TW386073B - Simultaneous preparation of caprolactam and hexamethylenediamine - Google Patents

Description

A7 B7 Revised page of Chinese specification of patent application No. 85115545 (October 1988) V. Description of the invention (: Starting from an 80% concentration aqueous solution, using alumina as a catalyst at 3005 ° C, The yield of lactam is 92%. EP-A 150 295 describes that 6-aminocapronitrile is reacted in the gas phase in the presence of copper / vanadium catalyst, hydrogen, water and ammonia at 290t, with 77% Yield of caprolactam. In addition, DE-A4 319 134 describes 6-aminocaproic acid, which is heated in water; in water, no catalyst is added in the liquid phase to convert to caprolactam. The document does not point out a method, using 牝 Wan to in the overall process including two processing steps, from adiponitrile via amine fermentation. Aminocapronitrile to obtain caprolactam scheme Brief description Figure 1 shows the flow chart of the method of the present invention (Please read the notes on the back before filling out this page) * The symbol of R1 Κ1 Κ2 Κ3 Κ4 Κ5 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs means the first distillation tower, the second distillation tower, and the third distillation tower. Four distillation column, fifth distillation column R2, cyclization reactor A, inert compound ADN, hexane HMI hexamethyleneimine, 0 This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______ B7 V. Description of the invention (1) This invention is about Method for simultaneously preparing caprolactam and hexamethylenediamine starting from adiponitrile. The present invention further relates to an improved method for the simultaneous separation of these materials from a mixture containing 6-aminocapronitrile and hexamethylenediamine. Method: The partial hydrogenation of adiponitrile to 6-aminohexanonitrile in the presence of ammonia and various catalysts has been fully described. For example, XJS 4 601 859 describes the use of catalysts based on the records of magnesium oxide. 'US 2 762 835 describes the use of Raney nickel, US 2 208 598 describes the use of nickel on alumina, and DE_A 848 654 describes the fixed bed catalysts based on steel / cobalt / zinc and iron / cobalt spinel. DE · A 954 416 describes the use of cobalt on silicone, and DE_A 4 235 466 describes the use of iron brocade. In the method described in WO 92/21650 'the amine group has been converted at a conversion rate of 700 /. The yield is 60%, and the yield of hexamethylenediamine is 9%, which is based on Raney nickel deposit. Under the 80% conversion rate, the yield is 62%. It is also known that 6-aminocapronitrile can react with water and release in the gas phase or liquid phase in the presence or absence of a catalyst. Caprolactam is produced from ammonia. For example, US 2 301 964 describes a method in which a 10- to 25% concentration of 6-aminocapsule solution is in the liquid phase and is converted at 250 to 290 ° C. To caprolactam, the yield is as high as 76%. Furthermore, a 6-aminohexanine solution with a concentration of 25 to 35% is added to the liquid phase at 22 ° C in water and an organic solvent is added in the presence of zinc compounds, copper compounds, lead compounds, and mercury compounds. The cyclization is described in A 2,029,540. A caprolactam yield of up to 83% was achieved here. The cyclization of 6-aminocapronitrile can also be performed in the gas phase ^ jS 2 357 484) __ -4- — This paper size applies to China National Standard (CNS) A4 (210X297 mm) --- ( Please read the precautions on the back before filling out this page.) · Revision page of Chinese manual for Patent Application No. 85115545 (October 88) A7 (…… —— B7 heart. +

V. Description of the invention (2a HMD hexamethylenediamine HS direction) 'Essence of matter' The item of the present invention is to provide a method for simultaneously preparing caprolactam and hexamethylenediamine starting from adipiconitrile. Furthermore, it is intended to provide a method for obtaining pure 6-aminohexanonitrile and hexamethylenediamine from a reaction mixture obtained by partial hydrogenation of adiponitrile in a continuous process, in another processing step Cyclization of 6 · aminocapronitrile to caprolactam. Furthermore, the by-products obtained in this method are reused as much as possible, and preferably recycled to a previous treatment stage. I have found that this project is achieved by starting from adiponitrile to produce caprolactam and hexamethylenediamine simultaneously, in which the adiponitrile is partially hydrogenated to obtain a 6-amine group A mixture of nitrile, hexamethylenediamine, ammonia, adiponitrile and hexamethyleneimine, and (b) subjecting the mixture obtained in (a) to distillation to obtain ammonia as a top product 'and bottom Product I 'Distillation is at a bottom temperature of 60 to 25 ° C and a pressure of 5 to 30 bar'. Compound a which is inert to the distillation conditions (read the precautions on the back before filling out this page) -pack.ir

m 1RH Printed by the Consumer Cooperatives of the Central Bureau of Standard Vehicles of the Ministry of Economic Affairs t wbbp l * rl MJB " 5a- A7 B7 No. 85115545 Patent Application Chinese Version Correction Sheet (October 88) V. Description of the invention (from 80% The concentration of the aqueous solution was started, and the yield of caprolactam was 92% using alumina as the catalyst at 30.5 ° C. EP-A 150 295 describes 6-aminocapronitrile in the gas phase, at In the presence of a copper / vanadium catalyst, hydrogen, water, and ammonia, the reaction was carried out at 290 t with caprolactam with a yield of 77%. Furthermore, DE-A4 319 134 describes 6-aminocaproic pickled hot cocks ^ In the water, no catalyst is added in the liquid phase to convert to caprolactam. None of the above documents point out a method that uses pentamidine to pass the adiponitrile through the brewing process in an overall process that includes two processing steps. Amine. Aminocapronitrile obtained caprolactam. Brief description Figure 1 shows the flow chart of the method of the present invention. (Please read the notes on the back before filling out this page.) * The symbol of R1 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs K1, K2, K3, K4, and K5 reactors, first distillation tower, second distillation tower, third distillation tower Fourth distillation column, fifth distillation column, R2 cyclization reactor, A, inert compound, ADN, adiponitrile, HMI, hexamethyleneimine, 0 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) Patent No. 85115545 Application A7 Correction Sheet of Chinese Manual (August 87) B7..X V. Description of Invention (15) ~ ^ ~ Ή ίΓ- ^ In the printed area of the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs The adiwax obtained contains relatively small amounts of high boilers. This distillation is carried out at a bottom temperature of 50 to 250 ° C and 10 to 300 mbar. Adiponitrile (ADN) from side stream product 2 (SA2) is made ) Is recycled to the reactor R1. HS is a high boiling substance. 'According to the present invention, the 6-aminocapronitrile obtained is converted into caprolactam. This cyclization can be performed in a liquid phase by known methods. Or in the gas phase, for example by the methods disclosed in US 2 301 964, US 2 357 484, EP-A 150 295 or DE-A 43 19 134, which are usually carried out by mixing 6-aminocapronitrile with water in Reaction in the liquid phase to obtain caprolactam and gas. In the reaction without catalyst, the temperature is selected from 200 to 375 ° C. And the reaction time is 10 to 90, preferably 10 to 30 minutes. Water is usually used as a solvent, and the content of 6-aminocapronitrile is generally selected to be lower than 30, preferably 10 to 25 weight. / 0 range Inside, 'based on water. In the liquid phase reaction in the presence of a catalyst, the temperature is usually selected from 50 to 330 ° C, and the amount of water is 6 to aminocapronitrile per mole, 1.3 to 50, preferably 1.3. To 30 mol, and the reaction time is 10 minutes to several hours. When using organic solvents, especially alcohols, the amount of water is generally selected from 1.3 to 5 moles per mole of 6-aminocapronitrile. In cyclization, the reaction mixture obtained is usually first treated by distillation to separate amines, water and any organic solvents. If a catalyst is used, the catalyst in the bottom product is generally separated from the caprolactam by one of the conventional methods and recycled to the cyclization reactor (R2 in the drawing). Crude caprolactam is generally converted to pure caprolactam by purification operations known per se, such as distillation, which can then be used to polymerize into caprolactam. -18-This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm); --- r—r -------- batch clothing ------ ΪΤ. ^ (Read Xianmin Read the notes on the reverse side and fill out this page) Revised page of Chinese specification of Patent Application No. 85115545 (October 88) A7 (…… —— B7 heart. +

V. Description of the invention (2a HMD hexamethylenediamine HS direction) 'Essence of matter' The item of the present invention is to provide a method for simultaneously preparing caprolactam and hexamethylenediamine starting from adipiconitrile. Furthermore, it is intended to provide a method for obtaining pure 6-aminohexanonitrile and hexamethylenediamine from a reaction mixture obtained by partial hydrogenation of adiponitrile in a continuous process, in another processing step Cyclization of 6 · aminocapronitrile to caprolactam. Furthermore, the by-products obtained in this method are reused as much as possible, and preferably recycled to a previous treatment stage. I have found that this project is achieved by starting from adiponitrile to produce caprolactam and hexamethylenediamine simultaneously, in which the adiponitrile is partially hydrogenated to obtain a 6-amine group A mixture of nitrile, hexamethylenediamine, ammonia, adiponitrile and hexamethyleneimine, and (b) subjecting the mixture obtained in (a) to distillation to obtain ammonia as a top product 'and bottom Product I 'Distillation is at a bottom temperature of 60 to 25 ° C and a pressure of 5 to 30 bar'. Compound a which is inert to the distillation conditions (read the precautions on the back before filling out this page) -pack.ir

m 1RH Printed by the Consumer Cooperatives of the Central Bureau of Standard Vehicles of the Ministry of Economic Affairs t wbbp l * rl MJB " 5a- Five A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed by the invention (3) or present in a mixture of inert compounds A It was boiled at 60 to 250 ° C under μ bar, and ammonia was not completely separated, and (c) the bottom product I, which basically contained 6 • aminohexanonitrile, hexamethylene dichloride Amine, hexamethylenenitrile, methyleneimine, one or more inert compounds A and ammonia, the ammonia content of which is lower than the ammonia content of the mixture used in stage (b), making them follow the same steam The product is a mixture of inert compound A, ammonia, and bottom product Π, which is the top of the product. This distillation is performed at a bottom temperature of 100 to 250 C and a pressure of 2 to 15 bar. The conditions are the first and the second. The pressures of the towers are coordinated with each other so that in each case a temperature of more than 20 ° is obtained at a bottom temperature not exceeding 250 ° C. (: The top temperature, or obtained in the condenser, the condensation at the top of the second column is performed at a lower temperature, and the top product containing pure or relatively concentrated ammonia is recycled to the first One column, or after its pressure has been increased by a compressor, the top product of the second column is recycled to the first column as a vapor, or to its condenser, the bottom product Π, which basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and one or more inert compounds A, which are subjected to distillation in the third column, and the one or more inert compounds are The top product, and bottom product m, are distilled at a bottom temperature of 50 to 25 ° C. and a pressure of 0.05 to 2 bar, with the proviso that the inert compound A obtained as the top product is fed to The second column, and if necessary, the distillation is performed in the presence of one or more compounds B which are inert to the distillation conditions and boil at 20 to 250 ° C at 0 to 3 bar, -6-this paper size applies China National Standard (CNS) A4 Specification (210X297mm) (Please read it first Please note this page and fill in this page again) \ Ί /-、, τ -J. A7 B7 Consumer cooperation of the Central Bureau of Quasi-Ministry of the Ministry of Economic Affairs, Du printed, and made progress. V. Description of the invention (4 (e) Tower bottom product, basic Containing 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and, if necessary, one or more inert compounds B for distillation in a fourth column, and The top product KP1 ′ is obtained. Its base does not contain hexamethyleneimine, if necessary, one or more inert compounds B are used, and it basically contains SA1, a branch of hexamethylenediamine. The temperature at the bottom of the column is 50. To 25 CTC and a pressure of 0.05 to 5 bar 'and to obtain the bottom product IV, and if necessary, the tower is equipped with a dividing wall in the area between the feed and the side take-out point (Petlyuk tower), so that The obtained hexamethylenediamine is substantially free of hexamethyleneimine and one or more inert compounds B and other low boiling materials, and the overhead product KP1 is fed to the third column, or only if necessary A part of the top product KP1 is fed to the third column, and the rest is removed, and the bottom product IV is basically contained 6 -Aminocapronitrile with adiponitrile and possibly high boilers, subjecting it to distillation in a fifth column to obtain 6-aminocapsules with a purity of at least 95% as a top product, and essentially containing Adiponitrile tributary products, and bottoming product V containing high boiling materials and a small amount of adiponitrile, and if necessary, this column is fitted with a dividing wall in the area between the feed and the side take-out point so that the obtained Adiponitrile contains relatively small amounts of high-carbon compounds. This distillation is at a bottom temperature of 50 to 250. (: and a pressure of 10 to 300 milligrams, and then the 6-aminocapronitrile thus obtained is cyclized. To obtain caprolactam. I have also found that a paper that contains 6-aminocapronitrile and hexamethylene diamine is compatible with Chinese National Standards (CNS) A4 (210X297 mm). M. * I · -I 1-1 ^ 1 m-- II (Please read the notes on the back before filling in this page)

1T A7 B7 Printed by the Central Standards Bureau, Ministry of Economic Affairs, Masonry Consumer Cooperative, V. Description of the Invention (Method for the simultaneous separation of these substances in pentad. Methods mentioned in 178 4 601 859, 118 2 762 835, 118 2 208 598, £-A 848 654, DE-A 954 416, DE-A 4 235 466 or WO 92/21650 Once carried out, this hydrogenation is generally achieved in the presence of nickel-, titanium-, iron-, or germanium-containing catalysts. These catalysts can be used in the form of supported catalysts or unsupported catalysts Examples of suitable catalyst carriers are alumina, silica, titanium dioxide, magnesium oxide, activated carbon, and spinel. Examples of suitable unsupported catalysts are Raney nickel and Raney cobalt. Space velocity of mouth catalyst Usually it is selected in the range of 0.05 to 10 ', preferably 0.1 to 5 kg of adiponitrile per liter of catalyst per hour. The hydrogenation is usually at 20 to 200 ° C, preferably 50 to 15 °. (: Below, and under a hydrogen partial pressure of 0.1 to 20, preferably 0.5 to 10 MPa. The hydrogenation is preferably based on a solvent, especially It is carried out in the presence of ammonia. The amount of ammonia is generally selected to be within the range of 0 to 10, preferably 0.05 to 3 kg of ammonia per kg of adiponitrile. The molar ratio of amine, and therefore the molar ratio of caprolactam to hexamethylenediamine, can be controlled by the selected conversion ratio of adiponitrile in each case. It is preferably 10 to 90%, The conversion ratio of adiponitrile is preferably 30% to obtain a high selectivity of 6-aminocapronitrile. Generally, the sum of 6-aminocapronitrile and hexamethylenediamine is% to, depending on the catalyst and reaction Depending on the conditions, in terms of quantity, hexamethyleneimine is the most important by-product. In a preferred embodiment, the reaction is performed in the following manner. (Read the precautions on the back before reading (Fill in this page)., 1τ ------] ---- ^ ----

Printed by A7 B7 in the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) Ammonia and lithium hydroxide or lithium compounds that will form lithium hydroxide under reaction conditions, preferably at 40 to 120 ° C It is 50 to 100 ° C, particularly preferably 60 to 90 ° C; the pressure is generally selected in the range of 2 to 12, preferably 3 to 10, and particularly preferably 4 to 8 MPa. The residence time basically depends on the desired yield, selectivity and desired conversion rate; usually the residence time is selected so that, for example, a range of 50 to 275, preferably 70 to 200 minutes, is reached to achieve the maximum yield. . The pressure and temperature range is preferably selected so that the reaction can proceed in the liquid phase. The general amount of ammonia used is such that the weight ratio of ammonia to dinitrile is 9: 1 to 0.1: 1, preferably 2.3: 1 to 0.25: 1, particularly preferably 1.5: 1 to 0.4: i. The amount of lithium hydroxide is usually selected in the range of 0.1 to 20, preferably 1 to 10% by weight, based on the amount of catalyst used. Lithium compounds of rubidium lithium oxide are formed under reaction conditions, examples of which are bell metals and alkyl groups and aryl bell compounds such as n-butyl faces and phenyl bells. The amount of these compounds is generally selected so that the amount of the above-mentioned bell hydroxide is obtained. Preferred catalysts are nickel-, ruthenium-, rhodium-, iron-, and cobalt-containing compounds, preferably of Raney type, especially Raney nickel and Raney cobalt. These catalysts can also be used in the form of supported catalysts. Carriers such as oxides, silica, zinc oxide, activated carbon, and titanium dioxide can be used (see Appl. Het. Cat. (1987), 106-122; Catalysis 1 (1981), 1-30). Niro (for example, available from BASF AG, Degussa and Grace) is particularly preferred. Can record-, title-, money-, iron- and gu-catalyst 'Periodic Table of Use Yjg _ -9- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)--LI I If .1— m -Λ: φ ----- I (Please read the notes on the back before filling out this page}-Order A7 B7 Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ) Group (Cr, Mo, W) and Vin group (Fe, Rir, Os, Co (in the case of nickel only), Rh, Ir, Pd, Pt) metal modification. Observations so far have been used in practice In particular, modified Raney nickel catalysts, such as those modified with chromium and / or iron, will result in higher aminonitrile selectivity (for preparation methods, see DE-A 2 260 978 and Bull. Soc. Chem. Inverse (1946), 208). The amount of catalyst is generally selected so that the amount of cobalt, ruthenium, rhodium, iron or green is 1 to 50, preferably 5 to 20 weight 0 /. , Based on the amount of dinitrile used. ™ These catalysts can be used as fixed bed catalysts in liquid phase or trickle bed procedures, or as suspended catalysts. In another preferred embodiment, the catalysts are Increase temperature and pressure In the presence of a solvent and a catalyst, adiponitrile is partially hydrogenated to 6-aminocapronitrile by using a catalyst (a) containing one selected from the group consisting of nickel, lead, iron, ruthenium, and rhodium. Metal-based compounds, and rhenium based on rhenium, 0.01 to 25, preferably 0 to 5% by weight, metal-based promoters, the metal is selected from the group consisting of palladium, platinum, iridium, Copper, silver, gold, chromium, molybdenum, tungsten, manganese, baht, zinc, cadmium, lead, arsenic, arsenic, antimony, bismuth and rare earth metals, and thorium based on (a), 0 to 5, It is preferably 0 to 3% by weight of a compound based on an alkali metal or a soil test metal, and 5 its attached hip strips. '' If m or money or ruthenium and metal or nickel and money based compounds are selected as ingredients ( a), if necessary, the accelerant (b) can be exempted: the preferred catalyst is the component, which contains at least one metal based (please read the precautions on the back before filling in this page): s- order

A7 B7 V. Description of the invention (Compound 'The metal is selected from the group consisting of nickel, cobalt, and iron in an amount of 10 to 95% by weight, and ruthenium and / or germanium' in an amount of (U to 5 weight. In each case based on the sum of ingredients (a) to (c), ingredient (b) contains at least one accelerator based on a metal selected from the group consisting of silver, copper, manganese, baht, lead and phosphorus, based on ⑻ is the basis. Its amount is 01 to 5 wt%, and component (c) contains at least one compound based on an alkali metal and an alkaline earth metal. The metal is selected from the group consisting of lithium, sodium, potassium, cesium, magnesium, and calcium. , Its amount is from 0 to 5% by weight. A particularly good catalyst is: Catalyst A, which contains 90% by weight of cobalt oxide (CoO), 5% by weight of manganese oxide (203), and 3% by weight. Phosphorus and 2% by weight copper oxide (NO2〇), catalyst B contains 20% by weight cobalt oxide (C00), 5% by weight manganese oxide (Mη203), and 0.3% by weight silver oxide (Ag2O). ), 70% by weight silica (SiO2), 35% by weight aluminum oxide (AI203), 0.4% by weight iron oxide (Fe203), 0.4% by weight magnesium oxide (MgO), and 0.4% by weight Calcium (< ^ 0), and Catalyst C, contains 20% by weight of nickel oxide (Ni〇), 67.42% by weight of silica (SiO2), 3.7% by weight of alumina (α1203), and 0.8% by weight Iron oxide (Fe203), 0_76 Printed by the Central Standard of the Ministry of Economic Affairs and printed by the Consumers 'Cooperative (' Read first, read the notes on the back, then fill out this page) Weight. Magnesium oxide (MgO), 1.92% by weight CaO), 83.4% by weight of sodium oxide (0%) and 2.0% by weight of oxidized (-^). The catalysts that can be used preferentially can be unsupported catalysts or supported catalysts. Examples of suitable support materials are porous oxides, such as oxides, stone cuts, aluminosilicates, lanthanum oxides, titanium dioxide, germanium oxide's, zinc oxide and zeolites, and activated carbon or mixtures thereof. The private paper scale is in accordance with the Chinese National Standard (CNS). It is printed by A21 __ ^ _. A7 __ ^ _. B7_ by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. It is carried out by mixing the precursor of component (a) and the precursor of component (component (b)), and the precursor of trace component (c) if necessary, in the carrier material (depending on the type of catalyst required). (Precise) in the presence or absence of precipitation, if necessary, the precursor of the formed catalyst is processed to obtain extrudate or pellets, and then dried and burned. Generally, the supported catalyst can also be The carrier is obtained by impregnating the solution of ingredients (a), (b) and (c) if needed, which can be added simultaneously or successively to individual ingredients by a method known per se, or by mixing ingredients (a), ( (b) and (c) spraying onto the carrier if necessary. Suitable precursors for ingredient (a) are usually water-soluble salts of the above metals, such as nitrate, chloride, acetate, formate and sulfate The preferred precursor of ingredient (b), usually Water-soluble salts or complex salts of the above metals, such as nitrates, vapors, acetates, sulfonates, and sulfates, and especially hexachloropinate, preferably nitrate and hexachloride Appropriate precursors of ingredient (c) are usually the water-soluble salts of the metal and soil metals mentioned above, such as thallium oxide, carbonate, nitrate, chloride, acetate, formate and sulfate, compared to Preferred are hydroxides and carbonates. Precipitation is usually from an aqueous solution, or by adding a precipitating agent, by changing the pH, or by changing the temperature. The catalyst precursors thus obtained are usually in the range of 80 to Dry at 150 ° C, preferably 80 to 120 ° C. Incineration is often carried out at 150 to 500 ° C, preferably 200 to 450 ° C, in an air stream containing air or nitrogen. _- 12-_ This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

'1.T The invention specification printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (10) After the sintering, the obtained catalyst material is generally exposed to the reducing atmosphere (activation). For example, it is exposed to In the case of hydrogen atmosphere or a mixture containing hydrogen and an inert gas (such as nitrogen) < for a period of 2 to 24 hours, in the case of a catalyst based on ruthenium or germanium as the element plutonium, it ranges from 80 to 250.匸, preferably at 80 to 180 ° C, or in the case of using a catalyst selected from the group consisting of one of nickel, palladium, and iron as a component ⑻, in the range of 200 to, more preferably 250 to 400X. The catalyst loading capacity here is preferably 200 liters per liter of catalyst. The activation of the catalyst can advantageously be carried out directly in the synthesis reactor, as it usually dispenses with the intermediate steps that must be carried out in other cases, meaning the purification of the surface ', which is usually between 20 and 80. 〇, preferably from 25 to 35. Your Majesty, use an oxygen / nitrogen mixture, such as air. Then, the activation of the passivated catalyst is preferably performed in a synthesis reactor at 180 to 50 ° C, preferably 200 to 350 C, in a hydrogen-containing atmosphere. These catalysts can be borrowed The liquid phase or trickle bed procedure is used as a fixed bed catalyst or as a suspension catalyst. If the reaction is carried out in suspension, usually 40 to 15 (rc, preferably 50 to 100 ° C, especially The temperature is preferably 60 to 90X: the temperature; the pressure is generally selected in the range of 2 to 20, preferably 3 to 10, and particularly preferably in the range of 4 to 9 MPa. The residence time is basically based on the desired yield and selectivity. And the desired conversion rate; usually the residence time is selected so that the maximum yield is achieved in the range of, for example, to 275, preferably 70 to 200 minutes. In the suspension process, the preferred solvent is ammonia , Amines, diamines, and triamines of 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine, and -13 MM scale are applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling out this page)-called ------ ¾.¾ clothing ------ order ------ • In man Ming (11 nsc% hips and cheeks, especially methanol and B, Yudan u cape, listening to black milk. It can be advantageous to choose a nitrile concentration of 10 to 90, preferably 30 to 骱, particularly preferred is 40 to 70% by weight, based on the sum of dinitrile and solvent. Amount of catalyst-generally selected in the range of 1 to 50, preferably 5 to 20% by weight, based on the dinitrile used The amount is based on. This suspension hydrogenation can be carried out batchwise or preferably in a liquid phase. It is carried out continuously, usually in the following manner: Hydrogenation can also be batchwise or continuously in a fixed-bed reactor by dripping urine or liquid. The phase procedure is carried out, usually at a temperature of 20 to 150 ° C, preferably 30 to 30 ° C, and a pressure of usually 2 to 30, preferably 3 to 20 paper. This hydrogenation is preferably based on It is carried out in the presence of a solvent, preferably an amine, diamine, or triamine, such as trimethylamine, triethylamine, monopropylamine, or dibutylamine, or an alcohol, preferably methanol or ethyl. Alas, particularly preferred is ammonia. In a preferred embodiment, the ammonia content is selected to be 1 to 10, preferably 2 to 6 grams per gram of adiponitrile. The catalyst space velocity is preferably The choice is 0.1 to 2.0 per liter per hour, preferably 03 to 10 kg of adiponitrile. Its conversion rate and therefore its selectivity can also be made here by changing the residence time. Partial hydrogenation The function can be performed in a conventional reactor (R1 in the drawing) suitable for this project. The distillation in the first column (stage ⑼; K1 in the drawing) is performed according to the present invention by the following method Wherein the mixture from stage VII basically contains 6-aminocapronitrile, hexamethylenediamine, ammonia, adiponitrile and hexamethyleneimine, preferably the following mixture, which basically contains i to 70%, preferably from $ to this paper size. Applicable to National Standards (CNS) A4 specifications ⑺〇 > < 297 public shame) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention ( 12) 40% by weight of 6-aminocapronitrile, 1 to 70, preferably 5 to 40% by weight adiponitrile, 0.1 to 70, preferably 1 to 40% by weight of hexamethylenediamine, 〇1 to 10, preferably 0.05 to 5% by weight of hexamethyleneimine, and 5 to 95, preferably 20 to 85% by weight of ammonia. It is carried out in a conventional steaming tower with a bottom temperature of up to 250 ° C, preferably 100 to 200 ° C, and a pressure of 5 to 30, preferably 12 to 25 bar, under one or more distillation conditions In the presence of compounds which are inert and boil at 60 to 220 ° C at 18 bar, ammonia is obtained as a top product and bottom product I '. The ammonia is not completely separated. According to the invention, a suitable compound A is a substance which is inert under distillation conditions and has a boiling point of 60 to 250 ° C, preferably 60 to 150 ° C at 18 bar. Examples are alkanes, naphthenes, aromatic hydrocarbons, naphthenes, alcohols, ethers, nitriles, and amines, especially c5_C8_alkanes and c2_ alcohols, especially N -Pentane, cyclohexane 'triethylamine, ethanol, acetonitrile, n-hexane, di-n-propyl ether, isopropanol, n-butylamine and benzene, with ethanol being particularly preferred. Compound A is usually 0.1 to 50, preferably 1 to 10 weight. /. The amount was added based on the bottom product I. In stage (c), the bottom product I basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine, one or more inert compounds A and ammonia 'ammonia content. Lower the ammonia content in the mixture obtained from stage 且 and used in stage (b), so that the bottom product of the 妾 is subjected to a second distillation to obtain one or more inert compounds A and ammonia as overhead products, And bottom product jj, the distillation temperature at the bottom is i⑻ to 250 «C, preferably 14 to 2⑻. C, this paper size applies to the standard (CNS) A4 size (2IGX) 97 public directors ---- --rj ------.---- (Read the notes on the back of Min Min before filling this page) Order A7 Β7 Description of the invention (13 and under 2 to 15 'preferably 4 to 12 bar The condition is that the pressures of the first and second towers (K2 in the drawing) are matched with each other, so that the top temperature of more than 2 (rc top temperature can be obtained at an individual bottom temperature not exceeding 250 ° C. Can also Advantageously, this condensation is carried out 'on the top of the second column at a lower temperature, and the overhead product consisting of pure or relatively highly concentrated ammonia is recycled. The first column, or after increasing the pressure using a compressor, recycles the overhead product of the second column as a vapor to the first column or to its condenser. In stage (d), 'substantially A bottom product Π containing 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and one or more inert compounds A, in the third column (K3 in the drawing) It undergoes distillation to obtain one or more inert compounds A as the top product and the bottom product m. The distillation system has a bottom temperature of 50 to 250 ° C, preferably 140 to 200 ° C, and To 2, preferably 0.2 to 1 bar, with the proviso that the obtained one or more inert compounds as overhead products are fed to a second column, and if necessary the distillation is based on one or more compounds It is carried out in the presence of B. This compound B is inert under distillation conditions, and is boiled at a specific pressure of 0. 3 bar at 20 to 25. (:, preferably at 60 to 70 eC. Boiling. Printed by the Bureau ’s Consumer Cooperatives ^-Γ ----: R: Preservation (Please read the precautions on the back before filling out this page), 1.τ. 化Examples of substance B are sintered, sintered, aromatic hydrocarbons, ring pits, alcohols, ethers, nitriles, and amines having the above properties, especially di-n-butyl ether, valeronitrile, N -Octane, cyclooctane, n-hexylamine, hexamethyleneimine and hexamethylenediamine, preferably hexamethyleneimine and / or hexamethylenediamine, particularly preferably hexamethylene In a preferred embodiment, hexamethyleneimine and / or hexamethyleneimine are selected.

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ---------_; ___ B7 ~ __ V. Description of the invention (14) Methylenediamine is used as compound B, or other compounds b are not added to the special line. The compound B is preferably added to the column K3 in an amount of 0.001 to 50, preferably 0.5 to 10% by weight, based on the bottom product X [as a reference. In stage (e), the bottom of the column is substantially made up of 6-aminohexanonitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and, if necessary, one or more inert compounds B The product m is subjected to distillation in a fourth column (K4 in the drawing) to obtain a column top product PK1, which basically contains hexamethyleneimine, if necessary, one or more inert compounds B and basic The side stream product SA1, which contains hexamethylenediamine, has a bottom temperature of 50 to 25 °. (: And the pressure is 0-5 to 1.5 bar, and the bottom product jv is obtained. If necessary, the tower is equipped with a partition wall in the area between the feed and the side removal point (Petlyuk tower), so that The obtained hexamethylenediamine is substantially free of 7T methyleneimine and one or more inert compounds B and other low boiling materials. If necessary, the top product KP1 and / or HMD 'silver from the side stream product SA1 Into the third column, or feed only a part of it to the third column if necessary, and remove the rest. In stage (f), the system contains substantially 6-aminocapronitrile and The bottom product IV of adiponitrile and possible high-boiling substances is subjected to distillation in the fifth column (K5 in the drawing), and the purity is at least 95%, preferably 99 to 99.9%. 6-Aminocapronitrile is used as the top product, and it mainly contains a side stream of adiponitrile and bottom product V. The bottom product ν is composed of high boilers and a small amount of adiponitrile. Install the partition wall between the feed and the side take-out point ________ -17- This paper size is suitable for financial standards (0 called 戍 4 specifications (2 Xian 297)) (Please read the first Notes on the page and then fill in}

Patent Application No. 85115545 A7 Revised Chinese Manual (August 87) B7..X V. Description of Invention (15) ~ ^ ~ Ή ίΓ- ^ Within the printed area of the Consumers' Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs So that the obtained hexamethylene wax contains a relatively small amount of high boilers. This distillation is carried out at a bottom temperature of 50 to 250 ° C and at 10 to 300 mbar. Adiponitrile (ADN) from side stream product 2 (SA2) was recycled to reactor R1. HS is a high boiler. 'According to the present invention, the obtained 6-aminocapronitrile is converted into caprolactam. This cyclization can be performed in a liquid or gas phase by known methods, for example by the methods disclosed in US 2 301 964, US 2 357 484, EP-A 150 295 or DE-A 43 19 134, which Caprolactam and gas are usually obtained by reacting 6-aminocapronitrile with water in the liquid phase. In the reaction without using a catalyst, the temperature is selected from 200 to 375 ° C, and the reaction time is 10 to 90, preferably 10 to 30 minutes. Water is generally used as the solvent, and the 6-aminocapronitrile content is generally selected to be less than 30, preferably 10 to 25 weight. In the range of / 0, '' is based on water. In the liquid phase reaction in the presence of a catalyst, the temperature is usually selected from 50 to 330 ° C, the amount of water is 6-aminocapronitrile per mole, 1.3 to 50, preferably 1.3 to 30 moles, and the reaction time For 10 minutes to several hours. When using organic solvents, especially alcohols, the amount of water is generally selected from 1.3 to 5 moles per mole of 6-aminocapronitrile. In cyclization, the reaction mixture obtained is usually first treated by distillation to separate amines, water and any organic solvents. If a catalyst is used, the catalyst in the bottom product is generally separated from the caprolactam by one of the conventional methods and recycled to the cyclization reactor (R2 in the drawing). Crude caprolactam is generally converted to pure caprolactam by purification operations known per se, such as distillation, which can then be used to polymerize into caprolactam. -18-This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm); --- r—r -------- batch clothing ------ ΪΤ. ^ (Read Xianmin Read the notes on the back and fill in this page again.) 5. Description of the invention (16) A7 B7 Printed by a Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. In a preferred embodiment, 6-aminocapronitrile and water are used. In the liquid phase, a heterogeneous catalyst reaction is used. This reaction is in the liquid phase, usually at 140 to 320 »c, preferably 160 to 280 ° c; the pressure is usually i to 25, preferably 5 to 150 bar, and the reaction mixture should be ensured at The conditions used are mainly liquid. Its retention time is generally 1 to 120, preferably 丨 to 90, especially 1 to 60 minutes. In some cases a 'cured residence time of 1 to 10 minutes is completely sufficient. Generally speaking, at least 0.001, preferably 0.1 to 20 ', especially 1 to 5 moles of water per mole of 6-aminocapronitrile is used. It may be advantageous to use it in water (in which case the solvent is also a reactant) or in a water / solvent mixture, in particular 5-50, particularly preferably 5-30 weight. In the form of k-degree liquid, 6. aminocapronitrile was used. Examples of solvents are alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tertiary-butanol, and polyols such as diethylene glycol and tetraethylene glycol Hydrocarbons such as petroleum ether, benzene, xylene and xylene, lactams such as tetrahydropyrrolidone and caprolactam, and alkyl-substituted lactams such as methylmethyltetrahydropyrrolidone, N- Methylcaprolactam and ethylcaprolactam, and carboxylic acids, preferably carboxylic acids of 1 to 8 carbon atoms. Ammonia can also be present in the reaction. However, mixtures of organic solvents can also be used. The mixture of solidified water and burned alcohol is particularly advantageous in some cases at a water / alkanol weight ratio of ^ 75 / 25-99, preferably 丨 -e.g. In principle, it is possible to use 6-aminocapronitrile as a reactant and at the same time as a solvent. Examples of heterogeneous catalysts that can be used are: second, third, or

(Please read the notes on the back before filling out this page) p Tul ·. ------ Order ^ ---- --ϋ In (an A7 B7 Printed by the Employees' Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs Description of the invention (17 7 group 7L element (acid, test or amphoteric oxygen oxygen magnesium, oxide shed, oxide name, tin oxide 'or crushed stone = form of algal, quartz or mixture thereof) Oxides of metals, such as dioxin, have a chemical formula or form sharp rutile or rutile, oxides, zinc oxide, and mixtures of oxides. Oxides of lanthanides and actinides, such as oxygen-dissolved hafnium dioxide Rhenium oxide and thorium oxide, rare earth mixed oxides, and mixtures thereof with the above-mentioned emulsifiers can also be used. Examples of other catalysts are: ,, Oxidation, Oxidation, Iron Oxide, Oxidation Complex, Oxidation Fine, Oxidation Crane and -Mixtures. Mixtures of the oxides with each other are also possible.-Some sulfide compounds and tellurides, such as zinc telluride, tin compounds, phoenix, sulfur, sulfur compounds, and It can be used. The above compounds can be transformed with the main group of the periodic table. Compounds may be doped, or may contain these compounds. Furthermore, zeolites, phosphates, and heteropolyacids, and acidic and basic ion exchangers, such as Naphion®, are examples of suitable catalysts. If necessary, this The catalyst in each case of copper, tin, zinc, manganese, iron, lead, nickel, ruthenium, palladium, platinum, silver or rhodium may contain up to 50 weight. 7. Depending on the composition of the catalyst, These catalysts can be used as unsupported catalysts or supported catalysts. For example, titanium dioxide can be used as a titanium dioxide extrudate 'or as a titanium dioxide coated on a carrier in a thin layer. All the methods described in the literature can be used to apply titanium dioxide to a support 'such as hard rock, alumina or titanium dioxide. Therefore, thin films of titanium dioxide can be made of titanium organics' such as titanium isopropylate or Hydrolysis of titanium butyrate, -20- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 father 297 male | (Please read the precautions on the back before filling this page)

Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (18 Or, it is coated by the hydrolysis of TlCl4 or other inorganic compounds. The sol containing titanium dioxide can also be used. It is zirconyl dichloride, aluminum nitrate and thorium nitrate. Suitable carriers are the oxide itself or other safe oxides such as the powder, extrudate or pillars of the second stone. The carrier used can be made with large pores. In order to improve the mass transfer, in another preferred embodiment, 6-aminocapronitrile uses water in the liquid phase, and is cyclized at the elevated temperature without using a catalyst. In the liquid phase without adding a catalyst, an aqueous solution of 6-aminocapronitrile is heated in the reactor to obtain a mixture I that basically contains water, caprolactam, and a high stagnation fraction (high stagnation). In this preferred embodiment, it is preferred to use an excess of water. Particularly preferred is 10 to 150 per mole of 6-aminocapronitrile, especially 20 to 1 mole of water. Aqueous solution of nitrile. In another preferred embodiment, 6-aminocapronitrile per mole This solution may be based generally further diluted to 5_25 6- wt% amine by adding an organic solvent 5 to 25 mole of water, and the base has bet the Examples of suitable solvents for the..:

Cjl-C4 · alkanols such as methanol, ethanol, n-propanol, isopropanol and butanol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and ethers such as Methyl tertiary-butyl ether and diethylene glycol ether, octadecanes, such as n-hexane, n-heptane, n-octane, n-nonon and n-decane, and cyclohexane , Benzene, toluene, xylene, lactams such as tetrahydrop-pyrrolidone and caprolactam, and Nq -C: 4. Alkyl alcohols such as N-methyltetrapyrrolidone, N- Methylcaprolactam and N-ethylcaprolactam. ____ -21 -____ This paper size applies to Chinese National Standards (CNS) M specifications (210 X 297 mm) ~~-(谙 Please read the precautions on the back before filling this page)

Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7-B7 V. Description of the invention (19 ^' " 〇 In a specific embodiment, 0 to 5, preferably 0 to 2% by weight Ammonia, hydrogen or nitrogen is added to the reaction mixture. The reaction is preferably carried out at 200 to 37 ° C, preferably 220 to 35 ° rc, particularly preferably 240 to 320 ° C. This reaction is usually carried out at superatmospheric pressure. The selected pressure is usually 0.1 to 50, preferably 5 to 25 MPa, so that the reaction mixture is preferably in a liquid phase. The duration of the reaction is basically determined by the selected program parameters, and it is continuous In the method, it is generally from 20 to 180, preferably from 20 to 90 minutes. Generally, lower conversion is obtained in a shorter reaction time, and the oligomers which have been observed to date which have been difficult to handle will be longer. It is formed within the reaction time. This cyclization is preferably performed continuously in a tubular reactor, a stirred tank, or a combination thereof. This cyclization can also be performed in a batch manner. The reaction time is usually 30 to 180 minutes. Discharge Is usually a mixture which basically contains 50 to 98, preferably 80 to 95% by weight water, and 2 to 50, preferably 5 to 20% by weight of the following mixture, which basically contains 50 to 90, preferably 65 to 85% by weight Ammonium, and 10 to 50, preferably 15 to 35 weight. High boiling point fraction (high boiling). In another embodiment, after partial hydrogenation and after removing ammonia and one or After a variety of inert compounds A (bottom product of column 3), any existing ground catalyst materials and high boilers are removed by evaporation or distillation. The way is to obtain unwanted substances as bottom product, and Feed the product from the top of the tower into the tower K4 -22- The X degree of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) C Read the precautions on the back first #Fill this purchase) ^^ 1 1H--I. .... In -— ^ 1; ^ —— I ^^ 1 n I:-Λ '^ 1 ^ 1 ^^ 1 m ml --------- /. K ---- Til—ί ·

I Consumption cooperation by employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du A7 ----------- B7 ^ _ V. Invention Outline ΰ〇γ:-Medium. 2. In another specific embodiment, the adiponitrile and the high-boiling system are taken out through the celestial part of the column R5 and fed to the stage ⑻. In this case, the liquid plutonium can also be removed from the bottom of the tower K5. The ADN from the tributary of column K5 can also be purified in another column. The hexamethylenediamine obtained according to the present invention can be further purified by conventional methods and used to prepare polymers and copolymers, such as polyamine 66. According to the present invention, part of the method for preparing caprolactam from adiponitrile can also be used for the simultaneous separation of 6-aminocapronitrile and hexamethylenediamine in a way that the distillate basically contains these compounds Mixture, in which (a) is a mixture containing 6-aminohexanonitrile, hexamethylenediamine, hexamethylene-nitrile, and methyleneimine, which is subjected to distillation to obtain ammonia as a top product and a column. Base product I. This distillation is carried out at a bottom temperature of 60 to 2500c and at a temperature of 5 to 30 bar in the presence of a mixture of a compound that is inert under the distillation conditions or an emotional compound A. The compound is The microbar system boils at 60 to 25 ° C, and ammonia is not completely separated, and (b) the bottom product I, which basically contains 6-aminohexanonitrile, hexamethylenediamine, Adiponitrile, hexamethyleneimine, one or more inert compounds A and ammonia, the ammonia content of which is lower than the ammonia content of the mixture used in stage (a), subjecting it to a second distillation to obtain inert compound A The mixture with ammonia is used as the top product and bottom product. The distillation system has a bottom temperature of 100. To 250 ° C and a pressure of 2 to 15 bar, with the proviso that the grace of the first and second towers cooperates with each other, so that in each case the top is obtained at a temperature not exceeding 220 ° C at the bottom The temperature is greater than 200 ° C, or __ -23 -____ This paper size is applicable to the Chinese National Standard (_CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling this page)

V. Description of the invention (21) Condensation printed on the top of the second tower by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, which is performed at a lower temperature, and is a tower top product composed of pure or relatively concentrated ammonia. , Is recirculated to the first tower, or after the pressure has been increased by a compressor, the top product of the second tower is recirculated as a vapor to the first tower or to its condenser, (C) The bottom product n which basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and one or more inert compounds A is subjected to distillation in the first column to obtain -Or more inert compounds as the top product and bottom product m, this distillation is performed at a bottom temperature of 50 to 25 (rc and pressure of 0.05 to 2 bar), with the proviso that the obtained product is used as the top product One or more inert compounds A are fed to the second column and, if necessary, the distillation is carried out in the presence of one or more compounds B, which are inert under the conditions of distillation and are Boiling at 20 to 250 ° C, so that it basically contains 6-amino Nitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and, if necessary, the bottom product 冚 of one or more inert compounds B, are subjected to distillation in a fourth column to obtain the top product kpi It basically contains hexamethyleneimine, if necessary, one or more inert compounds B and a tributary product that basically contains hexamethylenediamine. The bottom temperature of this column is 50 to 250X and the pressure is 0.05 to 15 bar, and the bottom product IV is obtained, and if necessary, the tower is equipped with a partition wall in the area between the feed and the side take-out point (Petlyuk tower), so that the hexamethylene diamine obtained is basically Does not contain hexamethyleneimine, one or more inert compounds B and other low boiling materials, read Aj 阋 read φ Note i tr -24 This paper size applies to China National Standard (CNS) A < 4 specifications (210X 297) (%) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (22)-Feed the top product KP1 to the third tower, or if necessary, feed only a part of the top product KP1 to The third tower and remove the rest, ^ (e) make the base The bottom product IV ′ containing 6-aminocapronitrile and adiponitrile and possible high-boiling substances on the bottom was subjected to distillation in a fifth column to obtain 6-amine with a purity of at least 95%. Caprocarbonitrile was used as a column The top product, and the tributary product basically containing adipide, and the bottom product V composed of high boiling materials and a small amount of adiponitrile, and if necessary, the tower is equipped with a partition wall, which is located at the feed and side and taken out The area between the points, so that the obtained adiponitrile contains a relatively small amount of high buddha, this distillation is carried out at a bottom temperature of 舄 50 to 250 ° C, and at 10 to 300 mbar. This novel method has the advantage that it provides a continuous method for obtaining caprolactam from adiponitrile and simultaneously obtaining hexamethylenediamine. Example (a) Hydrogenation of adiponitrile to 6-aminocapronitrile In a tubular reactor having a length of 2 meters and an inner diameter of 2.5 cm, 750 ml (1534 g) of 90% by weight CoO and 5% by weight Mn203 were filled , 3% by weight of P205 and 2% by weight of 0% catalyst, and then the catalyst in a hydrogen flow (5 liters / hour) at atmospheric pressure, by increasing the temperature from 30 ° C to 280 ° C, activated within 48 hours. After the temperature has dropped to 45 ° C (inlet) or 85 ° C (outlet), feed a mixture of 380 g / h adiponitrile, 380 g / h ammonia and 500 l / h tritium to 200 bar Reactor. In addition, this feed was cycled four times (about 3 kg / hour) to remove heat. Under these conditions, 70% adiponitrile was converted. Reaction mixing; --- ^ 25 -___ Bibiao 豕 T-π A4 centimeter 97 2 (谙 Notes on the back of the plate before filling out this page} Order Γ --- *-^ — i '' '- ---,-. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 ____B7__ V. Description of the Invention (23) The compound contains 50% by weight of ammonia, 15% by weight of ADN, 17.5% by weight of aminocapronitrile (ACN), 17.4% by weight HMD and 0.1% by weight of other substances (ACN selectivity: 50%, ACN + HMD selectivity: > 99%). (B) Hydrogenation mixture discharged from (a) by distillation treatment of hydrogenation mixture discharged The catalyst was removed and fed to the top of the first column with two theoretical plates. 5.0 kg of ammonia with 200 ppm ethanol was separated through the top at 47 ° C and 19 bar and used for hydrogenation (stage (A)). The bottom product of the first column, which is a reaction mixture containing ethanol and a small amount of ammonia, is fed to a second column having 10 theoretical plates at a bottom temperature of 180 ° C. 30 Weight: 0.22 kg of ammonia with 70% by weight of ethanol and trace amounts of hexamethyleneimine (HMI), hexamethylenediamine (HMD), ACN and ADN. The top of the tower was recycled to the first tower at 50 ° C and 10 bar. The bottom product of the second tower containing 39% ethanol and 100 ppm ammonia was fed at 177 ° C. In the third column with 10 theoretical plates, through the top of this column, 3.2 kg of ethanol was taken out at 47 ° C / 300 mbar and recycled to the second column. 5.0 kg of product was fed from the bottom of the third column to the fourth column with 35 theoretical plates. Via the top of this column, at 67 ° C / 90 mbar, 5 g of HMI containing 19% HMD was taken out From the 30th theoretical plate of this tower, 1.74 kg of HMD containing 155 ppm HMI and 100 ppm ACN was taken as the liquid tributary product and removed from this procedure. 3.25 kg of product that basically contained ACN and ADN was removed from The fourth tower _-2R -__ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)-Install

iT A7 B7 _ 5. Description of the invention (24)

The bottom was removed, it was at 181 ° C and it was fed to a fifth tower with 20 theoretical plates. A 1.75 kg ACN containing 185 ppm HMD and 100 ppm ADN was obtained at the top of the tower at 20 mbar and 120 ° C. 1.39 kg ADN containing 800 ppm ACN was taken out as the steam tributary at the lower part of the fifth tower product. At 190 ° C, 0.11 kg of ADN containing about 10% by weight of high-boiling matter was taken out through the bottom. (c) The cyclization of 6-aminocapronitrile to caprolactam makes a solution of 2 kg of ACN (obtained from (b)), 0.64 kg of water and 17.4 kg of ethanol at 220 ° C and 70 bar and the residence time For 15 minutes, the tube reactor was heated by an oil having a length / diameter ratio of 100 and containing 4 mm of titanium dioxide extrudate. The discharged reaction mixture contained 1.7 kg of caprolactam, 0,06 kg of 6-aminohexanoic acid ethyl ester, 0.1 kg of 6-aminohexanoic acid nitrile (determined by gas chromatography), and 0.1 kg of 6-aminohexanoic acid. Acids, and oligomers and polymers of caprolactam (determined by HPLC). From this, 1.6 kg of caprolactam was obtained. j——ί 7-^ ------ ^ β 装-(Please read the precautions on the back before filling this page)

II Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs __- 27- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

Patent No. 85115545 g ____________ Chinese version of the scope of patent application (August 1987) _ D8! _-^ Month fi ~ 16, the scope of patent application 87. Only 1!: Charge-· _. · ^ I 1 A method for preparing caprolactam and hexamethylenediamine simultaneously from hexamethylene, wherein (a) is a part of hydrogenation of adiponitrile to obtain 6-aminocapronitrile and hexamethylenediamine. A mixture of amine, ammonia, adiponitrile and hexamethyleneimine, and (b) subjecting the mixture obtained in mash to steaming to obtain ammonia as a top product and bottom product I. This distillation system Performed at a bottom temperature of 60 to 250 ° C and a pressure of 5 to 30 bar in the presence of a compound A, or a mixture of inert compounds A, which are inert under the conditions of the distillation, which is tied to 60 birds at 250 bar Boiling at ° C without ammonia being completely separated and printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (c) Tower bottom product I, which basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine, one or more inerts Compounds A and ammonia, the ammonia content of which is lower than the ammonia content of the mixture used in stage (b), so that it accepts the second steaming hall and can be used as one or more inert compounds A and ammonia as overhead products and A mixture of bottoms product II. This distillation is carried out at a bottom temperature of 100 to 250 ° C and a pressure of 2 to 15 bar, with the proviso that the pressure systems of the first and second columns are coordinated so that in each case Obtain a top temperature of more than 20 ° C at a bottom temperature not exceeding 250 ° C, or the condensation at the top of the second column, which is carried out at a lower temperature and contains pure or relatively high concentration ammonia top products Recycling to the first tower, or after the pressure has been used. After the shrinking machine is increased, the paper size of the top of the second tower is adapted to the Chinese National Standard (CNS) A4 specification (210X297 mm) Article 85115545 Patent Application No. g ____________ Chinese Patent Application Amendment (August 1987) _ D8! _-^ Month fi ~ 16. Patent application scope 87. Only 1!: Charge-· _. · ^ I 1. One Preparation of caprolactam and hexamethylene simultaneously from hexamethylene Method for diamine, wherein (a) is a mixture of adionitrile partially hydrogenated to obtain a mixture substantially containing 6-aminocapronitrile, hexamethylenediamine, ammonia, adiponitrile, and hexamethyleneimine , And (b) subjecting the mixture obtained in ⑻ to steaming cranes to obtain ammonia as a top product and bottom product I, this distillation is performed at a bottom temperature of 60 to 250 ° C and a pressure of 5 to 30 bar , In the presence of a compound A that is inert under distillation conditions, or a mixture of inert compound A, the compound is boiled at 60 birds at 250 ° C under 8 bar, and the ammonia has not been completely separated, and the center of the Ministry of Economic Affairs Printed by the Standards Bureau ’s Consumer Cooperative (please read the notes on the back before filling this page) (c) Tower bottom product I, which basically contains 6-aminohexanonitrile, hexamethylenediamine, adiponitrile, Hexamidineimine, one or more inert compounds A and ammonia, the ammonia content of which is lower than the ammonia content of the mixture used in stage (b), so that it accepts the second steaming hall and can be used as the overhead product A mixture of one or more inert compounds A with ammonia and bottoms product II. This distillation is carried out at The temperature is 100 to 250 ° C and the pressure is 2 to 15 bar, with the proviso that the pressure system of the first and second towers is matched with each other, so that in each case, the bottom temperature does not exceed 250 ° C. A top temperature above 20 ° C, or condensation at the top of the second column, is carried out at a lower temperature, and the top product containing pure or relatively high concentration ammonia is recycled to the first column, or After the pressure has been increased, the size of the paper on the top of the second tower will be adapted to the Chinese National Standard (CNS) A4 (210X297 mm). The product is recycled to the first column as a vapor, or to its condenser such that it essentially contains 6-aminocapronitrile, hexamethylene, diamine, adiponitrile, hexamethyleneimine and one or more inerts The bottom product Π ′ of compound A is subjected to a steaming chamber in the third column to obtain one or more inert compounds A as the top product and bottom product III. This distillation is performed at a bottom temperature of 50 to 250 ° C. and The pressure is performed at 0.05 to 2 bar, with the proviso that the inert compound A obtained as the top product of the column is silver. '· To the second column, and if necessary, the' distillation is inert to the distillation conditions It is carried out in the presence of one or more compounds B boiling at 20 to 250 ° C under 0.3 bar. · 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) (e ) Make the bottom product III, which basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine, and if necessary one or more inert compounds B, Distillation is performed in the column to obtain the top product KP1, which basically contains hexamethylene Amine, if necessary one or more inert compounds B and a side stream product SA1 which essentially contains hexamethylenediamine, the bottom temperature of this column is 50 to 250 ° C and the pressure is 0.05 to 1.5 bar, and the bottom of the column is obtained Product IV, and if necessary, this column is fitted with a dividing wall in the area between the feed and the side take-out point (Petlyuk tower) so that the hexamethylene diamine obtained is substantially free of hexamethylene Feed imine with one or more inert compounds B and other low stagnant products to the third column, or if required, only a portion of the top product KP1 to the third column, and the rest Partially removed, -2- The size of this paper is applicable to China National Standard (CNS) A4 (210 × 297 mm) The product is recycled to the first column as a vapor, or to its condenser such that it essentially contains 6-aminocapronitrile, hexamethylene, diamine, adiponitrile, hexamethyleneimine and one or more inerts The bottom product Π ′ of compound A is subjected to a steaming chamber in the third column to obtain one or more inert compounds A as the top product and bottom product III. This distillation is performed at a bottom temperature of 50 to 250 ° C. and The pressure is performed at 0.05 to 2 bar, with the proviso that the inert compound A obtained as the top product of the column is silver. '· To the second column, and if necessary, the' distillation is inert to the distillation conditions It is carried out in the presence of one or more compounds B boiling at 20 to 250 ° C under 0.3 bar. · 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) (e ) Make the bottom product III, which basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine, and if necessary one or more inert compounds B, Distillation is performed in the column to obtain the top product KP1, which basically contains hexamethylene Amine, if necessary one or more inert compounds B and a side stream product SA1 which essentially contains hexamethylenediamine, the bottom temperature of this column is 50 to 250 ° C and the pressure is 0.05 to 1.5 bar, and the bottom of the column is obtained Product IV, and if necessary, this column is fitted with a dividing wall in the area between the feed and the side take-out point (Petlyuk tower) so that the hexamethylene diamine obtained is substantially free of hexamethylene Feed imine with one or more inert compounds B and other low stagnant products to the third column, or if required, only a portion of the top product KP1 to the third column, and the rest Partially removed, -2- The size of this paper is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) A8 386073 c8s 6. Scope of patent application and (please read the precautions on the back before filling out this page.) (F) Make the bottom product containing 6-aminocapronitrile and adiponitrile and possible high boiling substances. IV. Distillation in the fifth column to obtain 6-aminocapronitrile with a purity of at least 95% as the top product, and a side stream product that essentially contains adiponitrile, and containing high boilers and a small amount of adiponitrile The bottom product V of the nitrile, and if necessary, this column is fitted with a dividing wall in the area between the feed and the side take-out point, so that the obtained adiponitrile contains a relatively small amount of high stagnate. The distillation is carried out at a bottom temperature of 50 to 250 ° C. and a pressure of 10 to 300 mbar, and then the 6-aminocapronitrile formed is cyclized to caprolactam. 2. The method according to item 1 of the scope of patent application, wherein adiponitrile from side stream 5 of the column is fed to stage ⑻. 3. — A method for the simultaneous separation of 6-aminocapronitrile and hexamethylenediamine by distilling a mixture containing essentially these compounds, which is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (a) A mixture basically containing 6-aminocapronitrile, hexamethylenediamine, ammonia, adiponitrile and hexamethyleneimine is subjected to distillation to obtain ammonia as a top product and bottom product I. This distillation system It is carried out at a bottom temperature of 60 to 250 ° C and at 5 to 30 bar in the presence of a compound A or a mixture of inert compounds A which are inert under the conditions of distillation, which is 60 to 250 ° at 18 bar It boils at C and ammonia is not completely separated, and (b) the bottom product I, which basically contains 6-aminocapronitrile and hexamethylenediamine-3- This paper is in accordance with Chinese national standards (CNS ) ΑΊ Specifications (210X297 mm) A8 386073 c8s 6. Scope of patent application and (please read the precautions on the back before filling out this page.) (F) Make the bottom product containing 6-aminocapronitrile and adiponitrile and possible high boiling substances. IV. Distillation in the fifth column to obtain 6-aminocapronitrile with a purity of at least 95% as the top product, and a side stream product that essentially contains adiponitrile, and containing high boilers and a small amount of adiponitrile The bottom product V of the nitrile, and if necessary, this column is fitted with a dividing wall in the area between the feed and the side take-out point, so that the obtained adiponitrile contains a relatively small amount of high stagnate. The distillation is carried out at a bottom temperature of 50 to 250 ° C. and a pressure of 10 to 300 mbar, and then the 6-aminocapronitrile formed is cyclized to caprolactam. 2. The method according to item 1 of the scope of patent application, wherein adiponitrile from side stream 5 of the column is fed to stage ⑻. 3. — A method for the simultaneous separation of 6-aminocapronitrile and hexamethylenediamine by distilling a mixture containing essentially these compounds, which is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (a) A mixture basically containing 6-aminocapronitrile, hexamethylenediamine, ammonia, adiponitrile and hexamethyleneimine is subjected to distillation to obtain ammonia as a top product and bottom product I. This distillation system It is carried out at a bottom temperature of 60 to 250 ° C and at 5 to 30 bar in the presence of a compound A or a mixture of inert compounds A which are inert under the conditions of distillation, which is 60 to 250 ° at 18 bar It boils at C and ammonia is not completely separated, and (b) the bottom product I, which basically contains 6-aminocapronitrile and hexamethylenediamine-3- This paper is in accordance with Chinese national standards (CNS ) ΑΊ Specifications (210X297 mm) 386073 8 8 8 8 ABCD Scope of patent application Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, adiponitrile, hexamethyleneimine, one or more inert compounds A and ammonia, the ammonia content of which is lower than that of the mixture used in stage (a), so that It accepts a second steaming hall to obtain a mixture of inert compounds A and ammonia as the top product and bottom product II. This distillation is performed at a bottom temperature of 100 to 250 ° C and a pressure of 2 to 15 bar. , With the proviso that the pressure systems of the first and second towers are coordinated with each other, so that in each case a top temperature greater than 20 ° C is obtained at a bottom temperature not exceeding 250 ° C, or at the top of the second tower Condensation is carried out at a lower temperature, and the overhead product consisting of pure or relatively highly concentrated ammonia is recycled to the first column, or after its pressure has been increased by a compressor, The top product of the second column is recycled as vapor to the first column or to its condenser, (c) so that it contains substantially 6-aminocapronitrile, hexamethylenediamine, adiponitrile, and hexamethylene. The bottom product II of methylimine and one or more inert compounds A, in The third column receives steaming cranes to obtain one or more inert compounds A as the top product and bottom product III. The distillation is performed at a bottom temperature of 50 to 250 ° C and a pressure of 0.05 to 2 bar. The condition is that one or more inert compounds A obtained as overhead products are fed to the second column, and if necessary, the distillation is performed in the presence of one or more compounds B, which are in distillation conditions The system is inert, sexual, and boils at 20 to 250 ° C at 0.3 bar. (D) Basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, and hexamethylene. Amine and if necessary, use one or more inert compounds (please read the precautions on the back before filling this page). 1T 386073 8 8 8 8 ABCD Scope of patent application Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, adiponitrile, hexamethyleneimine, one or more inert compounds A and ammonia, the ammonia content of which is lower than that of the mixture used in stage (a), so that It accepts a second steaming hall to obtain a mixture of inert compounds A and ammonia as the top product and bottom product II. This distillation is performed at a bottom temperature of 100 to 250 ° C and a pressure of 2 to 15 bar. , With the proviso that the pressure systems of the first and second towers are coordinated with each other, so that in each case a top temperature greater than 20 ° C is obtained at a bottom temperature not exceeding 250 ° C, or at the top of the second tower Condensation is carried out at a lower temperature, and the overhead product consisting of pure or relatively highly concentrated ammonia is recycled to the first column, or after its pressure has been increased by a compressor, The top product of the second column is recycled as vapor to the first column or to its condenser, (c) so that it contains substantially 6-aminocapronitrile, hexamethylenediamine, adiponitrile, and hexamethylene. The bottom product II of methylimine and one or more inert compounds A, in The third column receives steaming cranes to obtain one or more inert compounds A as the top product and bottom product III. The distillation is performed at a bottom temperature of 50 to 250 ° C and a pressure of 0.05 to 2 bar. The condition is that one or more inert compounds A obtained as overhead products are fed to the second column, and if necessary, the distillation is performed in the presence of one or more compounds B, which are in distillation conditions The system is inert, sexual, and boils at 20 to 250 ° C at 0.3 bar. (D) Basically contains 6-aminocapronitrile, hexamethylenediamine, adiponitrile, and hexamethylene. Amine and if necessary, use one or more inert compounds (please read the precautions on the back before filling this page). 1T 386073 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 6. The scope of patent application is 1.87. The bottom product ΙΠ of product B is subjected to distillation in the fourth column to obtain the top product PK1, which is basically Contains hexamethyleneimine, one or more inert compounds B if needed and when needed, and a side stream product SA1 that basically contains hexamethylenediamine. The bottom temperature of this column is 50 to 250 ° C and the pressure is 0.05. Up to 1.5 bar, and the bottom product IV is obtained, and if necessary, the tower is equipped with a partition wall in the area between the feed and the side take-out point (Petlyuk tower), so that the obtained hexamethylenediamine It is essentially free of hexamethyleneimine and one or more inert compounds B and other low stagnants, so that the overhead product KP1 is fed to the third column, or only a part of the overhead product KP1 is fed to it if necessary The third column, with the remainder removed, and (e) the bottom product IV, which essentially contains 6-aminocapronitrile and adiponitrile and possibly high boilers, is accepted in the fifth column Distillation to obtain 6-aminocapronitrile with a purity of at least 95% as an overhead product, and substantially containing The side stream products of adiponitrile and bottom product V composed of high boiling materials and a small amount of adiponitrile, and if necessary, this column is equipped with a partition wall in the area between the feed and the side take-out point, So that the adiponitrile obtained contains a relatively small amount of high boilers, this distillation is carried out at a bottom temperature of 50 to 250 ° C. and at 10 to 300 mbar. 4. The method according to claim 1 or 3, wherein ethanol is used as the inert compound A. -5-This paper size applies Chinese National Standard (CNS) A4g (210X297mm) (Please read the precautions on the back before filling this page) Binding. Order i.v_ 386073 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 6. The scope of patent application is 1.87. The bottom product ΙΠ of product B is subjected to distillation in the fourth column to obtain the top product PK1, which is basically Contains hexamethyleneimine, one or more inert compounds B if needed and when needed, and a side stream product SA1 that basically contains hexamethylenediamine. The bottom temperature of this column is 50 to 250 ° C and the pressure is 0.05. Up to 1.5 bar, and the bottom product IV is obtained, and if necessary, the tower is equipped with a partition wall in the area between the feed and the side take-out point (Petlyuk tower), so that the obtained hexamethylenediamine It is essentially free of hexamethyleneimine and one or more inert compounds B and other low stagnants, so that the overhead product KP1 is fed to the third column, or only a part of the overhead product KP1 is fed to it if necessary The third column, with the remainder removed, and (e) the bottom product IV, which essentially contains 6-aminocapronitrile and adiponitrile and possibly high boilers, is accepted in the fifth column Distillation to obtain 6-aminocapronitrile with a purity of at least 95% as an overhead product, and substantially containing The side stream products of adiponitrile and bottom product V composed of high boiling materials and a small amount of adiponitrile, and if necessary, this column is equipped with a partition wall in the area between the feed and the side take-out point, So that the adiponitrile obtained contains a relatively small amount of high boilers, this distillation is carried out at a bottom temperature of 50 to 250 ° C. and at 10 to 300 mbar. 4. The method according to claim 1 or 3, wherein ethanol is used as the inert compound A. -5-This paper size applies Chinese National Standard (CNS) A4g (210X297mm) (Please read the precautions on the back before filling this page) Binding. Order i.v_ A8 B8 C8 386073 5. The method according to the patent claim, which uses hexamethyleneimine or hexamethylenediamine as component B. 6. According to the method of Patent Application No. 3, _China uses ethanol as the inert compound A. : 7. The method according to item 3 of the scope of patent application, wherein hexamethyleneimine or hexamethylenediamine is used as component B. (Please read the precautions on the reverse side before filling out this page) Packing _, π, J Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs-6-This paper size applies to China National Standard (CNS) A4 (210X297 mm) A8 B8 C8 386073 5. The method according to the patent claim, which uses hexamethyleneimine or hexamethylenediamine as component B. 6. According to the method of Patent Application No. 3, _China uses ethanol as the inert compound A. : 7. The method according to item 3 of the scope of patent application, wherein hexamethyleneimine or hexamethylenediamine is used as component B. (Please read the notes on the back before filling out this page) Packing _, π, J Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -6-This paper size applies to China National Standard (CNS) A4 (210X297 mm)