Method for producing ethylenediamine

Abstract

The invention relates to a method for producing ethylenediamine, which comprises the following steps: preheating ethylene glycol and liquid ammonia, mixing with diluent gas, continuously passing through a catalyst bed layer, and reacting under the reaction conditions that the reaction temperature is 250-380 DEG C, the feed weight space velocity is 0.3-20 h <-1 > and the reaction pressure is 2.0-10.0 MPa to generate ethylenediamine. MCM-22, MCM-41, a ZSM-5 molecular sieve and an MCM-49 molecular sieve are subjected to metal oxide modified water vapor treatment to prepare the solid acid catalyst. The ethylene amine selectivity can reach 99%, and the catalyst stability is good. The catalyst is free of equipment corrosion in the production process, is an environment-friendly catalyst, and has a good industrial application prospect.

Description

Technical Field

[0001] This invention relates to the field of catalysis, and more specifically, to a method for producing ethyleneamine. Background Technology

[0002] Ethyleneamine is a general term for ethylenediamine products, including ethylenediamine (DEA), triethylenediamine (TEDA), and piperazine (PIP). These products, as important chemical raw materials, have wide applications in petroleum, textiles, pesticides, papermaking, pharmaceuticals, chemical fibers, and metallurgy. With the increasing demand for ethylenediamine products year by year, coupled with limited domestic production capacity, it has become one of the fine petrochemical intermediates urgently needing development in my country. Ethyleneamine belongs to the organic base class and has good solubility, being miscible with water or ethanol. Simultaneously, as an important fine chemical intermediate, ethylenediamine has wide applications in pesticides, pharmaceuticals, surfactants, low molecular weight polyamide resins, papermaking wet strength agents, and lubricant additives. Ethylenediamine is a good base and reducing agent. As an important chemical raw material and fine chemical intermediate, it can be used as a gasoline additive, emulsifier, epoxy resin curing agent, pharmaceutical, pesticide, dye, textile finishing agent, metal chelating agent, preservative, soil conditioner, antifreeze agent, and organic solvent. Piperazine is an important pharmaceutical intermediate and fine chemical raw material, widely used in the synthesis of antibacterial drugs, antihypertensive and hypoglycemic drugs, sedatives and analgesics, antihistamines, anthelmintics, and other drugs, as well as in the production of fine chemical products such as surfactants, preservatives, stabilizers, corrosion inhibitors, defoamers, vulcanizing agents, and coatings. Triethylenediamine is a very important and efficient catalyst in chemical production and is widely used in condensation reactions, polyurethane foam catalysis, pesticide synthesis, and the electroplating industry.

[0003] Currently, the production process of ethylene glycol uses ethanolamine and liquid ammonia as raw materials. However, the high price of ethanolamine is due to its production cost. In contrast, ethylene glycol has experienced significant overcapacity and price declines in recent years. Therefore, the production of ethylene glycol using ethylene glycol and liquid ammonia as raw materials has lower raw material costs and a promising market prospect. Summary of the Invention

[0004] To address the technical problem of high raw material costs in traditional ethylene amine production processes, this invention provides a method for producing ethylene amine. This method uses ethylene glycol and liquid ammonia as raw materials, producing ethylene amine under the action of a molecular sieve catalyst. Product selectivity can reach 99%, and the catalyst exhibits good stability. The production process does not corrode equipment or generate large amounts of industrial wastewater, making it an environmentally friendly and green production process for ethylene amine.

[0005] According to one aspect of the present invention, a method for producing ethylene glycol amine is characterized in that ethylene glycol and liquid ammonia, after preheating, are mixed with dilution gas and continuously passed through a solid acid catalyst bed at a reaction temperature of 250-380°C and a feed weight hourly space velocity of 0.3-10 h⁻¹. -1 The reaction is carried out under reaction conditions of 2.0-10.0 MPa to produce ethylene amine. The solid acid catalyst is prepared by modifying molecular sieves, steam treatment and acid treatment.

[0006] The solid acid catalyst is characterized by the following steps: (1) mixing molecular sieves with binder to form a solid, drying, and calcining at 550℃-700℃ for 4-10 hours; (2) further modifying the catalyst prepared in (1) with oxides, drying, and calcining at 550℃-700℃ for 3-10 hours; (3) treating the catalyst formed in step (2) with steam at 300-700℃; and (4) further treating the catalyst in step (3) with acid, drying, and calcining at 500℃-600℃ for 2-10 hours.

[0007] The feature is that the molecular sieve is one or more of MCM-41, MCM-22, MCM-49, and ZSM-5 molecular sieves, and the molar silicon-aluminum ratio is 20:1-300:1.

[0008] The binder is characterized in that it comprises one or more of silica sol, diatomaceous earth, silicon dioxide, aluminum oxide, or aluminum sol.

[0009] The feature is that the steam treatment is 100% steam, the treatment temperature is 300℃-700℃, the pressure is 1.0-50MPa, and the time is 0.5-10 hours.

[0010] The feature is that the inorganic acid used for acid treatment is dilute nitric acid, phosphoric acid, sulfuric acid or hydrochloric acid, and the solution is immersed at 30-80°C for 4-24 hours.

[0011] The oxide modification is characterized by comprising nickel oxide, copper oxide, zinc oxide, and magnesium oxide, with a weight content of 0.1-10%.

[0012] The characteristic feature is that the dilution gas is carbon dioxide or water vapor.

[0013] The characteristic feature is that the molar ratio of dilution gas to ethylene glycol is 0.5-20.

[0014] The advantages of this invention over the prior art are: (1) A method for producing ethylene glycol and liquid ammonia is provided, with excellent catalyst performance and good stability. The production cost is low. The production process is pollution-free and is a green and environmentally friendly new process technology.

[0015] (2) The production process of ethylene amine using this method is simple and can significantly reduce production costs compared with traditional production processes, resulting in good economic benefits. Detailed Implementation

[0016] The present invention will now be described in further detail with reference to specific embodiments. Other embodiments are considered and may be implemented without departing from the scope or spirit of the present invention. Therefore, the following detailed description is non-limiting.

[0017] The molecular sieves selected according to the technical solution of the present invention are one or more of MCM-41 molecular sieve, MCM-22 molecular sieve, MCM-49 molecular sieve, and ZSM-5 molecular sieve. The MCM-49 molecular sieve used in the present invention is synthesized according to the method in patent US5236575; the MCM-22 molecular sieve is synthesized according to the method in patent US4954325; and the MCM-41 and ZSM-5 molecular sieves are commercial products manufactured by the Catalyst Factory of Nankai University.

[0018] The present invention will now be described in more detail with reference to embodiments. It should be noted that these descriptions and embodiments are intended to facilitate understanding of the invention and are not intended to limit the invention. The scope of protection of the present invention is defined by the appended claims.

[0019] The analysis method in the embodiments of this application is as follows: Chromatographic analysis was performed using a Tianmei GC-7900 gas chromatograph. The chromatographic column was FFAP-5, 30 m × 0.25 mm × 0.25 μm. Chromatographic analysis conditions: column temperature: initial temperature 120℃, residence time 3 minutes, then ramped to 140℃ at a rate of 3℃ / min, held at that temperature for 10 minutes; carrier gas: high-purity nitrogen.

[0020] In the embodiments of this application, the conversion rate of ethylene glycol is 100%, and the ethylene amine selectivity is the sum of the weight percentages of ethylenediamine, piperazine, and triethylenediamine at the reactor outlet. Example 1

[0021] The preparation process of the solid acid catalyst is as follows: 20 g of MCM-22 molecular sieve (molar silicon-to-aluminum ratio of 20:1), 100 g of MCM-41 molecular sieve, 60 g of alumina, and 100 g of silica sol (weight percentage of 20%) were mixed, and an appropriate amount of 10% dilute nitric acid was added as an extrusion aid to form a column. The mixture was dried at 120℃ and calcined at 550℃ for 10 hours. The resulting material was cut into 1-3 mm columnar catalyst precursor A0. 3.8 g of nickel nitrate hexahydrate was added to 20 g of deionized water solution, followed by 20 g of A0. The mixture was impregnated for 12 hours, dried at 120℃, and calcined at 600℃ for 3 hours to obtain A1, wherein the weight percentage of nickel oxide was 5%. 20 g of A1 was steam-treated in a 100% steam atmosphere for 10 hours at 550℃ and 1.0 MPa to obtain A2. 20 g of A2 was impregnated with a 0.5 mol / L nitric acid aqueous solution at 30 °C. The weight ratio of A2 to the solution was 1:5. The impregnation time was 24 hours. The solid acid catalyst A was then calcined at 500 °C for 10 hours. Example 2

[0022] The preparation process of the solid acid catalyst is as follows: 60 g of ZSM-5 molecular sieve and 60 g of MCM-41 molecular sieve (molar silicon-to-aluminum ratio of 100:1) were mixed with 80 g of alumina, and an appropriate amount of 10% dilute nitric acid was added as an extrusion aid to form a column. The mixture was dried at 120℃ and calcined at 700℃ for 4 hours. The resulting material was cut into 1-3 mm sections to obtain columnar catalyst parent material B0. 3.66 g of zinc nitrate hexahydrate and 1.9 g of nickel nitrate hexahydrate were dissolved in 20 g of deionized water, and 20 g of B0 was added for impregnation for 10 hours. The mixture was dried at 120℃ and calcined at 550℃ for 10 hours to obtain B1, wherein the weight percentage of zinc oxide was 5% and the weight percentage of nickel oxide was 2.5%. 20 g of B1 was steam-treated in a 100% steam atmosphere for 0.5 hours at a temperature of 700℃ and a pressure of 1.0 MPa to obtain B2. 20 g of B2 was impregnated in a 0.5 mol / L nitric acid aqueous solution at 20 °C for 4 hours, with a weight ratio of B2 to solution of 1:5. The mixture was then calcined at 600 °C for 2 hours to obtain solid acid catalyst B. Example 3

[0023] The preparation process of the solid acid catalyst is as follows: 50 g of MCM-41 molecular sieve with a molar silicon-to-aluminum ratio of 50:1, 50 g of ZMS-5 molecular sieve with a molar silicon-to-aluminum ratio of 200:1, and 100 g of kaolin were mixed, and an appropriate amount of 10% dilute nitric acid was added as an extrusion aid to form strips. The mixture was dried at 120℃ and calcined at 550℃ for 4 hours. The resulting material was cut into 1-3 mm sections to obtain columnar catalyst parent material CO. 4.56 g of nickel nitrate hexahydrate and 0.11 g of magnesium acetate tetrahydrate were dissolved in 20 g of deionized water, and 20 g of CO was added for impregnation for 24 hours. The mixture was dried at 120℃ and calcined at 700℃ for 3 hours to obtain C1, in which the weight percentage of nickel oxide was 6% and the weight percentage of magnesium oxide was 0.1%. 20 g of C1 was subjected to steam treatment in a 100% steam atmosphere for 10 hours at a temperature of 300℃ and a pressure of 3.0 MPa to obtain C2. 20 g of C2 was impregnated in a 0.5 mol / L sulfuric acid aqueous solution at 40 °C for 10 hours, with a C2 to solution weight ratio of 1:5. The mixture was then calcined at 550 °C for 10 hours to obtain solid acid catalyst C. Example 4

[0024] The preparation process of the solid acid catalyst is as follows: 60 g of MCM-49 molecular sieve with a molar silicon-to-aluminum ratio of 30:1, 100 g of MCM-22 molecular sieve with a molar silicon-to-aluminum ratio of 50:1, and 100 g of silica sol (40% by weight of silica) were mixed. An appropriate amount of 10% dilute nitric acid was added as an extrusion aid and extruded into strips. The mixture was dried at 120℃ and calcined at 550℃ for 4 hours. The resulting material was cut into 1-3 mm pieces to obtain columnar catalyst precursor D0. 3.04 g of copper nitrate trihydrate was dissolved in 20 g of deionized water, and then 20 g of D0 was added for impregnation for 24 hours. The mixture was dried at 120℃ and calcined at 700℃ for 3 hours to obtain D1, in which the weight percentage of copper oxide was 5%. 20 g of D1 was subjected to steam treatment in a 100% steam atmosphere for 6 hours at a temperature of 450℃ and a pressure of 3.0 MPa to obtain D2. 20 grams of F2 were impregnated in a 0.5 mol / L hydrochloric acid aqueous solution at 30°C for 6 hours. The weight ratio of D2 to the solution was 1:5. The mixture was then calcined at 600°C for 2 hours to obtain solid acid catalyst D. Example 5

[0025] The preparation process of the solid acid catalyst is as follows: 20 g of MCM-41 molecular sieve with a molar silicon-to-aluminum ratio of 30:1, 50 g of ZSM-5 molecular sieve with a molar silicon-to-aluminum ratio of 300:1, 50 g of ZSM-5 molecular sieve with a molar silicon-to-aluminum ratio of 100:1, and 80 g of alumina are mixed and extruded into strips with an appropriate amount of 10% dilute nitric acid as an extrusion aid. The mixture is dried at 120℃ and calcined at 650℃ for 4 hours. The resulting material is cut into 1-3 mm sections to obtain columnar catalyst parent material E0. 0.38 g of nickel nitrate and 3.04 g of copper nitrate trihydrate are dissolved in 20 g of deionized water, and 20 g of E0 is added for impregnation. The mixture is dried at 120℃ and calcined at 600℃ for 10 hours to obtain E1, in which the weight percentage of nickel oxide is 0.5% and the weight percentage of copper oxide is 5%. E1 was prepared by steam treatment in a 100% steam atmosphere for 10 hours at 350℃ and 2.0 MPa. E2 was then prepared by impregnation of 20 g of E2 in a 0.2 mol / L sulfuric acid aqueous solution at 40℃ for 24 hours, with a weight ratio of E2 to solution of 1:5. The mixture was then calcined at 500℃ for 10 hours to obtain solid acid catalyst E. Example 6

[0026] The preparation process of the solid acid catalyst is as follows: 100g of MCM-22 molecular sieve with a molar silicon-to-aluminum ratio of 50:1 and 60g of MCM-22 molecular sieve with a molar silicon-to-aluminum ratio of 30:1 are mixed with 100g of silica sol with a weight percentage of 40% silica. An appropriate amount of 10% dilute nitric acid is added as an extrusion aid and the mixture is extruded into strips. The strips are dried at 120℃ and calcined at 550℃ for 4 hours. The resulting material is cut into 1-3 mm sections to obtain columnar catalyst parent material F0. 0.732g of zinc nitrate, 1.83g of copper nitrate, and 1.07g of magnesium acetate tetrahydrate are dissolved in 20g of deionized water. Then, 20g of F0 is added and the mixture is impregnated for 24 hours. The mixture is dried at 120℃ and calcined at 650℃ for 5 hours to obtain F1, in which the weight percentage of zinc oxide is 1%, copper oxide is 3%, and magnesium oxide is 1%. F2 was prepared by steam treatment of 20 g of F1 in a 100% steam atmosphere for 4 hours at a temperature of 600℃ and a pressure of 2.0 MPa. F2 was then impregnated in a 0.5 mol / L phosphoric acid aqueous solution at 80℃ for 4 hours, with a weight ratio of F2 to solution of 1:5, and calcined at 600℃ for 5 hours to obtain solid acid catalyst F. Example 7

[0027] The preparation process of the solid acid catalyst is as follows: 80g of MCM-41 molecular sieve (molar silicon-to-aluminum ratio of 30:1) and 80g of MCM-22 molecular sieve (molar silicon-to-aluminum ratio of 20:1) are mixed with 100g of silica sol (40% by weight of silica). An appropriate amount of 10% dilute nitric acid is added as an extrusion aid, and the mixture is extruded into strips. The strips are dried at 120℃ and calcined at 550℃ for 4 hours. The resulting material is cut into 1-3 mm sections to obtain columnar catalyst parent material G0. 2.2g of zinc nitrate and 2.28g of nickel nitrate are dissolved in 20g of deionized water. 20g of G0 is added and impregnated for 24 hours. The mixture is dried at 120℃ and calcined at 650℃ for 3 hours to obtain G1, wherein the weight percentage of nickel oxide is 3% and the weight percentage of zinc oxide is 3%. 20g of G1 is steam-treated in a 100% steam atmosphere at 500℃ and 5.0 MPa for 10 hours to obtain G2. 20 g of G2 was impregnated in a 0.5 mol / L nitric acid aqueous solution at 30 °C for 4 hours, with a weight ratio of G2 to solution of 1:5. The mixture was then calcined at 580 °C for 8 hours to obtain solid acid catalyst G. Example 8

[0028] The preparation process of the solid acid catalyst is as follows: 140 g of MCM-22 molecular sieve with a molar silicon-to-aluminum ratio of 80:1 was mixed with 20 g of silica and 40 g of alumina. An appropriate amount of 10% dilute nitric acid was added as an extrusion aid and the mixture was extruded into strips. The strips were dried at 120℃ and calcined at 550℃ for 4 hours. The resulting material was cut into 1-3 mm sections to obtain columnar catalyst parent material H0. 6.37 g of nickel chloride hexahydrate and 0.732 g of zinc nitrate were dissolved in 20 g of deionized water. 20 g of H0 was added and the mixture was impregnated for 12 hours. The mixture was dried at 120℃ and calcined at 700℃ for 5 hours to obtain H1, wherein the weight percentage of nickel oxide was 10% and the weight percentage of zinc oxide was 1%. 20 g of H1 was subjected to steam treatment in a 100% steam atmosphere for 4 hours at a temperature of 500℃ and a pressure of 3.0 MPa to obtain H2. 20 grams of H2 were impregnated in a 0.5 mol / L hydrochloric acid aqueous solution at 80°C for 12 hours, with a weight ratio of H2 to solution of 1:5. The mixture was then calcined at 560°C for 6 hours to obtain a solid acid catalyst H. Example 9

[0029] The catalysts prepared in Examples 1-8 were reacted with ethylene glycol and liquid ammonia in a fixed-bed reactor. The raw materials, ethylene glycol and liquid ammonia, along with a dilution gas, were preheated before being introduced into the reactor for reaction. The reaction products were analyzed by online chromatography. The catalyst loading was 20.0 g, and the weight hourly space velocity (WHSV) was 0.3–10 h⁻¹. -1The reaction temperature was 250–380 °C, the dilution gas was water vapor, and the molar ratio of dilution gas to ethylene glycol was 0.5–20:1. The molar ratio of the raw material liquid ammonia to ethylene glycol was 10:1. The reaction dilution gas for the catalysts prepared in Examples 1–4 was water vapor; the reaction dilution gas for the catalysts prepared in Examples 5–8 was carbon dioxide. The reaction results of the solid acid catalysts in each example after 100 hours of reaction are listed in Table 1.

[0030] Table 1 Catalytic reaction conditions and catalytic performance of solid acid catalysts catalyst Reaction temperature (°C) Reaction pressure (MPa) <![CDATA[Weight hourly space velocity (h -1 ).]]> Diluent gas / ethylene glycol (molar ratio) ethylenediamine selectivity Piperazine selectivity Triethylenediamine Ethyleneamine selectivity (%) A 280 3.0 1.0 3 65 20 13 98 B 250 2.0 0.3 2 66 18 11 96 C 270 4.0 0.5 1 68 15 15 98 D 300 6.0 3.0 0.5 75 13 11 99 E 320 5.0 5.0 5 72 15 11 98 F 380 10.0 10.0 2 60 30 8 98 G 330 6.0 5.0 5 65 13 10 99 H 350 8.0 2.0 20 63 20 15 98 The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for producing ethyleneamine, characterized in that, The raw materials, ethylene glycol and liquid ammonia, are preheated and then mixed with dilution gas and continuously passed through a solid acid catalyst bed. The reaction is carried out at a temperature of 250-380℃ and a feed weight hourly space velocity of 0.3-10 h⁻¹. -1 The reaction is carried out under reaction conditions of 2.0-10.0 MPa to produce ethylene amine. The solid acid catalyst is prepared by modifying molecular sieves, steam treatment and acid treatment.

2. The method for producing ethyleneamine according to claim 1, characterized in that, The preparation of solid acid catalysts includes: (1) mixing molecular sieves with binders to form a shape, drying, and calcining at 550℃-700℃ for 4-10 hours; (2) further modifying the catalyst prepared in (1) with oxides, drying, and calcining at 550℃-700℃ for 3-10 hours; (3) treating the catalyst formed in step (2) with steam at 300-700℃; (4) further treating the catalyst in step (3) with acid, drying, and calcining at 500℃-600℃ for 2-10 hours.

3. The method for producing ethyleneamine according to claim 1, characterized in that, The molecular sieve is one or more of MCM-41, MCM-22, MCM-49, and ZSM-5 molecular sieves, with a molar silica-alumina ratio of 20:1 to 300:

1.

4. The method for producing ethyleneamine according to claims 1 and 2, characterized in that, The binder includes one or more of silica sol, diatomaceous earth, silicon dioxide, aluminum oxide, or aluminum sol.

5. The method for producing ethyleneamine according to claims 1 and 2, characterized in that, The steam treatment uses 100% steam, with a treatment temperature of 300℃-700℃, a pressure of 1.0-5.0MPa, and a time of 0.5-10 hours.

6. The method for producing ethyleneamine according to claims 1 and 2, characterized in that, The inorganic acids used for acid treatment are dilute nitric acid, phosphoric acid, sulfuric acid, or hydrochloric acid, and the solution is immersed at 30-80°C for 4-24 hours.

7. The method for producing ethylene amine according to claims 1 and 2, characterized in that, Oxide modification includes nickel oxide, copper oxide, zinc oxide, and magnesium oxide, with a weight content of 0.1-10%.

8. The method for producing ethyleneamine according to claim 1, characterized in that, The dilution gas is carbon dioxide or water vapor.

9. The method for producing ethyleneamine according to claim 1, characterized in that, The molar ratio of dilution gas to ethylene glycol is 0.5-20.