^228 3 5 a? B7 五、發明説明（1 ) 本發明是有關於己内醯胺之合成方法，特別是有關於 以水、醇類、或水與醇類的混合液為溶劑，以擔體所支撐 之貴金屬為觸媒，將搭基戊酸（formyl valeric acid)或搭基戊 酸酯類（formyl va丨erate)直接氨化及環化成己内醯胺的技 術。 己内醯胺為尼龍6之原料，其經開環聚合即可成為尼 龍6。尼龍6之用途廣泛，主要作為纖維材料及工程塑膠之 用，例如衣著、地毯等紡織纖維及輪胎簾布，濾布...等工業 纖維、或做為汽車、機械零件、電子電機零組件...等工程塑 膠材料。 傳統之己内醯胺製法是以環己烷為原料，如美國專利 U.S_4,268,440，U.S-5,304,643等所揭示，將環己烧氧化成 醇、網油類（KA oil)，再經嚴化及貝克曼重組反應而合成己 内醯胺。此等方法的缺點是有大量的硫酸銨廢棄物生成， 不但生產成本過高且有廢棄物需處理之麻煩，因此許多其 它新的製程被開發出來。 經濟部中央標準局員工消費合作社印聚 ^^^1 n^i I. In— n n^— Γ* 爻 -V占 〈請先閱讀背面之注意事項再填寫本f ) 新的製程如美國專利4,730,040所揭示之以5-醛基戊酸 曱酯為原料，先以酸性觸媒在30〜200 °C將5-醛基戊酸-甲酯 水解為醛基戊酸，再以阮尼鎳或鈷為觸媒在超高壓及 50〜150 °C下，以過量之氨及氫氣進行反應，將醛基戊酸轉 換成6-胺基己酸，在分離未反應之氨、氫等氣體及觸媒後， 再在150〜370 °C，lOObar下將6-胺基己酸脫水環化為己内 醯胺，不但製程繁複，且產率不高。 美國專利4,730,041及4,731,445則揭示以醇為溶媒， 本紙張尺度適用中國國家標芈（CNS ) Λ4規格（210 X 297公釐） 4228 3 5 A7 B7 五、發明説明（2 ) 5- 醛基戊酸甲酯為原料直接加氫胺化之製程，其以矽酸鎂為 載體之鎳觸媒為觸媒，在過量之氨氣，氫氣，及40~130°C， 超高壓力下反應，先將5-醛基戊酸甲酯轉換為6-胺基己酸 曱酯，經分離未反應之氣體後，將6-胺基己酸甲酯水解成 6- 胺基己酸，再進行脫水環化或直接脫醇環化形成己内醯 胺，該製程雖減少了 5-醛基戊酸酯之水解步驟，但由於原 料之進料濃度極低(僅10%)，有大量之醇類需分離回用。曰 本專利ΝΟ·29148(1968)則揭示以氨水為溶媒之方法，其以 阮尼鎳為觸媒，在150 bar，230。(：下將5-醛基己酸酯直接 環化為己内醯胺，該製程不但產率低*且變化大。此外， 反應之壓力過高，而難達商業化實際生產之目的。 歐洲專利Eur. Pat. Appl. EP 729944則揭示以氨水先將 5-醛基戊酸氨化’再以氫化觸媒進行氫化為6_胺基己酸酯 類，再在200〜350 °C脫醇環化為己内醯胺，雖可改善反應 之壓力’但是多了一個氨化之步驟，使製程更複雜。 經濟部中央樣準局員工消费合作社印«. (請先閱讀背面之注意事項再填寫本頁) 丁 美國專利4,963,672則教導以5-醛基戊酸酯類直接進料 之方法，該製程以氧化鋁為載體之貴金屬釕為觸媒，在 40〜100 bar，80〜140。(：下’以過量之氨氣及氫氣進行反德， 將5-醛基戊酸甲酯轉化為6-胺基己酸甲酯，再將壓力降至 常壓，分離氫氣並以二曱苯置換氨氣後，再將壓力提高至 70〜100 bar及230〜350 °C，將卜胺基己酸甲酯直接進行脫醇 環化成己内酿胺，邊製程雖減少了大量醇類溶劑回收之麻 類，但製程仍相當繁複，不但其間要經加壓，減壓，再加 壓等操作，且以二曱笨置換氨氣，產生大量二甲苯需分離 太紙掁尺度適用中國國家榇準（CNS ) - Μ y /- 4228 3 5 A7 經濟部中央標隼局員工消t合作杜印裝 B7 五、發明説明（3 ) 回收之問題。 本發明之目的即為解決上述缺點，因而提供一種己内 酿胺之合成方法，經由一步驟反應即可直接將醛基戊酸或 其酿類’進行加氫氨化、酸化及脫水環化反應，而轉化為 己内酿胺’可簡化製程，免除繁複之反應' 分離程序及返 復的増壓及降壓操作。 為了逹成上述之目的，本發明己内醯胺之合成方法， 包括： ⑷將具有下列構造之搭基戊酸(formyl valeric acid)或 其酯類溶於一溶劑中， ii fl^ 228 3 5 a? B7 V. Description of the invention (1) The present invention relates to a method for the synthesis of caprolactam, and in particular to the use of water, alcohols, or a mixed solution of water and alcohols as solvents to support The precious metal supported by the body is a catalyst, a technology that directly aminates and cyclizes formyl valeric acid or formyl vaerate to caprolactam. Caprolactam is a raw material of nylon 6, which can be converted into nylon 6 by ring-opening polymerization. Nylon 6 has a wide range of uses, mainly as fiber materials and engineering plastics, such as textile fibers such as clothing, carpets, tire cords, filter cloths, and other industrial fibers, or as automotive, mechanical parts, electronic motor components .. . And other engineering plastic materials. The traditional caprolactam production method uses cyclohexane as a raw material, as disclosed in U.S. Patent No. 4,268,440, US-5,304,643, etc., cyclohexanene is oxidized to alcohols and KA oils, and the And Beckman recombination reaction to synthesize caprolactam. The disadvantage of these methods is that a large amount of ammonium sulfate waste is generated, not only the production cost is too high, but also the trouble of waste disposal, so many other new processes have been developed. Yin Ju ^^^ 1 n ^ i I. In— nn ^ — Γ * 爻 -V account (Please read the notes on the back before filling in this f) New process such as US patent 4,730,040 The disclosed method uses 5-aldol valerate as raw material, firstly hydrolyze 5-aldol valeric acid-methyl ester to aldol valeric acid at 30 ~ 200 ° C with acid catalyst, and then use Raney nickel or cobalt The catalyst is reacted with excess ammonia and hydrogen at ultrahigh pressure and 50 ~ 150 ° C to convert aldehyde valeric acid to 6-aminohexanoic acid, and to separate unreacted ammonia, hydrogen and other gases and catalyst Then, 6-aminocaproic acid is dehydrated and cyclized to caprolactam at 150 ~ 370 ° C and 100 bar, which not only has complicated manufacturing process, but also has low yield. U.S. patents 4,730,041 and 4,731,445 disclose that alcohol is used as the solvent. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 4228 3 5 A7 B7. 5. Description of the invention (2) A process for the direct hydrogenation and amination of methyl esters as raw materials. The nickel catalyst with magnesium silicate as the carrier is used as the catalyst. The reaction is carried out under excess pressure of ammonia, hydrogen, and 40 ~ 130 ° C. The methyl 5-aldehyde valerate is converted into the 6-aminohexanoic acid methyl ester. After separating the unreacted gas, the 6-aminohexanoic acid methyl ester is hydrolyzed to the 6-aminohexanoic acid, and then dehydrated and cyclized. Or it can be directly de-alcoholized and cyclized to form caprolactam. Although this process reduces the hydrolysis step of 5-aldehyde valerate, due to the extremely low feed concentration of the raw materials (only 10%), a large number of alcohols need to be separated Reuse. Japanese Patent No. 29148 (1968) discloses a method using ammonia as a solvent, which uses Raney nickel as a catalyst, at 150 bar, 230. (: Directly cyclize 5-aldehyde caproate to caprolactam, this process not only has low yield * and great changes. In addition, the reaction pressure is too high, and it is difficult to achieve the purpose of commercial production. Europe Patent Eur. Pat. Appl. EP 729944 reveals that the 5-aldehyde valeric acid is first ammoniated with ammonia water and then hydrogenated to 6-aminohexanoic acid esters with a hydrogenation catalyst, and then dealcoholized at 200 ~ 350 ° C. Cyclization to caprolactam, although it can improve the pressure of the reaction, but there is an additional ammoniation step, which makes the process more complicated. Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs «(Please read the precautions on the back before (Fill in this page) D. U.S. Patent No. 4,963,672 teaches a method of direct feeding with 5-aldehyde valerates. This process uses alumina as the carrier's precious metal ruthenium as the catalyst at 40 to 100 bar and 80 to 140. : The next step is to carry out anti-Germany with excess ammonia and hydrogen, convert methyl 5-aldehyde valerate to methyl 6-aminohexanoate, reduce the pressure to normal pressure, separate the hydrogen and replace it with diphenylbenzene. After ammonia gas, the pressure was increased to 70 ~ 100 bar and 230 ~ 350 ° C, and the methyl aminohexanoate was directly removed. Alcohols are cyclized to caprolactam. Although the side process reduces a lot of hemps recovered from alcohol solvents, the process is still quite complicated. Not only must it be pressurized, decompressed, and then pressurized, and it is replaced by dioxin. Ammonia gas to produce a large amount of xylene needs to be separated too much paper. The standard is applicable to China National Standards (CNS)-Μ y /-4228 3 5 A7 Employees of the Central Bureau of Standards, Ministry of Economic Affairs, cooperation Du printed B7 V. Description of invention ) The problem of recycling. The purpose of the present invention is to solve the above-mentioned shortcomings. Therefore, a method for synthesizing caprolactam is provided, which can directly hydrolyze aldehyde valeric acid or its fermentation products through a one-step reaction. And dehydration cyclization reaction, and the conversion to caprolactam 'simplifies the process and eliminates complicated reactions' separation procedures and repeated pressure and pressure reduction operations. In order to achieve the above purpose, the caprolactam of the present invention A synthetic method comprising: (1) dissolving formyl valeric acid or an ester thereof having the following structure in a solvent, ii fl
HC(CH2)4COR 其中R為H ' C^Cs的烷基、芳香基或環烷基， 其中該溶劑為水、醇類、或水與醇類的混合液；以及 (b)將搭基戊酸或其酯類之溶液，在溫度8〇〜3〇〇〇c 下，壓力10〜120大氣壓下，利用擔體所支撐之貴金屬為觸 媒，與氫氣、氨氣反應，進行加氫氨化、酸化及脫水環化 反應’而得到己内酿胺。 本發明所使用之觸媒為擔體所支撐之貴金屬，其活性 較咼，且同時具有加氫氨化及脫水或脫醇環化之雙重功 能。使得醛基戊酸或其酯類，可在過量之氫氣及氨氣下， 經由一步驟反應，進行加氫氨化、酸化及脫水環化反應， 本紙張尺度適用中國國家標準{ CNS M4規格{2丨0X297公嫠) (請先閲讀背面之注意事項再填寫本頁) 裝. A7 B7 4228 3 5 五、發明説明（4 ) 而轉化為己内醯胺。 適用於本發明較佳之貴金屬例如第νιΙΙΒ族金屬；可為 鉑、鈀、釕、铑，貴金屬之濃度為觸媒總含量的〇 〇5〜〖〇 〇 重量％，較佳之範圍為〇_ 1〜1 〇重量％，更佳之範圍為〇 5〜5 重量％之間。HC (CH2) 4COR where R is an alkyl, aromatic or cycloalkyl group of H'C ^ Cs, where the solvent is water, alcohols, or a mixed solution of water and alcohols; and (b) pentyl A solution of an acid or an ester thereof is reacted with hydrogen or ammonia at a temperature of 80 to 3000 c and a pressure of 10 to 120 atm to react with hydrogen and ammonia to perform hydrogenation and amination. , Acidification and dehydration cyclization 'to obtain caprolactam. The catalyst used in the present invention is a precious metal supported by a support, which has relatively low activity and has the dual functions of hydrogenation and amination, dehydration or dealcoholization. The aldehyde valeric acid or its esters can be reacted in one step under the conditions of excess hydrogen and ammonia to carry out hydro-amination, acidification and dehydration cyclization reactions. This paper standard applies to Chinese national standards {CNS M4 specifications { 2 丨 0X297 public 嫠) (Please read the precautions on the back before filling out this page). A7 B7 4228 3 5 V. Description of the invention (4) It is converted into caprolactam. The preferred precious metals suitable for the present invention, such as Group νιΙΙΒ metals; may be platinum, palladium, ruthenium, rhodium, the concentration of precious metals is from 0.05 to 〖wt% of the total catalyst content, and the preferred range is from 0 to 1 ~ 10% by weight, and a more preferable range is between 5 and 5% by weight.
適合於本發明的擔體並不特別限制，但較佳的選擇是 第II族元素或第IV族元素（亦即第IIA、IIB、IVA、IVB 族元素）所形成之氧化物或氧化物之混合物。第n族或第IV 族的金屬氧化物可形成具有固體酸'鹼特性之擔體，特別 適合應用於本發明中間產物6-胺基己酸之脫水環化。代表 性的第II族或第IV族的金屬氧化物例子包括二氧化矽、二 氧化鍅、二氧化鈦、氧化鈣、氧化鎂、及其混合物。 本發明擔體所支撐之貴金屬觸媒的製備方式是，先將 第π族或第IV族元素（如矽、鍅、鈦、鈣、鎂）的鹽類或氧 化物，經 >儿救法、共沉殿法 '或共研磨的方法，製得觸媒 擔體。接著再以共沉澱法、含浸法、表面塗佈法'或離子 交換法等方式，將貴金屬放置於擔體上。貴金屬的來源可 為氧化物、硝酸鹽類、氣化鹽類或金屬粉末。 . 依據本發明以下具體實施例的方式，將責金屬放置於 擔體上的方式是，將貴金屬之氯化鹽類配成5〜50重量％的 水溶液’再以浸潰蒸乾的方式使其附著於擔體上，或直接 以長時間浸泡，再過濾蒸乾的方式使附著於擔體上。適當 的浸泡時間以5小時以上為宜。 本發明擔體所支撐之貴金屬觸媒，亦可以鋅、錫、鋁、 6 本紙張尺度ίδ用中ϋϋ家樣準< CNS > M規格（2似297讀） (請先M讀背面之注意事項再填寫本頁) 裝 訂. 經濟部f央標準局貝工消费合作社，S-裝 A7 4228 3 5 五、發明説明（5 ) (請先閱讀背面之注意事項再填寫本頁) 鎊、銥、鎳、或其混合物加以改質，以調整觸媒之酸'鹼 性質（降低酸強度）’而增加觸媒之穩定性（壽命），增加己内 醯胺之產率，減少副產物之生成。實施的方式是，將鋅' 錫、鋁、篩、銥、或鎳等改質金屬，和貴金屬同時以共沉 法、含浸法、表面塗佈法、或離子交換法等方式放置於擔 體上。上述改質金屬的來源可為單純的鋅、錫、鋁、鎊、 銥、及鎳之金屬粉末，亦可為這些改質金屬的化合物，例 如氧化物、硝酸鹽類、或氣化鹽類等。依照實際的需求， 可使用一種以上的改質金屬或其化合物。 依據本發明以下具體實施例的方式，將改質金屬及貴 金屬同時放置於擔體上的方式是，將上述鋅'錫、鋁、諦、 銥、或鎳等改質金屬的鹽類配成5〜2〇重量％的水溶液，將 貝金屬之氣化鹽類配成5〜50重量％的水溶液，—起以浸潰 蒸乾的方式使其附著於擔體上，或直接以長時間浸泡再 過濾瘵乾的方式使附著於擔體上。適當的浸泡時間以5小 時以上為宜。適當的改質金屬用量在〇〜2〇重量％之間，較 佳者為0〜10重量％之間。 經濟部中央標隼局員x消费合作社印製 依據上述方式所得到之貴金屬擔體觸媒起始物（無·論是 否有添加改質金屬）’應再8代至5⑽。€通空氣赔燒及成型 製付適當尺寸的觸媒顆粒。並且，貴金屬擔體觸媒在使用 刖必須經氫氣還原處理，適合的還原條件為在氫氣流下， 於18〇 C至3〇〇〇c之間活化，時間4〜24小時之間。 依據本發明’以本發明特殊之貴金屬擔體觸媒來生產 己内醯胺的方式是，將醛基戊酸(f〇myl vderic acid)或其酯 本紙張尺度適用中國国）A4現格（-- 經濟部中央標嗥局員工消費合作社印製 4228 3 5 A7 -^___ _B7_ 五'發明説明（6) 類溶於水、醇類、或水與醇類的混合液中。接著再將醛基 戊酸或其酯類之溶液，在溫度80〜300°C下，壓力10〜120 大氣壓下，利用上述之本發明的擔體所支撐之貴金屬為觸 媒’與氫氣、氨氣反應，進行加氫氨化、酸化及脫水環化 反應，而得到己内醯胺。 適用於本發明的搭基戊酸（formyl valeric acid)或其醋 類’具有下列構造： iiThe support suitable for the present invention is not particularly limited, but a preferable choice is an oxide or an oxide formed by a Group II element or a Group IV element (that is, a Group IIA, IIB, IVA, or IVB element). mixture. The metal oxides of group n or group IV can form a support having solid acid'-base characteristics, and are particularly suitable for the dehydration cyclization of the intermediate product 6-aminohexanoic acid of the present invention. Representative examples of Group II or Group IV metal oxides include silicon dioxide, hafnium dioxide, titanium dioxide, calcium oxide, magnesium oxide, and mixtures thereof. The preparation method of the noble metal catalyst supported by the carrier of the present invention is that the salts or oxides of Group π or Group IV elements (such as silicon, hafnium, titanium, calcium, and magnesium) are firstly subjected to > Child Rescue , Co-sinking method, or co-grinding method to obtain a catalyst carrier. Then, the precious metal is placed on the support by a co-precipitation method, an impregnation method, a surface coating method, or an ion exchange method. Sources of precious metals can be oxides, nitrates, gasification salts or metal powders. . According to the following specific embodiments of the present invention, the method for placing the metal on the support is to prepare a 5 to 50% by weight aqueous solution of the noble metal chloride salt, and then immerse it to dry it. Attach to the support, or directly soak it for a long time, then filter and evaporate to make it adhere to the support. The appropriate soaking time is preferably more than 5 hours. The precious metal catalyst supported by the carrier of the present invention can also be used in zinc, tin, aluminum, 6 paper sizes, and the standard of the Chinese standard < CNS > M specification (2 reads like 297) (please read M on the back first) Note: Please fill in this page again) Binding. The Ministry of Economic Affairs, Central Standards Bureau, Shellfish Consumer Cooperative, S-Package A7 4228 3 5 V. Description of Invention (5) (Please read the notes on the back before filling this page) Pound, Iridium , Nickel, or a mixture thereof to modify the catalyst's acidity 'basicity (decrease acid strength)' to increase the stability (lifetime) of the catalyst, increase the yield of caprolactam, and reduce the formation of by-products . The implementation method is to place modified metals such as zinc, tin, aluminum, sieve, iridium, or nickel, and precious metals on the support at the same time by co-precipitation method, impregnation method, surface coating method, or ion exchange method. . The source of the above-mentioned modified metals may be pure zinc, tin, aluminum, pound, iridium, and nickel metal powders, or compounds of these modified metals, such as oxides, nitrates, or gasification salts. . According to actual needs, more than one modified metal or a compound thereof may be used. According to the following specific embodiments of the present invention, the modified metal and precious metal are placed on the support at the same time, and the salts of the modified metal such as zinc, tin, aluminum, osmium, iridium, or nickel are formulated into 5 ~ 20% by weight aqueous solution, prepared from 5 ~ 50% by weight of the gasified salt of shell metal, by attaching it to the carrier by dipping and steaming, or directly immersing it for a long time Filter and dry to attach to the support. The appropriate immersion time is more than 5 hours. A suitable amount of the modified metal is between 0 and 20% by weight, and more preferably between 0 and 10% by weight. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs x Consumer Cooperatives The starting materials of precious metal supported catalysts obtained in the above manner (with or without modified metals) should be used for 8 to 5 years. € Pass air to burn and shape to make catalyst particles of appropriate size. In addition, noble metal supported catalysts must be reduced by hydrogen during the use of rhenium. The suitable reduction conditions are activation at 180 ° C to 3000c under a hydrogen flow for 4 to 24 hours. According to the present invention, the method of producing caprolactam by using the special precious metal support catalyst of the present invention is to form f4myl vderic acid or its ester. The paper size is applicable to China A4. -Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, 4228 3 5 A7-^ ___ _B7_ Description of the invention (6) Type 6 is soluble in water, alcohol, or a mixture of water and alcohol. Then the aldehyde The solution of valproic acid or its esters is reacted with hydrogen and ammonia at a temperature of 80 to 300 ° C and a pressure of 10 to 120 atm using the precious metal supported by the support of the present invention as a catalyst. Hydrogenation, acidification and dehydration cyclization reaction to obtain caprolactam. Formyl valeric acid or vinegars suitable for the present invention have the following structure: ii
HC(CH2)4COR 其中R為H、C广Cs的烷基、芳香基或環烷基。較佳 的例子可為碳數為1至4的低級院酯類，或碳數6之芳香 酯類〇 相較於習知技術中以醛基戊酸或其酯類為起始物來合 成己内醯胺所使用的溶劑，本發明的一重要特徵為，不需 使用毒性較高之芳香烴為溶劑，僅以水、醇類、或水與醇 類的混合液做為進料的溶劑，即可得較高之己内醯胺產 率，且在較高的液體進料速度下仍可快速的獲得己内*醯胺 產物11 推測以含有水之混合醇類為溶媒時，在同時具有氫化 及酸、鹼性質之雙功能觸媒作用下，生成之6_胺基己酯中 間產物隨即產生水解反應而轉化成6_胺基己酸’並快速進 行分子内之脫水環化反應生成己内醯胺。水與醇類的混合 8 本紙張尺度適财關丨料（CNS)A4ii#-( 210X297^ ) (請先閱讀背面之注意事項再填寫本頁) -—知衣. 訂 4228 3 A7 B7 經濟部中央橾準局員工消费合作杜印裝 五、發明説明（7 ) 比例為1:10至10:1之間’以3:7至7:3之間為佳。醇的種 類則以含碳數為1至6的直鏈醇或支鏈醇為佳。溶媒的使用 量以不超過85重量％為宜’續增加溶媒之含量，對於己内 醯胺產率之提昇並無特別之助益。搭基戊酸或其自旨類在溶 劑中的濃度以2〜80重量％為宜。 本發明反應的方式可以混泥式連續攪拌槽反應器進 行’或以固定床管式反應器進行。以混泥式連續反應器進 行時，觸媒的用量以搭基戊酸（或酿類）及溶媒量5〜4〇重量 °/〇為宜’較佳的範圍為搭基戊酸醋類（或酸）及溶媒總量之 10〜25重量％，觸媒太少時反應之滯留時間必需延長，觸媒 量過多時對反應並無特別助益。反應的滯留時間為分鐘 〜60分鐘之間’反應的壓力為1〇〜120大氣壓，以3〇〜90大 氣壓為宜，續增高反應壓力並不能有效的增加己内醯胺之 產率。反應溫度為80〜300 °C之間，以110〜230 °C較佳。氫 氣與酯類（或酸）的比例為1〜20:1(摩爾比），其中以3〜15:1較 佳。氨氣與酯類（或酸）的比例為1〜40:1(摩爾比），其中以 5〜3 0:1為佳《在反應完成後’產物經内置之篩網分離觸媒 及背壓閥減壓分離氨氣及氫氣。未反應之氨氣及氫氣.迴流 繼續反應’生成之己内酿胺及溶媒再以氣相層析儀分析己 内醯胺之產率。以固定床進行反應時，液體之進料速度以 0.05〜lOhr·1之間，以1〜Shr·1最佳，其餘反應條件和混泥式 反應器條件相同。 本發明的另一重要特徵為，不論以5-裕基戊酸酷類或 5-酸基戊酸為進料原料，均可以一段反應的方式直接獲得高 (請先閲讀背面之注意事項再填寫本頁) 裝' 1 么··· 本紙張尺度適用中國圉家標窣（CNS > Α4現格（210'X 297公釐} 4228 0 經濟部中夬樣準局貝工消費合作社印策 A7 B7 五、發明説明（8 ) 產率之已内醯胺，而不必以兩段（或三段）反應的方式操作， 不必先將5-醛基戊酸（或酯類）先轉化為6_胺基己酸（或酯 類），再將6-胺基己酸（或酯類）脫水或脫醇環化成己内醯 胺。 為便於瞭解本發明之優異性’下面舉例特別說明本發 明己内酿胺合成法的特性’同時亦與其它方法如鎳觸媒或 其它溶媒之方法比較。混泥式連續反應是在兩個300ml _ 聯之不鏽鋼高壓爸反應器内進行’觸媒經粉碎後取通過4〇 至80篩網之觸媒顆粒，觸媒用量及反應條件說明於實施例 内。固定床反應是在1/2吋的不鏽鋼管式反應器内進行。觸 媒經粉碎後取通過40至80篩網之觸媒15克，反應條件說 明於實施例内，反應之產品經以氮氣逆向吹除未反應之氨 及氫氣後，收集並以HP 5890氣相層析儀分析，使用FID 檢測器偵测己内醯胺之含量。實施例内之轉化率及己内醯 胺產率依下列式（1)、（2)及（3)計算。下述實施例僅為適用於 本發明之代表性例，然而本發明之範圍不限於此等實施 例。 進料内5-醛基戊酸酯類產品内5-齡基戊酸酯類 · 轉化率，摩爾％= 或酸摩爾含量 —或酸摩爾含量 X 100。/。(1) 進料内5-醛基戊酸酯類(或酸)摩爾含量^^ 產品内己内醯胺摩爾含量 已内酿胺產率，摩爾％ =------ 100% (2) 進料内5-醛基戊酸醋類(或酸)摩爾含量 產品内6·胺基己酸產率，摩爾％ 孚胺基己酸產率’摩爾％亡----— X 100% (3) 進料内5-裕基戊酸酷類(或越〇摩爾含量 10 本紙張尺度適用中國國家標準（CNS ) Λ4規洛（210 X 297公釐） ^^^1 ^^^^1 1^1^1 i^i— I. ^^^1 ^^^1 I— i ^ϋ— m , . 、νβ. - - - -- (請先閱讀背面之注意事項再填寫本頁〕 4228 3 5 經濟部中央標"-局員工消費合作社印装 A7 B7 五、發明説明（9 ) 實施例一 取46.84克的丁酸锆[Zr(OC4H9)4]及183.09克的矽酸四 乙酯（Si(〇C2H5)4)加入300ml 攪拌溶解成锆及矽的 混合溶液，緩緩將10重量％的_氨水滴入攪拌中的錄及石夕的 混合溶液中，並調整為10，使產生白色沉澱’經過 濾’水洗乾燥後，以擠壓機成型為0.2厘米X 0.5厘米之顆 粒，經600 t通入空氣焙燒8小時，得觸媒擔if約_包主。 再打碎取通過40〜80網目的顆粒備用。 取前述觸媒顆粒15克，另以201克之氯化釕配成2〇〇ml 溶液浸泡1〇小時後，減壓蒸乾，再在105 °C烘烤16小時’ 將烘乾之觸媒顆粒置入固定床反應管内，以220 °c 還原6小時。將5-醛基戊酸乙酯：水：乙醇=25 : 30 : 45 之混合溶液以2.631^1的速度用高壓泵打入反應管。氫氣以 60ml/hr進入反應管，液氨則利用高壓泵以14ml/hr的速度 打入反應管，在混合區混合後，並在220 °C，50大氣壓下 與觸媒床接觸反應。產品經減壓後進入一滌氣管，以氮氣 將未反應之氨氣及氫氣吹除。產品經收集分析，其5-醛基 戊酸乙酯之轉化率為100%，己内醯胺之產率為85,3%*，6-胺基己酸之產率為7.5%。 實施例二 取日本Nippon Engelhard，以0.5%棘改質之1%纪/二 氧化鈦(K-UCL-09)擔體觸媒50克，打碎後取通過40〜80網 目之顆粒15克置入反應管内，將5-醛基戊酸甲酯：水：甲 醇=50 : 25 : 25的混合溶液以5.2hr_l的速度用高壓泵打入 11 本紙張尺度適用中國國家標準（CMS ) Λ4規格（210X 297公嫠） (請先閔讀背面之注意事項再填寫本頁) 裝 •-a· A7 4228^5 B7 五、發明説明（i〇 ) II J·' —^^^1 mfn itr ^^^^1 ^^^^1—' (請先閱讀背面之注意事項再填寫本頁) 反應管内。氫氣以480ml/min進入反應管，液氨則利用高壓 泵以56ml/hr的速度打入反應管，在混合區混合後，並在130 °C，70大氣壓下與觸媒床接觸反應。產品經收集分析，其 5-醛基戊酸曱酯之轉化率為100%，己内醯胺的產率為 78.5%，6-胺基己酸的產率為18.3%。 比較例一 取打碎為40〜80網目之氧化鎳/三氧化鎢（Ni0/W03)(曰 本Nissan Girdler T-4190)擔體觸媒15克，置入反應管内， 通入氫氣於300 °C活化8小時後。將5-醛基戊酸乙酯：水： 乙醇=25 : 30 : 45之混合溶液以2.631^1的速度用高壓泵 打入反應管中，以與實施例一完全相同的反應條件進行反 應，結果5-醛基戊酸曱酯之轉化率為100%，己内醯胺之產 率為8.8%，6-胺基己酸之產率為58.5%，6-胺基己酯之產 率為21.2%。由此結果可知觸媒如不同時具有高的氫化及 酸、鹼特性時，無法獲得高的己内醯胺產率。 比較例二 經濟部中失橾準局負工消費合作社印裝 取氧化鋁（4〇-80網目）顆粒15克，另以201克之氣化釕 配成200ml溶液浸泡10小時後，以與實施例一完全相-同的 條件配製2.5%釕/氧化鋁擔體觸媒。置入反應管中以氫氣在 220 °C還原6小時，再降溫至130 °C。將5-醛基戊酸甲酯溶 液（純度98.7%)以5.2hr^的速度用高壓泵打入反應管中，再 以與實施例二完全相同的反應條件進行反應，結果5-醛基 戊酸甲酯之轉化率為98.5%，己内醯胺之產率為2.3%，6-胺基戊酸曱酯的產率為83.8%。由此結果可知進料内如無水 12 本紙張尺度適用中國國家標隼（CNS ) A4規格（2!0X 297公釐） A7 4228 3 5 B7 五、發明説明（11 ) 的混合液存在，產品以中間產物6-胺基戊酸曱酯為主，無 法直接脫醇環化為己内醯胺。 實施例三 取打碎為40〜80網目之5%錄/氧化紹（曰本Nippon Engelhard 33-75030)觸媒15g置入反應管中。將5-醛基戊酸 乙酯：水：乙醇=15 : 40 : 55之混合溶液以7.9hr_l的速度 用高麼泵打入反應管中。氫氣以54ml/min之速度進入反應 管，液氨則利用高壓泵以50.5ml/hr的速度打入反應管，在 混合區混合後，並在250 °C，30大氣壓下與觸媒床接觸反 應。產品經分析結果其5-醛基戊酸乙酯之轉化率為100%， 己内醯胺之產率為90.3%，6-胺基己酸之產率為2.8%。 實施例四 與實施例一完全相同的方法，配製觸媒擔體僅改變丁 酸錯為72.0克之氣氧化锆，改變矽酸四乙酯為氣化錫6.5 克，加入300ml的蒸飽水，配成溶液後，以氨水調整pH， 生成之粉末經成型為0.2厘米X 0.5厘米之顆粒，再以600 °C通空氣活化。取前述觸媒顆粒15克，另以201克之氣化 釕配成200ml溶液浸泡24小時後，過濾去除濾液後，·再在 105 °C烘烤16小時。將烘乾之觸媒顆粒置入固定床反應管 内，以氫氣於l〇〇°C活化1小時，再以每小時15 °C的速度 升溫至220 °C，在220 °C再活化6小時。將5-醛基戊酸乙酯： 水：乙醇=80 : 5 : 15之混合溶液以5.3hi^的速度用高壓 泵打入反應管中，液氨則以90mi/hr的速度打入反應管，氫 氣以390ml/min進入反應管，在混合區混合後，在230 °C， 13 本紙張尺度適用中國國家標準（CNS > Λ4現格（210X297公釐） (讀先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央榡隼局員工消費合作社印製 經濟部中夬標準局員工消費合作社印裝 42283 d at B7 五、發明説明（12 ) 50大氣壓下與觸媒床接觸反應，產品經分析結果其5-醛基 戊酸乙酯之轉化率為99.3%，己内醯胺之產率為83.5%，6-胺基己酸之產率為10.7%，6-胺基己酯之產率為1.7%。 實施例五 取實施例一之觸媒擔體15g(40〜80mesh)，以與實施例 一完全相同之方法，僅改以201克之氯化釕及0.12克氯化 銥水溶液含浸配製觸媒，再以與實施例一完全相同之方法 還原觸媒。將5-醛基戊酸異丁酯：水：異丁醇=25 : 20 : 55之混合水溶液以2.63hr」的速度打入反應管，氫氣以 120ml/min的速度進入反應管，液氨則以28ml/hr的速度打 入反應管，在混合區混合後，在180 °C，30大氣壓下與觸 媒床接觸反應，產品經分析結果其5-醛基戊酸異丁酯之轉 化率為100%，己内醯胺之產率為91.4%，6-胺基己酸之產 率為3.8%。 實施例六 取實施例四中之觸媒擔體顆粒（40〜80mesh) 1 5克，以與 實施例一中完全相同之方法，僅改以50克之氣化釕及3,72 克硝酸鎳水溶液含浸配製觸媒，再以與實施例一完全-相同 之方法還原觸媒，及完全相同的條件進行反應，產物分析 結果，己内醯胺之產率為90.3%，6-胺基己酸之產率為 4·7%。 實施例七 與實施例一完全相同之方法配製觸媒，僅以202.4克的 氣氧化锆（ZrOCl2 . 8Η2〇)加入1公升的蒸餾水中，配成溶 14 本紙張尺度適用中國國家標準（CNS ) Λ4現格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 、-=9 經濟部中央標隼局員工消費合作社印裝 Α7 Β7 五、發明説明（13 ) 後’以敦水調整pH，生成之粉末經成型0.2厘米X 0.5厘 米之顆粒，再經600。(：通空氣活化備用。 取打碎為40〜80mesh之上述觸媒擔體顆粒，以與實施 例一完全相同之方法合成觸媒，僅改以0.51克氣化鉑及〇16 克之氣化錫配成之溶液含浸配製觸媒。再以與實施例一完 全相同之方法還原觸媒，將5-链基戊酸乙酯，水及乙醇 =25 : 55 : 20的混合溶液利用高壓泵以2〇hr-i的速度打入 管中，液氨則以40ml/hr的速度打入反應管，氫氣以 260ml/min進入反應管，在混合區混合後’在230 ’ 90 大氣壓下與觸媒床接觸反應。產品經分析結果其5搭基戊 酸乙酯之轉化率為97.8%，己内醒胺之產率為80.7%，6-胺基酸之產率為14.30/〇。 實施例八 與實施例一完全相同之方法配製觸媒擔體，僅改以362 克40%之矽溶膠（LUDOXaS級）及253克氫氧化鎂粉末，經 處練乾燥後成型為〇·2厘米X 〇.5厘米之顆粒，經6〇〇 通 入空氣焙燒10小時，得觸媒擔體。 取打碎為40〜80mesh之上述擔體顆粒，以與實施，例一 完全相同之方法配置觸媒及還原觸媒，僅改以402克之氣 化釕水溶液含浸配製觸媒’再以與實施例一完全相同之條 件進行反應，僅改5-醛基戊酸乙酯為5-醛基戊酸。產品經 分析結果5-醛基戊酸之轉化率為100%，己内醯胺之產率為 85.3°/。，6-胺基己酸之產率為7.6〇/〇。 實施例九 15 本紙張尺度適用中®國家標孪（CNS ) A4規格（2l〇X297公釐） I— .1 — - - >r· IIJ.t/. --.-1 1-1 ^^^1 ^^1 I— . . r · . - ' -V5- -. .- (請先閱讀背面之注意事項再填寫本頁) 422^ 422^ 經濟部中央標隼局員工消资合作社印製 A7 B7 五、發明説明（14 ) 取實施例—之觸媒擔體顆粒15克，以與實施例一完全 相同之方法配製及還原觸媒，僅改以〇 76克之氣化铑及〇, j 2 克氣化銀水溶液含浸配製觸媒，再以與實施例一完全相同 之條件進行反應。產品經分析結果5-醛基戊酸乙酯之轉化 為100% ,己内醯胺之產率為，6-胺基己酸之產率為 6.4%。 實施例十 取實施例一之觸媒擔體顆粒15克，以與實施例一完全 相同之方法配製及還原觸媒，僅改0.76克之氣化铑水溶液 含浸配製觸媒，將5·路基戊酸乙酯：水：乙醇=20 : 30 : 50之混合水溶液用高壓泵以3.7^1之速度打入反應管，液 氨則以46.5ml/hr之速度打入反應管，氫氣以370mI/min進 入反應管’在混合區混合後，並在230 °C，50大氣壓下與 觸媒床接觸反應。產品經分析結果5 -搭基戊酸乙醋之轉化 率為100% ’己内醯胺之產率為90.5%，6-胺基己酸之產率 為 5.8%。 實施例Ί 取 5%韵氧化紹（Nippon Engelhard 13-70010)觸媒-粉末 50克置入300ml之不鏽鋼混泥式高壓爸反應器中，内置5_ 醛基戊酸乙酯：水：乙醇=60 : 15 : 25之混合溶液150ml。 設定氫氣壓力為90大氣壓授拌速度為3 OOrpm，另用高壓 果以1 Oml/min的速度將上述混合溶液打入混泥式高壓爸反 應器中，液氨則以13ml/min的速度打入高壓釜反應器中， 於行反應。產品分析結果5-醛基戊酸乙酯之轉化 -----... ,· 卜 > 卜..，， 16 本紙张尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） 1^1 HI- ^^^1 f HI (^1 - -- ........ - - - I.=穴 1 -_ ^^^1 ^^^1 m , --- -- - (請先閲讀背面之注意事項再填寫本頁) i 4228 3^ α7 Β7 五、發明説明（15 ) 率為100%，己内醯胺之產率為89.7%，6-胺基己酸之產率 為 7.7%。 比較例三 取阮尼鎮觸媒（Grace Davison Raney 2724)50克，以與 實施例十一完全相同之反應條件進行反應，僅改以5-醛基 戊酸乙酯（純度為98.7%)為進料原料。產品分析結果5-醛基 戊酸乙酯之轉化率為93%，己内醯胺之產率為2.1%，6-胺 基己酸乙酯之產率為78.6%。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此項技藝者，在不脫離本發明之精 神和範圍内，當可作更動與潤飾，因此本發明之保護範圍 當視後附之申請專利範圍所界定者為準。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標嗥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（210X297公f )HC (CH2) 4COR where R is H, C, C, Cs alkyl, aromatic or cycloalkyl. Preferred examples are lower-grade esters having 1 to 4 carbon atoms, or aromatic esters having 6 carbon atoms. Compared with conventional techniques, aldehyde valeric acid or its esters are used as starting materials to synthesize hexanoic acid. An important feature of the present invention is that the solvent used for leptamine does not require the use of highly toxic aromatic hydrocarbons as the solvent, and only uses water, alcohols, or a mixed solution of water and alcohols as the feed solvent. A higher yield of caprolactam can be obtained, and caprolactam product can still be obtained quickly at a higher liquid feed rate. 11 It is speculated that when a mixed alcohol containing water is used as a solvent, Under the action of hydrogenation, acid and basic bifunctional catalysts, the 6-aminohexyl ester intermediate produced immediately undergoes a hydrolysis reaction and is converted into 6-aminohexanoic acid ', and the dehydration cyclization reaction in the molecule is rapidly generated to form Lactamine. Mixing of Water and Alcohol 8 Paper-size paper (CNS) A4ii #-(210X297 ^) (Please read the precautions on the back before filling this page)-Zhiyi. Order 4228 3 A7 B7 Ministry of Economic Affairs Du Yinzhuang, Consumer Co-operation of the Central Quasi-Bureau Bureau V. Invention Description (7) The ratio is between 1:10 and 10: 1 ', preferably between 3: 7 and 7: 3. The type of alcohol is preferably a linear or branched alcohol having 1 to 6 carbon atoms. The amount of the solvent used is preferably not more than 85% by weight, and the content of the solvent is increased, which has no special effect on the improvement of the caprolactam yield. The concentration of valproic acid or its moieties in the solvent is preferably 2 to 80% by weight. The reaction method of the present invention can be carried out by a mixed-type continuous stirred tank reactor 'or a fixed-bed tube reactor. When using a mixed type continuous reactor, the amount of catalyst used is preferably valproic acid (or brewing) and the amount of solvent is 5 to 40 weight ° / °. The preferred range is valproic acid vinegar ( Or acid) and 10-25% by weight of the total solvent. The reaction residence time must be extended when the catalyst is too small, and the reaction is not particularly helpful when the catalyst is too much. The residence time of the reaction is between minutes and 60 minutes. The reaction pressure is 10 to 120 atmospheres, preferably 30 to 90 atmospheres. Continuously increasing the reaction pressure cannot effectively increase the caprolactam yield. The reaction temperature is between 80 ~ 300 ° C, preferably 110 ~ 230 ° C. The ratio of hydrogen to esters (or acids) is 1 to 20: 1 (molar ratio), with 3 to 15: 1 being preferred. The ratio of ammonia gas to esters (or acids) is 1 ~ 40: 1 (molar ratio), of which 5 ~ 3 0: 1 is better. "After the reaction is completed, the product is separated by the built-in screen and the catalyst and back pressure. The valve is decompressed to separate ammonia and hydrogen. Unreacted ammonia and hydrogen. Reflux Continue the reaction to generate caprolactam and solvent and analyze the yield of caprolactam with a gas chromatograph. When the reaction is performed in a fixed bed, the feed rate of the liquid is between 0.05 and 10 hr · 1, and the optimum is between 1 and Shr · 1. The remaining reaction conditions are the same as those of the mixed reactor. Another important feature of the present invention is that, whether 5-pentylvaleric acid or 5-acylvaleric acid is used as the feed material, it can be directly obtained in a one-step reaction (please read the precautions on the back before filling in this Pages) 1 '... This paper size applies to Chinese standards (CNS > Α4 now (210'X 297 mm) 4228 0 The Ministry of Economic Affairs Central Bureau of Prototype and Bureau of Shellfish Consumer Cooperatives, India A7 B7 V. Description of the invention (8) Yield of caprylamine, without having to operate in a two-stage (or three-stage) reaction, without first converting 5-aldehyde valeric acid (or esters) to 6-amine Hexanoic acid (or esters), and then dehydration or dealcoholization of 6-aminohexanoic acid (or esters) to caprolactam. In order to facilitate the understanding of the superiority of the present invention, the following examples specifically illustrate the caprolactone of the present invention The characteristics of the amine fermentation method are also compared with other methods such as nickel catalyst or other solvent methods. The mixed type continuous reaction is performed in two 300ml_ stainless steel high pressure reactors. The catalyst particles passing through a 40 to 80 sieve are described in the examples. The fixed-bed reaction is carried out in a 1 / 2-inch stainless steel tube reactor. After the catalyst is crushed, 15 grams of the catalyst passed through a 40-80 screen is described. The reaction conditions are described in the examples. After the nitrogen gas was blown back by unreacted ammonia and hydrogen, it was collected and analyzed by HP 5890 gas chromatograph, and the content of caprolactam was detected using a FID detector. Conversion rate and caprolactam yield in the examples It is calculated according to the following formulae (1), (2), and (3). The following examples are only representative examples applicable to the present invention, but the scope of the present invention is not limited to these examples. 5-aldehyde group in the feed 5-age-based valerates in valerate products · Conversion rate, mol% = or molar acid content-or molar acid content X 100. (1) 5-aldehyde valerates in the feed ( Or acid) molar content ^^ The molar content of caprolactam in the product has the yield of internal amine, molar% = ------ 100% (2) 5-aldehyde valeric acid vinegar (or acid ) Molar content in the product 6. Aminohexanoic acid yield, mol% Molybdenylhexanoic acid yield 'mol %% -------- X 100% (3) 5-pentylvaleric acid in the feed (or More than 0 moles 10 This paper size applies Chinese National Standard (CNS) Λ4 gauge (210 X 297 mm) ^^^ 1 ^^^^ 1 1 ^ 1 ^ 1 i ^ i— I. ^^^ 1 ^^^ 1 I — I ^ ϋ— m,., Νβ.----(Please read the notes on the back before filling out this page) 4228 3 5 Central Standard of the Ministry of Economic Affairs " -Printed by the Consumer Cooperative of the Bureau A7 B7 V. Invention Explanation (9) Example 1 Take 46.84 g of zirconium butyrate [Zr (OC4H9) 4] and 183.09 g of tetraethyl silicate (Si (〇C2H5) 4), add 300 ml and stir to dissolve into a mixed solution of zirconium and silicon. Slowly put 10% by weight of _ ammonia into the mixed solution of Lu and Shi Xi under stirring, and adjust it to 10 so as to produce a white precipitate 'filtered', washed with water, dried, and then molded into an extruder to form 0.2 cm X 0.5 The centimeter particles are roasted for 8 hours by passing air through 600 t, and the catalyst is about _ bag owner. Break and take particles that pass through 40 ~ 80 mesh for later use. Take 15 g of the aforementioned catalyst particles, prepare another 200 ml solution with 201 g of ruthenium chloride and soak for 10 hours, evaporate to dryness under reduced pressure, and bake at 105 ° C for 16 hours. Place in a fixed-bed reaction tube and reduce at 220 ° c for 6 hours. The mixed solution of ethyl 5-aldehyde valerate: water: ethanol = 25: 30: 45 was driven into the reaction tube with a high-pressure pump at a speed of 2.631 ^ 1. Hydrogen enters the reaction tube at 60 ml / hr, and liquid ammonia is driven into the reaction tube at a speed of 14 ml / hr by a high-pressure pump. After mixing in the mixing zone, it is contacted with the catalyst bed at 220 ° C and 50 atmospheres to react. After the product is decompressed, it enters a scrubbing tube, and the unreacted ammonia and hydrogen are blown off with nitrogen. The product was collected and analyzed. The conversion of ethyl 5-aldehyde valerate was 100%, the yield of caprolactam was 85.3% *, and the yield of 6-aminohexanoic acid was 7.5%. Example 2 Take Nippon Engelhard from Japan, use 50% of 1% Ji / Titanium Dioxide (K-UCL-09) carrier catalyst with 0.5% spine modification, and crush it and take 15g of particles passing through 40 ~ 80 mesh and put into the reaction In the tube, a mixed solution of methyl 5-aldehyde valerate: water: methanol = 50: 25: 25 was driven into the 11 at a rate of 5.2 hr_l by a high-pressure pump. This paper size applies the Chinese National Standard (CMS) Λ4 specification (210X 297 (Public Note) (Please read the notes on the back before filling out this page.) 装 • -a · A7 4228 ^ 5 B7 V. Description of the Invention (i〇) II J · '— ^^^ 1 mfn itr ^^^^ 1 ^^^^ 1— '(Please read the notes on the back before filling this page) Inside the reaction tube. Hydrogen enters the reaction tube at 480 ml / min, and liquid ammonia is driven into the reaction tube at a speed of 56 ml / hr by a high-pressure pump. After mixing in the mixing zone, it is brought into contact with the catalyst bed at 130 ° C and 70 atm to react. After the product was collected and analyzed, the conversion rate of the 5-aldehyde valerate was 100%, the yield of caprolactam was 78.5%, and the yield of 6-aminocaproic acid was 18.3%. Comparative Example 1 15 grams of nickel oxide / tungsten trioxide (Ni0 / W03) (Nissan Girdler T-4190) carrier catalyst broken into 40 to 80 meshes was placed in a reaction tube, and hydrogen was introduced at 300 ° After 8 hours of C activation. The mixed solution of ethyl 5-aldehyde valerate: water: ethanol = 25: 30: 45 was driven into the reaction tube at a speed of 2.631 ^ 1 by a high-pressure pump, and the reaction was performed under exactly the same reaction conditions as in Example 1. Results The conversion rate of 5-aldehyde valerate was 100%, the yield of caprolactam was 8.8%, the yield of 6-aminohexanoic acid was 58.5%, and the yield of 6-aminohexyl ester was 21.2%. From this result, it can be seen that if the catalyst does not have high hydrogenation and acid and alkali characteristics at the same time, a high caprolactam yield cannot be obtained. Comparative Example 2 In the Ministry of Economic Affairs, the Bureau of Work and Consumer Cooperatives of the Ministry of Economic Affairs printed 15 grams of alumina (40-80 mesh) particles, and 201 grams of ruthenium gaseous solution was mixed into a 200ml solution for 10 hours. A 2.5% ruthenium / alumina support catalyst was prepared under exactly the same conditions. Put it in a reaction tube and reduce it at 220 ° C for 6 hours with hydrogen, and then reduce the temperature to 130 ° C. The methyl 5-aldehyde valerate solution (purity: 98.7%) was driven into the reaction tube with a high pressure pump at a rate of 5.2 hr ^, and the reaction was performed under exactly the same reaction conditions as in Example 2. As a result, 5-aldehyde pentyl The conversion of methyl ester was 98.5%, the yield of caprolactam was 2.3%, and the yield of 6-aminovalerate was 83.8%. From this result, it can be known that if there is no water in the feed, 12 paper sizes are applicable to Chinese National Standards (CNS) A4 specifications (2! 0X 297 mm) A7 4228 3 5 B7 5. The mixed solution of the invention description (11) exists, and the product is based on Intermediate product is 6-aminovaleric acid phosphonate, which cannot be directly de-alcoholized into caprolactam. Example 3 15 g of a 5% recording / oxidizing catalyst (Japanese Nippon Engelhard 33-75030) broken into 40 to 80 meshes was placed in a reaction tube. A mixed solution of ethyl 5-aldehyde valerate: water: ethanol = 15: 40: 55 was driven into the reaction tube at a speed of 7.9hr_l with a high pump. Hydrogen enters the reaction tube at a rate of 54ml / min, and liquid ammonia is driven into the reaction tube at a rate of 50.5ml / hr by a high-pressure pump. After mixing in the mixing zone, it is contacted with the catalyst bed at 250 ° C and 30 atmospheres to react. . As a result of analysis of the product, the conversion rate of ethyl 5-aldehyde valerate was 100%, the yield of caprolactam was 90.3%, and the yield of 6-aminohexanoic acid was 2.8%. The fourth embodiment is exactly the same as that in the first embodiment. The catalyst support is prepared only by changing the butyric acid to 72.0 grams of gas zirconium oxide, and changing the tetraethyl silicate to 6.5 grams of tin gasified gas. After the solution is formed, the pH is adjusted with ammonia water, and the resulting powder is shaped into particles of 0.2 cm x 0.5 cm, and then activated at 600 ° C with air. Take 15 g of the aforementioned catalyst particles, and immerse in 200 ml of a solution of 201 g of vaporized ruthenium for 24 hours, filter and remove the filtrate, and then bake at 105 ° C for 16 hours. The dried catalyst particles were placed in a fixed-bed reaction tube, activated with hydrogen at 100 ° C for 1 hour, then heated to 220 ° C at a rate of 15 ° C per hour, and activated at 220 ° C for another 6 hours. The mixed solution of ethyl 5-aldehyde valerate: water: ethanol = 80: 5: 15 was driven into the reaction tube with a high pressure pump at a speed of 5.3 Hi ^, and liquid ammonia was driven into the reaction tube at a speed of 90 mi / hr. Hydrogen enters the reaction tube at 390ml / min, and after mixing in the mixing zone, at 230 ° C, 13 paper standards are applicable to Chinese national standards (CNS > Λ4 grid (210X297mm)) (Read the precautions on the back before reading (Fill in this page) Order Printed by the Central Government Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives Printed by the Ministry of Economic Affairs and the Standard Bureau of the Ministry of Economic Affairs and the Consumers Cooperative Printed 42283 d at B7 V. Description of the invention (12) Contact with the catalyst bed at 50 atmospheres. The analysis results showed that the conversion rate of ethyl 5-aldehyde valerate was 99.3%, the yield of caprolactam was 83.5%, the yield of 6-aminohexanoic acid was 10.7%, and the yield of 6-aminohexyl ester The rate is 1.7%. Example 5: Take 15 g (40 ~ 80 mesh) of the catalyst carrier of Example 1, and in the same way as in Example 1, only impregnate with 201 g of ruthenium chloride and 0.12 g of iridium chloride aqueous solution. The catalyst was prepared, and the catalyst was reduced in exactly the same manner as in Example 1. The isobutyl 5-aldehyde valerate was: : Isobutanol = 25: 20: 55 mixed aqueous solution is driven into the reaction tube at a speed of 2.63hr ", hydrogen is fed into the reaction tube at a speed of 120ml / min, and liquid ammonia is driven into the reaction tube at a speed of 28ml / hr. After mixing in the mixing zone, it was contacted with the catalyst bed at 180 ° C and 30 atmospheres. After analysis of the product, the conversion of isobutyl 5-aldehyde valerate was 100%, and the yield of caprolactam was 91.4 The yield of 6-aminohexanoic acid is 3.8%. Example 6: Take 15 grams of the catalyst carrier particles (40 ~ 80 mesh) in Example 4, in exactly the same way as in Example 1, only The catalyst was prepared by impregnation with 50 g of ruthenium gas and 3,72 g of nickel nitrate aqueous solution, and then the catalyst was reduced in exactly the same way as in Example 1, and the reaction was carried out under exactly the same conditions. The result of product analysis, The yield of amine was 90.3%, and the yield of 6-aminohexanoic acid was 4.7%. Example 7 The catalyst was prepared in exactly the same manner as in Example 1, using only 202.4 g of zirconia (ZrOCl2. 8Η2). 〇) Add 1 liter of distilled water to make a solution of 14 paper standards applicable to Chinese National Standards (CNS) 0 × 297 mm) (Please read the precautions on the back before filling this page),-= 9 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (13) After adjusting the pH with water, generate The powder was shaped into particles of 0.2 cm x 0.5 cm, and then passed through 600. (: Activated by air for backup. Take the above-mentioned catalyst carrier particles broken into 40 ~ 80 mesh, and synthesize the catalyst in exactly the same way as in Example 1. The catalyst was impregnated with a solution of 0.51 g of platinum vaporized and 016 g of gasified tin only. Then the catalyst was reduced in exactly the same way as in Example 1. A mixed solution of ethyl 5-chainvalerate, water and ethanol = 25: 55: 20 was driven into the tube at a rate of 20hr-i by a high-pressure pump. In the process, liquid ammonia was injected into the reaction tube at a speed of 40 ml / hr, and hydrogen was introduced into the reaction tube at 260 ml / min. After mixing in the mixing zone, the catalyst was contacted with the catalyst bed at 230 '90 atm. As a result of analysis of the product, the conversion of ethyl 5-valerate was 97.8%, the yield of caprolactam was 80.7%, and the yield of 6-amino acid was 14.30 / 〇. Example 8 The catalyst carrier was prepared in exactly the same way as in Example 1. Only 362 g of 40% silica sol (LUDOXaS grade) and 253 g of magnesium hydroxide powder were used. After being processed and dried, they were formed into 0.2 cm. X 0.5 cm particles were roasted in air for 10 hours at 600 to obtain a catalyst support. Take the above-mentioned carrier particles broken into 40 ~ 80mesh, configure the catalyst and reduction catalyst in exactly the same way as in the implementation, example 1, only to impregnate the catalyst with 402 grams of the gasified ruthenium aqueous solution, and then follow the example. The reaction was carried out under exactly the same conditions, and only 5-aldehyde valerate was changed to 5-aldehyde valerate. As a result of analysis of the product, the conversion rate of 5-aldehyde valproic acid was 100%, and the yield of caprolactam was 85.3 ° /. The yield of 6-aminohexanoic acid was 7.60 / 0. Example 9 15 This paper is applicable to the standard of China® National Standard (CNS) A4 (2 10 × 297 mm) I— .1 —--> r · IIJ.t /. --.- 1 1-1 ^ ^^ 1 ^^ 1 I—.. R ·.-'-V5--. .- (Please read the notes on the back before filling out this page) 422 ^ 422 ^ Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Preparation A7 B7 V. Description of the invention (14) Take 15 grams of the catalyst carrier particles of the example-and formulate and reduce the catalyst in exactly the same way as in the first example. Only use 76 g of rhodium gas and 0, The catalyst was impregnated with 2 g of the gasified silver aqueous solution, and the reaction was performed under exactly the same conditions as in Example 1. As a result of analysis of the product, the conversion of ethyl 5-aldehyde valerate was 100%, the yield of caprolactam was 6.4%. Example 10: Take 15 g of the catalyst carrier particles of Example 1 and prepare and reduce the catalyst in exactly the same way as in Example 1. Only 0.76 g of the aqueous solution of vaporized rhodium was impregnated to prepare the catalyst. Ethyl acetate: water: ethanol = 20: 30: 50 mixed aqueous solution was driven into the reaction tube with a high pressure pump at a speed of 3.7 ^ 1, liquid ammonia was driven into the reaction tube at a speed of 46.5ml / hr, and hydrogen was entered at 370mI / min After mixing in the mixing zone, the reaction tube was brought into contact with the catalyst bed at 230 ° C and 50 atm to react. As a result of analysis of the product, the conversion rate of 5-ethyl ethylvalerate was 100%, the yield of caprolactam was 90.5%, and the yield of 6-aminocaproic acid was 5.8%. Example Ί Take 5% rhodium oxide (Nippon Engelhard 13-70010) catalyst-powder 50g and put it into a 300ml stainless steel mixed type high pressure dad reactor with built-in 5_ aldehyde valerate: water: ethanol = 60 : 15:25 mixed solution 150ml. Set the hydrogen pressure to 90 atmospheres and the mixing speed to 3 OOrpm. In addition, use a high-pressure fruit to drive the above mixed solution into the mixed-type high-pressure reactor at a speed of 1 Oml / min, and liquid ammonia at a speed of 13ml / min. In an autoclave reactor, the reaction is performed. Product analysis results: Conversion of 5-aldehyde valeric acid ethyl ester -----...,… &…… ,, 16 This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 1 ^ 1 HI- ^^^ 1 f HI (^ 1--........---I. = 穴 1 -_ ^^^ 1 ^^^ 1 m, ----- (Please read the notes on the back before filling this page) i 4228 3 ^ α7 Β7 V. Description of the invention (15) The rate is 100%, the yield of caprolactam is 89.7%, and the yield of 6-aminocaproic acid The rate was 7.7%. Comparative Example 3 50 grams of Grace Davison Raney 2724 catalyst was used, and the reaction was carried out under exactly the same reaction conditions as in Example 11. Only 5-ethyl aldehyde valerate (purity (98.7%) as the feedstock. Product analysis results showed that the conversion rate of ethyl 5-aldehyde valerate was 93%, the yield of caprolactam was 2.1%, and the yield of ethyl 6-aminohexanoate was 78.6%. Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make changes and decorations without departing from the spirit and scope of the present invention. The scope of protection of this invention (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297mmf)