WO2018121042A1 - 一种高品质精己二胺的生产方法 - Google Patents

一种高品质精己二胺的生产方法 Download PDF

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WO2018121042A1
WO2018121042A1 PCT/CN2017/108867 CN2017108867W WO2018121042A1 WO 2018121042 A1 WO2018121042 A1 WO 2018121042A1 CN 2017108867 W CN2017108867 W CN 2017108867W WO 2018121042 A1 WO2018121042 A1 WO 2018121042A1
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evaporator
temperature
sent
distillation
pressure
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PCT/CN2017/108867
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English (en)
French (fr)
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乔思怀
赵铎
陈聚良
高先明
王海营
王红专
郭卫东
欧玲
黄敏
白湘涛
刘水侠
赵时超
刘耀文
李振锋
霍美菊
刘永
张军伟
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河南神马尼龙化工有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification

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  • the invention belongs to the technical field of chemical industry, and particularly relates to a production method of high quality refined hexamethylene diamine.
  • Hexanediamine is an important raw material for chemical synthesis. It is mainly used in the production of nylon 66 and 610 resins. It can be used to make adhesives, additives for rubber products, stabilizers for textile and paper industry, bleaches, coatings, etc. Hexamethylenediamine can react with electrophilic compounds such as H+, alkyl halides, hydroxyl groups and other compounds to make various fiber fabrics and plastic products, and can also be used for synthesizing polyurethane foams and hexamethylene diisocyanate foams. , coatings and zeolites of the ZSN type.
  • Hexamethylenediamine can be produced by the hexanediol method and the caprolactam method.
  • the hexanediol method is obtained by hydrogenating caprolactone to 1,6-hexanediol, and then using a framework nickel catalyst for amination dehydration reaction.
  • the reaction is as follows:
  • the reaction temperature is 200 ° C
  • the pressure is 2.3 MPa
  • the yield is about 90%.
  • the caprolactam method is a gas phase reaction of caprolactam with ammonia in the presence of a phosphate (such as a phosphate of manganese, aluminum, calcium, barium or zinc) to form aminocapronitrile, the reaction temperature is about 350 ° C, and the yield is almost 100%.
  • a phosphate such as a phosphate of manganese, aluminum, calcium, barium or zinc
  • the resulting aminocapronitrile is further subjected to hydrogenation to form hexamethylenediamine, and the reaction is as follows:
  • the caprolactam method is generally used for processing small-scale production equipment such as caprolactam.
  • Hexamethylenediamine can also be produced by the adiponitrile method, and almost all methods for large-scale production of hexamethylenediamine are started by the adiponitrile method.
  • the preparation of hexamethylenediamine from adiponitrile is usually carried out by catalytic hydrogenation. It is industrially divided into high pressure method and low pressure method. The reaction is as follows:
  • the high pressure method uses a cobalt-copper catalyst, the reaction temperature is 100-135 ° C, the pressure is 60-65 MPa; the high-pressure method can also adopt an iron catalyst, the reaction temperature is 100-180 ° C, the pressure is 30-35 MPa, and the high-pressure reaction is carried out in the reactor.
  • the solvent may be liquid ammonia, and sometimes an aromatic hydrocarbon such as toluene may be added, and the selectivity of hexamethylene diamine is about 90% to 95%.
  • the low pressure method uses a nickel-based catalyst, and the reaction is carried out in an ethanol solution.
  • the reaction temperature is about 70 to 100 ° C
  • the pressure is about 1.8 to 2.7 MPa
  • the selectivity of hexamethylene diamine is up to 99%.
  • the purity of the raw material of adiponitrile is very high, and the semi-finished hexamethylene diamine formed by the reaction is subjected to azeotropic distillation with water, and then, after several times of vacuum distillation, high-quality hexamethylenediamine can be obtained.
  • the adiponitrile is made up of nickel, cobalt and the like as a catalyst, sodium hydroxide as a cocatalyst, and ethanol as a solvent for hydrogenation.
  • the hexamethylene diamine can be continuously reacted under a certain temperature and pressure, but in the production process of the diamine, Some side reactions occur, and the main by-products are azepane, aminocapronitrile, 1,2-diaminocyclohexane, N-ethylhexamethylenediamine, aminomethylcyclopentane, and the like.
  • azacycloheptane, 1,2-diaminocyclohexane and N-ethylhexamethylenediamine are all difficult to separate from hexamethylenediamine, and there are excess ethanol, sodium hydroxide and nickel-based catalyst in the mixture.
  • the composition, the presence of the above substances will affect the quality of the final product high-quality refined hexamethylene diamine and downstream users, such as color, purity and other indicators.
  • a method for producing high quality refined hexamethylene diamine comprising the following steps:
  • the adiponitrile, ethanol and sodium hydroxide are uniformly mixed according to a mass ratio of 50 to 90:40 to 80:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is at 70 to 100 ° C and a pressure of 1.8 to 2.7 MPa. Hydrogenation under conditions to obtain semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation;
  • the bottom liquid of the second evaporator is separated by centrifugation to obtain a clear liquid and a turbid liquid, and the clear liquid is sent to a sixth evaporator for distillation, and the turbid liquid is sent to a seventh evaporator for distillation; the second evaporator is subjected to distillation.
  • the product is sent to a third evaporator for distillation;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, and the overhead of the seventh evaporator is recovered and sent to the first evaporator;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator to facilitate the feeding of the overhead of the fourth evaporator to the third evaporator. in;
  • the bottom liquid of the fifth evaporator is sent to the sixth evaporator, and the top return port of the fifth evaporator is connected to the fourth evaporator, so that the top portion of the fifth evaporator is returned to the fourth evaporator.
  • the other part of the fifth evaporator is sent from the product outlet to the hexamethylene diamine tank, which is a high quality hexamethylene diamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 0.5 to 5 wt%;
  • the pressure in the first distiller is 40 to 130 mmHg, the temperature at the top of the vessel is 10 to 80 ° C, and the temperature at the bottom of the vessel is 90 to 160 ° C;
  • the pressure is 40-130mmHg, the top temperature is 90-150°C, the bottom temperature is 90-150°C, the third evaporator pressure is 5-60mmHg, and the top temperature is 60 ⁇ 130°C, the bottom temperature is 80 ⁇ 150°C;
  • the fourth evaporator pressure is 5 ⁇ 60mmHg, the top temperature is 60 ⁇ 130°C, the bottom temperature is 100 ⁇ 170°C;
  • the fifth evaporator pressure is 5 ⁇ 60mmHg, the top temperature is 60-130 ° C, the bottom temperature is 100-170 ° C;
  • the sixth evaporator pressure is 5-60 mmHg, the top temperature is 60-130 ° C, the bottom temperature is 100-170
  • the hydrogenation reaction is carried out by placing the reaction mixture in a three-phase boiling reactor and introducing hydrogen into the reaction, and the reaction liquid of the three-phase boiling reactor separates ethanol and sodium hydroxide to obtain a semi-finished product. amine.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the above-mentioned internal pressure of the evaporator refers to an absolute pressure
  • the nickel-based catalyst is a commercially available product.
  • the invention comprises the preparation of semi-finished hexamethylenediamine and the purification of high-quality hexamethylenediamine.
  • the organic solvent ethanol is used as a diluent, which is beneficial to recovery and reuse, and uses a nickel-based catalyst as a help.
  • the catalyst ensures the conversion rate of hexamethylenediamine; in order to ensure the purification purity of high-quality hexamethylenediamine, vacuum distillation technology is adopted, and according to the boiling point of impurities in the semi-finished hexamethylene diamine, the dehydration and removal are light under vacuum conditions.
  • Figure 1 is a flow chart showing the production process of the present invention.
  • a method for producing high quality refined hexamethylene diamine comprises the following steps:
  • the adiponitrile, ethanol, and sodium hydroxide are uniformly mixed at a mass ratio of 50:40:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is placed in a three-phase boiling reactor, and hydrogen gas is introduced thereto.
  • the reaction is carried out under the condition of °C and pressure of 1.8 MPa.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the reaction liquid of the three-phase boiling reactor separates the ethanol and sodium hydroxide. , obtaining a semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation, and the top outlet of the first evaporator communicates with the waste water pit, containing azacycloheptane
  • the production wastewater is discharged into the waste water pit from the top of the first evaporator;
  • the bottom liquid of the second evaporator is a mixture containing a high boiler and sodium hydroxide, and the bottom liquid of the second evaporator is centrifuged to obtain a clear liquid and a liquid liquid, and the clear liquid is sent to a sixth evaporator for distillation.
  • the turbid liquid is sent to the seventh evaporator for distillation; the overhead of the second evaporator is sent to the third evaporator for distillation;
  • the bottom liquid of the third evaporator and the overhead of the sixth evaporator are both sent to the fourth evaporator for distillation, and the top return port of the third evaporator is connected to the transfer tank, and is distilled through the third evaporator.
  • Distilled low-boiling substances such as diaminocyclohexane and aminomethylaminocyclopentane are discharged into a transfer tank;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, the overhead of the seventh evaporator is recovered and sent to the first evaporator, and the bottom liquid of the seventh evaporator is intermittently discharged into the relay. tank;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator; the bottom liquid of the fifth evaporator is sent to the sixth evaporator, The top outlet of the fifth evaporator is connected to the fourth evaporator, and the overhead of the fifth evaporator is sent to the semi-diamine tank to obtain high-quality hexamethylenediamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 0.5 wt%;
  • the pressure in the first distiller is 40 mmHg, the temperature at the top of the vessel is 10 ° C, the temperature at the bottom of the vessel is 90 ° C;
  • the pressure in the second evaporator is 40 mmHg, and the temperature at the top of the vessel 90 ° C, the bottom temperature is 90 ° C;
  • the third evaporator pressure is 5 mmHg, the top temperature is 60 ° C, the bottom temperature is 80 ° C;
  • the fourth evaporator pressure is 5 mmHg, the top temperature is 60 ° C, the bottom
  • the temperature is 100 ° C;
  • the pressure in the fifth evaporator is 5 mmHg, the temperature in the top is 60 ° C, the temperature in the bottom is 100 ° C;
  • the pressure in the sixth evaporator is 5 mmHg, the temperature in the top is 60 ° C, and the temperature in the bottom is 100
  • a method for producing high quality refined hexamethylene diamine comprising the following steps:
  • the adiponitrile, ethanol, and sodium hydroxide are uniformly mixed at a mass ratio of 60:50:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is placed in a three-phase boiling reactor, and hydrogen gas is introduced thereto.
  • the reaction is carried out under the condition of °C and a pressure of 2.0 MPa.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the reaction liquid of the three-phase boiling reactor separates the ethanol and sodium hydroxide. , obtaining a semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation, and the top outlet of the first evaporator communicates with the waste water pit, containing azacycloheptane
  • the production wastewater is discharged into the waste water pit from the top of the first evaporator;
  • the bottom liquid of the second evaporator is a mixture containing a high boiler and sodium hydroxide, and the bottom liquid of the second evaporator is centrifuged to obtain a clear liquid and a liquid liquid, and the clear liquid is sent to a sixth evaporator for distillation.
  • the turbid liquid is sent to the seventh evaporator for distillation; the overhead of the second evaporator is sent to the third evaporator for distillation;
  • the bottom liquid of the third evaporator and the overhead of the sixth evaporator are both sent to the fourth evaporator for distillation, and the third evaporator
  • the top reflux port is connected to the transfer tank, and is distilled through the third evaporator, and the low-boiling substances such as diaminocyclohexane and aminomethylaminocyclopentane are discharged into the transfer tank;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, the overhead of the seventh evaporator is recovered and sent to the first evaporator, and the bottom liquid of the seventh evaporator is intermittently discharged into the relay. tank;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator; the bottom liquid of the fifth evaporator is sent to the sixth evaporator, The top outlet of the fifth evaporator is connected to the fourth evaporator, and the overhead of the fifth evaporator is sent to the semi-diamine tank to obtain high-quality hexamethylenediamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 1.0 wt%;
  • the pressure in the first distiller is 60 mmHg, the temperature at the top of the vessel is 30 ° C, the temperature at the bottom of the vessel is 110 ° C;
  • the pressure in the second evaporator is 60 mmHg, the temperature at the top of the vessel It is 110 ° C, the bottom temperature is 110 ° C;
  • the third evaporator pressure is 15 mmHg, the top temperature is 80 ° C, the bottom temperature is 120 ° C;
  • the fourth evaporator pressure is 15 mmHg, the top temperature is 80 ° C, the bottom
  • the temperature is 120 ° C;
  • the pressure in the fifth evaporator is 15 mmHg, the temperature in the top is 80 ° C, the temperature in the bottom is 120 ° C;
  • the pressure in the sixth evaporator is 15 mmHg, the temperature in the top is 80 ° C, and the temperature in the bottom is
  • a method for producing high quality refined hexamethylene diamine comprising the following steps:
  • the adiponitrile, ethanol, and sodium hydroxide are uniformly mixed at a mass ratio of 70:60:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is placed in a three-phase boiling reactor, and hydrogen gas is introduced thereto.
  • the reaction is carried out under the condition of ° C and a pressure of 2.2 MPa.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the reaction liquid of the three-phase boiling reactor separates the ethanol and sodium hydroxide. , obtaining a semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation, and the top outlet of the first evaporator communicates with the waste water pit, containing azacycloheptane
  • the production wastewater is discharged into the waste water pit from the top of the first evaporator;
  • the bottom liquid of the second evaporator is a mixture containing a high boiler and sodium hydroxide, and the bottom liquid of the second evaporator is centrifuged to obtain a clear liquid and a liquid liquid, and the clear liquid is sent to a sixth evaporator for distillation.
  • the turbid liquid is sent to the seventh evaporator for distillation; the overhead of the second evaporator is sent to the third evaporator for distillation;
  • the bottom liquid of the third evaporator and the overhead of the sixth evaporator are both sent to the fourth evaporator for distillation, and the top return port of the third evaporator is connected to the transfer tank, and is distilled through the third evaporator.
  • Distilled low-boiling substances such as diaminocyclohexane and aminomethylaminocyclopentane are discharged into a transfer tank;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, and the overhead of the seventh evaporator is recovered and sent to the first
  • the bottom liquid of the evaporator and the seventh evaporator is intermittently discharged into the transfer tank;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator; the bottom liquid of the fifth evaporator is sent to the sixth evaporator, The top outlet of the fifth evaporator is connected to the fourth evaporator, and the overhead of the fifth evaporator is sent to the semi-diamine tank to obtain high-quality hexamethylenediamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 2.0 wt%;
  • the pressure in the first distiller is 80 mmHg, the temperature at the top of the vessel is 50 ° C, the temperature at the bottom of the vessel is 130 ° C;
  • the pressure in the second evaporator is 80 mmHg, the temperature at the top of the vessel 130 ° C, the bottom temperature is 130 ° C;
  • the third evaporator pressure is 30 mmHg, the top temperature is 100 ° C, the bottom temperature is 140 ° C;
  • the fourth evaporator pressure is 30 mmHg, the top temperature is 100 ° C, the bottom
  • the temperature is 140 ° C;
  • the pressure in the fifth evaporator is 30 mmHg, the temperature in the top is 100 ° C, the temperature in the bottom is 140 ° C;
  • the pressure in the sixth evaporator is 30 mmHg, the temperature in the top is 100 ° C, and the temperature in the bottom is 140 °
  • a method for producing high quality refined hexamethylene diamine comprising the following steps:
  • the adiponitrile, ethanol and sodium hydroxide are uniformly mixed at a mass ratio of 80:70:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is placed in a three-phase boiling reactor, and hydrogen gas is introduced at 100.
  • the reaction is carried out under the condition of °C and pressure of 2.5 MPa.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the reaction liquid of the three-phase boiling reactor separates the ethanol and sodium hydroxide. , obtaining a semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation, and the top outlet of the first evaporator communicates with the waste water pit, containing azacycloheptane
  • the production wastewater is discharged into the waste water pit from the top of the first evaporator;
  • the bottom liquid of the second evaporator is a mixture containing a high boiler and sodium hydroxide, and the bottom liquid of the second evaporator is centrifuged to obtain a clear liquid and a liquid liquid, and the clear liquid is sent to a sixth evaporator for distillation.
  • the turbid liquid is sent to the seventh evaporator for distillation; the overhead of the second evaporator is sent to the third evaporator for distillation;
  • the bottom liquid of the third evaporator and the overhead of the sixth evaporator are both sent to the fourth evaporator for distillation, and the top return port of the third evaporator is connected to the transfer tank, and is distilled through the third evaporator.
  • Distilled low-boiling substances such as diaminocyclohexane and aminomethylaminocyclopentane are discharged into a transfer tank;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, the overhead of the seventh evaporator is recovered and sent to the first evaporator, and the bottom liquid of the seventh evaporator is intermittently discharged into the relay. tank;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator; the bottom liquid of the fifth evaporator is sent to the sixth evaporator, The top of the evaporator of the five evaporator is connected to the fourth evaporator, the fifth steaming
  • the top product of the hair dryer is sent to the hexamethylene diamine tank to obtain high quality hexamethylene diamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 3.0 wt%;
  • the pressure in the first distiller is 100 mmHg, the temperature at the top of the vessel is 70 ° C, the temperature at the bottom of the vessel is 150 ° C;
  • the pressure in the second evaporator is 100 mmHg, the temperature at the top of the vessel 150 ° C, the bottom temperature is 150 ° C;
  • the third evaporator pressure is 50 mmHg, the top temperature is 120 ° C, the bottom temperature is 150 ° C;
  • the fourth evaporator pressure is 50 mmHg, the top temperature is 120 ° C, the bottom
  • the temperature is 160 ° C;
  • the pressure in the fifth evaporator is 50 mmHg, the temperature in the top is 120 ° C, the temperature in the bottom is 160 ° C;
  • the pressure in the sixth evaporator is 50 mmHg, the temperature in the top is 120 ° C, and the temperature in the bottom is 160
  • a method for producing high quality refined hexamethylene diamine comprising the following steps:
  • the adiponitrile, ethanol and sodium hydroxide are uniformly mixed at a mass ratio of 90:80:1, and then a nickel-based catalyst is added to obtain a reaction mixture, and the reaction mixture is placed in a three-phase boiling reactor, and hydrogen gas is introduced at 100
  • the reaction is carried out under the condition of °C and pressure of 2.7 MPa.
  • the gas from the gas phase outlet of the three-phase boiling reactor is washed with water and then re-introduced into the three-phase boiling reactor.
  • the reaction liquid of the three-phase boiling reactor separates the ethanol and sodium hydroxide. , obtaining a semi-finished hexamethylenediamine;
  • the semi-finished hexamethylene diamine is sent to the first evaporator for distillation, and the bottom liquid of the first evaporator is sent to the second evaporator for distillation, and the top outlet of the first evaporator communicates with the waste water pit, containing azacycloheptane
  • the production wastewater is discharged into the waste water pit from the top of the first evaporator;
  • the bottom liquid of the second evaporator is a mixture containing a high boiler and sodium hydroxide, and the bottom liquid of the second evaporator is centrifuged to obtain a clear liquid and a liquid liquid, and the clear liquid is sent to a sixth evaporator for distillation.
  • the turbid liquid is sent to the seventh evaporator for distillation; the overhead of the second evaporator is sent to the third evaporator for distillation;
  • the bottom liquid of the third evaporator and the overhead of the sixth evaporator are both sent to the fourth evaporator for distillation, and the top return port of the third evaporator is connected to the transfer tank, and is distilled through the third evaporator.
  • Distilled low-boiling substances such as diaminocyclohexane and aminomethylaminocyclopentane are discharged into a transfer tank;
  • the bottom liquid of the sixth evaporator is sent to the seventh evaporator for distillation, the overhead of the seventh evaporator is recovered and sent to the first evaporator, and the bottom liquid of the seventh evaporator is intermittently discharged into the relay. tank;
  • the bottom liquid of the fourth evaporator is sent to the fifth evaporator for distillation, and the top return port of the fourth evaporator is connected to the third evaporator; the bottom liquid of the fifth evaporator is sent to the sixth evaporator, The top outlet of the fifth evaporator is connected to the fourth evaporator, and the overhead of the fifth evaporator is sent to the semi-diamine tank to obtain high-quality hexamethylenediamine;
  • the mass percentage of the nickel-based catalyst in the reaction mixture is 5.0 wt%;
  • the pressure in the first distiller is 130 mmHg, the temperature at the top of the vessel is 80 ° C, the temperature at the bottom of the vessel is 160 ° C;
  • the pressure in the second evaporator is 130 mmHg, and the temperature at the top of the vessel
  • the bottom temperature is 150 ° C
  • the third evaporator pressure is 60 mmHg, the top temperature is 130 ° C, the bottom temperature is 150 ° C
  • the fourth evaporator pressure is 60 mmHg, the top temperature is 130 ° C, the bottom temperature 170 ° C
  • the fifth evaporator internal pressure is 60 mmHg, the top temperature is 130 ° C, the bottom temperature is 170 ° C
  • the sixth evaporator internal pressure is 60 mmHg, the top temperature is 130 ° C, the bottom temperature is 170 ° C
  • the seventh evaporation was 60 mmHg, the
  • the product quality indicators of the high quality refined hexamethylene diamine obtained by using Examples 1 to 5 are as follows:
  • the polarographic value is ⁇ 100 mmol IB/T-HMD, the total volatile base is ⁇ 4 mL/100 g, and the purity is ⁇ 99.9% (mass percentage).

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Abstract

本发明公开了一种高品质精己二胺的生产方法，包括半成品己二胺的制备和高品质精己二胺的提纯，具体是将己二腈、乙醇、氢氧化钠按一定质量比混合均匀，再加入镍基催化剂，进行加氢反应，得到半成品己二胺；然后将半成品己二胺进行多次蒸馏提纯，即得高品质精己二胺。本发明采用乙醇作稀释剂，有利于回收、再利用，采用镍基催化剂作助催化剂，保证了己二胺的转化率；采用真空精馏技术，根据半成品己二胺中杂质的沸点不同，在真空条件下经过脱水、脱除轻组分、脱除重组分，最后得到纯度≥99.9％(质量百分比)、极谱值≤100mmolIB/T-HMD、总挥发碱≤4mL/100g的高品质精己二胺产品。

Description

一种高品质精己二胺的生产方法 技术领域
本发明属于化工技术领域，具体涉及一种高品质精己二胺的生产方法。
背景技术
己二胺是化工合成的重要原料，主要用于生产尼龙66和610树脂，可用于制作粘合剂、橡胶制品的添加剂，纺织和造纸工业的稳定剂、漂白剂、涂料等。己二胺能与亲电性化合物如H+、卤代烷、羟基等化合物发生反应，以制成各种纤维织物和塑料制品，还可用于合成聚亚胺羧酸酯泡沫塑料和亚已基二异氰酸酯泡沫、涂料及ZSN类型沸石。
己二胺可以采用己二醇法和己内酰胺法生产，己二醇法是由己内酯加氢合成1，6-己二醇，再采用骨架镍催化剂进行氨化脱水反应制得，反应如下：
HOCH2(CH2)4CH2OH+2NH3─→H2N(CH2)6NH2+2H2O；
为了防止己二胺脱氢，反应时需加入少量氢，反应温度200℃，压力2.3MPa，收率约90％。
己内酰胺法是由己内酰胺与氨在磷酸盐(如锰、铝、钙、钡或锌的磷酸盐)催化剂存在下，进行气相反应生成氨基己腈，反应温度约350℃，收率几乎达100％，生成的氨基己腈再进行加氢反应生成己二胺，反应如下：
H2N(CH2)5CN+2H2─→H2N(CH2)6NH2；
己内酰胺法一般用于处理己内酰胺等外品的小型生产装置上。
己二胺还可以己二腈法生产，几乎所有大规模生产己二胺的方法都是由己二腈法出发的。己二腈制备己二胺通常采用催化加氢的方法，工业上分为高压法和低压法两种，反应如下：
NC(CH2)4CN+4H2─→H2N(CH2)6NH2。
其中，高压法采用钴－铜催化剂，反应温度100～135℃，压力60～65MPa；高压法也可采用铁催化剂，反应温度100～180℃，压力30～35MPa，高压法反应在反应器中进行，溶剂可采用液氨，有时还加入芳烃(如甲苯)，己二胺的选择性约90％～95％。低压法采用镍基催化剂，反应在乙醇溶液中进行，反应温度约70～100℃，压力约1.8～2.7MPa，己二胺的选择性可达99％；低压法制备过程中为了防止催化剂中毒，对己二腈原料的纯度要求很高，反应生成的半成品己二胺与水进行恒沸精馏，然后经数次负压蒸馏，便可获得高品质精己二胺。
己二腈以镍、钴等为催化剂，氢氧化钠为助催化剂，乙醇为溶剂进行加氢，在一定温度和压力下可以连续反应生产己二胺，但在已二胺的生产过程中，还发生一些副反应，主要副产物有氮杂环庚烷、氨基己腈、1，2-二氨基环己烷、N-乙基己二胺、氨基甲基环戊烷等。其中氮杂环庚烷、1，2-二氨基环己烷、N-乙基己二胺等均与己二胺较难分离，混合物中还有过剩的乙醇、氢氧化钠和镍基催化剂等组分，上述物质的存在将会影响最终产品高品质精己二胺及下游用户的产品质量，如色度、纯度等指标。
故如何选择具体的工艺流程和设备，来改善工艺生产过程，优化工艺生产条件，最大限度降低生产成本，生产出高品质精己二胺的技术非常关键。
发明内容
为了生产高品质的精己二胺，本发明的目的在于提供了一种高品质精己二胺的生产方法。
为了实现上述目的，本发明采用的技术方案为：
一种高品质精己二胺的生产方法，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比50～90：40～80：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物于70～100℃、压力1.8～2.7MPa的条件下加氢反应，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏；
第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器，便于第四蒸发器的器顶馏出物送入第三蒸发器中；
将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，便于第五蒸发器的器顶馏出物部分回流至第四蒸发器中，以维系体系内的压力，第五蒸发器的另一部分器顶馏出物从产品出口送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为0.5～5wt％；第一蒸馏器内压力为40～130mmHg，器顶温度为10～80℃，器底温度90～160℃；第二蒸发器内压力为40～130mmHg，器顶温度为90～150℃，器底温度90～150℃；第三蒸发器内压力为5～60mmHg，器顶温度为 60～130℃，器底温度80～150℃；第四蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第五蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第六蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第七蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃。
优选地，所述加氢反应是将反应混合物置于三相沸腾反应器内，并通入氢气进行反应，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺。
优选地，所述三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器。
上述蒸发器内压力均指的是绝对压力，所述镍基催化剂采用普通市售产品。
本发明包括半成品己二胺的制备和高品质精己二胺的提纯，为了保证半成品己二胺的制备效率，采用有机溶剂乙醇作稀释剂，有利于回收、再利用，采用镍基催化剂作助催化剂，保证了己二胺的转化率；为了保证高品质精己二胺的提纯纯度，采用真空精馏技术，根据半成品己二胺中杂质的沸点不同，在真空条件下经过脱水、脱除轻组分、脱除重组分，最后得到纯度≥99.9％(质量百分比)、极谱值≤100mmolIB/T-HMD、总挥发碱≤4mL/100g的高品质精己二胺产品。
附图说明
图1是本发明的生产工艺流程图。
具体实施方式
为了使本发明的技术目的、技术方案和有益效果更加清楚，下面结合具体实施例对本发明的技术方案作出进一步的说明。
实施例1
一种高品质精己二胺的生产方法，如图1所示，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比50：40：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物置于三相沸腾反应器内，并通入氢气，于70℃、压力1.8MPa的条件下进行反应，三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏，第一蒸发器的器顶回流口连通废水坑，含有氮杂环庚烷的生产废水从第一蒸发器的器顶排入废水坑；
第二蒸发器的器底液是含有高沸物和氢氧化钠混渣，第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏，第三蒸发器的器顶回流口连通中转罐，经第三蒸发器蒸馏，馏出的二氨基环己烷、氨基甲氨基环戊烷等低沸物排入中转罐；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器，第七蒸发器的器底液间歇排入中转罐；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为0.5wt％；第一蒸馏器内压力为40mmHg，器顶温度为10℃，器底温度90℃；第二蒸发器内压力为40mmHg，器顶温度为90℃，器底温度90℃；第三蒸发器内压力为5mmHg，器顶温度为60℃，器底温度80℃；第四蒸发器内压力为5mmHg，器顶温度为60℃，器底温度100℃；第五蒸发器内压力为5mmHg，器顶温度为60℃，器底温度100℃；第六蒸发器内压力为5mmHg，器顶温度为60℃，器底温度100℃；第七蒸发器内压力为5mmHg，器顶温度为60℃，器底温度100℃。
实施例2
一种高品质精己二胺的生产方法，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比60：50：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物置于三相沸腾反应器内，并通入氢气，于80℃、压力2.0MPa的条件下进行反应，三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏，第一蒸发器的器顶回流口连通废水坑，含有氮杂环庚烷的生产废水从第一蒸发器的器顶排入废水坑；
第二蒸发器的器底液是含有高沸物和氢氧化钠混渣，第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏，第三蒸发器的 器顶回流口连通中转罐，经第三蒸发器蒸馏，馏出的二氨基环己烷、氨基甲氨基环戊烷等低沸物排入中转罐；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器，第七蒸发器的器底液间歇排入中转罐；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为1.0wt％；第一蒸馏器内压力为60mmHg，器顶温度为30℃，器底温度110℃；第二蒸发器内压力为60mmHg，器顶温度为110℃，器底温度110℃；第三蒸发器内压力为15mmHg，器顶温度为80℃，器底温度120℃；第四蒸发器内压力为15mmHg，器顶温度为80℃，器底温度120℃；第五蒸发器内压力为15mmHg，器顶温度为80℃，器底温度120℃；第六蒸发器内压力为15mmHg，器顶温度为80℃，器底温度120℃；第七蒸发器内压力为15mmHg，器顶温度为80℃，器底温度120℃。
实施例3
一种高品质精己二胺的生产方法，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比70：60：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物置于三相沸腾反应器内，并通入氢气，于90℃、压力2.2MPa的条件下进行反应，三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏，第一蒸发器的器顶回流口连通废水坑，含有氮杂环庚烷的生产废水从第一蒸发器的器顶排入废水坑；
第二蒸发器的器底液是含有高沸物和氢氧化钠混渣，第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏，第三蒸发器的器顶回流口连通中转罐，经第三蒸发器蒸馏，馏出的二氨基环己烷、氨基甲氨基环戊烷等低沸物排入中转罐；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一 蒸发器，第七蒸发器的器底液间歇排入中转罐；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为2.0wt％；第一蒸馏器内压力为80mmHg，器顶温度为50℃，器底温度130℃；第二蒸发器内压力为80mmHg，器顶温度为130℃，器底温度130℃；第三蒸发器内压力为30mmHg，器顶温度为100℃，器底温度140℃；第四蒸发器内压力为30mmHg，器顶温度为100℃，器底温度140℃；第五蒸发器内压力为30mmHg，器顶温度为100℃，器底温度140℃；第六蒸发器内压力为30mmHg，器顶温度为100℃，器底温度140℃；第七蒸发器内压力为30mmHg，器顶温度为100℃，器底温度140℃。
实施例4
一种高品质精己二胺的生产方法，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比80：70：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物置于三相沸腾反应器内，并通入氢气，于100℃、压力2.5MPa的条件下进行反应，三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏，第一蒸发器的器顶回流口连通废水坑，含有氮杂环庚烷的生产废水从第一蒸发器的器顶排入废水坑；
第二蒸发器的器底液是含有高沸物和氢氧化钠混渣，第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏，第三蒸发器的器顶回流口连通中转罐，经第三蒸发器蒸馏，馏出的二氨基环己烷、氨基甲氨基环戊烷等低沸物排入中转罐；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器，第七蒸发器的器底液间歇排入中转罐；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸 发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为3.0wt％；第一蒸馏器内压力为100mmHg，器顶温度为70℃，器底温度150℃；第二蒸发器内压力为100mmHg，器顶温度为150℃，器底温度150℃；第三蒸发器内压力为50mmHg，器顶温度为120℃，器底温度150℃；第四蒸发器内压力为50mmHg，器顶温度为120℃，器底温度160℃；第五蒸发器内压力为50mmHg，器顶温度为120℃，器底温度160℃；第六蒸发器内压力为50mmHg，器顶温度为120℃，器底温度160℃；第七蒸发器内压力为50mmHg，器顶温度为120℃，器底温度160℃。
实施例5
一种高品质精己二胺的生产方法，包括以下步骤：
将己二腈、乙醇、氢氧化钠按照质量比90：80：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物置于三相沸腾反应器内，并通入氢气，于100℃、压力2.7MPa的条件下进行反应，三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺；
将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏，第一蒸发器的器顶回流口连通废水坑，含有氮杂环庚烷的生产废水从第一蒸发器的器顶排入废水坑；
第二蒸发器的器底液是含有高沸物和氢氧化钠混渣，第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏，第三蒸发器的器顶回流口连通中转罐，经第三蒸发器蒸馏，馏出的二氨基环己烷、氨基甲氨基环戊烷等低沸物排入中转罐；
将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器，第七蒸发器的器底液间歇排入中转罐；
将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
其中，反应混合物中镍基催化剂的质量百分比为5.0wt％；第一蒸馏器内压力为130mmHg，器顶温度为80℃，器底温度160℃；第二蒸发器内压力为130mmHg，器顶温度为 150℃，器底温度150℃；第三蒸发器内压力为60mmHg，器顶温度为130℃，器底温度150℃；第四蒸发器内压力为60mmHg，器顶温度为130℃，器底温度170℃；第五蒸发器内压力为60mmHg，器顶温度为130℃，器底温度170℃；第六蒸发器内压力为60mmHg，器顶温度为130℃，器底温度170℃；第七蒸发器内压力为60mmHg，器顶温度为130℃，器底温度170℃。
采用实施例1～5得到的高品质精己二胺的产品质量指标如下：
极谱值≤100mmolIB/T-HMD、总挥发碱≤4mL/100g、纯度≥99.9％(质量百分比)。

Claims (3)

  1. 一种高品质精己二胺的生产方法，其特征在于，包括以下步骤：
    将己二腈、乙醇、氢氧化钠按照质量比50～90：40～80：1混合均匀，再加入镍基催化剂，得到反应混合物，将反应混合物于70～100℃、压力1.8～2.7MPa的条件下加氢反应，得到半成品己二胺；
    将半成品己二胺送入第一蒸发器中蒸馏，第一蒸发器的器底液送入第二蒸发器中蒸馏；
    第二蒸发器的器底液经离心分离，得到清液和浊液，将清液送入第六蒸发器中蒸馏，浊液送入第七蒸发器中蒸馏；第二蒸发器的器顶馏出物送入第三蒸发器中蒸馏；
    将第三蒸发器的器底液及第六蒸发器的器顶馏出物均送入第四蒸发器中蒸馏；
    将第六蒸发器的器底液送入第七蒸发器中蒸馏，将第七蒸发器的器顶馏出物回收并送入第一蒸发器；
    将第四蒸发器的器底液送入第五蒸发器中蒸馏，第四蒸发器的器顶回流口连通第三蒸发器；
    将第五蒸发器的器底液送入第六蒸发器，第五蒸发器的器顶回流口连通第四蒸发器，第五蒸发器的器顶馏出物送入精己二胺罐，即得高品质精己二胺；
    其中，反应混合物中镍基催化剂的质量百分比为0.5～5wt％；第一蒸馏器内压力为40～130mmHg，器顶温度为10～80℃，器底温度90～160℃；第二蒸发器内压力为40～130mmHg，器顶温度为90～150℃，器底温度90～150℃；第三蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度80～150℃；第四蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第五蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第六蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃；第七蒸发器内压力为5～60mmHg，器顶温度为60～130℃，器底温度100～170℃。
  2. 根据权利要求1所述的高品质精己二胺的生产方法，其特征在于：所述加氢反应是将反应混合物置于三相沸腾反应器内，并通入氢气进行反应，三相沸腾反应器的反应生成液分离出乙醇、氢氧化钠后，得到半成品己二胺。
  3. 根据权利要求2所述的高品质精己二胺的生产方法，其特征在于：所述三相沸腾反应器气相出口出来的气体经水洗后重新通入三相沸腾反应器。
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