Application of bimetallic catalyst in synthesis of ethyleneamines and method for synthesis of ethyleneamines

Abstract

The application discloses application of a bimetallic catalyst in synthesis of ethylene amine and a synthesis method of the ethylene amine, and belongs to the technical field of synthesizing ethylene amine by an ethanol amine method. The synthesis of the ethylene amine takes monoethanolamine and liquid ammonia as raw materials, is carried out under hydrogen condition and under the action of the bimetallic catalyst, and the bimetallic catalyst is activated by low-temperature reduction or is not activated by reduction, and the temperature range of the low-temperature reduction activation is 110-220 DEG C. The synthesis method of the ethylene amine adopts the bimetallic catalyst activated by low-temperature reduction or not activated by reduction, and can obtain the catalytic activity and product selectivity equivalent to those of the bimetallic catalyst activated by high-temperature reduction in a conventional way, so that the overall economy and safety of production of the monoethanolamine hydrogenation to generate the ethylene amine are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the synthesis of ethylene amines by ethanolamine method, in particular to the application of bimetallic catalysts with or without reduction activation at low temperature in the synthesis of ethylene amines and the synthesis method of ethylene amines. BACKGROUND

[0002] Ethylene amine products refer to the chain polymers of ethylenediamine and cyclic piperazine amines and derivative products, mainly including ethylenediamine (EDA), diethylenetriamine (DETA), triethylenediamine (TEDA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), hydroxyethyl ethylenediamine (AEEA), and also including cyclic derivatives such as piperazine (PIP), hydroxyethyl piperazine (HEP) and aminoethyl piperazine (AEP) and the like. Ethylene amine series products are a kind of chemical with wide application, which has unique application in many aspects. For example, in the aspect of epoxy resin curing agent, epoxy resin is essential in the production of coatings, adhesives and composites, and ethylene amine as an epoxy resin curing agent helps to harden the epoxy resin, providing mechanical strength and chemical resistance. In the aspect of chelating agents, ethylene amines act as chelating agents in various industrial processes, which form stable complexes with metal ions, and these complexes are crucial in water treatment, pulp and paper processing and agriculture. In the aspect of agricultural chemicals, ethylene amines are often used to produce agricultural chemicals such as herbicides, fungicides and insecticides, which can improve the efficacy and stability of agricultural products. In the aspect of rubber chemicals, ethylene amines are used to produce rubber accelerators and processing aids, which can enhance the performance of rubber products. In addition, ethylene amines are also key ingredients in the production of polyamide resins, which can be used in the production of coatings, adhesives and molded plastics. These applications highlight the importance of ethylene amines in various industries.

[0003] Currently, the main methods for synthesizing ethylene amine products in industry are dichloroethane method and ethanolamine method. Among them, the ethanolamine method is that monoethanolamine (MEA) and ammonia (NH3) are hydrogenated to form ethylene amines under the action of a catalyst. MEA is a relatively cheap and easily available raw material, which provides an economic way in process investment, and can be flexibly expanded or reduced in scale according to production needs, which is very advantageous to producers who adjust production according to market demand. This method has the advantages of low process investment, small environmental pollution and low energy consumption, and is an attractive choice in industrial applications, and has gradually become the mainstream method.

[0004] In the ethanolamine method, the reaction intermediates of the amination process are also reactive, so it is inevitable to further react to generate more cyclic amine byproducts. However, the market demand for chain amines is higher than that for cyclic amines, and is expanding, so how to ensure high conversion of monoethanolamine while maintaining high selectivity of chain amines is a difficult problem in the industry. Developing catalysts with high conversion and high selectivity of chain amines is an important direction for the industry to solve this problem. The preparation of such catalysts usually involves strict selection of raw materials and precise process control.

[0005] For metal catalysts commonly used in the ethanolamine method, in order to improve the catalytic activity and meet the selectivity requirements of the reaction products, the catalyst is subjected to high-temperature reduction activation before being used for synthesis reaction, and the reduction activation temperature is as high as 300-550°C, 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 of MEA and the selectivity of the product, that is, to increase the ratio of NH3:MEA; but the disadvantages of high ammonia ratio are also very obvious, a large amount of unreacted liquid ammonia needs to be separated from the product by flashing, and then recycled to the reaction inlet by compression, and the process consumes more energy and energy.

[0006] The following will list several documents that embody the common practice of high-temperature reduction activation of catalysts and synthesis of ethyleneamine with high ammonia ratio:

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

[0008] Patent document CN101875014B discloses a catalyst for preparing ethylenediamine, the main active component of the catalyst is Ni or Co, the auxiliary agent is one or several of Re, Fe, Cu, Ru and B, etc. metal or oxide, the carrier is selected from AI2O3 or SiO2, etc., and the preparation method is one or several of precipitation method, impregnation method and hydrothermal synthesis method. The catalyst is reduced in hydrogen at 375 ℃ under normal pressure for 5 h before use, the reaction is carried out under relatively mild conditions, wherein the reaction temperature is 135-155 ℃, the hydrogen pressure is 6.5-8 MPa, the ratio of NH3:MEA is 10:1, and the EDA selectivity can reach more than 50% in the patent examples, but the conversion rate of MEA is relatively low, about 35%.

[0009] Patent document CN108067289A discloses a catalyst for producing ethylenediamine and piperazine under hydrogen condition and application thereof. The main active component of the catalyst is Ni, Co and Cu, the auxiliary agent is one or several of Fe, Cr, Re, Ru, B, Mg, etc. metal or oxide, and the catalyst carrier is molecular sieve HZSM-5, H-beta, H-MOR or HY, etc. The patent can obtain ethylenediamine or piperazine with high selectivity by changing different molecular sieves as carriers. In the examples of the invention, the catalyst needs to be activated before use, and the preferred condition is hydrogen reduction at 400 ℃, and the ratio of NH3:MEA in the reaction process is 10:1.

[0010] Patent document CN105457673B discloses an amination catalyst, the catalyst carrier is a material obtained by desiliconizing mordenite with NaOH, and the carrier is further modified by impregnating with metal ion and non-metal ion, the active center is Cr 3+ or Mn 2+ , the auxiliary agent is BO3 2- or F - , and contains anatase TiO2. The amination catalyst is suitable for the synthesis of ethylenediamine by the gas phase condensation amination reaction of ethanolamine and ammonia. The required reaction temperature in the patent document is 330 ℃, 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 composition catalyst for amination reaction, nickel and rhenium are supported on an alumina-silica support, which contains about 5 to about 65 wt% of silica and has a BET surface area of about 30 to about 450 square meters per gram. The patent finds that the selectivity of EDA can be improved by adding active component boron in the catalyst, and relatively less PIP and higher polyamines are obtained. The catalyst is reduced in hydrogen at 375 ℃ for 3 h before use, the ratio of NH3:MEA in the reaction is 10~12:1, and the selectivity of EDA can be more than 70%, but there is still the phenomenon of low MEA conversion rate.

[0012] Patent document US5750790 discloses a reduced amination catalyst, which uses transition phase alumina to support Ni and Re. By using a carrier selected from transition alumina, including transition alumina such as δ and θ alumina and mixed phase carrier materials such as γ-θ, δ-θ or θ-α alumina, the selectivity of non-cyclic 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. The reduction temperature of the catalyst used in the patent is 340 ℃, 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, and the second metal is ruthenium. A halogen-containing compound is added at any step in the process of impregnating the catalyst to prepare the active component on the oxide carrier. 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 enough temperature to reduce the corresponding compound to metal. The invention finds that the advantageous properties of this catalyst appear to be related to the presence of halogen therein, and higher yields of the desired primary amines and polyamines are obtained, and the formation of unwanted by-products is greatly reduced. The reduction temperature of the catalyst used is 400 ℃, the reaction is carried out in an autoclave, the ratio of NH3:MEA is 9.3:1, the MEA conversion rate of the modified catalyst is more than 50%, and the EDA selectivity is more than 60%.

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

[0015] From the above listed prior art documents, although the improvement methods of catalysts are different, these catalysts need to be reduced and activated by hydrogen at high temperature of 300-500℃ during preparation or before use, and in the reaction of catalytic production of ethylene amine from monoethanolamine and ammonia under hydrogen, NH3:MEA is 4-20:1, mostly above 10:1, to achieve the desired catalyst activity and product selectivity. In the synthesis of ethylene amine by hydrogenation of ethanolamine, high-temperature reduction and activation of the catalyst and high ammonia ratio of the raw materials have become a routine operation in the industry.

[0016] High-temperature hydrogen reduction of metal catalysts before use is a common activation method for catalysts, which aims to convert high-valence metals in metal compounds or metal oxides into low-valence metals, so as to better play a catalytic role in the reaction. However, the implementation of the high-temperature hydrogen reduction step requires high equipment, high energy consumption, long production cycle, and strict safety control. It is of great value to ensure efficient catalytic reaction production, achieve high activity and selectivity, improve target product yield, reduce byproduct formation, simplify catalyst manufacturing methods, adopt safer application methods, and improve the overall economy and safety of catalyst production and hydrogenation of monoethanolamine to produce ethylene amine.

[0017] High ammonia ratio of reaction raw materials can promote the proportion of chain ethylene amine product, increase the proportion of target product, and reduce the formation of byproducts, but a large amount of unreacted ammonia needs to be separated from the product by flashing, compressed and recycled to the reactor inlet for reuse, which causes the disadvantages of large catalytic unit reactor, high investment of reactant circulation pipeline, and high energy consumption of reactant circulation in production. Therefore, it is of great industry value to develop high-performance catalysts to reduce the ammonia ratio in the reaction while ensuring target conversion rate and target selectivity, thereby improving the economy of hydrogenation of monoethanolamine to produce ethylene amine. SUMMARY

[0018] In view of the above problems in the prior art, the inventors of the present application have found that, in the reaction of hydrogenation of ethanolamine to synthesize ethylene amine, low-temperature reduction and activation of the catalyst in the reactor or outside the reactor or without reduction and activation can achieve excellent catalytic activity and product selectivity, which is comparable to the performance of catalysts prepared by high-temperature reduction and activation under the same conditions. The inventors of the present application have further found that, in the reaction of hydrogenation of ethanolamine to synthesize ethylene amine, low ammonia ratio raw materials can also achieve reaction conversion rate and product selectivity comparable to high ammonia ratio when using catalysts reduced and activated at low temperature or without reduction and activation.

[0019] In the first aspect of the present application, the application of a bimetallic catalyst in the synthesis of ethylene amines is provided, wherein the synthesis of ethylene amines is carried out under hydrogenation conditions and in the presence of the bimetallic catalyst, and the bimetallic catalyst is activated by low-temperature reduction or is not activated by reduction, and the temperature range of the low-temperature reduction is 110-220 ℃.

[0020] In some embodiments of the present application, the temperature range of the low-temperature reduction is 130-210 ℃.

[0021] In some embodiments of the present application, the low-temperature reduction is carried out in the reactor for the synthesis of ethylene amines or outside the reactor.

[0022] In some embodiments of the present application, the low-temperature reduction is carried out outside the reactor for the synthesis of ethylene amines, and is carried out in the atmosphere of H2 or a mixture of H2 and inert gas, and after the completion of the low-temperature reduction, the catalyst is cooled to room temperature and is passivated in air. When the low-temperature reduction is carried out in the atmosphere of hydrogen, the standard volume space velocity of hydrogen is 10-500 h -1 , and the pressure is greater than 0.1 MPa.

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

[0024] In the second aspect of the present application, a method for the synthesis of ethylene amines is provided, wherein the synthesis of ethylene amines is carried out under hydrogenation conditions and in the presence of a bimetallic catalyst, and the bimetallic catalyst is activated by low-temperature reduction or is not activated by reduction, and the temperature range of the low-temperature reduction is 110-220 ℃.

[0025] In some embodiments of the second aspect of the present application, the temperature range of the low-temperature reduction is 130-210 ℃.

[0026] In some embodiments of the second aspect of the present application, the low-temperature reduction is carried out in the reactor for the synthesis of ethylene amines or outside the reactor.

[0027] In some embodiments of the second aspect of the present application, the low-temperature reduction activation is performed outside the reactor for synthesizing ethylene amine, and is performed in H2 or a mixed gas atmosphere of H2 and inert gas. After the low-temperature reduction activation is completed, the catalyst is cooled to room temperature and passivated in air.

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

[0029] In some embodiments of the second aspect of the present application, the reaction temperature for synthesizing ethylene amine is 160-280℃, the reaction pressure is 15-30 MPa, and the molar ratio of ammonia to monoethanolamine is 2-10:1.

[0030] In some embodiments of the second aspect of the present application, the molar ratio of ammonia to monoethanolamine in the raw material for synthesizing ethylene amine is less than 4:1; in specific embodiments of the present application, the molar ratio of ammonia to monoethanolamine is 2-3:1.

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

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

[0033] The present application has the following beneficial technical effects relative to the prior art:

[0034] ​The application applies the low-temperature reduction activated or non-reduction activated bimetallic catalyst to the single ethanol amine hydrogenation synthesis of ethylene amine, which can obtain similar excellent performance as the high-temperature reduction activated bimetallic catalyst catalyzing the single ethanol amine hydrogenation synthesis of ethylene amine, and the catalytic activity and product selectivity distribution of the two are equivalent, so that the application avoids the hydrogen high-temperature reduction of the catalyst, avoids the shortcomings of high equipment requirement, high investment, high energy consumption of high-temperature reduction process, long production cycle, safety hazards of hydrogen high-temperature leakage and the like in the high-temperature hydrogen reduction step, thereby reducing the energy consumption of the production process, shortening the production cycle, and improving the overall economy and safety of the single ethanol amine hydrogenation synthesis of ethylene amine production.

[0035] In addition, in the ethylene amine synthesis method of the application, the low ammonia ratio raw material can also obtain similar reaction conversion rate and product selectivity distribution as the high ammonia ratio raw material by using the low-temperature reduction activated or non-reduction activated bimetallic catalyst, which reduces the ammonia ratio in the reaction while ensuring the target conversion rate and target selectivity, avoids the increase of material consumption and energy consumption caused by a large amount of unreacted ammonia needing to be separated and recycled under the condition of high ammonia ratio, thereby improving the economy of the single ethanol amine hydrogenation synthesis of ethylene amine production, and having important industrial value. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 TPR curve of the catalyst before reaction in Example 15A of the application.

[0037] Figure 2 TPR curve of the catalyst before reaction in Example 20A of the application.

[0038] Figure 3 TPR curve of the catalyst before reaction in Comparative Example 1A of the application.

[0039] Figure 4 TPR curve of the catalyst after reaction in Example 15A of the application.

[0040] Figure 5 TPR curve of the catalyst after reaction in Example 20A of the application.

[0041] Figure 6 TPR curve of the catalyst after reaction in Comparative Example 1A of the application. DETAILED DESCRIPTION

[0042] The various aspects of the application will be described in detail below with reference to specific embodiments and exemplary examples, which are only used to illustrate the application and do not limit the scope and substance of the application.

[0043] The catalyst for the hydrogenation of monoethanolamine to ethyleneamine is reduced and activated at low temperature, and then the amination reaction is carried out, so that excellent catalytic activity and product selectivity can be obtained, and the performance is equivalent to that of the catalyst activated at high temperature under the same conditions. The low-temperature reduction and activation is relative to the high-temperature (300-550 DEG C) reduction and activation in the prior art. In the present application, the low-temperature reduction and activation refers to an activation temperature lower than 220 DEG C. For example, the temperature range of the low-temperature reduction and activation in the present application is 110-220 DEG C, preferably 130-210 DEG C. In the exemplary embodiments of the present application, the low-temperature reduction and activation temperature is 180-200 DEG C.

[0044] The low-temperature reduction and activation of the catalyst in the present application can be carried out separately before the catalyst is applied to the reaction of monoethanolamine to ethyleneamine, i.e. outside the ethyleneamine synthesis reactor, for example in a tubular furnace. The reduction and activation atmosphere can be H2 or a mixed atmosphere of H2 and inert gas, for example under a 5 vol% H2 / N2 atmosphere. When the activation is carried out under a H2 atmosphere, the standard volume space velocity of H2 is 10-500 h -1 , preferably the standard volume space velocity of H2 is 50-400 h -1 , more preferably the standard volume space velocity of H2 is 100-300 h -1 ; the activation temperature is 110-220 DEG C, preferably the activation temperature is 130-210 DEG C; the pressure is greater than 0.1 MPa, and the activation time is greater than 2 h. In addition, the catalyst activated outside the reactor is cooled to room temperature and then passivated in air before use.

[0045] The low-temperature reduction and activation of the catalyst in the present application can also be carried out in the ethyleneamine synthesis reactor. In some exemplary embodiments of the present application, the catalyst is activated in situ in the reactor for the synthesis of ethyleneamine. The catalyst is reduced and activated at low temperature under a H2 or mixed atmosphere of H2 and inert gas or under a H2 and liquid ammonia atmosphere. When the low-temperature reduction and activation is carried out under a H2 and liquid ammonia atmosphere, the standard volume space velocity of H2 is 10-500 h -1 , preferably the standard volume space velocity of H2 is 50-400 h -1 , more preferably the standard volume space velocity of H2 is 100-300 h -1 ; the volume space velocity of liquid ammonia is 1-10 h -1 , preferably the volume space velocity of liquid ammonia is 1-5 h -1 ; the activation temperature is 110-220 DEG C, preferably the activation temperature is 130-210 DEG C; the pressure is 15-25 MPa, preferably the pressure is 16-24 MPa; and the activation time is greater than 2 h.

[0046] The catalyst of the present application can also be directly loaded into the reactor for synthesizing ethylene amine without reduction activation, dried and calcined, and then used after purging with inert gas and without oxygen.

[0047] The catalyst of the present application can be all metal catalysts known in the art for hydrogenation ammination of ethanol amine to generate ethylene amine. In the specific embodiments of the present application, a supported bimetallic catalyst is used, which includes a carrier, an active component and an auxiliary agent. The carrier is Al2O3 and SiO2 or a mixture of the two, with a specific surface area of 50-300 m 2 / g, preferably 70-250 m 2 / g; the active component is Ni, and the auxiliary agent is Ru and / or Re. The metal content of the active component accounts for 5-30 wt% of the mass of the catalyst, preferably 7-23 wt%; and the metal content of the auxiliary agent accounts for 0.2-1 wt% of the mass of the catalyst, preferably 0.3-0.9 wt%. The bimetallic catalyst utilizes the synergistic effect of different metals to improve the performance of the catalyst, and provides better activity, selectivity and stability for the reduction ammination process. In the exemplary embodiments of the present application, the supported bimetallic catalyst used includes 10 wt% Ni-0.5 wt% Ru / SiO2, 10 wt% Ni-0.5 wt% Ru / Al2O3, 10 wt% Ni-0.5 wt% Re / SiO2, 10 wt% Ni-0.7 wt% Ru / Al2O3 and 20 wt% Ni-0.6 wt% Ru / Al2O3. The catalyst of the present application can also use other metal catalysts known in the art for hydrogenation ammination of ethanol amine to generate ethylene amine.

[0048] The preparation of the supported catalyst of the present application uses impregnation or co-precipitation to support the active component and the auxiliary agent on the carrier, which can be carried out in one step or multiple steps. The main steps for preparing the catalyst by impregnation include: preparing a metal salt solution of the required concentration containing the active component and the auxiliary agent, impregnating the metal salt solution on the carrier or intermediate catalyst at a certain temperature, and then drying and calcining. The impregnation temperature is 20-100℃, preferably 30-80℃, and the impregnation time is 2-8 hours; the drying and calcining are carried out in air atmosphere, the drying temperature is 80-150℃, preferably 100-120℃, and the drying time is greater than 3 h; the calcination temperature is 400℃-550℃, preferably 450-500℃; and the calcination time is 3-8 h, preferably 4-6 h.

[0049] The catalyst reduced and activated at low temperature or the catalyst not reduced and activated in the application is used for synthesizing ethylene amine, and the reaction temperature is 150-280℃, preferably 160-250℃, the reaction pressure is 12-30 MPa, preferably 16-26 MPa, the volume space velocity of monoethanolamine is less than 3 h -1 , preferably the volume space velocity of ethanolamine is 1-2 h -1 .

[0050] In the ethylene amine synthesis method of the application, the molar ratio of ammonia to monoethanolamine can be the 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).

[0051] In addition, the inventors of the application further found that in the ethylene amine synthesis method of the application, the catalyst reduced and activated at low temperature or the catalyst not reduced and activated is used, and the ammonia ratio in the reaction raw material monoethanolamine and liquid ammonia can be lower than the high ammonia ratio required under the conventional high temperature reduction and activation condition, that is, the molar ratio of ammonia to monoethanolamine is less than 4, and in the exemplary embodiment of the application, the molar ratio of ammonia to monoethanolamine is (2-3):1. The molar ratio of ammonia to monoethanolamine to hydrogen is (2-3):1:(0.01-1).

[0052] The application is further described below by examples. The performance of the catalyst prepared in each example is evaluated by ammination reaction in a fixed bed reactor. The product sample analysis is analyzed by Agilent 8860 gas chromatograph, the chromatographic column is Shimadzu SH-PolarX capillary chromatographic column, the detector is FID detector, the internal standard method is quantitative analysis, and the internal standard is 3-diethylamino-1-propanamine. The catalytic effect evaluation of each example is summarized in Tables 1 and 2.

[0053] Example 1A

[0054] S1: Preparation of catalyst (10wt%Ni-0.5wt%Ru / SiO2)

[0055] 55.3070 g of nickel nitrate was weighed and dissolved in deionized water to prepare a 55 mL salt solution, and then the SiO2 carrier was impregnated with the salt solution, and the specific surface area of the SiO2 carrier was 141 m 2 / g. Drying in a 110℃ oven for 6 h, calcining at 500℃ in a muffle furnace under air atmosphere for 4 h, and then naturally cooling to obtain an intermediate catalyst.

[0056] Take 1.3052 g of ruthenium chloride solid, add deionized water to prepare a 55 mL ruthenium chloride aqueous solution, and immerse the intermediate catalyst in the solution. Dry in an oven at 110 ℃ for 6 h, and then naturally cool to obtain the bimetallic catalyst, numbered as catalyst A.

[0057] S2: Activation of the catalyst

[0058] Activation of catalyst A in a hydrogen and liquid ammonia atmosphere in the reactor: take 50 mL of catalyst A and load it into the reactor, and after purging with nitrogen for 0.5 h, activate under the following conditions: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200 ℃, pressure 20 MPa, activation time 3 h.

[0059] S3: Ethylene amine synthesis

[0060] After the activation of catalyst A in the reactor is completed, start feeding to perform the hydrogenation amination reaction to synthesize ethylene amine. The reaction conditions are as follows: pressure 20 MPa, temperature 200 ℃, and monoethanolamine liquid volume space velocity 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), and sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0061] Example 2A

[0062] Ethylene amine synthesis

[0063] The catalyst and the catalyst activation method are the same as in Example 1A. On the basis of the ethylene amine synthesis in the above Example 1A, change the hydrogenation amination reaction conditions to continue the ethylene amine synthesis. The reaction conditions are as follows: pressure 20 MPa, temperature 210 ℃, and monoethanolamine liquid volume space velocity 1 h -1 , NH3: MEA: H2= 6: 1: 0.1 (molar ratio), and sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0064] Example 3A

[0065] S1: Preparation of the catalyst (10wt% Ni-0.5wt% Ru / Al2O3)

[0066] Take 55.3189 g of nickel nitrate, add deionized water to prepare a 55 mL salt solution, and immerse 100 g of Al2O3 support in the salt solution. The specific surface area of the Al2O3 support is 212 m 2 / g. Dry in an oven at 110 ℃ for 6 h, and then calcine in a muffle furnace under an air atmosphere at 500 ℃ for 4 h, and then naturally cool to obtain the intermediate catalyst.

[0067] Weigh 1.3423 g of ruthenium chloride solid and add deionized water to prepare a 55 mL ruthenium chloride aqueous solution. Use this solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then allow to cool naturally to obtain the bimetallic catalyst, designated as catalyst B.

[0068] S2: Catalyst activation

[0069] Catalyst B was activated in the reactor under a hydrogen and liquid ammonia atmosphere: 50 mL of catalyst B was packed into the reactor, and activation was carried out after purging with nitrogen for 0.5 h. Activation conditions: hydrogen space velocity 67.2 h⁻¹. -1 The liquid ammonia space velocity is 2.4 h⁻¹. -1 Temperature 200℃, pressure 20 MPa, activation time 3 h.

[0070] S3: Ethyleneamine Synthesis

[0071] After catalyst B is activated in the reactor, the feed begins to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 200 ℃, and liquid hourly space velocity (LHSV) of monoethanolamine is 1 h⁻¹. -1 The reaction mixture was NH3:MEA:H2 = 4:1:0.1 (molar ratio). Samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0072] Example 4A

[0073] Ethyleneamine Synthesis

[0074] The catalyst and its activation method are the same as in Example 3A. Based on the ethyleneamine synthesis in Example 3A, the hydroamination reaction conditions are changed to continue the ethyleneamine synthesis. The reaction conditions are: pressure 20 MPa, temperature 210 °C, and monoethanolamine liquid hourly space velocity of 1 h⁻¹. -1 The reaction mixture was NH3:MEA:H2 = 6:1:0.1 (molar ratio). Samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0075] Example 5A

[0076] Ethyleneamine Synthesis

[0077] The catalyst and its activation method were the same as in Example 3A. Based on the ethyleneamine synthesis in Example 4A, the hydroamination reaction conditions were modified to continue the ethyleneamine synthesis. The reaction conditions were: pressure 20 MPa, temperature 210 °C, and monoethanolamine liquid hourly space velocity (LHSV) of 1.8 h⁻¹. -1 The molar ratio of NH3:MEA:H2 was 4:1:0.05. After reacting for 2 hours, samples were taken for gas phase analysis. The reaction results are summarized in Table 1.

[0078] Example 6A

[0079] S1: Preparation of catalyst (10wt% Ni-0.5wt% Re / SiO2)

[0080] Take 27.6859 g of nickel nitrate and 0.3633 g of ammonium perrhenate, add deionized water to prepare a 48 mL salt solution, and use the salt solution to impregnate 50 g of SiO2 carrier with a specific surface area of 102 m 2 / g. Dry in an oven at 110 ℃ for 6 h, calcine in a muffle furnace under air atmosphere at 500 ℃ for 4 h, and then naturally cool to obtain a bimetallic catalyst, numbered as catalyst C.

[0081] S2: Activation of catalyst

[0082] Catalyst C was activated in a reactor under hydrogen and liquid ammonia atmosphere: 50 mL of catalyst C was loaded into the reactor, and after nitrogen blowing for 0.5 h, activation was carried out under the following conditions: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200 ℃, pressure 20 MPa, and activation time 3 h.

[0083] S3: Synthesis of ethylene amine

[0084] After the activation of catalyst C in the reactor was completed, the feeding was started, and the reaction of hydrogenation ammination was carried out to synthesize ethylene amine under the following conditions: pressure 20 MPa, temperature 220 ℃, and monoethanolamine liquid volume space velocity 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), and gas phase analysis was carried out after sampling after 2 h of reaction. The reaction results are summarized in Table 1.

[0085] Example 7A

[0086] S1: Preparation of catalyst (10wt% Ni-0.7wt% Ru / Al2O3)

[0087] Take 55.3026 g of nickel nitrate, add deionized water to prepare a 55 mL salt solution, and use the salt solution to impregnate 100 g of Al2O3 carrier with a specific surface area of 94 m 2 / g. Dry in an oven at 110 ℃ for 6 h, calcine in a muffle furnace under air atmosphere at 500 ℃ for 4 h, and then naturally cool to obtain an intermediate catalyst.

[0088] Weigh 1.8550 g of ruthenium chloride solid and add deionized water to prepare a 55 mL ruthenium chloride aqueous solution. Use this solution to impregnate the intermediate catalyst. Dry in an oven at 110 °C for 6 h, then allow to cool naturally to obtain the bimetallic catalyst, designated as catalyst D.

[0089] S2: Catalyst activation

[0090] Catalyst D was activated in the reactor under a hydrogen and liquid ammonia atmosphere: 50 mL of catalyst D was packed into the reactor, and activation was carried out after purging with nitrogen for 0.5 h. Activation conditions: hydrogen space velocity 67.2 h⁻¹. -1 The liquid ammonia space velocity is 2.4 h⁻¹. -1 Temperature 200℃, pressure 20 MPa, activation time 3 h.

[0091] S3: Ethyleneamine Synthesis

[0092] After catalyst D is activated in the reactor, the feed begins to carry out the hydroamination reaction to synthesize ethyleneamine. The reaction conditions are: pressure 20 MPa, temperature 205 °C, and liquid hourly space velocity (LHSV) of monoethanolamine is 1 h⁻¹. -1 The reaction mixture was NH3:MEA:H2 = 4:1:0.16 (molar ratio). Samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0093] Example 8A

[0094] Ethyleneamine Synthesis

[0095] The catalyst and its activation method are the same as in Example 7A. Based on the ethyleneamine synthesis in Example 7A, the hydroamination reaction conditions are changed to continue the ethyleneamine synthesis. The reaction conditions are: pressure 17 MPa, temperature 205 °C, and monoethanolamine liquid hourly space velocity of 1 h⁻¹. -1 The reaction mixture was NH3:MEA:H2 = 4:1:0.1 (molar ratio). Samples were taken for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0096] Example 9A

[0097] The catalyst is catalyst D from Example 7A.

[0098] S2: Catalyst activation

[0099] The catalyst was activated in an external tubular furnace under the following conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 ℃, and activation time 3 h. After natural cooling, it was passivated in ambient air for 2 h at an air flow rate of 150 mL / min. The resulting bimetallic catalyst was designated as catalyst D-LR.

[0100] S3: Ethylene amine synthesis

[0101] Take 50 mL of catalyst D-LR loaded in the reactor, nitrogen purging for 0.5 h, then start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4:1:0.1 (molar ratio), sample after reaction for 2 h for gas phase analysis. The reaction results are summarized in Table 1.

[0102] Example 10A

[0103] S1: Preparation of catalyst (10wt% Ni-0.7wt% Ru / Al2O3)

[0104] Take 55.3142 g of nickel nitrate, add deionized water to prepare a 55 mL salt solution, and use the salt solution to impregnate 100 g of Al2O3 carrier. The specific surface area of the Al2O3 carrier is 212 m 2 / g. Dry in a 110 ℃ oven for 6 h, calcine in a muffle furnace under air atmosphere at 500 ℃ for 4 h, and then naturally cool to obtain an intermediate catalyst.

[0105] Take 1.8493 g of ruthenium chloride solid, add deionized water to prepare a 55 mL ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in a 110 ℃ oven for 6 h, and then naturally cool to obtain a bimetallic catalyst, numbered as catalyst E.

[0106] S2: Activation of catalyst

[0107] Catalyst E is activated in a reactor under hydrogen and liquid ammonia atmosphere: take 50 mL of catalyst E and load it into the reactor, and then activate after purging with nitrogen for 0.5 h. Activation conditions: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200 ℃, pressure 20 MPa, activation time 3 h.

[0108] S3: Ethylene amine synthesis

[0109] After the activation of catalyst E in the reactor is completed, start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4:1:0.16 (molar ratio), sample after reaction for 2 h for gas phase analysis. The reaction results are summarized in Table 1.

[0110] Example 11A

[0111] Ethylene amine synthesis

[0112] The catalyst and the way of activation of catalyst are the same as example 10A, on the basis of the ethylene amine synthesis in the above-mentioned example 10A, the reaction conditions of the hydrogenative amination reaction are changed to continue the ethylene amine synthesis, the reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0113] Example 12A

[0114] S1: Preparation of catalyst (20wt% Ni-0.6wt% Ru / Al2O3)

[0115] Take 49.5967 g of nickel nitrate, add deionized water to prepare a 20 mL salt solution, use this salt solution to impregnate 40 g of Al2O3 carrier, the specific surface area of the Al2O3 carrier is 94 m 2 / g. Dry in a 110 ℃ oven for 6 h, calcine in a muffle furnace under air atmosphere at 500 ℃ for 4 h, and then naturally cool to obtain an intermediate catalyst.

[0116] Take 0.8125 g of ruthenium chloride solid, add deionized water to prepare a 20 mL ruthenium chloride aqueous solution, use the solution to impregnate the intermediate catalyst. Dry in a 110 ℃ oven for 6 h, and then naturally cool to obtain a bimetallic catalyst, numbered as catalyst F.

[0117] S2: Activation of catalyst

[0118] The catalyst F is activated in the reactor under the atmosphere of hydrogen and liquid ammonia: take 50 mL of catalyst F and pack it in the reactor, activate after purging with nitrogen for 0.5 h, the activation conditions: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 180 ℃, pressure 20 MPa, activation time 3 h.

[0119] S3: Ethylene amine synthesis

[0120] After the activation of catalyst F in the reactor is completed, the feeding is started, the hydrogenative amination reaction is carried out to synthesize ethylene amine, the reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0121] Example 13A

[0122] Ethylene amine synthesis

[0123] The catalyst and the way of activation of the catalyst were the same as in Example 12A. The ethylene amine synthesis was continued on the basis of the ethylene amine synthesis in the above-mentioned Example 12A by changing the conditions of the hydroamination reaction. The reaction conditions: pressure 20 MPa, temperature 200 °C, liquid hourly space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 6: 1: 0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0124] Example 14A

[0125] Ethylene amine synthesis

[0126] The catalyst and the way of activation of the catalyst were the same as in Example 12A. The ethylene amine synthesis was continued on the basis of the ethylene amine synthesis in the above-mentioned Example 13A by changing the conditions of the hydroamination reaction. The reaction conditions: pressure 17 MPa, temperature 195 °C, liquid hourly space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0127] Example 15A

[0128] S1: Preparation of catalyst (10 wt% Ni-0.5 wt% Ru / Al203)

[0129] Take 110.033 g of nickel nitrate, add deionized water to prepare a 110 mL salt solution, use this salt solution to impregnate 200 g of Al203 carrier, the specific surface area of the Al203 carrier is 94 m 2 / g. Dry in a 110 °C oven for 6 h, calcine in a muffle furnace under air atmosphere at 500 °C for 4 h, and then naturally cool to obtain an intermediate catalyst.

[0130] Take 2.6104 g of ruthenium chloride solid, add deionized water to prepare a 110 mL ruthenium chloride aqueous solution, use this solution to impregnate the intermediate catalyst. Dry in a 110 °C oven for 6 h, and then naturally cool to obtain a bimetallic catalyst, numbered as catalyst G.

[0131] S2: Activation of catalyst

[0132] Catalyst G was activated in a tube furnace, activation condition: H2atmosphere, H2flow rate 100 mL / min, temperature 200 ℃, activation time 3 h. After natural cooling, passivation in air at room temperature for 2 h, air flow rate 150 mL / min, after passivation, the bimetallic catalyst was obtained, numbered as catalyst G-LR.

[0133] S3: Ethylene amine synthesis

[0134] 50 mL catalyst G-LR was loaded into the reactor, after nitrogen purging for 0.5 h, the feed was started to carry out the hydrogenative amination reaction to synthesize ethylene amine, reaction condition: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), after reaction for 2 h, sampling was carried out for gas phase analysis. The reaction results are summarized in Table 1.

[0135] Example 16A

[0136] The catalyst was catalyst G in Example 15A.

[0137] S2: Activation of catalyst

[0138] Catalyst G was activated in the reactor under hydrogen and liquid ammonia atmosphere: 50 mL catalyst G was loaded into the reactor, after nitrogen purging for 0.5 h, activation was carried out, activation condition: hydrogen space velocity 67.2 h -1 , liquid ammonia space velocity 2.4 h -1 , temperature 200 ℃, pressure 20 MPa, activation time 3 h.

[0139] S3: Ethylene amine synthesis

[0140] After the activation of catalyst G in the reactor was completed, the feed was started to carry out the hydrogenative amination reaction to synthesize ethylene amine, reaction condition: pressure 20 MPa, temperature 202 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), after reaction for 2 h, sampling was carried out for gas phase analysis. The reaction results are summarized in Table 1.

[0141] Example 17A

[0142] The catalyst was catalyst G in Example 15A.

[0143] S2: Activation of catalyst

[0144] Catalyst G was activated in the reactor under mixed atmosphere of hydrogen and nitrogen: 50 mL of catalyst G was loaded into the reactor, purged with nitrogen for 0.5 h, and then activated under the following conditions: hydrogen space velocity 67.2 h-1, nitrogen space velocity 500 h-1, temperature 150 °C, pressure 0.1 MPa, and activation time 6 h. -1 -1

[0145] S3: Synthesis of ethylene amine

[0146] After the activation of catalyst G in the reactor was completed, the feeding was started, and the reaction of hydrogenation ammination was carried out to synthesize ethylene amine. The reaction conditions were as follows: pressure 20 MPa, temperature 200 °C, and liquid space velocity of monoethanolamine 1 h-1. The molar ratio of NH3: MEA: H2 was 4: 1: 0.1. After the reaction for 2 h, sampling was carried out for gas phase analysis. The reaction results are shown in Table 1. -1

[0147] Example 18A

[0148] S1: Preparation of catalyst (20wt% Ni-0.5wt% Ru / Al2O3)

[0149] 61.9354 g of nickel nitrate was weighed and dissolved in deionized water to prepare a 26 mL salt solution. 50 g of Al2O3 carrier with a specific surface area of 94 m2 / g was impregnated with the salt solution. The Al2O3 carrier was dried in an oven at 110 °C for 6 h and calcined at 500 °C in a muffle furnace under air atmosphere for 4 h, and then naturally cooled to obtain an intermediate catalyst. 2

[0150] 0.8199 g of ruthenium chloride solid was weighed and dissolved in deionized water to prepare a 20 mL ruthenium chloride aqueous solution. The intermediate catalyst was impregnated with the solution. The catalyst was dried in an oven at 110 °C for 6 h, and then naturally cooled to obtain a bimetallic catalyst, which was numbered as catalyst H.

[0151] S2: Activation of catalyst

[0152] Catalyst H was subsequently activated in a tube furnace under the following conditions: H2 atmosphere, H2 flow rate 100 mL / min, temperature 200 °C, and activation time 3 h. After natural cooling, passivation was carried out in air at room temperature for 2 h at an air flow rate of 150 mL / min. After passivation, a bimetallic catalyst was obtained, which was numbered as catalyst H-LR.

[0153] S3: Synthesis of ethylene amine

[0154] ​​​​Take 50 mL of catalyst H-LR to be loaded into the reactor, nitrogen purging for 0.5 h, then start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 17 MPa, temperature 190 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0155] Example 19A

[0156] Ethylene amine synthesis

[0157] The catalyst and the activation method of the catalyst are the same as catalyst H-LR in Example 18A. On the basis of the ethylene amine synthesis in the above Example 16A, the hydrogenation reaction conditions are changed to continue the synthesis of ethylene amine. Reaction conditions: pressure 15 MPa, temperature 190 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0158] Example 20A

[0159] Ethylene amine synthesis

[0160] The catalyst is catalyst D in Example 7A, without external activation and without in-situ activation.

[0161] Take 50 mL of catalyst D to be loaded into the reactor, nitrogen purging for 0.5 h, then start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 20 MPa, temperature 205 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0162] Comparative Example 1A

[0163] The catalyst is catalyst G in Example 15A.

[0164] S2: High temperature activation of the catalyst

[0165] Catalyst G is activated at high temperature in a tube furnace. Activation conditions: H2atmosphere, H2flow rate 100 mL / min, temperature 200 ℃, keep for 3 h, then increase the temperature to 450 ℃, keep for 4 h. After natural cooling, passivate in air at room temperature for 3 h, air flow rate 150 mL / min. After passivation, the bimetallic catalyst is obtained, numbered as catalyst G-HR.

[0166] S3: Ethylene amine synthesis

[0167] Take 50 mL of catalyst G-HR loaded in the reactor, nitrogen purging for 0.5 h, then start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 20 MPa, temperature 200 ℃, single ethanolamine liquid volume space velocity 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0168] Comparative Example 2A

[0169] S1: Preparation of catalyst (10wt% Ni / 0.5wt% Ru / Al2O3)

[0170] Take 44.0967 g of nickel nitrate, add deionized water to prepare a 52 mL salt solution, and use the salt solution to impregnate 80 g of Al2O3 support. The specific surface area of the Al2O3 support is 94 m 2 / g. Dry in a 110 ℃ oven for 6 h, calcine in a muffle furnace under air atmosphere at 500 ℃ for 4 h, and then naturally cool. Further high-temperature reduction activation is carried out in a tube furnace, with activation conditions of H2 atmosphere, H2 flow rate 100 mL / min, temperature 450 ℃, and activation time 4 h. After natural cooling, passivate in air at room temperature for 3 h, with air flow rate 150 mL / min. The intermediate catalyst is obtained after passivation.

[0171] Take 0.5394 g of ruthenium chloride solid, add deionized water to prepare a 26 mL ruthenium chloride aqueous solution, and use the solution to impregnate the intermediate catalyst. Dry in a 110 ℃ oven for 6 h, and then naturally cool to obtain the bimetallic catalyst, numbered as catalyst I.

[0172] S2: Activation of catalyst

[0173] The activation of the catalyst is carried out after the first metal impregnation during preparation, and no further activation is carried out after the second metal impregnation.

[0174] S3: Ethylene amine synthesis

[0175] Take 50 mL of catalyst I loaded in the reactor, nitrogen purging for 0.5 h, then start feeding to carry out the hydrogenation reaction to synthesize ethylene amine. Reaction conditions: pressure 20 MPa, temperature 200 ℃, single ethanolamine liquid volume space velocity 1 h -1 , NH3: MEA: H2= 4: 1: 0.1 (molar ratio), sample for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 1.

[0176] Comparative Example 3A

[0177] Ethylene amine synthesis

[0178] Catalyst and catalyst activation method are same as those of Comparative Example 2A, ethylene amine synthesis is continued on the basis of ethylene amine synthesis of the above-mentioned Comparative Example 2A, and the reaction conditions are changed. The reaction conditions are as follows: pressure 20 MPa, temperature 205 ℃, liquid hourly space velocity of monoethanolamine 1 h-1 -1 NH3: MEA: H2= 6: 1: 0.1 (molar ratio), and sampling for gas phase analysis is performed after 2 h of reaction. The reaction results are summarized in Table 1.

[0179] In order to further illustrate the technical effects of the application of the hydrogen-activated or unactivated catalyst to ethylene amine synthesis, the catalytic activity and product selectivity of the catalysts in the above examples and comparative examples for the synthesis of ethylene amine by hydrogenation amination reaction are detected and analyzed as follows.

[0180] 1. Catalyst effect evaluation

[0181] The catalysts of Examples 1A-20A and Comparative Examples 1A-3A are subjected to catalyst effect evaluation, and the results of reactant MEA conversion rate and product selectivity are summarized in Table 1.

[0182] The MEA conversion rate, ethylenediamine (EDA) selectivity, diethylenetriamine (DETA) selectivity, hydroxyethylethylenediamine (AEEA) selectivity, and piperazine (PIP) selectivity in Table 1 are defined as follows:

[0183]

[0184]

[0185]

[0186]

[0187]

[0188] Table 1. Catalyst evaluation results of Examples 1A-20A and Comparative Examples 1A-3A

[0189]

[0190] As can be seen from Table 1, in Examples 1A-20A of the application, the product of hydrogenation amination of monoethanolamine to generate ethylene amine is mainly chain products such as ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine, and when the single-pass conversion rate of ethanolamine is 45-60 wt%, the total selectivity of ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine is greater than 80 wt%.

[0191] 2. Temperature Programmed Reduction (TPR) analysis

[0192] The pre- and post-use catalysts were analyzed for their reduction properties by Temperature Programmed Reduction (TPR) method. The instrument was AUTOCHEM II 2920 of Micromeritics.

[0193] Specific operation: 50-60 mg sample was weighed into a U-shaped quartz tube, purged with He gas flow (50 mL / min) for 0.5 h, and then dried pretreated at 10 ℃ / min from room temperature to 150 ℃ for 1 h. After that, the heating was stopped and cooled to 50 ℃. After stabilization at 50 ℃ for 0.5 h, 10% H2 / Ar mixed gas (50 mL / min) was introduced, and purged for 0.5 h. After the baseline was stabilized, the sample was raised to a set high temperature, such as 800 ℃ or 600 ℃, in 10% H2 / Ar gas flow at a heating rate of 10 ℃ / min. The signal was collected by a thermal conductivity detector (TCD).

[0194] The catalysts of Example 15A, Example 20A and Comparative Example 1A were subjected to Temperature Programmed Reduction (TPR) analysis before and after the catalytic single-ethanolamine hydrogenation production of ethyleneamine reaction. The TPR curves of the catalysts of Example 15A, Example 20A and Comparative Example 1A before the reaction are shown in Figure 1 , Figure 2 and Figure 3 respectively, and the TPR curves of the catalysts after the reaction are shown in Figure 4 , Figure 5 and Figure 6 respectively.

[0195] As can be seen from Figure 1 , Figure 2 and Figure 3 , the TPR curves of the unused new catalysts activated by high-temperature hydrogen reduction are quite different from those of the unused new catalysts activated by low-temperature hydrogen, and those of the unused new catalysts without hydrogen activation.

[0196] As can be seen from Figure 4 , Figure 5 and Figure 6 , the post-use catalysts activated by high-temperature hydrogen reduction show similar TPR curves to those of the post-use catalysts activated by low-temperature hydrogen, and those of the post-use catalysts without hydrogen activation. This proves that they eventually have similar activities.

[0197] To verify that the low ammonia ratio of the reaction raw materials monoethanolamine and liquid ammonia can obtain the same reaction conversion rate and product selectivity as the high ammonia ratio in the ethylene amine synthesis reaction of the present application, the following examples will be carried out under low ammonia ratio conditions for ethylene amine synthesis.

[0198] Example 1B

[0199] Ethylene amine synthesis

[0200] The catalyst and the activation method of the catalyst are the same as in Example 1A, and on the basis of the above-mentioned Example 1A ethylene amine synthesis, the hydrogenation reaction conditions are changed to continue the ethylene amine synthesis, the reaction conditions are: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 2.5: 1: 0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0201] Example 2B

[0202] Ethylene amine synthesis

[0203] The catalyst and the activation method of the catalyst are the same as in Example 1A, and on the basis of the above-mentioned Example 1B ethylene amine synthesis, the hydrogenation reaction conditions are changed to continue the ethylene amine synthesis, the reaction conditions are: pressure 20 MPa, temperature 210 ℃, liquid volume space velocity of monoethanolamine 1.8 h -1 , NH3: MEA: H2= 2.5: 1: 0.05 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0204] Example 3B

[0205] Ethylene amine synthesis

[0206] The catalyst and the activation method of the catalyst are the same as in Example 3A, and on the basis of the above-mentioned Example 3A ethylene amine synthesis, the hydrogenation reaction conditions are changed to continue the ethylene amine synthesis, the reaction conditions are: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 , NH3: MEA: H2= 2.5: 1: 0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The reaction results are summarized in Table 2.

[0207] Example 4B

[0208] Ethylene amine synthesis

[0209] The catalyst and the way of activation of the catalyst were the same as in Example 3A. The ethylene amine synthesis was continued on the basis of the above-mentioned Example 3B ethylene amine synthesis by changing the conditions of the reductive amination reaction. The reaction conditions: pressure 20 MPa, temperature 210 °C, liquid hourly space velocity of monoethanolamine 1.8 h -1 NH3:MEA:H2 = 2.5:1:0.05 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The results of the reaction are summarized in Table 2.

[0210] Example 5B

[0211] Ethylene amine synthesis

[0212] The catalyst and the way of activation of the catalyst were the same as in Example 6A. The ethylene amine synthesis was continued on the basis of the above-mentioned Example 6A ethylene amine synthesis by changing the conditions of the reductive amination reaction. The reaction conditions: pressure 20 MPa, temperature 220 °C, liquid hourly space velocity of monoethanolamine 1 h -1 NH3:MEA:H2 = 2.5:1:0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The results of the reaction are summarized in Table 2.

[0213] Example 6B

[0214] Ethylene amine synthesis

[0215] The catalyst and the way of activation of the catalyst were the same as in Example 7A. The ethylene amine synthesis was continued on the basis of the above-mentioned Example 7A ethylene amine synthesis by changing the conditions of the reductive amination reaction. The reaction conditions: pressure 20 MPa, temperature 195 °C, liquid hourly space velocity of monoethanolamine 1 h -1 NH3:MEA:H2 = 2.5:1:0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The results of the reaction are summarized in Table 2.

[0216] Example 7B

[0217] Ethylene amine synthesis

[0218] The catalyst and the way of activation of the catalyst were the same as in Example 9A. The ethylene amine synthesis was continued on the basis of the above-mentioned Example 9A ethylene amine synthesis by changing the conditions of the reductive amination reaction. The reaction conditions: pressure 20 MPa, temperature 190 °C, liquid hourly space velocity of monoethanolamine 1 h -1 NH3:MEA:H2 = 2.5:1:0.1 (molar ratio), sampling for gas phase analysis after 2 h of reaction. The results of the reaction are summarized in Table 2.

[0219] Example 8B

[0220] Ethylene amine synthesis

[0221] Catalyst and catalyst activation mode same as Example 15A, Catalyst G-LR, on the basis of the above Example 15A ethylene amine synthesis, continue to carry out the synthesis of ethylene amine by changing the conditions of the hydrogenation reaction, reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 NH3:MEA:H2=2.5:1:0.1 (molar ratio), sample for gas phase analysis after 2 h reaction. The reaction results are summarized in Table 2.

[0222] Example 9B

[0223] Ethylene amine synthesis

[0224] Catalyst and catalyst activation mode same as Example 15A, Catalyst G-LR, on the basis of the above Example 15A ethylene amine synthesis, continue to carry out the synthesis of ethylene amine by changing the conditions of the hydrogenation reaction, reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 NH3:MEA:H2=2.5:1:0.1 (molar ratio), sample for gas phase analysis after 2 h reaction. The reaction results are summarized in Table 2.

[0225] Example 10B

[0226] Ethylene amine synthesis

[0227] Catalyst and catalyst activation mode same as Example 15A, Catalyst G-LR, on the basis of the above Example 15A ethylene amine synthesis, continue to carry out the synthesis of ethylene amine by changing the conditions of the hydrogenation reaction, reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 NH3:MEA:H2=2.5:1:0.1 (molar ratio), sample for gas phase analysis after 2 h reaction. The reaction results are summarized in Table 2.

[0228] Example 11B

[0229] Ethylene amine synthesis

[0230] Catalyst and catalyst activation mode same as Example 15A, Catalyst G-LR, on the basis of the above Example 15A ethylene amine synthesis, continue to carry out the synthesis of ethylene amine by changing the conditions of the hydrogenation reaction, reaction conditions: pressure 20 MPa, temperature 200 ℃, liquid volume space velocity of monoethanolamine 1 h -1 NH3:MEA:H2=2.5:1:0.1 (molar ratio), sample for gas phase analysis after 2 h reaction. The reaction results are summarized in Table 2.

[0231] Comparative Example 1B

[0232] Ethylene amine synthesis

[0233] The catalyst and the catalyst activation mode were the same as catalyst G-HR in Comparative Example 1A, and the ethylene amine synthesis was continued on the basis of the above-mentioned ethylene amine synthesis of Comparative Example 1A by changing the conditions of the hydrogenative amination reaction. The reaction conditions were: pressure 20 MPa, temperature 200 ℃, and liquid hourly space velocity of monoethanolamine 1 h -1 NH3: MEA: H2= 2.5: 1: 0.1 (molar ratio), and the reaction was sampled for gas phase analysis after 2 h. The reaction results are summarized in Table 2.

[0234] Table 2. Catalyst evaluation results of Examples 1B-11B and Comparative Examples 1B-2B

[0235]

[0236] Comparative Example 2B

[0237] Ethylene amine synthesis

[0238] The catalyst and the catalyst activation mode were the same as Comparative Example 2A, and the ethylene amine synthesis was continued on the basis of the above-mentioned ethylene amine synthesis of Comparative Example 2A by changing the conditions of the hydrogenative amination reaction. The reaction conditions were: pressure 20 MPa, temperature 200 ℃, and liquid hourly space velocity of monoethanolamine 1 h -1 NH3: MEA: H2= 2.5: 1: 0.1 (molar ratio), and the reaction was sampled for gas phase analysis after 2 h. The reaction results are summarized in Table 2.

[0239] The catalysts in the above-mentioned Examples 1B-11B and Comparative Examples 1B-2B were evaluated for effectiveness, and the results of the conversion of the reactant MEA and the selectivity of the products are summarized in Table 2.

[0240] As can be seen from Table 2, in Examples 1B-11B, although the molar ratio of NH3: MEA was reduced to less than 4, the molar ratio of NH3: MEA was 2-3, the conversion of monoethanolamine and the selectivity of the products were comparable to those of the high ammonia ratio, specifically, the product of the hydrogenative amination of monoethanolamine to form ethylene amine was mainly chain products such as ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine, and the conversion of monoethanolamine was 45-60 wt%, and the total selectivity of ethylenediamine, diethylenetriamine, and hydroxyethylethylenediamine was greater than 80 wt%.

[0241] It should be noted that, in this text, the terms "comprising", "containing" or any other variant thereof are intended to cover non-exclusive inclusions, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or further includes elements inherent to such a process, method, article or device. Without more limitations, the elements defined by the language "comprising" do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0242] The above examples are only used to illustrate the technical solutions of the present application, and cannot limit the protection scope of the present application; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified or some technical features can be replaced by equivalents without departing from the essence and scope of the present application; and these modifications or equivalent replacements still belong to the scope covered by the present application.

Claims

1. A process for the synthesis of ethyleneamines, starting from monoethanolamine and liquid ammonia, under hydrogenation conditions and in the presence of a bimetallic catalyst, characterized in that, The bimetallic catalyst is activated by low-temperature reduction, and the temperature range of the low-temperature reduction is 130-200℃; The bimetallic catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active component comprises Ni, and the metal content of the active component accounts for 10-20wt% of the mass of the catalyst; the auxiliary agent comprises Ru, and the metal content of the auxiliary agent accounts for 0.5-0.7wt% of the mass of the catalyst; The molar ratio of ammonia to monoethanolamine is 2-4:

1. The conversion rate of monoethanolamine is 45-60%, and the total selectivity of ethylenediamine, diethylenetriamine and hydroxyethylethylenediamine in the synthetic product is greater than 80%.

2. The method of synthesis of claim 1, wherein, The temperature range of the low-temperature reduction is 150-200℃.

3. The method of synthesis of claim 1 or 2, wherein, The low-temperature reduction is performed in a reactor for synthesizing ethyleneamine or outside the reactor.

4. The method of synthesis of claim 3, wherein, The low-temperature reduction is performed outside the reactor for synthesizing ethyleneamine, and is performed in an atmosphere of H2 or a mixture of H2 and inert gas; after the low-temperature reduction is completed, the catalyst is cooled to normal temperature and is passivated in air.

5. The method of synthesis of claim 3, wherein, The low-temperature reduction is performed in a reactor for synthesizing ethyleneamine, and the catalyst is subjected to low-temperature reduction in an atmosphere of H2 or a mixture of H2 and inert gas or in an atmosphere of H2 and liquid ammonia.

6. The method of synthesis of claim 1, wherein, The molar ratio of ammonia to monoethanolamine is 2-3:

1.

7. The method of synthesis of claim 1, wherein, The support comprises Al2O3 and / or SiO2, with a specific surface area of 50 to 300 m 2 / g.

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