TW524793B

TW524793B - A process for continuous hydrogenation of adiponitrile

Info

Publication number: TW524793B
Application number: TW87115038A
Authority: TW
Inventors: Sourav Kumar Sengupta; Theodore Augur Koch; Karl Robert Krause
Original assignee: Du Pont
Priority date: 1998-03-26
Filing date: 1998-09-10
Publication date: 2003-03-21
Also published as: MY117780A

Abstract

A process for continuous hydrogenation of adiponitrile (ADN) to hexamethylene diamine (HMD) and optionally to amninocapronitrile (ACN) involving the catalytic hydrogenation of adiponitrile at relatively low temperature (e.g., 75 DEG C) and pressure (e.g., 500 psig) using a sponge cobalt catalyst (Raney® Co) in a reaction medium that is substantially free of caustic. In such a process periodic addition of water controls the production of side reaction products and the periodic addition of ammonium hydroxide rejuvenates the catalyst. Hexamethylene diamine is an important intermediate for the synthesis of polyamides such as Nylon-6,6 and aminocapronitrile is a potential intermediate of Nylon-6.

Description

524793 .}·?-^π Λ7 B7 五、發明説明（，）相關申請案之前後參照申請人請求1997年3月28日所提出申請之臨時申請案 60/042，126之優先權利益。璧1_明背景 1.發明範圍：本發明係關於一種使己二腈（MN)連續氫化成己二胺 (HMD)與胺基己腈（ACN)之改良方法。更明確但非以限制方式言之’本發明係關於一種在低溫與壓力下，於海绵狀鈷觸媒存在下，及在實質上不含苛性鹼之反應媒質中，使 ADN連續氫化之方法。 - 2·相關技藝之描述：此項技藝中一般已知，腈類之氫化作用可經由使氫化觸媒與含有腈、氫及鹼金屬或鹼之溶液接觸而達成。反應產物典型上含有一級胺作爲所要之產物，及一或多種二級與三級胺作爲附加之副產物。咸認二級胺係經由一級胺與亞胺中間物之反應而形成，經由一級胺之部份氫化而形成。另一方面，三級胺係爲二級胺與其他亞胺中間物間、之反應產物。用以達成此種氫化作用之各種替代方法已被提出，包括在攪拌式熱壓鋼反應器中之批次處理，或使用固定床或氣泡流動反應器之連續處理。例如，在美國專利3,758,584與3,773,832中，固定床反應器已被使用於ADN之氫化作用。HMD係經由使ADN在填充床反應器中，於過量氫與無水氨存在下，在85至185°C之溫度及4,000至6,000 psig之壓力下氫化而製成。使鈷或鐵氧化物 ^ ^it] t ^ ^ ( (\NS ) AmM ( 21()/ 297公# ) 一 " ' ~ ~ ------—囔丨 (詔先閱讀背而之注意事項再填寫本頁、11 524793 Α7 Β7 五、發明説明 2 a % 消 f·： Aίί 卬 γ. 在jOO至600 C範圍之溫度下造粒、瑕燒及在氫與氨之混合物中還原。此方法之主要缺點爲其需要高溫與壓力，大量氨，使用於此方法中之鐵或鈷氧化物觸媒之還原，及伴隨著熱移除之困難。再者，使用於此方法中之觸媒，其成本已正隨著時間而增加。美國專利4,429，159與4,491，673係描述在泡塔反應器中使用 Raney®鎳觸媒。所述方法係使用較低壓力（2〇〇至5〇〇與溫度（低於10(TC )。但是，此方法使用大量苛性鹼，以保持觸媒之活性、選擇性及壽命。因此，其需要昂貴之純化步驟，以產生高純度HMD。、一種製備HMD之方法，係揭示於美國專利5，1〇5,〇15中，其中HMD係在固定床反應器中，於粒狀Cr與Μ促進之Raney® Co觸媒存在下’經由使ADN氫化而製成。此反應係於至少 5重量％氨（以ADN爲基準）存在下，在溫度與壓力個別在 60至125°C及50至5,000psi之範圍内進行。此種方法之缺點係爲本性上必須回收、純化、壓縮及再循環氨（作爲溶劑使用）。分枝狀脂族二胺自其相應二腈之製備，係描述於美國專利4,885,391中。此專利揭示使用鉻促進之海綿狀鈷觸媒，於0.5至4.0重量。/。水存在下，在約80至ι5〇χ：之溫度下，及在約400至2,50〇!)啦之壓力下，使2_甲基戍二腈氫化成2-甲基-1，5-戊二胺。雖然並不清楚分枝狀脂族二腈是否將以如同直鏈脂族二腈之相同方式表現，但顯而易見的是，此方法造成許多副產物，包括一些環狀縮合產物。這會在反應木紙匕尺度埤川( (，NS ) Λ4現梢（17^297公筇） ---------_噃_丨 (詞先閱讀背面之注意事項再填寫本頁)524793.} ·?-^ Π Λ7 B7 V. Description of the Invention (,) The relevant application shall be referred to before and after the application. The applicant requested the priority benefit of the provisional application 60 / 042,126 filed on March 28, 1997.璧 1_Background 1. The scope of the invention: The present invention relates to an improved method for continuous hydrogenation of adiponitrile (MN) to hexamethylenediamine (HMD) and aminocapronitrile (ACN). More specifically, but not by way of limitation, the present invention relates to a method for continuously hydrogenating ADN at low temperature and pressure in the presence of a sponge-like cobalt catalyst and in a reaction medium that is substantially free of caustic. -2 · Description of related technologies: It is generally known in this technology that hydrogenation of nitriles can be achieved by contacting a hydrogenation catalyst with a solution containing nitrile, hydrogen, and an alkali metal or alkali. The reaction product typically contains a primary amine as the desired product and one or more secondary and tertiary amines as additional by-products. The secondary amine is formed by the reaction of the primary amine and the imine intermediate, and is formed by the partial hydrogenation of the primary amine. On the other hand, tertiary amines are reaction products between secondary amines and other imine intermediates. Various alternative methods to achieve this hydrogenation have been proposed, including batch processing in stirred hot-pressed steel reactors, or continuous processing using fixed bed or bubble flow reactors. For example, in U.S. Patents 3,758,584 and 3,773,832, fixed bed reactors have been used for the hydrogenation of ADN. HMD is made by hydrogenating ADN in a packed bed reactor in the presence of excess hydrogen and anhydrous ammonia at a temperature of 85 to 185 ° C and a pressure of 4,000 to 6,000 psig. Make cobalt or iron oxide ^ ^ it) t ^ ^ ((\ NS) AmM (21 () / 297 公 #) a " '~ ~ -------- 囔丨 (诏 Read the back first Note: Please fill in this page again, 11 524793 Α7 Β7 V. Description of the invention 2 a% Elimination f: A ί 卬 γ. Granulation, calcination and reduction in a mixture of hydrogen and ammonia at a temperature ranging from jOO to 600 C. The main disadvantages of this method are that it requires high temperature and pressure, a large amount of ammonia, the reduction of iron or cobalt oxide catalysts used in this method, and the difficulties associated with thermal removal. Furthermore, the contact used in this method Cost, which has been increasing over time. U.S. Patent Nos. 4,429,159 and 4,491,673 describe the use of Raney® nickel catalysts in bubble column reactors. The process uses a lower pressure (200 to 5 〇〇 and temperature (less than 10 (TC). However, this method uses a large amount of caustic to maintain the catalyst's activity, selectivity and longevity. Therefore, it requires expensive purification steps to produce high-purity HMD. A method for preparing HMD is disclosed in U.S. Patent 5,105,015, where HMD is in a fixed bed reactor It is made by hydrogenating ADN in the presence of granular Cr and M-promoted Raney® Co catalysts. This reaction is in the presence of at least 5% by weight ammonia (based on ADN), at temperatures and pressures of 60 to Performed at 125 ° C and in the range of 50 to 5,000 psi. The disadvantage of this method is that it is essential to recover, purify, compress and recycle ammonia (used as a solvent). The branched aliphatic diamine is derived from its corresponding dinitrile. The preparation is described in U.S. Patent No. 4,885,391. This patent discloses the use of chromium-promoted sponge-like cobalt catalysts at 0.5 to 4.0 wt.% In the presence of water at a temperature of about 80 to 50 ° C, and at Under the pressure of about 400 to 2,50 〇!), 2-methyl fluorene dinitrile is hydrogenated to 2-methyl-1,5-pentanediamine. Although it is not clear whether the branched aliphatic dinitrile will It behaves in the same way as a linear aliphatic dinitrile, but it is clear that this method causes many by-products, including some cyclic condensation products. This will react at the scale of the reaction paper (匕, NS) Λ4 ( 17 ^ 297 公筇) ---------_ 噃 _ 丨 (Read the notes on the back of the word before filling in this page)

、1T ——___!：i 五、發明説明（3 ) _ 以及分離期間導致較低產率之所要產物。此外，會有大量 (¾先閱讀背而之注意事項再填寫本頁) 水存在，必肩將其連續菜送至反應容器中，以維持觸媒活性。發明摘述鑒於上述，本發明之一項目的係爲提供一種於適當海綿狀姑觸媒存在下，實質上不含任何無機鹼及/或水，經由使己二腈氫化，連續製造己二胺及/或胺基己腈之低溫與低壓方法。另一項目的，係爲提供一種使觸媒於原位再生之合宜方式，且因此延長觸媒之有效壽命，這是在商業化生產過程中被視爲必須之一項特色。. 因此’本發明係提供一種在實質上不含苛性鹼之反應媒質中’使己二腈連續氫化成爲己二胺及視情況成爲胺基己腈之改良方法，其包括步驟爲： (i) 於海綿狀鈷觸媒存在下，及於實質上不含苛性鹼之反應媒貝中’在25至150 C之溫度下’及在高達2,000 psig之壓力下，使己二腈與氫接觸，歷經足以使至少一部份該己二腈轉化成己二胺及視情況成爲胺基己腈之時間； (ii) 連續添加己二腈至反應媒質中； (iii) 自反應媒質中連續移除己二胺及視情況移除胺基己月青 •，及 (iv) 回收己二胺及視情況回收胺基己腈。上述根據本發明之方法，進一步提供其他步驟，以控制副反應產物之產生： (i)當5與11間之莫耳百分比之雙六亞甲基三胺（BHMT)出 ___________________ ____-_6z____ 木紙怀尺度Μ川中㈨( 21()/ 297公# ) _ — 524793 Λ7 B7 五、發明説明（ 41T ——___ !: i V. Description of the invention (3) _ and the desired product which results in lower yield during separation. In addition, there will be a large amount of water (¾ read the precautions before filling in this page), and the continuous dishes must be sent to the reaction container to maintain the catalyst activity. Summary of the Invention In view of the above, one of the items of the present invention is to provide a continuous production of hexamethylene diamine in the presence of a suitable sponge-like catalyst, substantially free of any inorganic base and / or water, by hydrogenating adiponitrile And / or low temperature and low pressure methods of aminocapronitrile. The other project is to provide a suitable way to regenerate the catalyst in situ, and thus extend the effective life of the catalyst. This is a feature considered necessary in the commercial production process. Therefore, the present invention provides an improved method for continuously hydrogenating adiponitrile to hexamethylene diamine and optionally amine caprocarbonitrile in a reaction medium that is substantially free of caustic, which includes the steps of: (i) Contact adiponitrile with hydrogen in the presence of a sponge-like cobalt catalyst, and at a temperature of 25 to 150 C in a reaction medium that is substantially free of caustic alkali, and at a pressure of up to 2,000 psig. Time sufficient to convert at least a portion of the adiponitrile to adipamide and optionally amine caprocarbonitrile; (ii) continuous addition of adiponitrile to the reaction medium; (iii) continuous removal of hexamethylene from the reaction medium Diamine and optionally amine caprocyanine •, and (iv) hexamethylene diamine and optionally amine caprocarbonitrile. The above-mentioned method according to the present invention further provides other steps to control the production of side reaction products: (i) when the molar percentage between 5 and 11 of bishexamethylenetriamine (BHMT) is ___________________ ____-_ 6z____ wood Paper Huai scale Μ 川中㈨ (21 () / 297 公 #) — 524793 Λ7 B7 V. Description of the invention (4

A .义:〕 »3 .1 消iiη 印現在此反應產物中時，添加水至反應媒質中，及 (ii)當ΒΗΜΤ在此反應產物中之含量降至低於1莫耳百分比時’即中斷添加至反應媒質中之水。根據本發明之方法，亦藉由週期性地添加有效量之氫氧化銨至反應媒質之步驟，提供觸媒在原位之復原。發明詳沭雖然本發明予人之感覺是大致上可應用於從相應之直鏈脂族腈或多腈製造任何直鏈脂族多胺及/或胺基腈，其中係採用海綿狀鈷觸媒，但本發明將就一種較佳方法，描述此種製法。 . 本發明亦予人感覺係爲一種合宜、低溫及低壓方法之代表，其係於適當海綿狀C〇觸媒存在下，使己二腈氫化，以連續製造己二胺及/或胺基己腈。因此，此方法可廣爲使用糸己一胺及/或胺基己腈之商業化生產。 ”正如將於稍後在實例中説明者，此方法典型上係經由在壓力下，、於可性驗溶液存纟下，4吏所要之產物與氫接觸而發車又佳係在4見掉式或以其他方式經充分撥動之熱壓锅反應容器中，在達到所要之操作溫度時，連續加入反 ^ ^ "如己一如。依此方式，此連續操作最後將實質上不含苛性鹼溶液（亦於稍饴+ & , 、稍後在貫例中説明）。本發明之一項重要具體貫施例，包括隹 & 十# # 、進仃虱化反應，實質上不含水及/ 或％可性驗溶液。此觸媒較佳爲一種細八、"μ … 、77 <鉻與鎳改質（，，鉻與鎳促進，丨）之 ’母、，，帛狀鈷。”海綿狀金屬” Λ ^馬一種具有擴張多孔性”骨架”或 (誚先閱讀背面之注意事項再填寫本頁、1Τ 524793 A7 B7 % 消 A ii 五、發明説明（ )母綿狀”結構之金屬，較佳爲具有溶解銘，視情況含有促進劑之基質金屬（例如鈷或鎳）。以至少一種金屬促進劑包括鎳、鉻、鐵及鉬所改質之海綿狀鉛，係爲特別有用的。海綿狀金屬觸媒亦含有表面含水氧化物，被吸附之氫基團及氫氣泡在孔隙中。此種觸媒可市購得自w· R· Grace公司與活化金屬（Activated Metals)公司，並含有約0.5至6.0重量％鉻及0.5至6.0重量。/。鎳。此種觸媒及其製備方法，係揭示於 EPO申請案編號〇,212,986中。本發明之方法可在固定床（滴流床）中，或在漿液相中使用海綿狀金屬觸媒進行。當採用此種刮用固定床觸媒之方法時，觸媒係呈具有粒子大小在約〇.03至〇4〇英吋範圍内之顆粒形式。當採用此種利用漿液相觸媒之方法時，觸媒係呈細分形式，較佳係低於約100/,大小，最佳範圍爲2〇至75 β 0 舰氫化反應可在介於25至航之相對較低溫度範圍下進仃，車父佳，皿度圍爲50至125°C，而最佳範圍爲7〇至100 C。於較低溫度下，氫化反應速率變得太緩慢，且控制放熱反應溫度之程序變得太複雜以致不實用。另一方面、，較高溫度經常會引致不想要之縮合產物之形&,其結果是作馬廢料，而造成所要產物（己二胺或胺基己腈)之較低選擇性與產率。本發明之經改良氫化方法，可在相對較低麼力下進行。使己二腈虱化之目前實施之商業方法，如在美國專利 3,758,584與仰,832中所述者，係在高譽與溫度下進行，並 (請先閱讀背而之注意事項再填寫本頁木祕尺成ip卜1:1.¾r(’NS) 524793 Λ 五、發明説明 6 部 Η j 需要向投資。使用低壓方法之優點，係爲其降低工業製程之投質成本。本發明之氫化反應可在氫壓力下進行，其範圍從足以保持所要產物商業化生產所必須之反應物與產物之可接受流量之壓力，至低於2000psi (13.79 MPa)之壓力。但是，操作壓力之較佳範圍爲100至1,500 psi (0.69 MPa至10.34 MPa)，最佳範圍爲 250 至 1000 psi (1.72 至 6.89 MPa)。本發明之一項重要目的，係爲使己二胺或胺基己腈之選擇性’及因此是產率，在起始二腈之最高可能轉化率下達到最大程度。己二胺與胺基己腈之產率，係依操作條件，包括溫度、壓力、氫流率、觸媒之量與種類、溶劑之性質與濃度、所添加無機驗之存在與不存在及空間速度等而定。對本發明之目的而言，”空間速度” 一詞係定義爲每小時每單位觸媒重量，被銀入反應器中之己二腈之單位重量。當己二胺與胺基己腈個別爲所要之產物時，典型上，應將己二腈加入反應器中，以致使己二腈之空間速度在0.5至5.0 之範圍内。使己二胺及/或胺基己腈達到最大程度之己二腈之最佳空間速度，可容易地由熟諳此藝者使用習、用技術測定。當己二腈之添加速率低於或高於此處所述之空間速度時，所要化合物之選擇性與產率會急驟地減少，而造成較低觸媒活性及縮短之觸媒壽命。可用於進行根據本發明連續操作之反應器，一般而言係包括任何習用氫化反應器。此種反應器之實例，包括但不限於柱狀流動反應器、連續攪拌槽反應器及泡塔反應器° 一種不被限制於此反應中之泡塔反應器之實例’已被描止 9- (ii先閱讀背面之注意事項再填寫本頁訂A. Meaning:] »3.1.1 When printed on this reaction product, add water to the reaction medium, and (ii) When the content of BΗMT in this reaction product drops below 1 mole percentage, that is, The water added to the reaction medium is discontinued. According to the method of the present invention, the step of periodically adding an effective amount of ammonium hydroxide to the reaction medium is provided to restore the catalyst in situ. Detailed description of the invention Although the present invention feels that it is generally applicable to the production of any linear aliphatic polyamine and / or amino nitrile from the corresponding linear aliphatic nitrile or polynitrile, a sponge-like cobalt catalyst is used therein However, the present invention will describe such a manufacturing method in terms of a preferred method. The present invention also feels like a representative of a suitable, low temperature and low pressure method, which is the hydrogenation of adiponitrile in the presence of an appropriate sponge-like C0 catalyst to continuously produce hexamethylenediamine and / or amine Nitrile. Therefore, this method can be widely used for the commercial production of hexamethylene monoamine and / or amino capronitrile. "As will be explained later in an example, this method is typically carried out under pressure in the presence of a test solution, where the desired product comes into contact with hydrogen, and is best seen in the following formula. Or in another way, in the autoclave reaction container that has been fully agitated, when the desired operating temperature is reached, the reaction is continuously added as it has been. In this way, this continuous operation will be substantially free of causticity at the end. Alkali solution (also described later in the example), an important specific embodiment of the present invention, including the &#tenth;### reaction, which is essentially free of water And / or% testability solution. The catalyst is preferably a kind of fine, fine, " μ…, 77 < chromium and nickel modified (,, chromium and nickel promoted, 丨), the mother, Cobalt. "Sponge-like metal" Λ ^ a kind of expanded porous "skeleton" or (诮 read the precautions on the back before filling out this page, 1T 524793 A7 B7% consumption A ii 5. Description of the invention () mother cotton-like " Structured metal, preferably a matrix metal with a dissolution inscription and optionally an accelerator (Such as cobalt or nickel). Sponge lead modified with at least one metal accelerator including nickel, chromium, iron, and molybdenum is particularly useful. Sponge metal catalysts also contain surface oxides that are adsorbed by Hydrogen groups and hydrogen bubbles are in the pores. Such catalysts are commercially available from w · R · Grace and Activated Metals, and contain about 0.5 to 6.0% by weight of chromium and 0.5 to 6.0% by weight. Nickel. This catalyst and its preparation method are disclosed in EPO Application No. 0,212,986. The method of the present invention can be used in a fixed bed (trickle bed) or in a slurry phase using a sponge-like metal catalyst. When using this method of scraping fixed bed catalyst, the catalyst is in the form of particles with a particle size in the range of about 0.03 to 0.40 inches. In the medium method, the catalyst system is in a subdivided form, preferably the size is less than about 100 /, the optimal range is 20 to 75 β 0. The hydrogenation reaction can be at a relatively low temperature range between 25 and 100 °. In the car, the car is good, the temperature range is 50 to 125 ° C, and the optimal range is 7 °. 100 C. At lower temperatures, the hydrogenation reaction rate becomes too slow, and the procedures for controlling the exothermic reaction temperature become too complicated to be practical. On the other hand, higher temperatures often cause the formation of unwanted condensation products. & As a result, it is used as horse waste, resulting in lower selectivity and yield of the desired product (hexamethylenediamine or aminocapronitrile). The improved hydrogenation method of the present invention can be carried out at relatively low power. The currently implemented commercial methods to make adiponitrile lice, such as those described in U.S. Patent Nos. 3,758,584 and Yang, 832, are performed at a high reputation and temperature, and (please read this precaution before filling out this Page wood secret ruler becomes IP 1: 1: 1.r ('NS) 524793 Λ 5. Description of the invention 6 Departments 需要 j need to invest in. The advantage of using a low pressure method is to reduce the cost of quality for industrial processes. The hydrogenation reaction of the present invention can be carried out under hydrogen pressure, which ranges from a pressure sufficient to maintain an acceptable flow rate of reactants and products necessary for commercial production of the desired product, to a pressure lower than 2000 psi (13.79 MPa). However, the preferred range of operating pressure is 100 to 1,500 psi (0.69 MPa to 10.34 MPa), and the optimal range is 250 to 1000 psi (1.72 to 6.89 MPa). An important object of the present invention is to maximize the selectivity of hexamethylenediamine or aminocapronitrile 'and therefore the yield at the highest possible conversion of the starting dinitrile. The yields of hexamethylenediamine and aminocapronitrile are based on operating conditions, including temperature, pressure, hydrogen flow rate, amount and type of catalyst, nature and concentration of solvents, presence and absence of added inorganic substances, and space Speed and so on. For the purposes of the present invention, the term "space velocity" is defined as the unit weight of adiponitrile that is fed into the reactor by silver per unit weight of catalyst per hour. When hexamethylenediamine and aminocapronitrile are the desired products individually, typically, adicarbonitrile should be added to the reactor so that the space velocity of adiponitrile is in the range of 0.5 to 5.0. The optimal space velocity of hexamethylenediamine and / or aminecapronitrile to the maximum extent can be easily determined by those skilled in the art using conventional techniques. When the adiponitrile is added at a rate lower or higher than the space velocity described herein, the selectivity and yield of the desired compound will decrease sharply, resulting in lower catalyst activity and shortened catalyst life. Reactors which can be used to carry out continuous operations according to the present invention generally include any conventional hydrogenation reactor. Examples of such reactors include, but are not limited to, columnar flow reactors, continuous stirred tank reactors, and bubble column reactors. An example of a bubble column reactor not limited to this reaction has been described 9- (ii Read the notes on the back before filling out this page to order

V 524793 A7 B7 五、發明説明 •ί- 又b 消 Aii印於美國專利4,429，159中。柱狀流動與連續攪拌槽桶反應器之説月，已被&己述於由〇ctave LevenSpiel所著，其標題爲"化學反應工程’’之書籍中。除非另有指明，否則在下述實例中説明之己二腈之氫化作用，係在由熱壓鍋工程師所設計與製造之3〇〇(^熱壓鍋中進行。此300 cc反應器係由具有最大可容許工作壓力（gyp) 在300 C下爲約1500 psig之赫史特合金（Hastelloy)-C所構成。於反應器中之混合，係以磁偶合之葉輪進行，裝載於空心軸上，並以電馬達驅動。攪摔器之速度係以頻閃光監控。反-應器係以400瓦特外部加熱帶加熱。- 反應器具有熱電偶插入物、安全片及兩個裝有5毫米不銹鋼玻料之1/8"浸潰腳，意即個別用以添加液體至反應器中，及自反應器中取出產物。使氫經由攪拌器空心軸連續銀入熱壓鍋反應器中。進入反應器中之氫流率，係藉Bro〇ks ®質量流量控制器計量與監控。於反應器中之壓力係以 Grove反壓#1節器保持。己二腈係使用注射器栗（26〇d系歹ij ) 連續餵至反應器中。使反應器經過減壓槽桶連接至1升產物接受器。在實驗操作開始時及在特定時間間隔（7與16小時之時間間隔）下收集試樣。使收集自產物接受器之試樣熔解，及溶解於異丙醇（溶劑）中。添加環十二烷作爲產物試樣之内標準，並在5890A Hewlett-Packard毛細管氣相層析儀分析。應明瞭的是，提出下述實例係爲更完整地·!：正實及進一步説明本發明之各個別方面與特徵，且因此應感覺到此等實木紙恨次度十( (，NS ) Λ4%格（21()〆297公筇請先閱讀背而之注意事項再填寫本頁) 、11 524793V 524793 A7 B7 V. Description of the invention •-b Aii is printed in US Patent 4,429,159. The column-shaped flow and continuous stirred tank reactors have been described in a book by Octave LevenSpiel entitled "Chemical Reaction Engineering". Unless otherwise specified, the hydrogenation of adiponitrile described in the following examples was performed in a 300 ° C autoclave designed and manufactured by an autoclave engineer. This 300 cc reactor The maximum allowable working pressure (gyp) is about 1500 psig of Hastelloy-C at 300 C. The mixing in the reactor is carried out by magnetically coupled impellers and loaded on a hollow shaft. It is driven by an electric motor. The speed of the stirrer is monitored by stroboscopic flash. The reactor is heated by a 400 watt external heating belt.-The reactor has a thermocouple insert, a safety sheet and two 5 mm stainless steel glass 1/8 " immersion foot, which means individually used to add liquid to the reactor, and take out the product from the reactor. The hydrogen is continuously passed through the hollow shaft of the stirrer into the autoclave reactor. Enter the reactor The hydrogen flow rate is measured and monitored by a Brooxs® mass flow controller. The pressure in the reactor is maintained by a Grove back pressure # 1 node. Adiponitrile is a syringe pump (26〇d series) ij) is continuously fed into the reactor. The reactor is passed through The decompression tank was connected to a 1 liter product receiver. Samples were collected at the beginning of the experiment and at specific time intervals (7 and 16 hour intervals). The samples collected from the product receiver were melted and dissolved in Isopropanol (solvent). Cyclododecane was added as an internal standard for the product samples and analyzed on a 5890A Hewlett-Packard capillary gas chromatograph. It should be understood that the following examples are presented as more complete. !: Justify and further explain the various aspects and features of the present invention, and therefore you should feel that these solid papers hate ten times ((, NS) Λ 4% grid (21 () 〆 297 public 筇 Please read the back first) Note for this page, please fill in this page), 11 524793

A 1Γ 五、 -發明彳元明 —---A 1Γ Fifth,-Invention 彳元明 -----

部屮 η 卑 Λ II -Τ ίι'ί /、 ίί 卬 V 例係爲非限制性，及意謂說明本發明，而非意謂以任何方式不適當地限制之。實例1_ 在水與苛性驗不存在下之JJMD合成：將120克HMD、0.6亳升苛性鹼溶液（50%氫氧化鈉）及15克 (7.5克無水觸媒，在7·5克水中）預活化之Raney®鈷觸媒 (W. R· Grace 2774)裝填在反應器中。將熱壓鍋密封，以氮沖洗數次，及試驗壓力在500 psig下。在確保沒有滲漏後，將反應器加熱至75°C並將攪拌器打開（12〇〇 rpm)。俟達到所要之反應溫度後，立即藉由調整反壓調·節器，將反應器壓力設定至500psig，並將氫流率設定爲_標準立方公分（sccm 。然後，在每小時12克之速率下，將adn連續添加至反應器中。產物在反應器中之停留時間爲1〇小時。之產量及產物分佈，作爲在流程中之時間，以及每克觸媒被餵入之ADN克數之函數，係在表丨中提出。在流程中你小時後，藉感應偶合電漿（ICP)分析，未檢測出苛性鹼（伴隨著起始NaOH之鈉）i存在。而且，在816小時後添加氫氧化銨水溶液，並在888小時停止，及再一次於1〇35小時後開始、，並持續直到實驗操作結束。添加氫氧化銨之目的，係爲以實例説明觸媒之在原位復原。 (讀先閱讀背而之注意事項再填寫本頁) 訂 -11 ^ 524793 A7 B7 五、發明説明（9 表1 在流程中之時間 (小時） 0 24.0 72.0 120.0 168.0 216.0 240.0 288.0 336.0 384.0 432.0 480.0 528.0 576.0 624.0 672.0 720.0 768.0 816.0 864.0 888.0 941.0 987.0 1035.0 1083.0 1131.0 1179.0 被銀入之 ADN克數 /每克觸媒 0.0 37.2 111.5 185.8 260.1 334.4 371.6 445.9 520.2 594.5 668.8 743.1 817.4 891.7 966.1 1040.4 1114.7 1189.0 1263.3 1337.6 1374.8 1456.8 1528.0 1602.3 1676.7 1751.0 1825.3 製成之 HMD (克） 0.0 269.7 809.4 1362.2 1913.0 2464.4 2739.6 3292.6 3843.8 4384.9 4932.2 5473.2 6016.3 6557.8 7098.6 7627.1 8148.7 8668.1 9188.4 9719.8 9988.2 10577.4 11087.4 11615.3 12160.2 12703.2 13242.5 HMD(°/〇) 100.0 99.4 97.2 99.7 98.0 98.7 98.6 99.2 99.3 95.4 97.7 97.9 97.2 96.9 97.5 93.1 93.6 93.1 93.6 96.1 96.3 95.3 94.7 94.5 97.6 97.6 97.0 產物分佈 ^vooooooooooooooooooooooooooo N 0·0.0·0·0·0·0·0·0:0·0·0·0·0·0·0·0·0·0·0·0·0·0·0·0·0.0. Ac 00 3 008000900000000000000000 0.0.2· 0·0·0.0·0·0· 2· 0·0·0·0·0·0·0·0·0·0·0·00.0· 00.0. BHMT(%) 0.0 0.4 0.3 0.3 0.3 0.5 1.2 0.6 0.5 1.5 2.3 2.1 2.6 2.9 2.3 5.5 6.4 6.9 6.4 .3.9 3.7 4.7 5.3 5.5 2.4 2.4 2.1 (¾先閱讀背而之注意事項再填寫本頁比較實例重複實例1之實驗操作，惟使用120克甲基戊二胺 -12- 木紙锿尺度垧⑴中家樣4 ( (，NS ) Λ4)见格（210/297公犛) 524793The example of the Ministry 屮 Λ II -Τ ίι'ί, ίί 卬 V is non-limiting, and means to illustrate the present invention, and does not mean to improperly limit it in any way. Example 1_ Synthesis of JJMD in the absence of water and caustic test: 120 g of HMD, 0.6 l of caustic solution (50% sodium hydroxide) and 15 g (7.5 g of anhydrous catalyst in 7.5 g of water) Activated Raney® cobalt catalyst (W.R. Grace 2774) was charged into the reactor. The autoclave was sealed, flushed several times with nitrogen, and the test pressure was at 500 psig. After ensuring that there were no leaks, the reactor was heated to 75 ° C and the stirrer was turned on (1200 rpm).俟 After the desired reaction temperature is reached, immediately adjust the reactor pressure to 500 psig by adjusting the backpressure regulator and the hydrogen flow rate to _standard cubic centimeters (sccm.). Then, at a rate of 12 grams per hour ADN is continuously added to the reactor. The residence time of the product in the reactor is 10 hours. The yield and product distribution are a function of the time in the process and the number of grams of ADN fed per gram of catalyst. It is proposed in Table 丨. After you are in the process for an hour, by inductively coupled plasma (ICP) analysis, the presence of caustic alkali (with the sodium of the initial NaOH) i is not detected. Moreover, hydrogen is added after 816 hours The ammonium oxide aqueous solution was stopped at 888 hours, and started again after 1035 hours, and continued until the end of the experimental operation. The purpose of adding ammonium hydroxide is to illustrate the restoration of the catalyst in situ by an example. Read first and then read the precautions before filling out this page) Order-11 ^ 793 793 A7 B7 V. Description of the invention (9 Table 1 Time in the process (hours) 0 24.0 72.0 120.0 168.0 216.0 240.0 288.0 336.0 384.0 432.0 480.0 5 28.0 576.0 624.0 672.0 720.0 768.0 816.0 864.0 888.0 941.0 987.0 1035.0 1083.0 1131.0 1179.0 grams of ADN per gram of silver / catalyst 0.0 37.2 111.5 185.8 260.1 334.4 371.6 445.9 520.2 594.5 668.8 743.1 817.4 891.7 966.1 1040.4 1114.7 1189.0 1263.3 1337.6 1374.8 1456.8 1528.0 1602.3 1676.7 1751.0 1825.3 HMD (g) 0.0 269.7 809.4 1362.2 1913.0 2464.4 2739.6 3292.6 3842.6 4383.8 4384.9 4932.2 5473.2 6016.3 6557.8 7098.6 7627.1 8148.7 8668.1 9188.4 9189.8 9719.8 9988.2 10577.4 11087.4 11615.3 12160.2 12703.2 98.0 99.0 94.0 92.9 94.0 94.0 94.0 98.6 99.2 99.3 95.4 97.7 97.9 97.2 96.9 97.5 93.1 93.6 93.1 93.6 96.1 96.3 95.3 94.7 94.5 97.6 97.6 97.0 Product distribution ^ vooooooooooooooooooooooooooo N 0 · 0.0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 ············· 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0.0 · 0.0. Ac 00 3 008000900000000000000000 0.0.2 · 0 · 0 · 0.0 · 0 · 0 · 2 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 0 · 00.0 · 00.0. BHMT (%) 0.0 0.4 0.3 0.3 0.3 0.5 1.2 0.6 0.5 1.5 2.3 2.1 2.6 2.9 2.3 5.5 6.4 6.9 6.4 .3.9 3.7 4.7 5.3 5.5 2. 4 2.4 2.1 (¾Read the precautions on the back before filling in this page. Comparative Example Repeat the experimental operation of Example 1, but use 120 grams of methylpentanediamine-12-wood paper 锿 scale 垧 ⑴ home sample 4 ((,, NS) Λ4) See the case (210/297 male) 524793

AT B7 次五、發明説明（ (MPMD)(所要之產物）代替HMD，且反應係在130°C下進行，AT B7 times 5. The description of the invention ((MPMD) (the desired product) replaces HMD, and the reaction is carried out at 130 ° C,

I 代替75°C。其結果顯示在上述操作條件下，甲基戊二腈 (MGN)之反應，產生不想要之副產物。所得之數據係在表 A中提出。I instead of 75 ° C. The results showed that under the above-mentioned operating conditions, the reaction of methylglutaronitrile (MGN) resulted in unwanted by-products. The data obtained are presented in Table A.

表A 在流程中被銀入之之時間 MGN克數 HMD 產物分佈 (小時） / 每克觸媒 MPMD(%) *3MePip(%) C6-胺（％) MGN(%) 其他（％) 0.0 0.0 100.0 0.0 0.0 0.0 0.0 24.0 37.2 3.6 65.5 14.0 1.40 15.5 48.0 74.4 20.1 44.6 12.8 0.4 22.1 72.0 111.5 12.2 60.9 11.6 1.1 14.2 96.0 148.8 6.4 70.0 10.2 1.7 11.7 120.0 185.8 10.9 60.8 9.5 0.9 17.9 * 3_甲基六氫吡淀酮實例2 以類似實例1之方式，在基本上相同條件下進行第操作，惟在每小時0.6毫升之速率下連續添加水至反應器中。所得數據係在表2中提出。 ' 、表2 --------7-#衣一丨 (¾先閱讀背而之注意事項再填寫本頁jTable A Time of silver in the process MGN grams HMD Product distribution (hours) / MPMD per gram catalyst (%) * 3MePip (%) C6-amine (%) MGN (%) Others (%) 0.0 0.0 100.0 0.0 0.0 0.0 0.0 24.0 37.2 3.6 65.5 14.0 1.40 15.5 48.0 74.4 20.1 44.6 12.8 0.4 22.1 72.0 111.5 12.2 60.9 11.6 1.1 14.2 96.0 148.8 6.4 70.0 10.2 1.7 11.7 120.0 185.8 10.9 60.8 9.5 0.9 17.9 * 3_methylhexahydropyridone Example 2 In a similar manner to Example 1, the first operation was performed under substantially the same conditions, except that water was continuously added to the reactor at a rate of 0.6 ml per hour. The data obtained are presented in Table 2. '、 Table 2 -------- 7- # 衣一丨 (¾Read the precautions before filling in this page j

、1T ·· 部 η .杓 π .1 消 1V 合 ίΐ 印在流程中被餵入之製成之〈時間 ADN克數HMD 產物分佈 (小時） /每克觸媒 (克） HMD(%) ACN(%) ADN(%) BHMT(%) 0.0 0.0 0.0 100.0 0.0 0.0 0.0 24.0 37.2 278.7 100.0 0.0 0.0 0.0 48.5 75.1 563.1 100.0 0.0 0.0 0.0 9i.〇 140.9 1056.6 100.0 0.0 0.0 0.0 120.7 186.8 1401.1 100.0 0.0 0.0 0.0 145.0 224.5 1683.6 100.0 0.0 0.0 0.0 （（、NS ) Λ4现格（210/ 297公筇） 524793 A7 B7 五、發明説明（ή ) 169.0 190.0 219.0 258.7 284.0 308.0 331.0 354.0 377.0 418.0 448.0 471.0 494.4 517.0 540.0 584.0 607.0 630.0 653.0 680.0 702.0 261.6 294.2 339.0 400.5 439.7 476.8 512.4 548.0 583.7 647.1 693.6 729.2 764.8 800.4 836.0 904.1 939.7 975.3 1010.9 1052.7 1086.8 1962.3 2206.1 2536.8 2993.0 3280.2 3551.9 3807.4 4062.9 4318.1 4772.5 5104.5 5356.3 5604.0 5852.6 6098.6 6567.5 6809.0 7043.1 7274.4 7537.7 7743.8 100.0 100.0 97.7 98.2 97.2 98.0 97.1 96.3 96.4 95.2 95.5 94.2 93.7 93.0 92.1 91.7 90.4 87.3 86.4 85.2 70.1 實例3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0:0 0.0 0.0 0.0 0.0 0.0 13.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0,0 0.0 0.0 7.7 0.0 0.0 2.3 1.8 2.8 2.0 2.9 3.7 3.6 4.5 4.5 5.8 6.3 7.0 7.9 8.3 9.6 11.5 12.5 13.4 5.5 霉消於合f; 印 V: 添加稀苛性鹼溶液之作用：再一次以類似實例1之方式，在基本上相同條件、下、進行第三次操作，惟在每小時0.6毫升之速率下連續添加1重量 °/。苛性鹼水溶液至反應器中。所得數據係在表3中提出。木紙屯尺度巧·丨丨、 1T ·· 部 η. 杓 π .1 Elimination 1V combined ΐ 印 Printed in the process and made of <time ADN grams of HMD product distribution (hours) / catalyst per gram (g) HMD (%) ACN (%) ADN (%) BHMT (%) 0.0 0.0 0.0 100.0 0.0 0.0 0.0 24.0 37.2 278.7 100.0 0.0 0.0 0.0 48.5 75.1 563.1 100.0 0.0 0.0 9i.〇140.9 1056.6 100.0 0.0 0.0 0.0 120.7 186.8 1401.1 100.0 0.0 0.0 0.0 145.0 224.5 1683.6 100.0 0.0 0.0 0.0 ((, NS) Λ4 is present (210/297 gong) 524793 A7 B7 V. Description of the invention (price) 169.0 190.0 219.0 258.7 284.0 308.0 331.0 354.0 377.0 418.0 448.0 471.0 494.4 517.0 540.0 584.0 607.0 630.0 653.0 680.0 702.0 261.6 294.2 339.0 400.5 439.7 476.8 512.4 548.0 583.7 647.1 693.6 729.2 764.8 800.4 836.0 904.1 939.7 975.3 1010.9 1052.7 1086.8 1962.3 2206.1 2536.8 2993.0 3280.2 3551.9 3807.4 4062.9 4318.1 4772.5 5104.5 5359.0 5604.0 5852.6 6098.6 656 7.5 97.7 97.0 97.0 9.0 100.0 704 4.0 96.3 96.4 95.2 95.5 94.2 93.7 93.0 92.1 91.7 90.4 87.3 86.4 85.2 70.1 Example 3 0 .0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0 0 0.0 0.0 0.0 0.0 0.0 13.4 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0,0 0.0 0.0 7.7 0.0 0.0 2.3 1.8 2.8 2.0 2.9 3.7 3.6 4.5 4.5 5.8 6.3 7.0 7.9 8.3 9.6 11.5 12.5 13.4 5.5 Mildew disappears f; India V: The effect of adding a dilute caustic solution: Once again in a manner similar to Example 1, under basically the same conditions, Then, the third operation is performed, but 1 weight ° / is continuously added at a rate of 0.6 ml per hour. An aqueous caustic solution is introduced into the reactor. The data obtained are presented in Table 3. Wooden paper scales

HI -14- 1¾¾ 家標7 ( (’NS ) A4i,t格（210x297公梦) (邙先閱讀背而之注意事項再填寫本頁}HI -14- 1¾¾ Family logo 7 ((’NS) A4i, t grid (210x297 public dream) (邙 read the precautions before filling in this page)

524793 A7 B7 五、發明説明（12 在流程中被銀入之製成之之時間 ADN克數 HMD (小時） /每克觸媒 (克） 0.0 0.0 0.0 20.0 31.0 230.8 68.0 105.3 782.4 117.0 181.1 1341.2 164.0 253.9 1872.1 210.0 325.1 2384.2 248.0 383.9 2799.3 296.0 458.3 3324.0 344.0 532.6 3829.9 392.0 606.9 4345.8 446.0 690.5 4932.6 494.0 764.8 5440.4 542.0 839.1 5924.2 590.0 913.4 6346.4 641.0 992.4 6740.7 685.0 1060.5 6934.5 757.0 1172.0 7114.5 表3 HMD(%) 100.0 99.6 98.7 97.9 96.8 95.5 92.8 94.2 90.5 91.8 93.3 90.0 84.3 75.5 59.1 30.3 19.5 產物分佈 %) 0.00.0.0000006199625 0·0·0·0·0.0·0·0·0.0· 1 48.42125.21. .00.00 0 0 9 0 4 0 3 7.1.00.4.8 ο.ο.ο.οοο 10.2.10.2.4 77.43.58. ο 4 3 1 2 5 3 8 ο 1 8 2 7 5· 3 1 ο· ο* L 2 3 4 5· 5· 7· 7 4 OJ 2 2 2 1 誚先閱讀背而之注意事項再填寫本頁部中-φ:^:卑而消资合：實例4 胺基己腈之選擇性合成：以類似實例1之方式進行第四次操作，惟反應係在5〇〇 cc 為壓鋼中進行，並將200克HMD、〇·6毫升苛性驗溶液（5〇重量。。氩氧化鈉）及10克（5.0克無水觸媒，在5.0克水中）預活化之Raney®鉛（Grace 2724)裝填於反應器中。ADN之進料速率 ’係保持在每小時18克下，停留時間爲ιι·ι小時。所得數據係在表4中提出。表4 . 7^ " —-----—------ " I \3 ^ 广紙张尺度W⑴十1¾ 1¾家標今（(’NS )八现格（ 210X297公筇了 )24793 ίι 五、發明説明（ A 7 B7 13 在流程中之時間 (小時y 〇.〇 2.3 9.3 18.3 26.3 42.3 5〇.〇 66.8 74.3 9〇.8 95.3 被餵入之 ADN克數 /每克觸媒 0.0 7.8 32.2 63.6 91.4 175.0 174.2 232.5 258.6 316.1 331.8 口 Q此，在已描述及舉例説明具有明後，應明瞭的是，下述而是提供與申請專利範圍才目當之範圍。產物分佈 HMD(%) ACN(%) 100.0 0.0 0.0 100.0 0.0 0.0 95.9 0.0 0.0 98.6 0.0 0.0 58.9 16.2 23.6 49.5 26.9 21.3 53.1 24.2 19.0 43.7 24.5 28.5 29.6 25.8 42.0 35.0 25.2 36.9 26.3 25.3 46.1 ADN(%) BHMT(0/ ο ο π π 定程度特申請專利範圍並 0.0 0.04.1 0.0 0.0 0.0 0.0 〇.0 〇.0 〇.0 0.0 異性之非被如此限之每一要件及其等效事项524793 A7 B7 V. Description of the invention (12 ADN gram time HMD (hours) per gram of catalyst (g) 0.05 0.0 0.0 20.0 31.0 230.8 68.0 105.3 782.4 117.0 181.1 1341.2 164.0 253.9 1872.1 210.0 325.1 2384.2 248.0 383.9 2799.3 296.0 458.3 3324.0 344.0 532.6 3829.9 392.0 606.9 4345.8 446.0 690.5 4932.6 494.0 764.8 5440.4 542.0 839.1 5924.2 590.0 913.4 6346.4 641.0 992.4 6740.7 685.0 1060.5 6934.5 757.0 1172.0 7.14.5 Table 3 9MD 95.5 90.0 94.2 90.5 91.8 93.3 90.0 84.3 75.5 59.1 30.3 19.5 Product distribution%) 0.00.0.0000006199625 0 · 0 · 0 · 0 · 0.0 · 0 · 0 · 0.0 · 1 48.42125.21. .00.00 0 0 9 0 4 0 3 7.1.00.4 .8 ο.ο.ο.οοο 10.2.10.2.4 77.43.58. Ο 4 3 1 2 5 3 8 ο 1 8 2 7 5 · 3 1 ο · ο * L 2 3 4 5 · 5 · 7 · 7 4 OJ 2 2 2 1 阅读 Please read the precautions below and then fill out the section of this page -φ: ^: 卑和消合合: Example 4 Selective Synthesis of Amino Capronitrile: Perform the same procedure as in Example 1 Four operations, but the reaction is in 500cc steel And pre-activated Raney® lead (Grace 2724) with 200 g HMD, 0.6 ml caustic test solution (50 wt. Sodium argon oxide) and 10 g (5.0 g anhydrous catalyst in 5.0 g water). Fill the reactor. The feed rate of ADN was maintained at 18 grams per hour and the residence time was ι · ι hours. The data obtained are presented in Table 4. Table 4. 7 ^ " —-----—------ " I \ 3 ^ Wide paper scale W⑴10 1¾ 1¾ family icon (('NS) eight appearance grid (210X297) ) 24793 Ⅴ. Description of the invention (A 7 B7 13 Time in the process (hours y 〇.〇2.3 9.3 18.3 26.3 42.3 50.〇66.8 74.3 90.8. 95.3 grams of ADN fed per gram contact Media 0.0 7.8 32.2 63.6 91.4 175.0 174.2 232.5 258.6 316.1 331.8 Q. After having been described and exemplified, it should be clear that the following is provided only within the scope of the scope of patent application. Product distribution HMD ( %) ACN (%) 100.0 0.0 0.0 100.0 0.0 0.0 95.9 0.0 0.0 98.6 0.0 0.0 58.9 16.2 23.6 49.5 26.9 21.3 53.1 24.2 19.0 43.7 24.5 28.5 29.6 25.8 42.0 35.0 25.2 36.9 26.3 25.3 46.1 ADN (%) BHMT (0 / ο ο π π To a certain extent, the scope of patent application is 0.0 0.04.1 0.0 0.0 0.0 0.0 〇.0 〇.0 〇.0 0.0 Each element of the opposite sex is not so limited and its equivalent

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Claims

524793 A8 B8 C8 D8. Announcement I. Patent application scope 1. A method for continuously hydrogenating adiponitrile to hexamethylene diamine and optionally amine caprocarbonitrile in a reaction medium that is substantially free of caustic alkali, and includes it The steps are: (i) in the presence of a sponge-like cobalt catalyst, and in a reaction medium that is substantially free of caustic, at a temperature of 25 to 15 (TC's) and at a pressure of up to 2,000 psig, The nitrile is contacted with hydrogen for a time sufficient to convert at least a portion of the adiponitrile to hexamethylenediamine and optionally to aminocapronitrile; (ii) continuously adding adiponitrile to the reaction medium; (iii) from The reaction medium continuously removes hexamethylenediamine and optionally removes aminecapronitrile; and (iv) recovers the hexamethylenediamine and optionally recovers the aminecapronitrile. 2. Method according to item 1 of the scope of patent application Which further comprises: (i) when a mole percentage of dihexamethylenetriamine (BHMT) between 5 and 11 is present in the reaction product, adding water to the reaction medium, and (ii) when BHMT is in When the content of this reaction product drops below 1 mole percentage, the addition is interrupted. Water added to the reaction medium. 3. The method according to item 1 of the scope of patent application, wherein the amount of adiponitrile supplied to the reaction medium is 0.5 to 5.0 g / hour per gram of catalyst. 4. According to The method of claim 3, wherein the sponge-like cobalt is modified by at least one of the nickel, chromium, iron, and molybdenum groups in an amount of 0.5 to 6.0% by weight. Method, which further includes periodicity --- Lu Chang-C, please read the notes on the back before filling out this page} Order printed paper from the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ttΒ1 -17- Public 7 9 2 524793 A8 B8 C8 D8 々 The scope of patent application is the step of adding an effective amount of ammonium hydroxide to the reaction medium to restore the catalyst. -------: 丨-(please first Read the notes on the back and fill in this page), 1T Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _-18- This paper table size is applicable to China National Standard (CNS) A4 specifications (210X297 mm)