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CN-122010744-A - Method for preparing ethylenediamine from ethanolamine

CN122010744ACN 122010744 ACN122010744 ACN 122010744ACN-122010744-A

Abstract

The invention discloses a method for preparing ethylenediamine from ethanolamine, which comprises the steps of enabling ethanolamine to contact an Mn-Co-Cu@HoS-1 catalyst in the presence of hydrogen and an ammonia source to carry out amination reaction to generate ethylenediamine, wherein the main active components of the catalyst are manganese, the auxiliary agent is cobalt and copper, and the carrier is an all-silicon S-1 molecular sieve with a hollow structure, namely a HoS-1 molecular sieve. According to the invention, the Mn-Co-Cu@HoS-1 catalyst is adopted, so that the amination reaction can be efficiently carried out under milder conditions (140-160 ℃ and 1-5 MPa), and the safety risk and energy consumption of an industrial process are greatly reduced. Under the regulation and control of the catalyst, the reaction shows high selectivity, the ethylenediamine selectivity can reach 51.3 percent, the activity and the selectivity of the catalyst are still stable after the catalyst continuously runs for 80 hours, the catalyst shows excellent thermal stability and sintering resistance, the thermal stability is good, the cycle service life is long, and the catalyst has good industrial continuous production application potential.

Inventors

  • ZHU XUEDONG
  • Cheng Yaokun
  • CHEN HUILIN
  • WANG DAN
  • ZHANG RUI
  • ZHOU BIN
  • LI RUIJIANG
  • ZHANG QI
  • SHEN JIAN
  • LIU XIAOHUI

Assignees

  • 华东理工大学
  • 宁夏倬昱新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260123

Claims (8)

  1. 1. A method for preparing ethylenediamine from ethanolamine is characterized in that ethanolamine is contacted with a Mn-Co-Cu@HoS-1 catalyst in the presence of hydrogen and an ammonia source to carry out amination reaction to generate ethylenediamine, wherein the main active components of the catalyst are manganese, the auxiliary agent is cobalt and copper, and the carrier is an all-silicon S-1 molecular sieve with a hollow structure, namely a HoS-1 molecular sieve.
  2. 2. The method for preparing ethylenediamine from ethanolamine according to claim 1, wherein the Mn-Co-cu@hos-1 catalyst is obtained by loading manganese, cobalt and copper on a HoS-1 molecular sieve support by an isovolumetric impregnation method, followed by drying and calcination treatment.
  3. 3. The method for preparing ethylenediamine from ethanolamine according to claim 2, wherein the total loading of the metal in the catalyst is 15 to 30% of the mass of the catalyst, and the total loading of the metal is calculated as a single metal.
  4. 4. The method for preparing ethylenediamine from ethanolamine according to claim 2, wherein the total loading of the metal in the catalyst is 15 to 25% of the mass of the catalyst, and the total loading of the metal is calculated as a single metal.
  5. 5. The method for preparing ethylenediamine from ethanolamine according to claim 3 or 4, wherein in the Mn-Co-cu@hos-1 catalyst, the mass of manganese is 12 to 20% by weight of the catalyst, the mass of cobalt is 1 to 7% by weight of the catalyst, and the mass of copper is 2 to 5% by weight of the catalyst.
  6. 6. The method for producing ethylenediamine from ethanolamine according to claim 1, wherein the ammonia source is aqueous ammonia and the molar ratio of the ammonia source to ethanolamine is (1 to 10): 1.
  7. 7. The method for preparing ethylenediamine from ethanolamine according to claim 1, wherein the ammonia source is aqueous ammonia and the molar ratio of the ammonia source to ethanolamine is 5:1.
  8. 8. The process for preparing ethylenediamine from ethanolamine according to claim 1, wherein the reaction temperature is 140 to 160 ℃, the reaction pressure is 1 to 5MPa, and the volume space velocity of ethanolamine is 0.1 to 2h -1 .

Description

Method for preparing ethylenediamine from ethanolamine Technical Field The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing ethylenediamine from ethanolamine. Background Ethylenediamine (EDA) is an important organic chemical intermediate and has wide application in the production of pharmaceuticals, chelating agents, surfactants, pesticides, fabric softeners, and resin polymers. Global market analysis shows that the demand of ethylenediamine has a continuously growing trend and is one of petrochemical products worth developing greatly. Current commercial ethylenediamine synthesis processes mainly include the dichloroethane process and the ethanolamine (MEA) reductive amination process. The dichloroethane method is gradually eliminated because of serious equipment corrosion and environmental pollution problems caused by the use of halogen. The ethanolamine reductive amination method is widely focused on because of rich sources of raw materials and relatively green routes. However, the existing ethanolamine reductive amination method still faces a series of challenges that the reaction is usually carried out under high pressure conditions, the equipment requirement is high, the energy consumption is high, and the catalyst is mainly added with noble metals (such as Re) or transition metals, so that the cost is high, and the mass production and the application are not favored. Meanwhile, the catalyst has insufficient long-term operation stability, the activity and the selectivity are rapidly attenuated in the continuous operation process, the service life is short, and frequent regeneration or replacement is required. Therefore, the development of a catalyst with high stability, high ethylenediamine selectivity and proper cost under mild conditions has important significance for promoting the industrial application of the ethanolamine reductive amination process. Disclosure of Invention The invention aims at the defects in the prior art, and provides a method for preparing ethylenediamine from ethanolamine, wherein the method can achieve higher ethylenediamine selectivity under milder reaction conditions by adopting a Mn-Co-Cu@HoS-1 catalyst, and the catalyst has excellent thermal stability and sintering resistance. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: A method for preparing ethylenediamine from ethanolamine comprises the steps of enabling ethanolamine to be in contact with a Mn-Co-Cu@HoS-1 catalyst in the presence of hydrogen and an ammonia source to carry out amination reaction to generate ethylenediamine, wherein the main active components of the catalyst are manganese, the auxiliary agent is cobalt and copper, and the carrier of the catalyst is an all-silicon S-1 molecular sieve with a hollow structure, namely a HoS-1 molecular sieve. In the catalyst, metal is uniformly encapsulated in the all-silicon S-1 molecular sieve with a hollow structure, and the hollow shell structure can not only stabilize metal particles and inhibit sintering of the metal particles, but also promote rapid diffusion of ethanolamine molecules to metal centers, so that the selectivity of ethylenediamine is improved and the catalytic reaction activity is improved. The Mn-Co-Cu@HoS-1 catalyst is further prepared by loading manganese, cobalt and copper on a HoS-1 molecular sieve carrier by adopting an isovolumetric impregnation method, and then drying and calcining the catalyst. The invention further provides that the total loading of the metal in the catalyst is 15-30% of the mass of the catalyst, preferably 15-25%, and the total loading of the metal is calculated by metal simple substance. The invention further provides that in the Mn-Co-Cu@HoS-1 catalyst, the mass of manganese is 12-20% of the weight of the catalyst, the mass of cobalt is 1-7% of the weight of the catalyst, and the mass of copper is 2-5% of the weight of the catalyst. The invention further provides that the ammonia source is aqueous ammonia and the molar ratio of the ammonia source to the ethanolamine is (1-10): 1, preferably 5:1. The invention is further arranged that the reaction temperature is 140-160 ℃, the reaction pressure is 1-5 MPa, and the volume space velocity of the ethanolamine liquid is 0.1-2 h -1. Compared with the prior art, the invention has the following beneficial effects: According to the invention, the Mn-Co-Cu@HoS-1 catalyst is adopted, so that the amination reaction can be efficiently carried out under milder conditions (140-160 ℃ and 1-5 MPa hydrogen pressure), and the safety risk and energy consumption of an industrial process are greatly reduced. Under the regulation and control of the catalyst, the reaction shows high selectivity, the ethylenediamine selectivity can reach 51.3 percent, the activity and the selectivity of the catalyst are still stable after the catalyst continuously runs for 80 hours, the catalyst sh