A7 __ B7 五、發明説明（1 ) 本發明係有關一種於超大氣壓力下於多相催化劑及水存 在下，使6 -胺基己腈加熱而製備己内醯胺之改良方法。 數種專利及文獻刊物揭示使己二腈之一個腈基氫化而製 備6-胺基己腈。阮尼_之使用則揭示於例如DE 836 938， DE 848 654 (均為 BASF)及 US 5 151 543 (杜邦）；動力學 研究則敘述 C. Mathieu等人；Chem. Eng· Sci. ϋ (1922), 2289-2294。 US 4 628 085 (Allied)敘述在氣相中於特定酸性矽膠 (Porasil A)上，於30〇υ下使6-胺基己腈與水反應。藉Μ 水（14%)，氨（6.3%)及氫/氮稀釋為1.9%基質*可Μ超 過95%之選擇率Μ定量轉化率獲得己內醸胺，但需注意轉 化率及選擇率在僅150小時內即因去活化作用而各降低至 少5 % 〇 類似之氣相製程亦敘述US 4 625 023 (Allied)。此處 ，6 -胺基己腈，己二腈，氨，水及載體氣體之高度稀釋氣 流係通過矽膠及氧化銅/氧化鉻/氧化鋇-氧化鈦催化劑 床。己內醯胺在8 5%轉化率之選擇率為91%。催化劑去活 化之問題經過討論旦降低此問題之測量亦經進行，但沒有 有關此種成功方法之資料。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 這呰方法均具有催化劑快速去活化之缺點，此問題並未 解決。 US 2 245 129 (杜邦）敘述藉使50%強度之6-胺基己睛 水溶液加熱至220 t 20小時而製備線性聚醯胺之方法，並 無有關己内_胺形成之資料。 -4- 本紙張尺度適用中國國家標準（CNS ) Α·4規格（2!0'乂297公釐） A7 B7 五、發明説明（2 ) 另一方面，US 2 301 964敘述胺基己腈（呈水溶液）在 285 °C下未催化地轉化成己内醢胺，產率本質上低於80% 且得到未再加K敘述之殘留物。 FR-A 2 029 540敘述一種藉催化劑使6-胺基己腈環化成 己内醯胺之方法，所用催化劑為金屬鋅或鋼粉或教I、鉛、 汞或具有自21至30原子數或具有自39至48原子數之元素之 氧化物，氫氧化物，鹵化物或氰化物。所述催化劑係Μ於 批次攪拌之壓熱鍋中之懸浮液催化劑使用。己内醯胺獲得 Μ產率達83%。然而，完全自所霈產物己內醯胺中分離出 催化劑存在有困難，係由於己内醯胺可與所用金屬之可溶 性成份形成化合物或由機械攪拌而形成非常细顆粒之故。 已知，溶於水中之6-胺基己酸（DS 3 485 821 )可在 150-350 t：下環化成己內醯瞭。 DE-C 952 442掲示一種藉兩階段所使5-甲醯戊酸酯在氫 化條件下胺化而得除了胺基己酸酯Μ外之己内醯胺之方法 Ο 經濟、那中央標準局員工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁) US 3 988 319 (亦參見DE 2 535 689)掲示一種於甲醇 或乙醇作為溶劑中使6 -胺基己酸環化之方法。然而，為了 避免6 -胺基己酸之二次反應*後者需緩慢置於溶液中，而 不會蓄積成固體，此目的則需要約170 °C之溫度。再者， 溶液之水含量需不超過40%，否則會形成開鏈聚合物。當 再使用醇時，反應釋出之水需經分離出。 然而，U S 3 9 8 8 3 1 9之作者亦陳述在I n d . E n g . C h e m . Process Des. Dev. 1_L (1978), 9-16 中，6-胺基己酸於 -5 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） B7 五、發明説明（3 ) 水中環化成己内醣胺會引起相當量之寡聚物，除非使用濃 度低於13%且溫度約為300¾。 A. Blade-Font, Tetrahedron Lett. ΖΧ. (1980), 2 443-2446敘述6-胺基己酸Μ於甲笨中之懸浮液，在氧化 鋁或矽膠存在下，Μ移除反應之水之情況下之環化反應。 為了完全解吸己内醯胺，催化劑需Μ二氯甲烷/甲醇洗滌 且聚合物Μ乙醚沈澱。反應時間20小時後己內醢胺於氧化 鋁上之產率為82%，於氧化矽上為75%。 ΕΡ 271 815揭示藉溶解酯於芳族烴中使6-胺基己酸酷環 化成己内醯胺之反應，係在100至3201D下進行環化且同時 分離除去消除之醇。 ΕΡ-Α 376 122揭示藉溶解酯於芳族烴中使6-胺基己酸磨 環化成己内醢胺之反應，係在使用水之情況下，於230至 350Τ，特別是自260至340¾下進行。 經濟部中央標準局員工消費合作社印製 (請先聞讀背面之注意事項再填寫本頁) 已知聚醯胺6可斷裂而得己内醯胺，此斷裂係在酸性或 鹼性催化劑之作用下，在高溫下，經常係在氣流即低壓力 下進行。Chem. Ing. Techn. _(1973)，1510 敍述 K超 熱氣流之斷裂製程之技術步驟，其必需濃縮己内醸胺/水 溶液供操作。於EP 209 021中，斷裂係於流體化氧化鋁床 中進行。EP 529 470係使用碳酸鉀作為聚醯胺6斷裂之催 化劑，且反應係在250至320Ϊ：下藉減壓蒸餾同時移除己内 醯胺而進行。 目前所有製程之缺點為聚醯胺6斷裂成己内釀胺在分離 大量水及移除催化劑（如磷酸及其鹽，碳酸鉀或鹼金屬氧 -6- 本紙張尺度適用中國國家標準（CNS ) ( 210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 化物）方面非常耗費能源。在氣相反應之情況中，聚合物 通常係加熱至270 - 400 °C且在流體化床反應器中與水一起 斷裂。由於催化劑床之附聚而會引起副產物形成及去活化 作用。 本發明之一目的係提供一種自6-胺基己腈製備己內醯胺 之改良方法，其係在K高選擇性且所用催化劑不會快速去 活化之技術可行方式進行。再者*此方法可在不產生多量 低沸物及/或高沸物下進行。 吾人發現此目的可藉使6-胺基己腈在多相催化劑及水存 在下，於超大氣壓力下加熱而製備己內醮胺之方法達成* 其中： (a) 6-胺基己腈，或本質上含6-胺基己腈之混合物•與 水及低沸點或高沸點醇，在反應器A中於多相催化 劑存在下加熱，得混合物I ， (b) 接著混合物I經蒸餾，得頂餾份，己内醯胺及底部 產物*若混合物中存在有氨則需在蒸餾前先移除氛 ，且接著 (cl) 頂餾份饋入階段（a)之反應器A中，若需要，頂餾 份在饋入反應器A之前，可與階段U>所用之醇或 水或6-胺基己腈混合，或 (c2) 頂餾份若需要可與階段（b)之底部產物一起饋入反 應器B中，若需要，頂餾份在饋入反應器B前，可 與階段（a)所用之醇或水或6-胺基己腈混合*接著 依類似於階段（b)之蒸餾法，得己內醸胺，及 -7- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -----------參-- C (請先鬩讀背面之注意事項再填寫本頁) 卜訂 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（5 )A7 __ B7 V. Description of the invention (1) The present invention relates to an improved method for preparing caprolactam by heating 6-aminocapronitrile in the presence of a heterogeneous catalyst and water under superatmospheric pressure. Several patents and publications disclose the preparation of 6-aminocapronitrile by hydrogenating one of the nitrile groups of adiponitrile. The use of Nguyen Ni is disclosed in, for example, DE 836 938, DE 848 654 (all BASF) and US 5 151 543 (DuPont); kinetic studies describe C. Mathieu et al .; Chem. Eng · Sci. Ϋ (1922 ), 2289-2294. US 4 628 085 (Allied) describes the reaction of 6-aminocapronitrile with water in a gas phase on a specific acidic silicone (Porasil A) at 300 ° C. By diluting M water (14%), ammonia (6.3%), and hydrogen / nitrogen to 1.9% substrate *, the selectivity of M can exceed 95%. Quantitative conversion can obtain caprolactam, but it should be noted that the conversion and selectivity Reductions of at least 5% each due to deactivation in just 150 hours. Similar gas phase processes are also described in US 4 625 023 (Allied). Here, a highly dilute stream of 6-aminocapronitrile, adiponitrile, ammonia, water and carrier gas is passed through a bed of silica gel and a copper oxide / chromia / barium oxide-titanium oxide catalyst. The selectivity for caprolactam at a conversion of 85% was 91%. The issue of catalyst deactivation has been discussed and measures have been taken to reduce this problem, but no information is available on such successful methods. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) This method has the disadvantage of rapid catalyst deactivation, and this problem has not been solved. US 2 245 129 (DuPont) describes a method for preparing linear polyamidoamine by heating a 50% strength 6-aminohexanone aqueous solution to 220 t for 20 hours. There is no information on the formation of caprolactam. -4- This paper size applies the Chinese National Standard (CNS) A · 4 specification (2! 0 '乂 297 mm) A7 B7 V. Description of the invention (2) On the other hand, US 2 301 964 describes amino capronitrile ( As an aqueous solution) at 285 ° C without catalytic conversion to caprolactam, the yield is essentially less than 80% and a residue without additional K description is obtained. FR-A 2 029 540 describes a method for cyclizing 6-aminocapronitrile to caprolactam by using a catalyst, such as metal zinc or steel powder or I, lead, mercury, or having a number of atoms from 21 to 30 or Oxides, hydroxides, halides or cyanides with elements from 39 to 48 atoms. The catalyst is used as a suspension catalyst in a batch-stirred autoclave. Caprolactam yielded an M yield of 83%. However, it is difficult to completely separate the catalyst from the caprolactam product, which is due to the fact that caprolactam can form compounds with the soluble components of the metal used, or it can form very fine particles by mechanical stirring. It is known that 6-aminohexanoic acid (DS 3 485 821) dissolved in water can be cyclized to caprolactam at 150-350 t :. DE-C 952 442 shows a method for obtaining caprolactam other than aminocaproate M by the amination of 5-methylvalerate under hydrogenation conditions in two stages. Economy, the staff of the Central Bureau of Standards Consumption cooperation printed by Du (please read the notes on the back before filling this page) US 3 988 319 (see also DE 2 535 689) shows a method for cyclizing 6-aminohexanoic acid in methanol or ethanol as a solvent . However, in order to avoid the secondary reaction of 6-aminohexanoic acid *, the latter needs to be slowly placed in solution without accumulating into solids, and a temperature of about 170 ° C is required for this purpose. Furthermore, the water content of the solution should not exceed 40%, otherwise open-chain polymers will be formed. When alcohol is reused, the water released from the reaction needs to be separated. However, the authors of US 3 9 8 8 3 1 9 also stated in Ind. Eng. C hem. Process Des. Dev. 1_L (1978), 9-16, 6-aminohexanoic acid in -5-this Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) B7 V. Description of the invention (3) Cyclization to caprolactam in water will cause a considerable amount of oligomers, unless the concentration is lower than 13% and the temperature is about It is 300¾. A. Blade-Font, Tetrahedron Lett. XX. (1980), 2 443-2446 describes a suspension of 6-aminohexanoic acid M in methylbenzyl. In the presence of alumina or silicone, M removes the water of reaction. In the case of cyclization. To completely desorb caprolactam, the catalyst was washed with M dichloromethane / methanol and the polymer was precipitated with Methyl ether. After 20 hours of reaction time, the yield of caprolactam on alumina was 82% and on silica was 75%. EP 271 815 discloses that the reaction of 6-aminohexanoic acid to caprolactam by dissolving an ester in an aromatic hydrocarbon is cyclized at 100 to 3201D and the eliminated alcohol is separated and removed at the same time. ΕΡ-Α 376 122 revealed that the reaction of grinding cyclization of 6-aminohexanoic acid to caprolactam by dissolving an ester in an aromatic hydrocarbon is from 230 to 350T, especially from 260 to 340¾ using water. Carry on. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) It is known that polyamidoamine 6 can be broken to obtain caprolactam. This breaking is based on the role of acid or alkaline catalyst Down, under high temperature, often under the air flow, that is, under low pressure. Chem. Ing. Techn. _ (1973), 1510 describes the technical steps of the K super hot gas flow breaking process, which must be concentrated by caprolactam / water solution for operation. In EP 209 021, the fracture is carried out in a fluidized alumina bed. EP 529 470 uses potassium carbonate as a catalyst for the cleavage of polyamidamine 6, and the reaction is carried out at 250 to 320 Ϊ: by vacuum distillation while removing caprolactam. The disadvantage of all current processes is that polyamine 6 is broken into caprolactam, which is used to separate a large amount of water and remove catalysts (such as phosphoric acid and its salts, potassium carbonate or alkali metal oxygen-6). This paper applies Chinese national standards (CNS) (210X297 mm) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The invention description (4) compounds) consumes a lot of energy. In the case of gas-phase reactions, the polymer is usually heated to 270-400 ° C and broken with water in a fluidized bed reactor. The agglomeration of the catalyst bed causes by-product formation and deactivation. An object of the present invention is to provide an improved method for preparing caprolactam from 6-aminocapronitrile, which is carried out in a technically feasible manner with high K selectivity and the catalyst used will not be rapidly deactivated. Furthermore * this method can be carried out without generating a large amount of low boilers and / or high boilers. I have found that this purpose can be achieved by heating 6-aminocapronitrile in the presence of a heterogeneous catalyst and water under superatmospheric pressure to prepare caprolactam * where: (a) 6-aminocapronitrile, Or a mixture containing 6-aminocapronitrile in nature • with water and low-boiling or high-boiling alcohols, heated in reactor A in the presence of a heterogeneous catalyst to obtain mixture I, (b) followed by distillation of mixture I to obtain Top fraction, caprolactam and bottom product * If ammonia is present in the mixture, the atmosphere must be removed before distillation, and then (cl) the top fraction is fed to reactor A in stage (a), if required Before the top fraction can be fed into reactor A, it can be mixed with the alcohol or water or 6-aminocapronitrile used in stage U > or (c2) the top fraction can be combined with the bottom product of stage (b) if necessary Feed into reactor B. If necessary, the top fraction can be mixed with the alcohol or water or 6-aminocapronitrile used in stage (a) before feeding into reactor B. Then follow similar steps as in stage (b) Distillation method to obtain caprolactam, and -7- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) --------------- ( (Please read the precautions on the back before filling out this page.) Invoicing Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (5)
fdl) 來自階段（b) ，·底部產物饋入階段（a)之反應器A ，或 (d2) 若需要之水及低沸點或高沸點醇若需要可加至底部 產物中，接著後者於另一個反應器C中，類似於階 段（a)般加熱*得反應之馮合物，藉蒸餾由其中獲 得己内醸胺，或 (d3) 添加水至底部產物中，接著在未添加催化劑下，於 反應器D中加熱，得反應之混合物，藉蒸餾自該反 應混合物中得到己内醣胺，或 (d4) 已添加水及鹼之底部產物於反應器E中加熱，得反 應之混合物，藉蒸餾於其中獲得己内釀胺。 本發明中使用作為起始物之6-胺基己腈通常由已知方法 使己二腈進行氫化所得者，如述於DE-A 836 938，DE-A 848 654 或US 5,151,543之方法。 亦可能於反應器A中導入本質上含有6 -胺基己腈及己二 胺之混合物，當處理依本發明製得之己内醢胺時，可得己 二腈及/或己内醯胺，及高沸點餾份（高沸物）如6-胺基己 醯胺，6-胺基己酸，聚己内醯胺及己內醯胺之寡聚物及進 一步得到之6-胺基己酸酯，且6-胺基己酸酯可為低沸點或 高沸點，端視酯殘基而定。 依據本發明，6-胺基己睛係與水反應，每奠耳6-胺基己 睛較好使用自0.01至35*特佳為自1至10奠耳之水。依據 本發明，可又使用低沸點或高沸點醇，較好可選用稀釋成 ]至50%重量之6-胺基己睛。 -8 - 本1 我張尺度適用中國國家標準（CNS ) M規格（21〇'x297公釐） _ 1裝 . 訂 -V、、 ... (請先聞讀背面之注意事項再填寫本頁) 經濟部中央梯準局員工消費合作社印製 A7 B7 五、發明説明（6 ) 低沸點醇為在5毫巴（mbar)下具有不超過低於己内醯胺 沸點10¾之沸點者，例如Cn-io烷醇，特別是甲醇，乙酵 ，正丙醇，異丙醇，正丁醇，異丁醇或第二丁醇，特別是 甲醇或乙醇。 高沸點酵為在5毫巴下具有至少髙於己內醯胺沸點10¾ 之沸點者，例如聚醚醇如四乙二酵。 於又一具體例中，可於反應混合物中添加0至5 ，較好 自0.1至2%重量之氨及/或氫及/或氮。 可用之多相催化劑實例為，例如，週期表第二，第三或 第四主族元素；酸性、鹼性或兩性氧化物如氧化鈣，氧化 隹美，氧化硼，氧化鋁，氧化錫或氧化矽，如焦化氧化矽， 矽膠，矽藻土，石英或其混合物，及週期表第二至第六亞 族金鼷之氧化物如氧化鈦（呈非晶型或銳钛礦或金紅石態 )，氧化皓，氧化鉾，氧化鎂或其混合物。例如鑭係及锕 系之氧化物如氧化鈽，氧化钍，氧化繒，氧化釤，氧化钕 ，稀土混合之氧化物及其與前述氧化物之混合物亦可使用 。再者，催化劑可為例如；氧化釩，氧化鈮，氧化鐵，氧 化鉻，氧化絪，氧化鎢及其混合物。這些氧化物與第二， 第三及第四主族之氧化物之混合物亦可使用；亦可使用某 些硫化物，硒化物及碲化物如碲化鋅，晒化鋅，硫化鉬， 硫化鎢及鎳、鋅及鉻之硫化物。 前述化合物可摻雜週期表1及7主族化合物或可含有這 些化合物。 其他催化劑為例如沸石，磷酸鹽及雑多酸及酸性及鹼性 -9- 本紙張A度適用中國國家標率（CNS ) A4規格（210X297公釐） — — — ——— —i n I i n I ^ I , -; /-------. , (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 _____B7__ 五、發明説明（7 ) 離子交換劑如Naphion*®。 若需要，這些化合物各情況下可含有達50%重量之銅* 錫，鋅，錳，鐵，鈷，鎳，釕，鈀，鉑，銀或鍩。 視催化劑之組成而定，後者可使用作為未支撐或經支撐 催化劑，例如氧化鈦可Μ氧化鈦擠出物使用或K於載體上 之薄膜之氧化钛使用。目前可見者顯示文獻中所述之所有 方法可用Κ塗佈二氧化鈦至載體上如氧化矽，氧化鋁或二 氧化锆。因此，薄層二氧化钛可應用有機鈦之水解如異丙 基钛或丁基鈦或應用於四氣化鈦或其他無機含鈦化合物之 水解。含氧化钛之溶液亦可使用。 依據本發明，階段（a>之反應係在100至32 0t! *較好自 16 0至280 t：，特佳自180至2601：下進行。 通常，階段（a)之反應係在超大氣壓力下進行，壓力通 常選擇自0.1至50，較好自0.5至25 MPa。 反應器A中反應之停留時間，本質上係視所選用之製程 參數而定，且於連續製程中，通常自1至300 ，較好自5 至120分鐘。較短反應時間通常轉化率會降低，而目前顯 現較長之反應時間會導致寡聚物形成増加，因此大量寡聚 物需再循環供斷裂。 環化反應（階段（a))較好於反應器A中連續進行，較好 於反應管中*於攪拌釜中或其姐合中進行。 環化反應（階段U))亦可藉批次進行，此情況之反應時 間通常自30至300分鐘。 依據本發明，反應器A之排出物為本質上由水，醇，在 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先鬩讀背面之注意事項再填寫本頁) J-裝. 訂 Α7 Β7 五、發明説明（8 ) 反應中由形成之6-胺基己酸與所用之醇反應所得之6-胺基 己酸酯*己内醯胺，氨及高沸點化合物（高沸物）如6-胺基 己醱胺及己内_胺之寡聚物所組成之混合物I。 依據本發明，階段（b)中，混合物I係藉習知方法蒸餾 而得頂餾份，己内醣胺及底部產物。若由階段（a)之混合 物I含有氨•則依據本發明，該氨需在蒸餾前移除。氨可 藉習知方法移除，例如蒸餾法，或使惰性氣流通過混合物 I 〇 混合物I之處理可於較佳具體例中，藉蒸餾法Μ先共沸 蒸除水及任何低沸點酵•並使所得殘留物進行一或多次進 一步蒸餾或藉單一蒸餾管柱中蒸餾混合物I而逐漸或同時 進行。 於較佳具體例中，首先在10至500 ，較好50至350毫巴 之減壓下進行蒸餾而得水及可能之醇，且蒸餾殘留物在自 90至220°C，較好自100至16〇υ，在自〇.〇1至1 ，較好自 0.5至300毫巴下進行進一步蒸餾，得頂餾份，己內醣胺 及底部產物。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 頂餾份一般本質上含有低沸點之6-胺基己酸烷酯*未轉 化之6-胺基己腈及水（除非已完全移除）及所用之醇（若其 為低沸點者）。 通常，底部產物本質上係由高沸點成份構成，如己内醯 胺之寡聚物· 6-胺基己醯胺，6-胺基己酸，及視所用醇而 定之高沸點6 -胺己酸酯及若有使用之高沸點酵。 依據本發明，若需要與任何事先分離出之酵與水一起之 -11- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） A 7 B7 五、發明説明（9 ) 頂餾份再循環至反應器A (階段U1))中，且頂餾份在饋入 反應器A之前*可與階段（a)所用之醇及/或水及/或 6-胺基己膊混合。 依據本發明，階段U)中所得之頂餾份可視情況饋入反 應器B (階段（c2))中，若需要可與階段（b)之底部產物一 起饋人且若需要可與事先分離出之任何醇及水一起饋人’ 且頂餾份在饋入反應器B之前*可與階段（a)所用之醇及 /或水及/或6-胺基己腈混合。反應器B中之反應條件係 選擇為相對於反應器A之條件。反應器B之經反應混合物 係類似於階段（b)般操作，己内醯胺係於一或多次蒸餾階 段中獲得。 除了前述變數*階段（b)所得之底部產物可依據本發明 於階段（c2)中藉4種其他方法操作，即 於階段（dl)中，階段（b)之底部產物饋人階段（a)之反 應器A中，或 經濟部中央標準局員工消費合作社印製 (請先閣讀背面之注意事項再填寫本頁) 於階段（d2)中，若需要，水及低沸點或高沸點醇可加至 底部產物中*較好為0.：[-至25-倍，特佳為0.15-至15-倍 重量之水及較好1-至25-倍，特佳為3-至15-倍重量之水， 於另一個反應器C中依類似於階段（a>般進行加熱，得經 反應之混合物，藉蒸餾，較好依類似於階段（b)般蒸餾由 其中獲得己内醯胺，或 (d3) 水可添加至底部產物中，較好添加5-至25-倍，特 佳7-至15-倍重量之水，並在未添加催化劑下於反 應器D中進行加熱，其中反應條件係選擇至類似於 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) 反應器A之條件，但溫度選擇在200至3501：,較好 自280至320TC，且停留時間自5至240分鐘，得經 反應之混合物，由其中藉蒸餾較好類Μ於階段（b> 般蒸餾而得己内醢胺，或 fd4) 於其中已加入水及鹼之底部產物於反應器E中加熱 ，得經反應之混合物，由其中藉蒸餾，較好類似於 階段（b)蒸餾而得己内醢胺；底部產物之加熱係在 通常自0.1至50，較好自1至10毫巴之減壓力，於 通常為1至10，較好自1至3%重量之鹼存在下，於 反應器E中，較好於反應管中•在自200至400 υ， 較好自280至320t：下進行。 理論上，底部產物當然亦可藉晋知方法操作，例如使其 進行一種習知氣相製程或進行一次Μ酸性催化劑之一般操 作方法。然而，由於習知製程之缺點，Μ前述新穎具體例 (c2)及（dl)至（d4)較佳。 所用之鹸較好為鹼金靥氫氧化物及鹼金鼷碳酸鹽如氫氧 化鈉，氬氧化鉀，碳酸納及碳酸鉀，或其混合物，特佳為 氫氧化納及/或氫氧化鉀。 此新穎方法之優點為己内醯胺偽K高選擇率及高產率之 技術實行方式自6-胺基己腈獲得己内釀胺，而無所用催化 劑快速去活化之問題，且未產生大量之低沸物及高沸物。 實例 實例1 -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） . 衣 I 訂 -' ...、... · (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（11 ) (8)以7〇111]./11使10%重量6-胺基己睛，3.2%重量水及乙 酵（剩餘物）之溶液在100巴下導人加熱至2301：之反應 管（容積20毫升，直徑6毫米及長度710毫米且填有 呈1.5毫米擠出物之氧化钛（銳钛礦））。 反應混合物藉氣相層析定量評估得下列產率（無乙酵 及水）：91%己内醢胺，4% 6-胺基己酸乙酯及1%6-胺基己腈。 20 0小時内收集之產物氣流不含乙醇及水，且所得粗 製内醸胺經蒸餾，得56克低沸點成份（低沸物）及126 克高沸點成份(高沸物）及1232克己内醢胺。低沸物本 質上由6-胺基己酸乙酯及未反應之6-胺基己腈所構成 ，且高沸物本質上由寡聚物所構成。 (b)添加445克水至126克寡聚物，56克低沸物（得自 (a))及1.200克6-胺基己腈中，且混合物Μ乙酵稀釋， 得10%強度重量之溶液。此溶液在7〇 ml/h之速率再 泵入於230¾及100巴之反應器中，Μ氣相層析法測定 排出產物之產率（未計算乙酵及水）為：87%己內醸胺 ，3% 6-胺基己酸乙酯及0.5% 6-胺基己腈。 經濟部中央標準局員工消費合作社印製 (請先鬩讀背面之注意事項再填寫本頁) 蒸餾後，由第二次排出物中獲得11 82克己内醸胺，36克 低沸物及150克高沸物。合計自2600克6-胺基己腈獲得 36克可再循環之低沸物，150克高沸物及2432克己内醯胺 。總產率為93%且選擇率為98%。 實例2 (a) Κ100 ml/h使10%重量6-胺基己臃* 16.0%重量水及 -14- 本紙張尺度適用中國國家標準（CNS ) A4^格（210X297公釐） 經濟部中央標準局員工消費合作社印製 A7 ___ _Βλ___ 五、發明説明（12 ) 乙醇（刺餘物）之溶液，於200巴下導入加熱至230¾之 反應器（容積20毫升，直徑6毫米及長度710毫米且 填有呈1.5毫米擠出物之氧化鈦（銳鈦磯））。 Μ氣相層析定量評估反應混合物，得下列產率（無乙 酵及水）：93%己內醯胺及2% 6-胺基己酸乙酯。 Κ 200小時內收集之產物氣流不含水及乙醇，且所得 粗製內醣胺經蒸餾，得55克低沸點成份（低沸物）及 140克高沸點成份（高沸物）及1820克己内醯胺。低沸 物本質上係由6 -胺基己酸乙酷構成，且高沸物本質上 由寡聚物構成。 (b>添加3830克水至140克寡聚物，55克低沸物（得自實 例2a)及2200克&-胺基己腈中*混合物Μ乙酵稀釋， 得10%強度重量溶液。此溶液Μ100 ral/h速率再泵經 在260¾及200巴之反應器，排出產物之產率藉氣相層 分析（未計算乙醇及水）為：91%己內醯胺及2 % 6-胺 基己酸乙酯。 蒸餾後，自第二次排出物中得2 129克己内醢胺，57克低 沸物及1 96克高沸物。 合計自4200克6-胺基己腈得57克可再循環之低沸物， 196克高沸物及3945克己内醯胺。總產率為94%且選擇率 為 99% ° 實例3 (a)以1 5 ml/h使10%重量6-胺基己腈，3.2%重量水及乙 酵（刺餘物）之溶液，於100巴下導入加熱至2 00 t：之反 -1 5 - 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） (請先鬩讀背面之注意事項再填寫本頁) •裝_ 訂 Λ 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（u) 應管（容積2 0毫升，直徑6毫米及長度710毫米，並 填有里1 · 5毫米擠出物之氧化鈦（銳鈦礦））。 反應混合物以氣相層析定β評诂得下列產率（無乙醇 及水）：88%己内蘸胺，及4% 6-胺基己酸乙酯及4 % 6-胺基己腈。 200小時內收集之產物氣流不含乙醇及水’且所得粗 製内醸胺經蒸餾，得29克低沸點成份（低沸物）及12克 高沸點成份（髙沸物）及260克己内醣胺。低沸物本質 上由6-胺基己酸乙酯及未反應之6-胺基己腈所構成， 且高沸物本質上係由寡聚物構成.。 (b)添加94克水至12克寡聚物’ 29克低沸物（得自實例 3a)及260克6-胺基己腈中，且混合物K乙醇稀釋* 得10¾強度重量之溶液，此溶液以1〇〇 «^八之速率再 泵經在2 50Ό及200巴之反應器’排出物產物之產率以 氣相曆析法測定（未計算乙酵及水）為：91%己內醯胺 及2 % 6 -胺基己酸乙酯。 蒸餾後，自第二次排出物得265克己内醯胺’ 83克低沸 物及25克高沸物。 合計自560克6-胺基己腈得83克可再循環之低沸物’ 25克高沸物及525克己内醸胺。總產率為94%且選擇率為 99% ° -16- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐了 (請先閣讀背面之注意事項再填寫本頁) •裝· 訂-fdl) from stage (b), the bottom product is fed into reactor A of stage (a), or (d2) if needed, water and low-boiling or high-boiling alcohols can be added to the bottom product if needed, and the latter is then added to another In a reactor C, the reaction Feng compound is heated similar to stage (a), and caprolactam is obtained therefrom by distillation, or (d3) water is added to the bottom product, and then without catalyst, Heating in reactor D to obtain the reaction mixture. Distillation to obtain caprolactam from the reaction mixture, or (d4) the bottom product to which water and alkali have been added is heated in reactor E to obtain the reaction mixture. Distilled therein to obtain caprolactam. The 6-aminocapronitrile used as the starting material in the present invention is usually obtained by hydrogenating adiponitrile by a known method, such as the method described in DE-A 836 938, DE-A 848 654 or US 5,151,543. It is also possible to introduce into the reactor A a mixture containing essentially 6-aminocapronitrile and hexamethylene diamine. When processing caprolactam prepared according to the present invention, adiponitrile and / or caprolactam can be obtained , And high-boiling fractions (high-boiling substances) such as 6-aminohexanoic acid, 6-aminohexanoic acid, polycaprolactam and oligomers of caprolactam and further obtained 6-aminohexanox Acid esters, and 6-aminohexanoic acid esters can be low boiling or high boiling, depending on the ester residue. According to the present invention, 6-aminocapsules are reacted with water, and water of 6-aminocapsules per mole is preferably used from 0.01 to 35 * particularly preferably from 1 to 10 moles. According to the present invention, a low-boiling or high-boiling alcohol may be used again, and preferably 6-aminohexanoic acid diluted to 50% by weight may be selected. -8-This 1-sheet scale applies Chinese National Standard (CNS) M specifications (21〇'297 mm) _ 1 pack. Order -V ,, ... (Please read the precautions on the back before filling out this page ) A7 B7 printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs. 5. Description of the invention (6) Low-boiling alcohols have a boiling point at 5 mbar not lower than the boiling point of caprolactam, such as Cn -ioalkanols, especially methanol, ethyl acetate, n-propanol, isopropanol, n-butanol, isobutanol or second butanol, especially methanol or ethanol. High-boiling yeasts are those having a boiling point at 5 mbar of at least 10¾ of caprolactam, such as polyether alcohols such as tetraethylene glycol. In another specific example, 0 to 5 and preferably 0.1 to 2% by weight of ammonia and / or hydrogen and / or nitrogen may be added to the reaction mixture. Examples of useful heterogeneous catalysts are, for example, elements of the second, third or fourth main group of the Periodic Table; acidic, basic or amphoteric oxides such as calcium oxide, rame oxide, boron oxide, alumina, tin oxide or oxide Silicon, such as coking silicon oxide, silica gel, diatomaceous earth, quartz, or mixtures thereof, and oxides of the second and sixth subgroups of the periodic table, such as titanium oxide (in the amorphous or anatase or rutile state) , Halo oxide, hafnium oxide, magnesium oxide or mixtures thereof. For example, the oxides of the lanthanide series and the actinide series such as ytterbium oxide, ytterbium oxide, ytterbium oxide, ytterbium oxide, neodymium oxide, rare earth mixed oxides, and mixtures thereof with the foregoing oxides can also be used. Furthermore, the catalyst may be, for example, vanadium oxide, niobium oxide, iron oxide, chromium oxide, hafnium oxide, tungsten oxide, and mixtures thereof. Mixtures of these oxides with the oxides of the second, third, and fourth main groups can also be used; certain sulfides, selenides, and tellurides such as zinc telluride, zinc zinc, molybdenum sulfide, and tungsten sulfide can also be used And nickel, zinc and chromium sulfides. The aforementioned compounds may be doped with the main group compounds of the Periodic Tables 1 and 7 or may contain these compounds. Other catalysts are, for example, zeolites, phosphates and polyacids, and acidity and alkalinity. 9- This paper A degree is applicable to China National Standard (CNS) A4 specifications (210X297 mm) — — — ——— —in I in I ^ I,-; / -------., (Please read the notes on the back before filling out this page) A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _____B7__ 5. Description of the invention (7) Ion exchangers such as Naphion * ®. If desired, these compounds may each contain up to 50% by weight of copper * tin, zinc, manganese, iron, cobalt, nickel, ruthenium, palladium, platinum, silver or rhenium. Depending on the composition of the catalyst, the latter can be used as an unsupported or supported catalyst, for example, titanium oxide can be used as a titanium oxide extrudate or titanium oxide on a carrier film. Presently it has been shown that all methods described in the literature can be used to coat titanium dioxide on a carrier such as silica, alumina or zirconia. Therefore, thin-layer titanium dioxide can be applied to the hydrolysis of organic titanium such as isopropyl titanium or butyl titanium or to the hydrolysis of titanium tetragas or other inorganic titanium-containing compounds. Titanium oxide-containing solutions can also be used. According to the present invention, the reaction in stage (a >) is performed at 100 to 32 0t! * Preferably from 160 to 280 t :, particularly preferably from 180 to 2601 :. Generally, the reaction in stage (a) is at superatmospheric pressure. Under pressure, the pressure is usually selected from 0.1 to 50, preferably from 0.5 to 25 MPa. The residence time of the reaction in reactor A is essentially determined by the process parameters selected, and in continuous processes, usually from 1 From 300 to 300, preferably from 5 to 120 minutes. Shorter reaction times usually reduce the conversion rate, while currently appearing longer reaction times will lead to increased oligomer formation, so a large number of oligomers need to be recycled for fragmentation. Cyclization The reaction (stage (a)) is preferably carried out continuously in reactor A, and preferably in a reaction tube * in a stirred tank or in its sisterhood. The cyclization reaction (stage U)) can also be carried out in batches, The reaction time in this case is usually from 30 to 300 minutes. According to the present invention, the effluent from reactor A is essentially water and alcohol. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the precautions on the back before filling This page) J-pack. Order A7 B7 V. Description of the invention (8) In the reaction, 6-aminohexanoate * caprolactam, ammonia and Mixture I of oligomers of high-boiling compounds (high-boiling substances) such as 6-aminohexamidine and caprolactam. According to the present invention, in stage (b), the mixture I is distilled by a conventional method to obtain the top fraction, caprolactamine and bottom product. If mixture I from stage (a) contains ammonia, according to the invention, this ammonia needs to be removed before distillation. Ammonia can be removed by conventional methods, such as distillation, or by passing an inert gas stream through mixture I. Mixture I can be removed in a preferred embodiment by azeotropically distilling water and any low-boiling enzyme by distillation M The resulting residue is subjected to one or more further distillations or gradually or simultaneously by distillation of mixture I in a single distillation column. In a preferred embodiment, water and possible alcohols are first obtained by distillation under a reduced pressure of 10 to 500, preferably 50 to 350 mbar, and the distillation residue is from 90 to 220 ° C, preferably from 100 Further distillation is carried out at from 0.001 to 1, preferably from 0.5 to 300 mbar, to obtain an overhead fraction, caprolactam and a bottom product. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The top fraction generally contains low-boiling 6-aminohexanoic acid alkyl ester * unconverted 6-aminohexanoic acid. Nitrile and water (unless completely removed) and the alcohol used (if it has a low boiling point). Generally, the bottom product is essentially composed of high-boiling components, such as the oligomers of caprolactam · 6-aminohexamidine, 6-aminohexanoic acid, and high-boiling 6-aminehexan depending on the alcohol used Acid esters and high boiling point yeast if used. According to the present invention, if it is necessary to accompany any yeast and water that have been separated in advance -11- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A 7 B7 V. Description of the invention (9) Top fraction Recycle into reactor A (stage U1)) and the tops fraction can be mixed with the alcohol and / or water and / or 6-amino group used in stage (a) before feeding into reactor A *. According to the present invention, the top fraction obtained in stage U) may be fed into reactor B (stage (c2)) according to the circumstances, and may be fed together with the bottom product of stage (b) if necessary, and may be separated from it in advance if necessary. Any alcohol and water are fed together 'and the overheads can be mixed with the alcohol and / or water and / or 6-aminocapronitrile used in stage (a) before feeding into reactor B *. The reaction conditions in reactor B are selected relative to those in reactor A. The reacted mixture of reactor B is operated similarly to stage (b), and caprolactam is obtained in one or more distillation stages. In addition to the aforementioned variables * the bottom product obtained in stage (b) can be operated by 4 other methods in stage (c2) according to the present invention, that is, in stage (dl), the bottom product of stage (b) is fed to stage (a) In reactor A, or printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). In stage (d2), if necessary, water and low-boiling or high-boiling alcohols can be used. * To the bottom product is preferably 0: [-to 25-times, particularly preferably 0.15- to 15-times weight of water and preferably 1 to 25-times, particularly preferably 3- to 15-times The weight of water is heated in another reactor C similarly to stage (a >) to obtain the reacted mixture. By distillation, preferably distillation is similar to stage (b) to obtain caprolactam from it. Or (d3) water can be added to the bottom product, preferably 5- to 25-fold, particularly preferably 7- to 15-fold by weight of water, and heated in reactor D without adding a catalyst, wherein the reaction Conditions are selected to be similar to -12- This paper size applies to China National Standard (CNS) A4 (210X297 mm) Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the quasi bureau A7 B7 V. Description of the invention (10) Conditions of reactor A, but the temperature is selected from 200 to 3501 :, preferably from 280 to 320TC, and the residence time is from 5 to 240 minutes. The mixture is obtained by distillation in a better stage (b > general distillation to obtain caprolactam, or fd4). The bottom product to which water and alkali have been added is heated in reactor E to obtain a reacted mixture. Caprolactam is obtained therefrom by distillation, preferably similar to the distillation in stage (b); the heating of the bottom product is usually at a reduced pressure from 0.1 to 50, preferably from 1 to 10 mbar, and is usually 1 To 10, preferably from 1 to 3% by weight in the presence of a base in reactor E, preferably in a reaction tube • from 200 to 400 υ, preferably from 280 to 320 t: theoretically, at the bottom Of course, the product can also be operated by known methods, such as making it perform a conventional gas phase process or a general operation method of M acid catalyst. However, due to the shortcomings of the conventional process, the aforementioned new specific examples (c2) and ( dl) to (d4) are preferred. The hydrazone used is preferably alkali metal hydrazone And alkaline metal carbonates such as sodium hydroxide, potassium argon oxide, sodium carbonate and potassium carbonate, or mixtures thereof, particularly sodium hydroxide and / or potassium hydroxide. The advantage of this novel method is caprolactam pseudo K. The high-selectivity and high-yield technical implementation method obtains caprolactam from 6-aminocapronitrile without the problem of rapid deactivation of the catalyst used, and does not produce a large amount of low-boiling and high-boiling substances. Example Example 1 -13- The size of this paper applies to the Chinese National Standard (CNS) A4 (210X297 mm). I order -'..., ... (Please read the notes on the back before filling this page) A7 B7 5 2. Description of the invention (11) (8) Use 7〇111] ./ 11 to make a solution of 10% by weight 6-aminohexanox, 3.2% by weight of water and acetic acid (residue) heated to 2301 at 100 bar : Reaction tube (20 ml in volume, 6 mm in diameter and 710 mm in length and filled with titanium oxide (anatase) in the form of an extrudate of 1.5 mm). The reaction mixture was quantitatively evaluated by gas chromatography to obtain the following yields (without ethyl acetate and water): 91% caprolactam, 4% 6-aminohexanoic acid ethyl ester, and 1% 6-aminohexanoic acid nitrile. The product gas stream collected within 200 hours did not contain ethanol and water, and the crude crude linamine was distilled to obtain 56 g of low-boiling components (low-boiling substances) and 126 g of high-boiling components (high-boiling substances) and 1232 g of caprotone amine. Low-boiling substances are essentially composed of ethyl 6-aminohexanoate and unreacted 6-aminohexanonitrile, and high-boiling substances are essentially composed of oligomers. (b) Add 445 grams of water to 126 grams of oligomers, 56 grams of low boiling materials (obtained from (a)) and 1.200 grams of 6-aminocapronitrile, and dilute the mixture with acetonitrile to obtain 10% strength and weight. Solution. This solution was pumped into a reactor of 230¾ and 100 bar at a rate of 70ml / h. The yield of the discharged product determined by gas chromatography (without calculation of acetic acid and water) was: 87% caprozone Amine, 3% 6-aminohexanoic acid ethyl ester and 0.5% 6-aminohexanoic acid nitrile. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). After distillation, 11 82 g of caprolactam, 36 g of low boiling substances and 150 g are obtained from the second discharge. High boiling matter. A total of 36 g of recyclable low boilers, 150 g of high boilers and 2432 g of caprolactam were obtained from 2600 g of 6-aminocapronitrile in total. The total yield was 93% and the selectivity was 98%. Example 2 (a) KK 100 ml / h makes 10% by weight of 6-aminohexamidine * 16.0% by weight of water and -14- This paper size applies to Chinese National Standard (CNS) A4 ^ (210X297 mm) Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 ___ _Βλ ___ V. Description of the Invention (12) The solution of ethanol (thorn residue) was introduced at 200 bar into a reactor heated to 230¾ (20 ml in diameter, 6 mm in diameter and 710 mm in length and filled in) There is titanium oxide (anatase) which is an extrudate of 1.5 mm). Quantitative evaluation of the reaction mixture by gas chromatography gave the following yields (without ethyl acetate and water): 93% caprolactam and 2% 6-aminohexanoic acid ethyl ester. Κ The product gas stream collected within 200 hours was free of water and ethanol, and the obtained crude glucosamine was distilled to obtain 55 g of low-boiling components (low-boiling substances), 140 g of high-boiling components (high-boiling substances), and 1820 g of caprolactam. . Low-boiling substances are essentially composed of ethyl 6-aminohexanoate, and high-boiling substances are essentially composed of oligomers. (b > Add 3830 g of water to 140 g of oligomer, 55 g of low boiling material (obtained from Example 2a) and 2200 g of & -aminocapronitrile * mixture M acetonitrile to dilute to obtain a 10% strength weight solution. This solution was pumped at a rate of M100 ral / h through a reactor at 260¾ and 200 bar. The yield of the discharged product was determined by gas phase layer analysis (not calculated ethanol and water): 91% caprolactam and 2% 6-amine Ethyl caproate. After distillation, 2 129 g of caprolactam, 57 g of low boiling and 196 g of high boiling were obtained from the second discharge. A total of 57 g was obtained from 4200 g of 6-aminocapronitrile. Recyclable low boiler, 196 g high boiler and 3945 g caprolactam. The total yield is 94% and the selectivity is 99%. Example 3 (a) 10% by weight at 15 ml / h 6- Aminocapronitrile, 3.2% by weight water and acetonitrile (thorn residue) solution, introduced at 100 bar and heated to 200 t: inverse -1 5-This paper size applies to Chinese national standards (CNS> A4 specifications ( 210X297 mm) (Please read the precautions on the back before filling out this page) • Packing _ Order Λ Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (u) Shoulder tube (volume 20 ml, straight Titanium oxide (anatase) with a diameter of 6 mm and a length of 710 mm, filled with an extrudate of 1.5 mm. The reaction mixture was evaluated by gas chromatography β to obtain the following yields (without ethanol and water) : 88% caprolactam dipped in amine, and 4% 6-aminohexanoic acid ethyl ester and 4% 6-aminocapronitrile. The product gas stream collected within 200 hours was free of ethanol and water 'and the crude crude limidine was distilled To obtain 29 g of low-boiling point components (low-boiling matter) and 12 g of high-boiling point components (simmering matter) and 260 g of caprolactam. The low-boiling matter is essentially composed of ethyl 6-aminohexanoate and unreacted 6- Aminocapronitrile, and the high boilers essentially consist of oligomers. (B) Add 94 grams of water to 12 grams of oligomers' 29 grams of low boilers (from Example 3a) and 260 grams of 6 -Aminocapronitrile, and the mixture K diluted with ethanol * to give a 10¾ strength weight solution, this solution was pumped through the reactor at a rate of 100 «^ eight and the yield of the effluent product Gas phase analysis (without calculation of acetic acid and water) was: 91% caprolactam and 2% 6-aminohexanoic acid ethyl ester. After distillation, 265 g of caprolactam was obtained from the second discharge. '83 Low boilers and 25 grams of high boilers. A total of 83 grams of recyclable low boilers were obtained from 560 grams of 6-aminocapronitrile. 25 grams of high boilers and 525 grams of caprolactam. The total yield was 94% and The selection rate is 99% ° -16- This paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 mm (please read the precautions on the back before filling out this page) • Binding-Order-