily need to be calcined. A preferable range of the content of ions and / or compounds of one or more elements selected from the group of elements I to XVII depends on the kind of titanium and / or cobalt silicate zeolite or the kind or form of the element contained therein. In general, a preferred range is a zeolite containing titanium and / or cobalt and silicon as zeolite constituent elements per lg, and containing from 0.05 to 10 mg equivalents, more preferably from 0.01 to 5 mg equivalents. The titanium and / or cobalt silicate zeolites used in the present invention can be used for this purpose or added with binders such as silica, diatomite, kaolin, bentonite, alumina, silica-alumina, etc., and water, polyvinyl alcohol After vinyl acetate, it is molded into a desired shape such as a solid cylinder, a hollow cylinder, etc. by a tablet press or an extruder. Use this molding as a fixed bed catalyst. Alternatively, the titanium and / or cobalt silicate zeolite is mixed with a binder such as silica, diatomaceous earth, kaolin, bentonite, alumina, silica-alumina, etc., and water is obtained, and then the slurry is spray-dried. And liquid to form spherical microsphere beads, which are used as fluidized bed catalysts. In order to manufacture titanium and / or cobaltite zeolites containing ions and / or compounds of one or more elements selected from the group of elements to the group of elements, the above-mentioned titanium and / or starting stones that have been molded into a desired shape can be made. The salt stagnation stone contains ions and / or compounds by the above-mentioned ion exchange method, infiltration method, impregnation method, and the like. In any of the above methods, the catalyst obtained by calcination in the atmosphere of air, nitrogen, carbon dioxide, etc. at 350 to 800t for several hours' paper size applies to China National Standard (CNS) A4 specification (21Q x 297 public love)-1 311582 -------------- Installation—— (Please read the precautions on the back before filling this page)-Thread · 572897 A7 B7 V. Description of the invention (8) to give the strength of the molded object The volatile components contained in the binder and the like are removed, but since the catalyst is heated in the reactor during the gas-phase contact reaction, the catalyst does not necessarily need to be calcined. The production of the pyridine base of the present invention can be carried out in a fixed bed reactor, a fluidized bed reactor or a moving bed reactor. An example of the method of the present invention using a fixed bed reactor will be explained as follows. The catalyst of the present invention is filled in a reaction tube. A mixed gas of aliphatic aldehyde and / or aliphatic brewery I and ammonia is introduced into this reaction tube, and a gas phase reaction is applied. A mixed gas of an aliphatic acid and / or an ammonia and ammonia can also be fed together with water, an inert gas such as nitrogen and / or methanol. The combination of aliphatic chain and / or aliphatic ketone and the suitable ratio of aliphatic aldehyde and / or aliphatic amine to ammonia varies depending on the desired pyridine base. For example, in order to produce a bituminite-methylpyridine as a main component, a combination of acetaldehyde and formaldehyde as aliphatic aldehydes and / or aliphatic ketones is used, and acetaldehyde ·· formaldehyde ·· ammole of Mo is preferably i ·· 0.3-3: 0 · 5_5. In this case, when additional methanol is used, it is preferred that the amount of methanol is 0.5 mol or less per 1 mol of ethyl alcohol. Formosa can be made into formaldehyde (formal water). In order to produce α-methylpyridine and fluorenylpyridine as a main component, acetaldehyde is used as a combination of an aliphatic aldehyde and / or an aliphatic ketone, and the mole of acetone is preferably 1: 0.8-3. The selectivity of α-methylpyridine can be improved when ethyl is reacted with ammonia according to the method of the present invention. A mixture of aliphatic aldehydes, aliphatic ketones and ammonia, and if necessary water, inert gases such as nitrogen and / or methanol, at a space velocity of 100 to 10,000 hr · 1, preferably 300 to 3,000 hr · 1 ( sv) through the catalyst. The reaction temperature is 300 to 700 ° C, preferably 350 to 600 ° C. The reaction pressure can be lower than the atmospheric pressure (please read the precautions on the back before filling this page). Printed on the paper printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This paper applies Chinese national standards (CNS> A4 size (210 X 297 mm)). 8 311582 572897 Printed by A7 B7 in cooperation with employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) to several atmospheres, but the reaction pressure is usually preferably atmospheric to 2 atmospheres. After the reaction is performed as described above, it can be condensed and flowed out of the reaction tube. The pyridine base contained in the reaction gas. Alternatively, the solvent can be dissolved in a suitable solvent by contacting the solvent with the reaction gas containing the pyridine base. The resulting condensate or solution can be distilled to recover the pyridine. When the catalyst is reacted for a long time When it deteriorates during the period, it can be regenerated according to the traditional catalyst regeneration method. That is, the air is passed through the catalyst layer at a high temperature not exceeding the heat-resistant temperature of the catalyst, preferably 350 to 800 ° C, to be burnt and deposited on the catalyst. Carbon on the medium. If necessary, the air can be diluted with water vapor, nitrogen, carbon dioxide, etc. [Examples] The following examples are more specific The present invention will be further described, but the scope of the present invention is not limited. Catalyst M Preparation Example 1 According to the method described in iikiLSJOL, 130, 440 (1991), titanium silicate was synthesized as follows. 566 g of tetra-n-butylammonium hydroxide ( 〇436 m〇1) of a mixture of 20% by weight of methanol bath and 455 g (2.18 mol) of tetraethyl orthosilicate was placed in a Peirce reaction vessel equipped with a stirrer and a dropping funnel. While stirring, a 300% by weight isopropyl alcohol solution of 2,300 g of tetrabutyl titanate (〇33 冚 〇1) was added dropwise from the dropping funnel, and then kept stirring for about 30 minutes. Add 79 g of steam Dispense water to the resulting mixture while stirring to allow the reaction to continue for 2 hours while removing alcohols at 75 to 80 C. The resulting reaction mixture is cooled and then transferred to the southern pressure flea and maintained at 170 ° C for 2 days while stirring. Then, the cooling is high, ㈣ 屮 _ this standard (CNS) A4 size coffee χ 9 311582------------- ^ i — — — — — — ^ ----!! Line (Please read the precautions on the back before filling this page) 572897 A7 ___________ B7 V. Description of Invention (1G) Autoclave, filter the contents to obtain crystals. The crystals obtained were washed with ion-exchanged water, dried at 100 ° C for 8 hours, and then calcined at 550 t for 16 hours in an air flow. The obtained calcined material was analyzed, and the analysis results showed that it was 50% Si / Ti (atomic ratio). Titanosilicate having a MEL type crystal structure. The obtained titanosilicate was added to 1 liter of a 5% aqueous solution of ammonium vaporized, and then stirred at 50 to 60 ° C. for 1 hour, followed by filtration for ion exchange. The residue obtained by filtration was ion-exchanged three times in the same manner as described above. The finally obtained residue was washed with water until the concentration of C / · ions in the washing solution became 1 ppm or lower, and then dried at 16 hours to obtain [] 114+ state titanium silicate. In the air at 550. (: Further calcined for 6 hours to obtain H + state titanosilicate. Catalyst Preparation Example 2 According to the method described in JP-A-63-543 58, cobalt silicate was synthesized as follows. 100 g of orthosilicic acid was mixed in an autoclave. Tetraethyl ester (0.48 mol) and 217.5 g of a 10% by weight aqueous solution of tetra-n-propyl hydroxide (0.96 mol). To the resulting mixture was added 5.7 g of cobalt acetoacetonate (Πΐ) (〇β〇ι 6 mol) and the mixed solution of ethylene glycol were stirred at the same time, and then continuously stirred for about 30 minutes. After that, the resulting mixture was heated to 105 ° C and stirred at the same temperature for 120 hours for hydrothermal synthesis. The autoclave was cooled and the contents were filtered To obtain crystals. Rinse the crystals with ion-exchanged water until the pH of the washing solution reaches 7.3. The resulting product is dried at 1 20 ° C for 16 hours, and then calcined at 550 ° C for 4 hours in an air flow. The analysis results showed that it was a cobalt silicate having an MFI-type crystal structure with a si / c0 (atomic ratio) of 25. The obtained dream dream salt was -II I — 1 in the same manner as in Catalyst Preparation Example 1. — — — — — — I — · II (Please read the notes on the back before (Write this page) lrj · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 10 311582 572897 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 、 Explanation of the invention (11 plus ion parent exchange, water washing, drying and calcination to obtain NH / state cobalt silicate and H + state cobalt silicate. Catalyst Preparation Example 3 According to the method described in JP-A_2-209867, aluminum is synthesized as follows Silicate. / ¾¾ 433.4g of distilled water, sulfate sulfate, 558g of tetra-n-propylammonium bromide and 40g of sulfuric acid to obtain solution A. 3230g of distilled water and 453g of sodium silicate # 3 are obtained to obtain solution B. 754g Distilled water and i89g of sodium gasification to obtain solution C. The solution c was placed in a stainless steel autoclave, and both solutions A and B were added dropwise while stirring vigorously. The mixture was controlled to maintain the pH in the range of 9.5 to 11. Seal The temperature of the autoclave was raised to ι60 ° C, and the mixture was continuously stirred for 2 () hours of hydrothermal synthesis. At this time, the gauge pressure was no more than 0.5 to 0.6 MPa (5 to 6 kg / cm2). After the reaction was completed, the mixture Cold part to room temperature, filter the contents of the autoclave Obtain crystals from the reaction. Add this crystal to distilled water, stir and rinse, then filter. Repeat the above rinse and filter until the ion concentration in the filtrate becomes! Ppm or lower. After that, dry the crystals at 110 C for 16 hours, then It was calcined in air at 530 C for 4 hours. Analysis of the calcined material revealed that it was a Na + acid salt with MFI type crystal structure with Si / A / (atomic ratio) of 100. The obtained Na + aluminosilicate was subjected to ion exchange, water washing, drying and calcination in the same manner as in Catalyst Preparation Example 1 to obtain NH / aluminosilicate and N + aluminosilicate. Disk Media Preparation Example 4 According to the method described in JP-A-2-2 098 67, iron silicate was synthesized as follows. From 19g of iron nitrate (111) 9 hydrate, 34g of vaporized tetra-n-propylammonium and steaming --- --- ------------------ --- line < Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 11 311582 572897 A7 V. Description of the invention (12) The composed aqueous solution is called solution A. A suspension consisting of 70 g of fuming dioxide and distilled water is called solution m4g, a solution consisting of sodium hydroxide and distilling water is called solution c. The solution c was placed in a non-steel steel autoclave, and the solution AAB was added thereto at the same time while stirring and mixing. The sealed high pressure dad raised the temperature to 160t, and then continuously searched for hydrothermal synthesis for 60 hours. 1) 11 changed from 12 · 4 to filter the contents of the high mill to obtain a solid. Rinse the solid with distilled water until {) 11 of the lotion reaches 7.3. The analysis result of solid state analysis showed that it was a Na \ state ferric silicate having an MFI type crystal structure with an atomic ratio of 25%. In the same manner as in Catalyst Preparation Example 1, ion exchange, water washing, drying, and calcination were performed on the obtained Na + ferric silicate to obtain nh4 + ferric silicate and H + ferric silicate. Catalyst Preparation Example 5 According to Catalyst Preparation Example 4, Na + -state gallium silicate, NH / -state gallium silicate and H + -state gallium silicate were obtained, but i9g gallium nitrate (111) 8 hydrate was used instead of the catalyst. The iron nitrate (III) 9 hydrate used in the preparation of the vehicle 4 was used. The Na + -state gallium silicate was analyzed, and the analysis results showed that it had an MFI type crystal structure and a Si / Ga (atomic ratio) of 25. Example 1 The H + -state titanium silicate (H + -state Ti / Si) obtained in Example 1 was compressed at a pressure of 39 Mpa, and then ground to obtain a uniform particle size of 1.0 to 1.7 mm (10 to 16 mesh). particle. The production of pyridine bases using these particles as a catalyst was performed in the following manner. Fill 6g of the catalyst obtained above into a glass reaction tube with an inner diameter of 20mm. Page size This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 mm 12 311582 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumption Yesterday 572897
五、發明說明（u) 中。於3 80 C加熱反應管之觸媒填充部分，再將2 76〇 m//hr 之氨氣及2.48g/hr之乙醛饋入此觸媒填充部分。自饋入乙 醛開始30分鐘後，使流出反應管的反應氣體吹入水中2〇 分鐘以使反應氣體中可溶成分溶於水中。藉氣體色層分析 術分析所得之溶液，結果示於表3。 吡啶鹼的產率係基於施加反應之乙醛總破數，再依據 下列計算式予以計算。 吡啶產率（％)=[(所製得之吡啶總碳原子數）/(施加反應之 乙醛總碳原子數）]χ 1〇〇 α、冷或r-甲基吡啶產率（％> = [(所製得之α、召或r -甲基吡啶總碳原子數）/(施加反應 之乙醛總碳原子數）]x 1〇〇 實施例2 依據實施例1相同的方式進行吡啶鹼的製造，但使用 觸媒製備例2所獲得之Η+態鈷矽酸鹽（Η+態Co/Si)取代實 施例1所使用之H+態鈦石夕酸鹽。結果示於表3。 比較例1 依據實施例1相同方式進行吡啶鹼的製造，但使用觸 媒製備例3所獲得之態銘石夕酸鹽（H+態A"Si)取代實施 例1所使用之H+態鈦矽酸鹽。結果示於表3。 比較例2 依據實施例1相同方式進行吡啶鹼的製造，但使用觸 媒製備例4所獲得之H+態鐵矽酸鹽（H+態Fe/Si)取代實施 例1所使用之H+態欽矽酸鹽。結果示於表3。 — — — — — — — — — — 111 ^ i — — — — — — ^--— — — — — — (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度刺帽國家標準(210 X 297公釐) 13 311582 572897 A7 B7 五、發明說明（14 ) 比較例3 -------------裝 i — (請先閱讀背面之注意事項再填寫本頁) 依據實施例1相同方式進行D比咬驗的製造，但使用觸 媒製備例5所獲得之H+態鎵矽酸鹽（H+態 Ga/Si)取代實施 例1所使用之H+態鈦石夕酸鹽。結果示於表^ 表3 編號 觸媒 i l 率（％) Py aPc j3 Pc 7 Pc 總計 實施例1 H+態 Ti/Si 1.2 34.2 0 12.1 47.5 實施例2 H+態 Co/Si 1.6 27.0 0 12.8 41.4— 比較例1 H+態 A//Si 5.1 17.6 0 18.5 41.2 比較例2 H+態 Fe/Si 3.2 18.6 0 17.5 39.3 比較例3 H+態 Ga/Si 2.5 17.3 0 19.3 39.15. Description of the invention (u). The catalyst-filled portion of the reaction tube was heated at 3 80 C, and then 2 760 m / hr of ammonia and 2.48 g / hr of acetaldehyde were fed into this catalyst-filled portion. After 30 minutes from the start of feeding acetaldehyde, the reaction gas flowing out of the reaction tube was blown into water for 20 minutes to dissolve the soluble components in the reaction gas. The resulting solution was analyzed by gas chromatography, and the results are shown in Table 3. The yield of pyridine base is based on the total acetaldehyde breakdown of the applied reaction, and it is calculated based on the following formula. Yield of pyridine (%) = [(Total number of carbon atoms of pyridine obtained) / (Total number of carbon atoms of acetaldehyde applied to reaction)] x 100a, cold or r-methylpyridine yield (% > [(Total number of carbon atoms of α, zirconium or r-methylpyridine produced) / (Total number of carbon atoms of acetaldehyde to which the reaction is applied)] x 100. Example 2 was performed in the same manner as in Example 1. For the production of pyridine base, the Hf + cobalt silicate (Hf + Co / Si) obtained in Catalyst Preparation Example 2 was used instead of the H + titanate oxalate used in Example 1. The results are shown in Table 3. Comparative Example 1 The pyridine base was produced in the same manner as in Example 1, except that the state augerite (H + state A " Si) obtained in Catalyst Preparation Example 3 was used instead of the H + state titanium silicon used in Example 1. The results are shown in Table 3. Comparative Example 2 The pyridine base was produced in the same manner as in Example 1, except that the H + -state iron silicate (H + -state Fe / Si) obtained in Catalyst Preparation Example 4 was used instead of the examples. The H + state is used in 1. The results are shown in Table 3. — — — — — — — — — — 111 ^ i — — — — — — ^ --— — — — — (First Read the notes on the back side and fill in this page) National standard for paper caps (210 X 297 mm) 13 311582 572897 A7 B7 V. Description of the invention (14) Comparative example 3 ----------- -装 i — (Please read the precautions on the back before filling in this page) The D ratio bite test was made in the same manner as in Example 1, but the H + state gallium silicate (H +) obtained in Catalyst Preparation Example 5 was used. State Ga / Si) replaces the H + state titanite salt used in Example 1. The results are shown in Table ^ Table 3 No. catalyst il rate (%) Py aPc j3 Pc 7 Pc Total Example 1 H + state Ti / Si 1.2 34.2 0 12.1 47.5 Example 2 H + state Co / Si 1.6 27.0 0 12.8 41.4— Comparative example 1 H + state A // Si 5.1 17.6 0 18.5 41.2 Comparative example 2 H + state Fe / Si 3.2 18.6 0 17.5 39.3 Comparative example 3 H + Ga / Si 2.5 17.3 0 19.3 39.1
Py :卩比啶產率 a Pc : α -甲基吡唆產率 iSPc:召-甲基吡啶產率 rPc: r·甲基吡啶產率 實施例3 經濟部智慧財產局員工消費合作社印製 將13.93g欲予浸滲之觸媒製備例1所獲得之H+態鈦矽 酸鹽添加至由溶解1.68g硝酸鉛至18.14g水中所製備之溶 液中。於120°C乾燥所得產物5小時，然後，在空氣流動 中於550°C煅燒5小時，獲得含有以金屬計7重量％用量 之Pb的鈦矽酸鹽（每lg鈦矽酸鹽，0.73毫克當量）。 以實施例1相同方式進行吡啶鹼的製造，但使用上述 獲得之含>b之鈦矽酸鹽（7%Pb-Ti/Si)取代實施例1所使用 之H+態鈦矽酸鹽。結果示於表4。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 14 311582 經濟部智慧財產局員工消費合作钍印製 572897 A7 ------- ------- 五、發明說明（I5 ) 實施例4 將19.4g觸媒製備例2所獲得之H+態姑矽酸鹽添加至 由溶解0.96g硝酸鉛至14.2g水中所製備之溶液中，再將 之混合。於120°C乾燥所得之混合物5小時，然後，在空 氣流動中於550°C锻燒5小時，以獲得含有以金屬計3重 量％用量之Pb的鈷矽酸鹽（每lg鈷矽酸鹽，0.30毫克當 量）〇 以實施例1相同方式進行吡啶鹼的製造，但使用上述 獲得之含Pb之鈷矽酸鹽（3% Pb-Co/Si)取代實施例1所使 用之H+態鈦矽酸鹽。結果示於表4。 實施你丨5 將74.4g觸媒製備例2所獲得之H+態钴矽酸鹽添加至 由溶解 59.54g 仲鎢酸銨[5(NH4)20 · 12W03 · 5H20]至 200g 水中所製備之溶液中，再將之混合。於120°C乾燥所得之 混合物5小時，然後，在空氣流動中於55(^c锻燒5小時， 獲得含有以金屬計7重量％用量之w的鈷矽酸鹽（每lg鈷 矽酸鹽，2.46毫克當量）。 以實施例1相同方式進行吡啶鹼的製造，當使用上述· 獲得之含有W之鈷矽酸鹽（7% W-Co/Si)取代實施例1所使 用之H+態鈦矽酸鹽。結果示於表4。 复A例6 將7.44g觸媒製備例2所獲得之H'態鈷矽酸鹽添加至 由令解2.55g硝酸鋅6水合物至1〇 4g水中所製備之溶液 中，再將之混合。於12(TC乾燥所得之混合物5小時，然 t S a (CNS)A4 ^ (210 x 297 , 15 3職 ^--------------^ (請先閱讀背面之注意事項再填寫本頁) 572897 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明（l6 ) 後，在空氣流動中於550°C锻燒5小時，獲得含有以金屬 «十7重量％用量之&的始石夕酸鹽（每lg始石夕酸鹽，2.3毫 克當量）。 以實施例1相同方式進行吡啶鹼的製造，但使用上述 獲得之含有Zn之鈷矽酸鹽（7% Zn-Co/Si)取代實施例1所 使用之H+態鈦矽酸鹽。結果示於表4。 實施例7 將7.44g觸媒製備例2所獲得之H+態鈷砍酸鹽添加至 由溶解0.73g硝酸鉈⑴至i〇.4g水中所製備之溶液中，再 將之混合。於120°C乾燥所得之混合物5小時，然後，在 空氣流動中於5 5 0 °C煅燒5小時，獲得含有以金屬計7重 量％用量之17的鈷矽酸鹽（每lg鈷矽酸鹽，〇·37毫克當 量）。 以實施例1相同方式進行π比咬驗的製造，但使用上述 獲得之含有Ί7之鈷矽酸鹽（7%T/-Co/Si)取代實施例i所使 用之H+態鈦矽酸鹽。結果示於表4。 實施例8 將7.44g觸媒製備例2所獲得之H+態鈷矽酸鹽添加至 由溶解1.75g石肖酸鑛6水合物至l〇.4g水中所製倚之溶液 中’再將之混合。於120C乾餘所得之混合物5小時，然 後，在空氣流動中於550°C煅燒5小時，獲得含有以金屬 計7重量％量之La的始石夕酸鹽（每lg姑;6夕酸鹽，1 63毫克 當量）。 以實施例1相同方式進行吡啶鹼的製造，但使用上述 ί裝--- (請先閱讀背面之注意事項再填寫本頁) 訂： 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 16 311582 572897 A7 B7 五、發明說明（17 ) 獲得之含有La之鈷矽酸鹽（7%La_c〇/Si)取代實施例1所 使用之H+態鈦矽酸鹽9結果示於表4。 實施例9 將7.44g觸媒製備例2所獲得之Η+態鈷矽酸鹽添加至 由溶解3.32g硫酸銦9水合物至1〇 4g水中所製備之溶液 中，再將之混合。於12(TC乾燥所得之混合物5小時，然 後’在空氣流動申於5 5 0 °C煅燒5小時，獲得含有以金屬 計7重量％量之In的鈷矽酸鹽（每lg鈷矽酸鹽，197毫克 當量）。 以實施例1相同方式進行吡啶鹼的製造，但使用上述 獲得之含有In之鈷矽酸鹽（7% In-Co/Si)取代實施例1所使 用之H+態鈦矽酸鹽〇結果示於表4。 表4 編號 觸媒 產率(％) Py a Pc j3Pc 7 Pc 總計 實施例3 7% Pb-Ti/Si 1.1 52.1 0 17.0 70.2 實施例4 3%Pb-Co/Si 1.1 51.6 0 20· 1 72.8 實施例5 7% W-Co/Si 1.0 28.0 0 15.5 44.5 實施例6 7% Zn-Co/Si 1.0 34.9 0 17.2 53.1 實施例7 h 7%T/-Co/Si 0.9 38.5 0 14.4 53.8 實施例8 7%La-Co/Si 1.8 29.9 0 11.8 43.5 實施例9 7% In-Co/Si 1·8 29.9 0 11.8 43.5Py: pyridine yield a Pc: α-methylpyridine yield iSPc: sum-methylpyridine yield rPc: r · methylpyridine yield Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 13.93 g of the titanium silicate in the H + state obtained in Preparation Example 1 of the catalyst to be impregnated was added to a solution prepared by dissolving 1.68 g of lead nitrate in 18.14 g of water. The obtained product was dried at 120 ° C for 5 hours, and then calcined at 550 ° C for 5 hours in an air flow to obtain a titanium silicate containing 7% by weight of Pb as a metal (0.73 mg per lg of titanium silicate). equivalent). Production of a pyridine base was performed in the same manner as in Example 1, except that the titanium silicate containing > b (7% Pb-Ti / Si) obtained above was used in place of the titanium silicate in the H + state used in Example 1. The results are shown in Table 4. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 14 311582 Cooperative printing by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 572897 A7 ------- ------- V. DESCRIPTION OF THE INVENTION (I5) Example 4 19.4 g of the H + -state phosphosilicate obtained in Catalyst Preparation Example 2 was added to a solution prepared by dissolving 0.96 g of lead nitrate into 14.2 g of water, and then mixed. The resulting mixture was dried at 120 ° C for 5 hours, and then calcined at 550 ° C for 5 hours in an air flow to obtain a cobalt silicate containing 3% by weight of Pb as a metal (per lg of cobalt silicate (0.30 mg equivalent). The production of pyridine base was performed in the same manner as in Example 1, except that the Pb-containing cobalt silicate (3% Pb-Co / Si) obtained above was used instead of the H + state titanium silicon used in Example 1. Acid salt. The results are shown in Table 4. Put it into practice 5 Add 74.4 g of the cobalt silicate in the H + state obtained in Catalyst Preparation Example 2 to a solution prepared by dissolving 59.54 g of ammonium paratungstate [5 (NH4) 20 · 12W03 · 5H20] into 200 g of water, and then Of blending. The resulting mixture was dried at 120 ° C. for 5 hours, and then calcined at 55 ° C. for 5 hours in an air flow to obtain a cobalt silicate containing 7% by weight of metal (per lg of cobalt silicate). , 2.46 mg equivalent). The pyridine base was produced in the same manner as in Example 1. When the cobalt silicate containing W (7% W-Co / Si) obtained above was used instead of the H + titanium used in Example 1. The results are shown in Table 4. Compound A Example 6 7.44 g of the cobalt silicate obtained in Catalyst Preparation Example 2 was added to 2.55 g of zinc nitrate hexahydrate in 104 g of water. The prepared solution was mixed again. The mixture was dried at 12 ° C for 5 hours, and then t S a (CNS) A4 ^ (210 x 297, 15 3 positions ^ ------------- --- ^ (Please read the precautions on the back before filling this page) 572897 Printed A7 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. After the invention description (l6), it is calcined in air at 550 ° C for 5 hours To obtain an osparite salt (2.3 mg equivalent per gram of osparite salt) in an amount of & 10% by weight of metal. The pyridine base was prepared in the same manner as in Example 1. The Zn-containing cobalt silicate (7% Zn-Co / Si) obtained above was used instead of the H + -state titanium silicate used in Example 1. The results are shown in Table 4. Example 7 7.44 g of The H + -state cobalt cholate obtained in the second preparation example 2 was added to a solution prepared by dissolving 0.73 g of europium nitrate to i.4 g of water, and then mixed. The resulting mixture was dried at 120 ° C for 5 hours. Then, it was calcined at 55 ° C. for 5 hours in an air flow to obtain a cobalt silicate containing 17% by weight based on the amount of metal (37 mg equivalent per lg of cobalt silicate). 1 The production of the π ratio bite test was performed in the same manner, but the cobalt silicate containing ytterbium 7 (7% T / -Co / Si) obtained above was used in place of the H + -state titanium silicate used in Example i. The results are shown in Table 4. Example 8 7.44 g of the cobalt silicate in the H + state obtained in Catalyst Preparation Example 2 was added to a solution prepared by dissolving 1.75 g of shiosamate hexahydrate to 10.4 g of water. They were mixed. The resulting mixture was dried at 120C for 5 hours, and then calcined at 550 ° C for 5 hours in an air flow to obtain 7% by weight of L in metal A starting stone salt (per lg; hexanate, 163 mg equivalent). The pyridine base was produced in the same manner as in Example 1, but using the above package --- (Please read the note on the back first Please fill in this page for matters) Order: This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 16 311582 572897 A7 B7 V. Description of the invention (17) Cobalt silicate containing La obtained (7 % La_co / Si) is shown in Table 4 in place of the H + titanium titanosilicate 9 used in Example 1. Example 9 To a solution prepared by dissolving 3.32 g of indium sulfate 9-hydrate into 104 g of water was added 7.44 g of the cobalt sulphate + cobalt silicate obtained in Catalyst Preparation Example 2 and mixed. The resulting mixture was dried at 12 ° C for 5 hours, and then calcined in air at 5 50 ° C for 5 hours to obtain a cobalt silicate containing 7% by weight of In as a metal (per lg of cobalt silicate , 197 mg equivalent). The pyridine base was produced in the same manner as in Example 1, except that the cobalt silicate containing In obtained (7% In-Co / Si) obtained above was used instead of the H + state titanium silicon used in Example 1. The results are shown in Table 4. Table 4 No. Catalyst Yield (%) Py a Pc j3Pc 7 Pc Total Example 3 7% Pb-Ti / Si 1.1 52.1 0 17.0 70.2 Example 4 3% Pb-Co / Si 1.1 51.6 0 20.1 72.8 Example 5 7% W-Co / Si 1.0 28.0 0 15.5 44.5 Example 6 7% Zn-Co / Si 1.0 34.9 0 17.2 53.1 Example 7 h 7% T / -Co / Si 0.9 38.5 0 14.4 53.8 Example 8 7% La-Co / Si 1.8 29.9 0 11.8 43.5 Example 9 7% In-Co / Si 1.8 89.9 0 11.8 43.5
Py :吡啶產率 a Pc : α -甲基吡啶產率 召Pc :点-甲基吡啶產率 r Pc: r -甲基11比咬產率 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 17 311582 (請先閱讀背面之注意事項再填寫本頁) -裝-------—訂------— I-線Py: pyridine yield a Pc: α-methylpyridine yield Call Pc: dot-methylpyridine yield r Pc: r-methyl 11 specific bite yield This paper size applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) 17 311582 (Please read the precautions on the back before filling in this page) -Install --------- Order -------- I-line
經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs