Application of bimetallic catalyst in vinylamine synthesis and vinylamine synthesis method

Abstract

The invention discloses application of a bimetallic catalyst in vinylamine synthesis and a vinylamine synthesis method, and belongs to the technical field of vinylamine synthesis through an ethanolamine method.The vinylamine synthesis is carried out with monoethanolamine and liquid ammonia as raw materials in the presence of hydrogen under the action of the bimetallic catalyst, the bimetallic catalyst is subjected to low-temperature reduction activation or not subjected to reduction activation, and the temperature range of low-temperature reduction activation is 110-220 DEG C. According to the vinylamine synthesis method disclosed by the invention, the bimetallic catalyst subjected to low-temperature reduction activation or not subjected to reduction activation is adopted, so that catalytic activity and product selectivity which are equivalent to those of the conventional bimetallic catalyst subjected to high-temperature reduction activation can be obtained; therefore, the overall economy and safety of the production of vinylamine by hydroamination of monoethanolamine are improved.

Description

Technical Field

[0001] The invention relates to the synthesis of ethyleneamine by an ethanolamine process, and in particular to the application of a bimetallic catalyst activated by low-temperature reduction or not activated by reduction in the synthesis of ethyleneamine and a method for synthesizing ethyleneamine. Background Art

[0002] Ethyleneamine products refer to the chain polymers of ethylenediamine and cyclic piperazine amines and derivatives, mainly including ethylenediamine (EDA), diethylenetriamine (DETA), triethylenediamine (TEDA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), hydroxyethylethylenediamine (AEEA), and also include cyclic derivatives such as piperazine (PIP), hydroxyethylpiperazine (HEP) and aminoethylpiperazine (AEP). Ethyleneamine products are a widely used chemical with unique applications in many aspects. For example, in epoxy resin curing agents, epoxy resins are essential in the production of coatings, adhesives and composites. Ethyleneamines as epoxy resin curing agents help harden epoxy resins and provide mechanical strength and chemical resistance. In terms of chelating agents, ethyleneamines act as chelating agents in various industrial processes. They form stable complexes with metal ions. These complexes are essential in water treatment, pulp and paper processing, and agriculture. In agrochemicals, ethyleneamine is often used to make agrochemicals such as herbicides, fungicides and insecticides, which can improve the efficacy and stability of agricultural products. In rubber chemicals, ethyleneamine is used to produce rubber accelerators and processing aids, which can enhance the performance of rubber products. In addition, ethyleneamine is also a key ingredient in the production of polyamide resins, which can be used in the manufacture of coatings, adhesives and molded plastics. These applications highlight the importance of ethyleneamine in various industries.

[0003] At present, the main methods for synthesizing ethyleneamine products in industry are the ethylene dichloride method and the ethanolamine method. Among them, the ethanolamine method is the hydrogenation of monoethanolamine (MEA) and ammonia (NH3) in the presence of a catalyst to produce ethyleneamine. MEA is a relatively cheap and easily available raw material, which provides an economical way in process investment and can be flexibly expanded or reduced according to production needs, which is very beneficial for manufacturers who adjust production according to market demand. This method has the advantages of low process investment, low environmental pollution, and low energy consumption. It is an attractive choice in industrial applications and has gradually become a mainstream method.

[0004] In the ethanolamine process, the intermediate products of the amination process are also reactive, so they will inevitably react further to generate more cyclic amine by-products. However, the market demand for chain amines is different from that for cyclic amines. The demand for chain amines is higher and is constantly expanding. Therefore, how to ensure high conversion rate of monoethanolamine while maintaining high selectivity of chain amines is a difficult problem in the industry. Developing catalysts with high conversion rate and high selectivity for chain amines is an important direction for the industry to solve this problem. The preparation of such catalysts usually involves strict raw material selection and precise preparation process control.

[0005] For metal catalysts commonly used in the ethanolamine process, in order to improve catalytic activity and meet the selectivity requirements of the reaction products, the catalysts are subjected to high-temperature reduction activation before being used in the synthesis reaction. The reduction activation temperature is as high as 300~550℃, which has become a common practice in the industry. In addition, in the ethyleneamine synthesis process, a high ammonia ratio method is usually adopted to improve the conversion rate of MEA and the selectivity of the product, that is, to increase the ratio of NH3:MEA; but the disadvantages of a high ammonia ratio are also very obvious. A large amount of unreacted liquid ammonia needs to be separated from the product by flash evaporation, and then compressed and circulated to the reaction inlet. The process with a high ammonia ratio has high material and energy consumption.

[0006] The following are several references that reflect the conventional practice of high temperature reduction activation of catalysts and the use of high ammonia ratios to synthesize ethyleneamine:

[0007] Patent document CN109908900B discloses a supported catalyst for preparing ethyleneamine by the monoethanolamine method. The main active components of the catalyst are Ni, Co, and Cu, and the auxiliary agent is at least one of Fe, Cr, Re, Ru, B, Mg, and Ba. The carrier is Al2O3, SiO2, Al2O3-SiO2, HZSM-5, or H-β molecular sieve. The roasting gas for preparing the catalyst in the document is one or more of air, N2, Ar, H2, NO, O2, and NO2. When the ratio of NH3:MEA is 10:1, the reaction can obtain ethylenediamine with a selectivity of 32.6%-54.2%. The catalyst reduction temperature in the document is 350~550℃, and the reduction time is 1.5~6.0h.

[0008] Patent document CN101875014B discloses a catalyst for preparing ethylenediamine, wherein the main active component of the catalyst is Ni or Co, the auxiliary agent is one or more metals or oxides such as Re, Fe, Cu, Ru and B, the carrier is selected from Al2O3 or SiO2, etc., and the preparation method is one or more of precipitation method, impregnation method and hydrothermal synthesis method. The catalyst of the invention is reduced in hydrogen at 375 ℃ for 5 h at normal pressure before use, and the reaction is carried out under relatively mild conditions, wherein the reaction temperature is 135-155 ℃, the hydrogen pressure is 6.5-8 MPa, and the ratio of NH3:MEA is 10:1. In the patent embodiment, the selectivity of EDA can reach more than 50%, but the conversion rate of MEA is relatively low, at about 35%.

[0009] Patent document CN108067289A discloses a catalyst for producing ethylenediamine and piperazine under hydrogenation conditions and its application. The main active components of the catalyst are Ni, Co, and Cu, and the additives are one or more metals or oxides such as Fe, Cr, Re, Ru, B, and Mg. The catalyst carrier is a molecular sieve HZSM-5, H-β, H-MOR, or HY. The patent can obtain ethylenediamine or piperazine with high selectivity by changing different molecular sieves as carriers. In the embodiment of the invention, the catalyst needs to be activated before use. The preferred condition is hydrogen reduction at 400 ° C, and the ratio of NH3:MEA during the reaction is 10:1.

[0010] Patent document CN105457673B discloses an amination catalyst, wherein the catalyst carrier is a material obtained by desiliconizing mordenite using NaOH, and the carrier is further modified by impregnation with metal ions and non-metal ions, and the active center is Cr 3+ or Mn 2+ , the auxiliary agent is BO3 2- or F - , and contains anatase TiO2. The invented amination catalyst is suitable for synthesizing ethylenediamine by gas phase condensation amination reaction of ethanolamine and ammonia. The reaction temperature required in the patent document is 330 °C, and the ratio of NH3:MEA is as high as 21:1. The reaction conversion rate of MEA is 54%, and the selectivity of ethylenediamine can reach 87%.

[0011] Patent document US6534441B1 discloses a nickel / rhenium composite catalyst for amination reaction, in which nickel and rhenium are supported on an alumina-silica carrier, which contains about 5 to about 65% by weight of silica and has a BET surface area of ​​about 30 to about 450 square meters / gram. The patent found that adding the active component boron to the catalyst can improve the selectivity of EDA, resulting in relatively less PIP and higher polyamines. The catalyst of the invention is reduced in hydrogen at 375 ° C for 3 h before use. The ratio of NH3:MEA in the reaction is 10~12:1, and the selectivity of EDA can reach more than 70%, but there is still a phenomenon of low MEA conversion rate.

[0012] Patent document US5750790 discloses a reductive amination catalyst, which uses transition phase alumina to support Ni and Re. By using a carrier selected from transition alumina, including transition alumina of δ and θ alumina and a carrier material of a mixed phase such as γ-θ, δ-θ or θ-α alumina, the selectivity of acyclic products and the activity of the catalyst are improved, and the amount of rhenium can be reduced. This effectively improves the conversion rate of MEA and the selectivity of EDA. In this patent, the reduction temperature used by the catalyst is 340 ° C, and the ratio of NH3:MEA is 10:1.

[0013] Patent document US4992587 discloses a halogen-modified amination catalyst, the main active component of which is nickel and / or cobalt, the second metal is ruthenium, and a halogen-containing compound is added at any step in the process of preparing the active component on the oxide support by impregnation of the catalyst for modification. The nickel compound and / or cobalt compound and ruthenium compound are reduced to the corresponding metal in one or more steps by reacting the catalyst intermediate with hydrogen at a high temperature sufficient to reduce the corresponding compound to the metal. The invention found that the favorable performance of this catalyst seems to be related to the presence of halogen therein, and a higher yield of the desired primary amine and polyamine is obtained, and the formation of unwanted by-products is greatly reduced. The reduction temperature used by the catalyst is 400°C, the reaction is carried out in an autoclave, the ratio of NH3:MEA is 9.3:1, and the MEA conversion rate of the modified catalyst is above 50%, and the EDA selectivity is above 60%.

[0014] Patent document US5321160 discloses an ethyleneamine catalyst, the main active component of which is Ni, the second metal is one of Re, Ir, Pt or Pd, and the auxiliary is a rare earth metal, selected from at least one rare earth element of scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. The reduction temperature of the catalyst of the invention is 500 ° C, the ratio of NH3:MEA is 6.5:1, the MEA conversion rate is above 60%, and the EDA selectivity is above 50%.

[0015] It can be seen from the above-listed prior art documents that, although the catalyst improvement methods are different, these catalysts need to be reduced and activated by high-temperature hydrogen at 300-500°C during the preparation process or before use, and in the reaction of catalyzing monoethanolamine and ammonia to produce ethyleneamine under hydrogen conditions, the NH3:MEA ratio is 4-20:1, and most of them are above 10:1, in order to achieve the desired catalyst activity and product selectivity. In the synthesis of ethyleneamine by hydrogen amination of ethanolamine, high-temperature reduction and activation of the catalyst and high ammonia ratio of the reaction raw materials have become routine operations in the industry.

[0016] High-temperature hydrogen reduction of metal catalysts before use is a common activation method for catalysts. Its purpose is to convert high-valent metals in metal compounds or metal oxides into low-valent metals in order to better catalyze the reaction. However, the implementation of the high-temperature hydrogen reduction step has high requirements for equipment, high energy consumption in the production process, long production cycle, and strict control of safety measures. How to ensure efficient catalytic reaction production of catalysts, achieve high activity and high selectivity, increase the yield of target products, reduce the formation of by-products, simplify the manufacturing method of catalysts, adopt safer application methods, and improve the overall economy and safety of catalyst production and monoethanolamine hydrogenation to produce ethyleneamine production is of great value.

[0017] The high ammonia ratio of the reaction raw materials can promote the proportion of chain ethyleneamine products, increase the proportion of target products, and reduce the formation of by-products, but at the same time, a large amount of unreacted ammonia needs to be separated from the product by flash evaporation, compressed after separation and recycled to the reactor inlet for reuse. This process results in disadvantages such as large catalytic unit reactor, high investment in reactant circulation pipelines, and high reactant circulation energy consumption in production. Therefore, the invention of high-performance catalysts can reduce the ammonia ratio in the reaction while ensuring the target conversion rate and target selectivity, which can improve the economic efficiency of the production of ethyleneamine by hydrogenation of monoethanolamine, and has important industry value. Summary of the invention

[0018] In view of the above problems existing in the prior art, the inventors of the present invention have found through research that in the reaction of synthesizing ethyleneamine by hydroamination using the ethanolamine method, the catalyst is activated by low-temperature reduction inside or outside the reactor or is not activated by reduction, and excellent catalytic activity and product selectivity can be achieved, which are equivalent to the performance of preparing ethyleneamine using a catalyst activated by high-temperature reduction under the same conditions. The inventors of the present invention have further found that in the reaction of synthesizing ethyleneamine by hydroamination using the ethanolamine method, when a catalyst activated by low-temperature reduction or is not activated by reduction is used, a reaction conversion rate and product selectivity equivalent to those with a high ammonia ratio can be achieved using a low ammonia ratio raw material.

[0019] In a first aspect of the present invention, a bimetallic catalyst is provided for use in ethyleneamine synthesis. The ethyleneamine synthesis is carried out using monoethanolamine and liquid ammonia as raw materials under hydrogen conditions and the action of the bimetallic catalyst. The bimetallic catalyst is activated by low-temperature reduction or not, and the temperature range of the low-temperature reduction activation is 110-220°C.

[0020] In some embodiments of the present invention, the temperature range of the low-temperature reduction activation is 130-210°C.

[0021] In some embodiments of the present invention, the low-temperature reduction activation is performed in a reactor for ethyleneamine synthesis or outside the reactor.

[0022] In some embodiments of the present invention, the low-temperature reduction activation is carried out outside the reactor for synthesizing ethyleneamine, and is carried out in an atmosphere of H2 or a mixture of H2 and an inert gas. After the low-temperature reduction activation is completed, the catalyst is cooled to room temperature and passivated in air. When the low-temperature reduction activation is carried out in a hydrogen atmosphere, the standard volume space velocity of hydrogen is 10 to 500 h / min. -1 , pressure greater than 0.1MPa.

[0023] In some embodiments of the present invention, the bimetallic catalyst comprises a carrier, an active component, and an additive, wherein the carrier comprises Al2O3 and / or SiO2, and has a specific surface area of ​​50 to 300 m 2 / g; the active component includes Ni, and the metal content of the active component accounts for 5~30wt% of the catalyst mass; the auxiliary agent includes Ru and / or Re, and the metal content of the auxiliary agent accounts for 0.2~1wt% of the catalyst mass.

[0024] In a second aspect of the present invention, a method for synthesizing ethyleneamine is provided. The method uses monoethanolamine and liquid ammonia as raw materials and is carried out under hydrogen conditions and the action of a bimetallic catalyst. The bimetallic catalyst is used after low-temperature reduction activation or without reduction activation. The temperature range of the low-temperature reduction activation is 110-220°C.

[0025] In some embodiments of the second aspect of the present invention, the temperature range of the low-temperature reduction activation is 130-210°C.

[0026] In some embodiments of the second aspect of the present invention, the low-temperature reduction activation is performed in a reactor for ethyleneamine synthesis or outside the reactor.

[0027] In some embodiments of the second aspect of the present invention, the low-temperature reduction activation is carried out outside the reactor for synthesizing ethyleneamine, and is carried out in an atmosphere of H2 or a mixed atmosphere of H2 and an inert gas. After completing the low-temperature reduction activation, the catalyst is cooled to room temperature and passivated in air.

[0028] In some embodiments of the second aspect of the present invention, the low-temperature reduction activation is carried out in a reactor for synthesizing ethyleneamine, and the catalyst is subjected to low-temperature reduction activation in an atmosphere of H2 or a mixed atmosphere of H2 and inert gas or in an atmosphere of H2 and liquid ammonia. When the low-temperature reduction activation is carried out in an atmosphere of H2 and liquid ammonia, the standard volume space velocity of H2 is 10 to 500 h -1 , pressure is 15~25 MPa.

[0029] In some embodiments of the second aspect of the present invention, the synthesis reaction temperature of ethyleneamine is 160-280° C., the reaction pressure is 15-30 MPa, and the molar ratio of ammonia:monoethanolamine is 2-10:1.

[0030] In some embodiments of the second aspect of the present invention, the molar ratio of ammonia:monoethanolamine in the ethyleneamine synthesis reaction raw material is less than 4:1; in a specific embodiment of the present invention, the molar ratio of ammonia:monoethanolamine is 2~3:1.

[0031] In some embodiments of the second aspect of the present invention, the bimetallic catalyst comprises a carrier, an active component, and an additive, wherein the carrier comprises Al2O3 and / or SiO2, and has a specific surface area of ​​50 to 300 m 2 / g; the active component includes Ni, and the metal content of the active component accounts for 5~30wt% of the catalyst mass; the auxiliary agent includes Ru and / or Re, and the metal content of the auxiliary agent accounts for 0.2~1wt% of the catalyst mass.

[0032] In some embodiments of the second aspect of the present invention, when the conversion rate of monoethanolamine is 45-60%, the selectivity of ethylenediamine, diethylenetriamine and hydroxyethylethylenediamine in the synthetic product is greater than 80% in total.

[0033] Compared with the prior art, the present invention has the following beneficial technical effects: The invention applies a bimetallic catalyst that has been activated by low-temperature reduction or has not been activated by reduction to the hydroamination of monoethanolamine to synthesize ethyleneamine, and can obtain excellent performance similar to that of the bimetallic catalyst that has been activated by high-temperature reduction to catalyze the hydroamination of monoethanolamine to synthesize ethyleneamine, and the catalytic activity and product selectivity distribution of the two are equivalent. Therefore, the invention avoids the high-temperature reduction of hydrogen by the catalyst, and avoids the disadvantages of the high-temperature hydrogen reduction step, such as high equipment requirements, high investment, high energy consumption in the high-temperature reduction process, long production cycle, and potential safety hazards of high-temperature hydrogen leakage, thereby reducing the energy consumption of the production process, shortening the production cycle, and improving the overall economy and safety of the production of ethyleneamine by the hydroamination of monoethanolamine.

[0034] In addition, in the ethyleneamine synthesis method of the present invention, a bimetallic catalyst that has been activated by low-temperature reduction or not is used, and a low ammonia ratio raw material can also achieve a reaction conversion rate and product selectivity distribution equivalent to those of a high ammonia ratio raw material. The ammonia ratio in the reaction is reduced while ensuring the target conversion rate and target selectivity, thereby avoiding the disadvantages of increased material and energy consumption due to the need for flash separation and circulation of a large amount of unreacted ammonia in the case of a high ammonia ratio, thereby improving the economic efficiency of the production of ethyleneamine by hydrogenation of monoethanolamine, which has important industry value. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the TPR curve of the catalyst before the reaction of Example 15A of the present invention.

[0036] Figure 2 This is the TPR curve of the catalyst before the reaction of Example 20A of the present invention.

[0037] Figure 3 This is the TPR curve of the catalyst before the reaction of Comparative Example 1A of the present invention.

[0038] Figure 4 This is the TPR curve of the catalyst after the reaction of Example 15A of the present invention.

[0039] Figure 5 This is the TPR curve of the catalyst after the reaction of Example 20A of the present invention.

[0040] Figure 6 This is the TPR curve of the catalyst after the reaction of Comparative Example 1A of the present invention. DETAILED DESCRIPTION

[0041] Various aspects of the present invention will be described in detail below in conjunction with specific implementation methods and exemplary embodiments. These specific descriptions and exemplary embodiments are only used to illustrate the present invention and do not limit the protection scope and essential content of the present invention.

[0042] The present invention only needs to perform low-temperature reduction activation on the catalyst used for synthesizing ethyleneamine by hydrogen amination of ethanolamine and then perform amination reaction, so as to obtain excellent catalytic activity and product selectivity, which is equivalent to the performance of preparing ethyleneamine by using a catalyst activated by high-temperature reduction under the same conditions. The low-temperature reduction activation is relative to the high-temperature (300-550°C) reduction activation in the prior art. In the present invention, low-temperature reduction activation means that the activation temperature is lower than 220°C. For example, the temperature range of the low-temperature reduction activation of the present invention is 110-220°C, preferably 130-210°C. In an exemplary embodiment of the present invention, the low-temperature reduction activation temperature is 180-200°C.

[0043] The catalyst of the present invention can be activated at low temperature by reduction before the catalyst is applied to the reaction of hydroamination of monoethanolamine to form ethyleneamine, that is, it can be performed outside the ethyleneamine synthesis reactor, for example, it can be activated in a tubular furnace. The reduction activation atmosphere can be H2 or a mixed atmosphere of H2 and an inert gas, for example, it can be performed under a 5 vol% H2 / N2 atmosphere. When the activation is performed under a H2 atmosphere, the standard volume space velocity of H2 is 10 to 500 h -1 The preferred H2 standard volume space velocity is 50~400 h -1 , more preferably the H2 standard gas volume space velocity is 100~300h -1 The activation temperature is 110-220°C, preferably 130-210°C; the pressure is greater than 0.1 MPa, and the activation time is greater than 2 h. In addition, the activated catalyst is cooled to room temperature outside the reactor and passivated in the air before use.

[0044] The low-temperature reduction activation of the catalyst of the present invention can also be carried out in an ethyleneamine synthesis reactor. In some exemplary embodiments of the present invention, the catalyst is activated in situ in a reactor for synthesizing ethyleneamine, and the catalyst is subjected to low-temperature reduction activation in an atmosphere of H2 or a mixed atmosphere of H2 and inert gas or in an atmosphere of H2 and liquid ammonia. When the low-temperature reduction activation is carried out in an atmosphere of H2 and liquid ammonia, the standard volume space velocity of H2 is 10 to 500 h -1 The preferred H2 standard volume space velocity is 50~400 h -1 , more preferably the H2 standard volume space velocity is 100 to 300 h -1 ; The volumetric space velocity of liquid ammonia is 1~10 h -1 The preferred liquid ammonia volume space velocity is 1~5 h -1 ; The activation temperature is 110~220 ℃, preferably 130~210 ℃; the pressure is 15~25 MPa, preferably 16~24 MPa; the activation time is greater than 2h.

[0045] The catalyst of the present invention can also be used without reduction activation. The catalyst after drying and calcination can be directly loaded into the reactor for synthesizing ethyleneamine and purged with inert gas to be used after oxygen is removed.

[0046] The catalyst of the present invention can be any metal catalyst known in the art for use in the hydroamination of ethanolamine to produce ethyleneamine. In a specific embodiment of the present invention, a supported bimetallic catalyst is used, which includes a carrier, an active component, and an additive; wherein the carrier is Al2O3 and SiO2 or a mixture of the two, and the specific surface area is 50-300 m 2 / g, preferably 70~250 m 2 / g; the active component is Ni, the auxiliary agent is Ru and / or Re, the metal content of the active component accounts for 5-30wt% of the catalyst mass, preferably 7-23wt%; the metal content of the auxiliary agent accounts for 0.2-1 wt% of the catalyst mass, preferably 0.3-0.9wt%. The bimetallic catalyst uses the synergistic effect of different metals to improve the catalyst performance and provide better activity, selectivity and stability for the reductive amination process. In an exemplary embodiment of the present invention, the supported bimetallic catalyst used includes: 10wt% Ni-0.5wt% Ru / SiO2, 10wt% Ni-0.5wt% Ru / Al2O3, 10wt% Ni-0.5wt% Re / SiO2, 10wt% Ni-0.7wt% Ru / Al2O3, 20wt% Ni-0.6wt% Ru / Al2O3. The catalyst of the present invention can also use other metal catalysts known in the art for the hydrogen amination of ethanolamine to produce ethyleneamine.

[0047] The preparation of the supported catalyst of the present invention adopts an impregnation method or a coprecipitation method to load the active components and auxiliary agents onto the carrier, and the impregnation can be carried out in one step or in multiple steps. Among them, the main steps of preparing the catalyst by the impregnation method include: preparing a metal salt solution containing active components and auxiliary agents at the required concentration, impregnating the metal salt solution into the carrier or intermediate catalyst at a certain temperature, and then drying and roasting. Among them, the impregnation temperature is 20~100℃, preferably the impregnation temperature is 30~80℃, and the impregnation time is 2~8 hours; drying and roasting are carried out in an air atmosphere, the drying temperature is 80~150℃, preferably the drying temperature is 100~120℃, and the drying time is greater than 3 hours; the roasting temperature is 400℃~550℃, preferably the roasting temperature is 450~500℃; the roasting time is 3~8h, preferably the roasting time is 4~6h.

[0048] When the catalyst activated by low-temperature reduction or the catalyst not activated by low-temperature reduction is used for ethyleneamine synthesis, monoethanolamine and liquid ammonia are used as reaction raw materials, and the reaction temperature for synthesizing ethyleneamine under hydrogen conditions and the action of the catalyst is 150-280° C., preferably 160-250° C.; the reaction pressure is 12-30 MPa, preferably 16-26 MPa; the volume space velocity of monoethanolamine is less than 3 h -1 The preferred volumetric space velocity of ethanolamine is 1 to 2 h -1 .

[0049] In the ethyleneamine synthesis method of the present invention, the molar ratio of ammonia to monoethanolamine can be a conventional high ammonia ratio, for example, the molar ratio of ammonia to monoethanolamine is (4-10): 1. The molar ratio of ammonia to monoethanolamine to hydrogen is (4-10): 1: (0.01-1).

[0050] In addition, the inventors of the present invention have further discovered through research that in the ethyleneamine synthesis method of the present invention, using a catalyst activated by low-temperature reduction or a catalyst not activated by reduction, the ammonia ratio in the reaction raw materials monoethanolamine and liquid ammonia can be lower than the high ammonia ratio required in the conventional high-temperature reduction activation, that is, the molar ratio of ammonia:monoethanolamine is lower than 4. In an exemplary embodiment of the present invention, the molar ratio of ammonia:monoethanolamine is (2-3):1. The molar ratio of ammonia:monoethanolamine:hydrogen is (2-3):1:(0.01-1).

[0051] The present invention is further described below by examples. The performance of the catalyst prepared in each example was evaluated by amination reaction using a fixed bed reactor. The product sample analysis was analyzed using an Agilent 8860 gas chromatograph, the chromatographic column was a Shimadzu SH-PolarX capillary chromatographic column, the detector was an FID detector, and the internal standard method was used for quantitative analysis, and the internal standard was 3-diethylamino-1-propylamine. The catalytic effect evaluation of each example is summarized in Table 1 and Table 2.

[0052] Example 1A S1: Preparation of catalyst (10wt%Ni-0.5wt%Ru / SiO2) Weigh 55.3070 g of nickel nitrate and add deionized water to prepare 55 mL of salt solution. Use this salt solution to impregnate 100 g of SiO2 carrier. The specific surface area of ​​SiO2 carrier is 141 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0053] Weigh 1.3052 g of ruthenium chloride solid, add deionized water to prepare 55 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst A.

[0054] S2: Activation of catalyst Catalyst A was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst A was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200℃, pressure 20 MPa, activation time 3 h.

[0055] S3: Ethyleneamine synthesis After the catalyst A is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0056] Example 2A Ethyleneamine synthesis The catalyst and catalyst activation method are the same as those in Example 1A. On the basis of the synthesis of ethyleneamine in Example 1A, the hydroamination reaction conditions are changed to continue the synthesis of ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 210 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=6:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0057] Example 3A S1: Preparation of catalyst (10wt%Ni-0.5wt%Ru / Al2O3) Weigh 55.3189 g of nickel nitrate and add deionized water to prepare 55 mL of salt solution. Use this salt solution to impregnate 100 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 212 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0058] Weigh 1.3423 g of ruthenium chloride solid, add deionized water to prepare 55 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst B.

[0059] S2: Activation of catalyst Catalyst B was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst B was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200℃, pressure 20 MPa, activation time 3 h.

[0060] S3: Ethyleneamine synthesis After the catalyst B is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0061] Example 4A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 3A. On the basis of the synthesis of ethyleneamine in Example 3A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 210 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=6:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0062] Example 5A Ethyleneamine synthesis The catalyst and the activation method of the catalyst are the same as those in Example 3A. Based on the synthesis of ethyleneamine in Example 4A, the hydroamination reaction conditions are changed to continue the synthesis of ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 210 °C, monoethanolamine liquid volume space velocity 1.8 h -1 , NH3:MEA:H2=4:1:0.05 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0063] Example 6A S1: Preparation of catalyst (10wt%Ni-0.5wt%Re / SiO2) Weigh 27.6859 g nickel nitrate and 0.3633 g ammonium perrhenate, add deionized water to prepare 48 mL salt solution, and use this salt solution to impregnate 50 g SiO2 carrier. The specific surface area of ​​SiO2 carrier is 102 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain a bimetallic catalyst, which was numbered as catalyst C.

[0064] S2: Activation of catalyst Catalyst C was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst C was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200℃, pressure 20 MPa, activation time 3 h.

[0065] S3: Ethyleneamine synthesis After the catalyst C is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 220 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0066] Example 7A S1: Preparation of catalyst (10wt%Ni-0.7wt%Ru / Al2O3) Weigh 55.3026 g of nickel nitrate and add deionized water to prepare 55 mL of salt solution. Use this salt solution to impregnate 100 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 94 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0067] Weigh 1.8550 g of ruthenium chloride solid, add deionized water to prepare 55 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst D.

[0068] S2: Activation of catalyst Catalyst D was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst D was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1, liquid ammonia space velocity 2.4 h -1 , temperature 200℃, pressure 20 MPa, activation time 3 h.

[0069] S3: Ethyleneamine synthesis After the catalyst D was activated in the reactor, the feed was started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 205 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.16 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0070] Example 8A Ethyleneamine synthesis The catalyst and the activation method of the catalyst are the same as those in Example 7A. On the basis of the synthesis of ethyleneamine in Example 7A, the hydroamination reaction conditions are changed to continue the synthesis of ethyleneamine. The reaction conditions are: pressure 17 MPa, temperature 205°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0071] Example 9A The catalyst was Catalyst D in Example 7A.

[0072] S2: Activation of catalyst The catalyst was activated in an off-site tubular furnace under the following conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 °C, and activation time 3 h. After natural cooling, it was passivated in air at room temperature for 2 h with an air flow rate of 150 mL / min. After passivation, a bimetallic catalyst was obtained, which was numbered as catalyst D-LR.

[0073] S3: Ethyleneamine synthesis 50 mL of catalyst D-LR was loaded into the reactor and purged with nitrogen for 0.5 h before starting the feed for hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0074] Example 10A S1: Preparation of catalyst (10wt%Ni-0.7wt%Ru / Al2O3) Weigh 55.3142 g of nickel nitrate and add deionized water to prepare 55 mL of salt solution. Use this salt solution to impregnate 100 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 212 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0075] Weigh 1.8493 g of ruthenium chloride solid, add deionized water to prepare 55 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, and then cool naturally to obtain a bimetallic catalyst, numbered as catalyst E.

[0076] S2: Activation of catalyst Catalyst E was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst E was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200℃, pressure 20 MPa, activation time 3 h.

[0077] S3: Ethyleneamine synthesis After the catalyst E was activated in the reactor, the feed was started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.16 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0078] Example 11A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 10A. On the basis of the synthesis of ethyleneamine in Example 10A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0079] Example 12A S1: Preparation of catalyst (20wt%Ni-0.6wt%Ru / Al2O3) Weigh 49.5967 g of nickel nitrate and add deionized water to prepare 20 mL of salt solution. Use this salt solution to impregnate 40 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 94 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0080] Weigh 0.8125 g of ruthenium chloride solid, add deionized water to prepare 20 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst F.

[0081] S2: Activation of catalyst Catalyst F was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst F was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 180℃, pressure 20 MPa, activation time 3 h.

[0082] S3: Ethyleneamine synthesis After the catalyst F is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0083] Example 13A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 12A. On the basis of the synthesis of ethyleneamine in Example 12A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=6:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0084] Example 14A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 12A. Based on the synthesis of ethyleneamine in Example 13A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 17 MPa, temperature 195°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4: 1: 0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0085] Example 15A S1: Preparation of catalyst (10wt%Ni-0.5wt%Ru / Al2O3) Weigh 110.033 g of nickel nitrate and add deionized water to prepare 110 mL of salt solution. Use this salt solution to impregnate 200 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 94 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0086] Weigh 2.6104 g of ruthenium chloride solid, add deionized water to prepare 110 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered catalyst G.

[0087] S2: Activation of catalyst Catalyst G was subsequently activated in a tube furnace under the following activation conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 °C, and activation time 3 h. After natural cooling, it was passivated in air at room temperature for 2 h with an air flow rate of 150 mL / min. After passivation, a bimetallic catalyst was obtained, which was numbered as catalyst G-LR.

[0088] S3: Ethyleneamine synthesis 50 mL of catalyst G-LR was loaded into the reactor and purged with nitrogen for 0.5 h before starting the feed for hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0089] Example 16A The catalyst was Catalyst G in Example 15A.

[0090] S2: Activation of catalyst Catalyst G was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst G was loaded into the reactor and activated after nitrogen purge for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200 ℃, pressure 20 MPa, activation time 3 h.

[0091] S3: Ethyleneamine synthesis After the catalyst G is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 202 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0092] Example 17A The catalyst was Catalyst G in Example 15A.

[0093] S2: Activation of catalyst Catalyst G was activated in a mixed atmosphere of hydrogen and nitrogen in the reactor: 50 mL of catalyst G was loaded into the reactor and activated after purging with nitrogen for 0.5 h. The activation conditions were: hydrogen hourly velocity 67.2 h -1 , nitrogen space velocity 500 h -1 , temperature 150 ℃, pressure 0.1 MPa, activation time 6 h.

[0094] S3: Ethyleneamine synthesis After the catalyst G is activated in the reactor, the feed is started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0095] Example 18A S1: Preparation of catalyst (20wt%Ni-0.5wt%Ru / Al2O3) Weigh 61.9354 g of nickel nitrate and add deionized water to prepare 26 mL of salt solution. Use this salt solution to impregnate 50 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 94 m 2 / g. It was dried in an oven at 110 °C for 6 h, calcined in a muffle furnace at 500 °C for 4 h in an air atmosphere, and then naturally cooled to obtain an intermediate catalyst.

[0096] Weigh 0.8199 g of ruthenium chloride solid, add deionized water to prepare 20 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst H.

[0097] S2: Activation of catalyst Catalyst H was subsequently activated in a tube furnace under the following activation conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 °C, and activation time 3 h. After natural cooling, it was passivated in air at room temperature for 2 h with an air flow rate of 150 mL / min. After passivation, a bimetallic catalyst was obtained, which was numbered as catalyst H-LR.

[0098] S3: Ethyleneamine synthesis 50 mL of catalyst H-LR was loaded into the reactor and purged with nitrogen for 0.5 h before starting the hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 17 MPa, temperature 190 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0099] Example 19A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those of the catalyst H-LR in Example 18A. The hydroamination reaction conditions were changed on the basis of the synthesis of ethyleneamine in the above Example 16A to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 15 MPa, temperature 190°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0100] Example 20A Ethyleneamine synthesis The catalyst was Catalyst D in Example 7A, and neither ex situ activation nor in situ activation was performed.

[0101] 50 mL of catalyst D was loaded into the reactor. After nitrogen purging for 0.5 h, the feed was started to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 205 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0102] Comparative Example 1A The catalyst was Catalyst G in Example 15A.

[0103] S2: High temperature activation of catalyst Catalyst G was activated at high temperature in a tube furnace under the following activation conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 °C, maintained for 3 h, then heated to 450 °C and maintained for 4 h. After natural cooling, it was passivated in room temperature air for 3 h with an air flow rate of 150 mL / min. After passivation, a bimetallic catalyst was obtained, which was numbered as catalyst G-HR.

[0104] S3: Ethyleneamine synthesis 50 mL of catalyst G-HR was loaded into the reactor and purged with nitrogen for 0.5 h before starting the feed for hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0105] Comparative Example 2A S1: Preparation of catalyst (10wt%Ni / 0.5wt%Ru / Al2O3) Weigh 44.0967 g of nickel nitrate and add deionized water to prepare 52 mL of salt solution. Use this salt solution to impregnate 80 g of Al2O3 carrier. The specific surface area of ​​Al2O3 carrier is 94 m 2 / g. Dry in an oven at 110 °C for 6 h, calcine in a muffle furnace at 500 °C for 4 h in an air atmosphere, and after natural cooling, further perform high-temperature reduction activation in a tube furnace. The activation conditions are: H2 atmosphere, H2 flow rate 100 mL / min, temperature 450 °C, and activation time 4 h. After natural cooling, passivate in air at room temperature for 3 h, with an air flow rate of 150 mL / min, to obtain an intermediate catalyst.

[0106] Weigh 0.5394 g of ruthenium chloride solid, add deionized water to prepare 26 mL of ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then cool naturally to obtain a bimetallic catalyst, numbered as catalyst I.

[0107] S2: Activation of catalyst The activation of the catalyst was carried out after the first metal impregnation in the preparation process, and no further activation was carried out after the second metal impregnation.

[0108] S3: Ethyleneamine synthesis 50 mL of catalyst I was loaded into the reactor and purged with nitrogen for 0.5 h before starting the feed for hydroamination reaction to synthesize ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=4:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0109] Comparative Example 3A Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Comparative Example 2A. On the basis of the synthesis of ethyleneamine in Comparative Example 2A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 205 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA:H2=6:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0110] In order to further illustrate the technical effect of the present invention of applying the catalyst activated by hydrogen at low temperature or not activated to ethyleneamine synthesis, the catalytic activity and product selectivity of the catalysts in the above embodiments and comparative examples in the hydroamination reaction to synthesize ethyleneamine will be tested and analyzed below.

[0111] 1. Catalyst effect evaluation The catalyst effects of the catalysts of Examples 1A-20A and Comparative Examples 1A-3A were evaluated, and the results of the MEA conversion rate and product selectivity are summarized in Table 1.

[0112] The MEA conversion, ethylenediamine (EDA) selectivity, diethylenetriamine (DETA) selectivity, hydroxyethylethylenediamine (AEEA) selectivity and piperazine (PIP) selectivity in Table 1 are defined as follows:

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] Table 1. Catalyst evaluation results of Examples 1A-20A and Comparative Examples 1A-3A

[0119] As can be seen from Table 1, in Examples 1A-20A of the present invention, the products of ethyleneamine generated by the hydroamination of monoethanolamine are mainly chain products such as ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine, wherein when the single-pass conversion rate of ethanolamine is 45-60 wt%, the combined selectivity of ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine is greater than 80 wt%.

[0120] 2. Temperature Programmed Reduction (TPR) Analysis The reduction properties of the catalysts before and after use were analyzed by the Temperature Programmed Reduction (TPR) method using the AUTOCHEM II 2920 from Micromeritics.

[0121] Specific operation: Weigh 50-60 mg of sample and place it in a U-shaped quartz tube. After purging with He gas flow (50 mL / min) for 0.5h, heat it from room temperature to 150 ℃ at 10℃ / min for drying pretreatment for 1h. Then stop heating and cool it to 50 ℃. After stabilizing at 50℃ for 0.5h, pass 10% H2 / Ar mixed gas (50 mL / min) and purge for 0.5h. After the baseline is stable, the sample is heated to the set high temperature, such as 800℃ or 600℃, at a heating rate of 10℃ / min in 10% H2 / Ar gas flow. The thermal conductivity detector (TCD) collects the signal.

[0122] Before and after catalyzing the reaction of producing ethyleneamine by hydroamination of monoethanolamine, the catalysts of Example 15A, Example 20A and Comparative Example 1A were subjected to temperature programmed reduction (TPR) analysis. The TPR curves of the catalysts of Example 15A, Example 20A and Comparative Example 1A before the reaction were as follows: Figure 1 , Figure 2 and Figure 3 As shown, the TPR curves of the catalysts after the reaction are as follows Figure 4 , Figure 5 and Figure 6 shown.

[0123] Depend on Figure 1 , Figure 2 and Figure 3 It can be seen that the TPR curves of the unused new catalyst after high-temperature hydrogen reduction activation, the unused new catalyst after low-temperature hydrogen activation, and the unused new catalyst without hydrogen activation are completely different.

[0124] Depend on Figure 4 , Figure 5 and Figure 6It can be seen that the used catalyst activated by high-temperature hydrogen reduction, the used catalyst activated by low-temperature hydrogen, and the used catalyst not activated by hydrogen show similar TPR curves, which proves that they ultimately have similar activities.

[0125] In order to verify that the use of low ammonia ratio monoethanolamine and liquid ammonia as reaction raw materials in the ethyleneamine synthesis reaction of the present invention can obtain a reactant conversion rate and product selectivity comparable to those under high ammonia ratio conditions, the following examples will carry out ethyleneamine synthesis under low ammonia ratio conditions.

[0126] Example 1B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 1A. Based on the synthesis of ethyleneamine in Example 1A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0127] Example 2B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 1A. Based on the synthesis of ethyleneamine in Example 1B, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 210°C, monoethanolamine liquid volume space velocity 1.8 h -1 , NH3:MEA:H2=2.5:1:0.05 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0128] Example 3B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 3A. Based on the synthesis of ethyleneamine in Example 3A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0129] Example 4B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 3A. Based on the synthesis of ethyleneamine in Example 3B, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 210°C, monoethanolamine liquid volume space velocity 1.8 h -1 , NH3:MEA:H2=2.5:1:0.05 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0130] Example 5B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 6A. Based on the synthesis of ethyleneamine in Example 6A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 220°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0131] Example 6B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 7A. Based on the synthesis of ethyleneamine in Example 7A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 195°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0132] Example 7B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 9A. Based on the synthesis of ethyleneamine in Example 9A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 190°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0133] Example 8B Ethyleneamine synthesis The catalyst and the inactivated direct application of the catalyst are the same as those in Example 20A. Based on the synthesis of ethyleneamine in Example 20A, the hydroamination reaction conditions are changed to continue the synthesis of ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 205°C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0134] Example 9B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those of the catalyst G-LR in Example 15A. The hydroamination reaction conditions were changed on the basis of the synthesis of ethyleneamine in Example 15A to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0135] Example 10B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 16A. Based on the synthesis of ethyleneamine in Example 16A, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0136] Example 11B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those in Example 10B. Based on the synthesis of ethyleneamine in Example 10B, the hydroamination reaction conditions were changed to continue the synthesis of ethyleneamine. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=3:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0137] Comparative Example 1B Ethyleneamine synthesis The catalyst and the activation method of the catalyst were the same as those of the catalyst G-HR in Comparative Example 1A. The hydroamination reaction conditions were changed on the basis of the ethyleneamine synthesis in Comparative Example 1A to continue the ethyleneamine synthesis. The reaction conditions were: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0138] Table 2. Catalyst evaluation results of Examples 1B-11B and Comparative Examples 1B-2B

[0139] Comparative Example 2B Ethyleneamine synthesis The catalyst and catalyst activation method are the same as those in Comparative Example 2A. On the basis of the synthesis of ethyleneamine in Comparative Example 2A, the hydroamination reaction conditions are changed to continue the synthesis of ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 °C, monoethanolamine liquid volume space velocity 1 h -1 , NH3:MEA: H2=2.5:1:0.1 (molar ratio), and samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0140] The effects of the catalysts in the above Examples 1B-11B and Comparative Examples 1B-2B were evaluated, and the results of the reactant MEA conversion rate and product selectivity are summarized in Table 2.

[0141] It can be seen from Table 2 that in Examples 1B-11B, although the molar ratio of NH3: MEA is reduced to less than 4 and the molar ratio of NH3: MEA is 2-3, the conversion rate of monoethanolamine and the selectivity of the product are comparable to the results of high ammonia ratio. Specifically, the products of ethyleneamine produced by the hydroamination of monoethanolamine are mainly chain products such as ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine. When the single-pass conversion rate of ethanolamine is 45-60wt%, the combined selectivity of ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine is greater than 80wt%.

[0142] It should be noted that, in this article, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the term "includes" do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0143] The above embodiments are only used to illustrate the technical solutions of the present invention and cannot be used to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, ordinary technicians in this field should understand that: without departing from the essence and scope of the present invention, the technical solutions recorded in the aforementioned embodiments can still be modified, or some of the technical features therein can be replaced by equivalents; and these modifications or equivalent replacements still fall within the scope covered by the present invention.

Claims

1. Application of a bimetallic catalyst in ethyleneamine synthesis, wherein the ethyleneamine synthesis is carried out using monoethanolamine and liquid ammonia as raw materials under hydrogenation conditions and the action of the bimetallic catalyst, wherein the bimetallic catalyst is activated by low-temperature reduction or is not activated, and the temperature range of the low-temperature reduction activation is 110-220°C.

2. The use according to claim 1, wherein: The temperature range of the low-temperature reduction activation is 130-210°C.

3. The use according to claim 1 or 2, wherein: The low-temperature reduction activation is carried out in the reactor for ethyleneamine synthesis or outside the reactor.

4. The use according to claim 3, wherein: The low-temperature reduction activation is carried out outside the reactor for synthesizing ethyleneamine, and is carried out in an atmosphere of H2 or a mixed atmosphere of H2 and an inert gas. After the low-temperature reduction activation is completed, the catalyst is cooled to room temperature and passivated in the air.

5. The use according to claim 1, wherein: The bimetallic catalyst comprises a carrier, an active component and an additive. The carrier comprises Al2O3 and / or SiO2 and has a specific surface area of ​​50 to 300 m 2 / g; the active component includes Ni, and the metal content of the active component accounts for 5~30wt% of the mass of the catalyst; the auxiliary agent includes Ru and / or Re, and the metal content of the auxiliary agent accounts for 0.2~1wt% of the mass of the catalyst.

6. A method for synthesizing ethyleneamine, wherein the method uses monoethanolamine and liquid ammonia as raw materials, is carried out under hydrogen conditions and the action of a bimetallic catalyst, and is characterized in that: The bimetallic catalyst is used after low-temperature reduction activation or without activation, and the temperature range of the low-temperature reduction activation is 110-220°C.

7. The synthesis method according to claim 6, wherein The temperature range of the low-temperature reduction activation is 130-210°C.

8. The synthesis method according to claim 6 or 7, wherein The low-temperature reduction activation is carried out in the reactor for ethyleneamine synthesis or outside the reactor.

9. The synthesis method according to claim 8, wherein The low-temperature reduction activation is carried out outside the reactor for synthesizing ethyleneamine, and is carried out in an atmosphere of H2 or a mixed atmosphere of H2 and an inert gas. After the low-temperature reduction activation is completed, the catalyst is cooled to room temperature and passivated in the air.

10. The synthesis method according to claim 8, wherein The low-temperature reduction activation is carried out in a reactor for synthesizing ethyleneamine, and the catalyst is subjected to low-temperature reduction activation in an atmosphere of H2 or a mixed atmosphere of H2 and inert gas or in an atmosphere of H2 and liquid ammonia.

11. The synthesis method according to claim 6, wherein The synthesis reaction temperature of ethyleneamine is 160~280℃, the reaction pressure is 12~30 MPa, and the molar ratio of ammonia:monoethanolamine is 2~10:

1.

12. The synthesis method according to claim 6, wherein The molar ratio of ammonia:monoethanolamine is less than 4:

1.

13. The synthesis method according to claim 12, wherein The molar ratio of ammonia:monoethanolamine is 2~3:

1.

14. The synthesis method according to claim 6, wherein The bimetallic catalyst comprises a carrier, an active component and an additive. The carrier comprises Al2O3 and / or SiO2 and has a specific surface area of ​​50 to 300 m 2 / g; the active component includes Ni, and the metal content of the active component accounts for 5~30wt% of the mass of the catalyst; the auxiliary agent includes Ru and / or Re, and the metal content of the auxiliary agent accounts for 0.2~1wt% of the mass of the catalyst.

15. The synthesis method according to claim 6, wherein The conversion rate of monoethanolamine is 45-60%. Among the synthetic products, the selectivity of ethylenediamine, diethylenetriamine and hydroxyethylethylenediamine is greater than 80% in total.

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