Preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine

Abstract

The invention provides a preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine, which comprises the following steps: reacting iminodiacetonitrile with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protective agent to generate N1-(2-aminoethyl)-1, 2-ethylenediamine, wherein the catalyst protective agent comprises one or more of nickel carbonyl, carbonyl iron, nickel tetramine and cobalt tetramine. According to the present invention, the catalytic activity reduction of the hydrogenation catalyst can be inhibited, the deactivation of the hydrogenation catalyst can be avoided, and the selectivity and the yield of the N1-(2-aminoethyl)-1, 2-ethylenediamine can be improved.

Description

Technical Field

[0001] The present invention relates to a N 1 The invention discloses a method for preparing -(2-aminoethyl)-1,2-ethylenediamine, belonging to the field of amine compound synthesis. Background Art

[0002] N 1 -(2-aminoethyl)-1,2-ethylenediamine (DETA), also known as diethylenetriamine, is a yellow, hygroscopic, transparent, viscous liquid with a pungent ammonia odor and easily absorbs moisture and carbon dioxide in the air. Diethylenetriamine is widely used, for example, in the synthesis of polyamide resins, paper reinforcing agents, metal chelating agents, surfactants, lubricants, epoxy resin curing agents and other materials.

[0003] At present, DETA is mainly produced by the ethylene dichloride (EDC) amination method or the ethanolamine (MEA) method. Among them, the EDC amination method is characterized by the fact that no catalyst is used in the reaction process, and it is a fast, exothermic reaction. Since the main product ethylenediamine (EDA) has stronger alkalinity and nucleophilicity than the raw material NH3, it is very easy to participate in the reaction as an intermediate product to trigger a series of reactions to generate DETA or other polyethylene polyamines. Therefore, the products obtained by the EDC amination method are widely distributed, mainly linear polyethylene polyamines. The EDC amination method has problems such as high energy consumption in the production process, serious equipment corrosion, serious three waste problems, and high cost, which limit the application of the EDC amination method.

[0004] The MEA method is the hydroamination of MEA (also known as MEA reductive amination or direct amination), which refers to the process in which the raw materials MEA and NH3 react under the action of a catalyst and in an H2 atmosphere to produce amine products and water, wherein the amine product is mainly EDA, and high value-added DETA, PIP and piperazine derivatives are by-products. The MEA hydroamination is a gas-liquid-solid three-phase reaction, and the catalyst used is a dehydrogenation-hydrogenation catalyst composed of transition metals. The reaction temperature and pressure are usually in the range of 150-200°C and 3-30MPa, respectively, and the reactor used can be an autoclave or fixed bed reactor. The MEA method generally has problems such as easy carbon deposition and deactivation of the catalyst and high cost of ethylenediamine raw materials, which limits its application.

[0005] Relatively speaking, the preparation of corresponding organic amines by hydrogenation of nitriles has the advantages of simpler process and more environmentally friendly process, and has gradually been widely used. Among them, hydrogenation of iminodiacetonitrile (IDAN) under the action of hydrogenation catalyst is a feasible direction for preparing DETA. However, in the process of preparing DETA by hydrogenation reaction of IDAN, the hydrogenation catalyst used is mainly a metal catalyst. Since raw materials such as IDAN are easily decomposed under high temperature and other conditions to produce CN -Factors such as these can easily lead to reduced activity of hydrogenation catalysts or even catalyst deactivation. In particular, industrial-grade IDAN is currently commonly used to prepare DETA. Industrial-grade IDAN cannot be used directly due to the large amount of impurities and needs to be pretreated with deacidification before being used to prepare DETA. After deacidification and other pretreatments, industrial-grade IDAN is prone to polymerization and decomposition. In particular, when IDAN enters the hydrogenation reactor, it is easy to decompose at high temperatures to produce CN. - It is easy to complex with the hydrogenation catalyst, causing the hydrogenation catalyst to be continuously lost, and even blocking the catalyst pores, causing the catalyst activity to decrease or even deactivate.

[0006] For example, US2002058842 discloses a hydrogenation reaction of IDAN in N,N-dimethylformamide (DMF) system with Raney cobalt as catalyst under the conditions of reaction temperature of 100°C and reaction pressure of 190 bar, but there are problems such as catalyst deactivation; WO2008104583A1 discloses a method for preparing DETA by hydrogenating a mixture of IDAN and aminoacetonitrile, but there are problems such as raw materials such as IDAN and aminoacetonitrile are easily decomposed to produce CN - , resulting in reduced catalyst activity or even inactivation, and because aminoacetonitrile is easily polymerized and decomposed at room temperature, the product composition in the reaction liquid is complex and changeable, affecting the subsequent separation of DETA and other defects.

[0007] In addition, in the process of preparing DETA by hydrogenation reaction of IDAN, the conversion rate of IDAN and the selectivity of DETA need to be further improved.

[0008] In summary, in the process of preparing DETA by hydrogenation reaction of IDAN, how to suppress the decrease in activity of the hydrogenation catalyst, avoid deactivation of the hydrogenation catalyst, and improve the conversion rate of IDAN and the selectivity of DETA are technical problems that need to be solved urgently in this field. Summary of the invention

[0009] The present invention provides a N 1 The method for preparing (2-aminoethyl)-1,2-ethylenediamine can inhibit the decrease in the activity of the hydrogenation catalyst, avoid the deactivation of the hydrogenation catalyst, and improve the conversion rate of IDAN and the selectivity of DETA, thereby effectively overcoming the defects of the prior art.

[0010] The present invention provides a N 1 The preparation method of -(2-aminoethyl)-1,2-ethylenediamine comprises the following steps: reacting iminodiacetonitrile with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protective agent to generate N 1-(2-aminoethyl)-1,2-ethylenediamine; wherein the catalyst protecting agent comprises one or more of carbonyl nickel, carbonyl iron, tetraamine nickel, and tetraamine cobalt.

[0011] According to one embodiment of the present invention, the hydrogenation catalyst comprises one or more of Raney nickel, Raney cobalt and a supported catalyst; preferably, the supported catalyst comprises a carrier and an active component supported on the carrier, the carrier comprises one or more of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, magnesium oxide, activated carbon, diatomaceous earth, and silica gel, and the active component comprises one or more of sodium, potassium, titanium, manganese, iron, cobalt, copper, molybdenum, nickel, ruthenium, rhodium, palladium, and platinum.

[0012] According to one embodiment of the present invention, the mass ratio of the hydrogenation catalyst to the iminodiacetonitrile is 5% to 40%.

[0013] According to one embodiment of the present invention, the mass ratio of the catalyst protecting agent to the hydrogenation catalyst is 1% to 10%.

[0014] According to one embodiment of the present invention, the reaction liquid system further includes an auxiliary agent, and the auxiliary agent includes a metal oxide and / or a metal hydroxide; preferably, the metal element in the metal oxide includes an alkali metal and / or an alkaline earth metal, and the metal element in the metal hydroxide includes an alkali metal and / or an alkaline earth metal.

[0015] According to one embodiment of the present invention, the mass ratio of the auxiliary agent to the hydrogenation catalyst is 10% to 20%.

[0016] According to one embodiment of the present invention, the alkali metal includes lithium and / or potassium; and / or the alkaline earth metal includes calcium.

[0017] According to one embodiment of the present invention, the solvent includes one or more of dioxane, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, n-butanol, ethyl acetate, and butyl acetate.

[0018] According to one embodiment of the present invention, the reaction conditions are: reaction temperature is 80°C to 180°C, hydrogen pressure is 3MPa to 8MPa, and reaction time is 60min to 300min.

[0019] According to one embodiment of the present invention, the iminodiacetonitrile is obtained by pre-treating an iminodiacetonitrile raw material, and the pre-treatment process comprises: extracting the iminodiacetonitrile raw material with an extractant to obtain the iminodiacetonitrile; wherein the extractant comprises water and a first organic solvent; preferably, the pre-treatment process comprises: extracting the iminodiacetonitrile raw material with an extractant to obtain a raw material liquid containing the iminodiacetonitrile; the process of reacting iminodiacetonitrile with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protecting agent comprises: adding the raw material liquid containing the iminodiacetonitrile to the reaction liquid system, and reacting the iminodiacetonitrile with hydrogen to generate N 1 -(2-aminoethyl)-1,2-ethylenediamine, generating the N 1 -(2-aminoethyl)-1,2-ethylenediamine; wherein, during the process of adding the raw material liquid containing the iminodiacetonitrile into the reaction liquid system, the space velocity of the raw material liquid containing the iminodiacetonitrile is 1 to 5 g / min.

[0020] The implementation of the present invention has at least the following beneficial effects: IDAN is reacted with hydrogen in the presence of a solvent, a hydrogenation catalyst and a catalyst protective agent to generate N 1 -(2-aminoethyl)-1,2-ethylenediamine, by introducing a specific catalyst protector (the catalyst protector includes one or more of carbonyl nickel, carbonyl iron, tetraamine nickel, and tetraamine cobalt) in the process of preparing DETA through the hydrogenation reaction based on IDAN, the activity of the hydrogenation catalyst can be maintained, the decrease in the activity of the hydrogenation catalyst can be suppressed, the deactivation of the hydrogenation catalyst can be avoided, the stable and continuous production of DETA can be ensured, and the conversion rate of IDAN and the selectivity of DETA can be improved, and the yield of DETA can be improved, which is of great significance for practical industrial applications. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to better understand the scheme of the present invention, the present invention is further described in detail below. The specific implementation methods listed below are only for describing the principles and features of the present invention. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0022] The embodiment of the present invention provides an N 1 The method for preparing ethylenediamine (DETA) comprises the following steps: reacting iminodiacetonitrile (IDAN) with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protective agent (hereinafter referred to as hydrogenation reaction) to generate N 1-(2-aminoethyl)-1,2-ethylenediamine (DETA); wherein the catalyst protecting agent comprises one or more of carbonyl nickel, carbonyl iron, tetraamine nickel, and tetraamine cobalt.

[0023] In the above-mentioned preparation process of DETA, by reacting IDAN with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protector, both the conversion rate of IDAN and the selectivity of DETA can be improved, thereby improving the yield of DETA.

[0024] According to the inventors' research, in the above-mentioned preparation process of DETA, during the hydrogenation reaction, the catalyst protective agent can react with the free CN generated in the reaction system due to the decomposition of IDAN and other factors. - Combination, thus avoiding CN - The complexation with the hydrogenation catalyst and the resulting adverse effects on the adsorption performance and pore structure of the hydrogenation catalyst ensure that the main body of the hydrogenation catalyst is not destroyed and lost, thereby maintaining the activity of the hydrogenation catalyst, avoiding the deactivation of the hydrogenation catalyst, and improving the service life of the catalyst to ensure the stable and continuous production of DETA. Specifically, after repeated hydrogenation reactions (such as 5 batches) using the hydrogenation catalyst, a high conversion rate of IDAN and DETA selectivity can still be maintained, thereby improving the yield of DETA.

[0025] Specifically, the above-mentioned hydrogenation catalyst may include a metal catalyst and / or a supported catalyst. The metal catalyst may specifically include Raney nickel and / or Raney cobalt. The supported catalyst includes a carrier and an active component supported on the carrier. The carrier includes one or more of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, magnesium oxide, activated carbon, diatomaceous earth, and silica gel. The active component includes one or more of sodium element, potassium element, titanium element, manganese element, iron element, cobalt element, copper element, molybdenum element, nickel element, ruthenium element, rhodium element, palladium element, and platinum element.

[0026] In some embodiments, the hydrogenation catalyst includes one or more of Raney nickel, Raney cobalt and the above-mentioned supported catalyst. In the preparation process of DETA, the hydrogenation catalyst is used, and the above-mentioned catalyst protector is introduced into the reaction liquid system, which is conducive to further inhibiting the reduction of the catalytic activity of the hydrogenation catalyst, avoiding the deactivation of the hydrogenation catalyst, and further taking into account the improvement of the conversion rate of IDAN and the selectivity of DETA, thereby improving the yield of DETA.

[0027] In some embodiments, in the above-mentioned reaction liquid system, the mass ratio of the hydrogenation catalyst to IDAN can be 5% to 40%, for example, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 25%, 28%, 30%, 33%, 35%, 38%, 40% or a range composed of any two of them, which is beneficial to improve the conversion rate of IDAN and the selectivity of DETA, and improve the yield of DETA.

[0028] In some embodiments, in the above-mentioned reaction liquid system, the mass ratio of the catalyst protectant to the hydrogenation catalyst can be 1% to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or a range composed of any two of them, which is beneficial to further inhibit the reduction of the catalytic activity of the hydrogenation catalyst and increase the service life of the hydrogenation catalyst.

[0029] In some embodiments, the reaction liquid system further includes an auxiliary agent, which may include metal oxides and / or metal hydroxides, wherein the metal elements in the metal oxides include alkali metals and / or alkaline earth metals, and the metal elements in the metal hydroxides include alkali metals and / or alkaline earth metals. By introducing the auxiliary agent into the reaction liquid system, the conversion rate of IDAN and the selectivity of DETA are further improved, and the yield of DETA is improved.

[0030] Specifically, the alkali metal may include lithium (Li) and / or potassium (K), and / or the alkaline earth metal may include calcium (Ca). That is, the metal element in the metal oxide may include one or more of Li, K, and Ca, and the metal element in the metal hydroxide may include one or more of Li, K, and Ca.

[0031] In some specific embodiments, the metal oxide may include one or more of lithium oxide, potassium oxide, and calcium oxide.

[0032] In some specific embodiments, the metal hydroxide may include one or more of lithium hydroxide (LiOH), potassium hydroxide, and calcium hydroxide.

[0033] Specifically, in the above-mentioned reaction liquid system, the mass ratio of the auxiliary agent to the hydrogenation catalyst (i.e., the mass fraction of the added amount of the auxiliary agent relative to the hydrogenation catalyst) can be 10% to 20%, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or a range composed of any two thereof, which is beneficial to improve the conversion rate of IDAN and the selectivity of DETA, and improve the yield of DETA.

[0034] In the preparation process of DETA, the solvent used may include a second organic solvent, specifically one or more of dioxane, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, n-butanol, ethyl acetate, and butyl acetate, which is beneficial to maintaining the activity of the hydrogenation catalyst, improving the conversion rate of IDAN and the selectivity of DETA, and improving the yield of DETA.

[0035] In some embodiments, in the preparation process of the above-mentioned DETA, the mass ratio of IDAN to the solvent (i.e., the mass fraction of IDAN in the solvent) can be 5% to 20%, for example, 5%, 8%, 10%, 13%, 15%, 18%, 20% or a range consisting of any two thereof.

[0036] In the embodiment of the present invention, a conventional reactor in the art may be used to carry out the hydrogenation reaction, for example, a semi-batch reactor may be used to carry out the hydrogenation reaction.

[0037] Specifically, the conditions of the hydrogenation reaction may be: a reaction temperature of 80°C to 180°C, for example, 80°C, 100°C, 120°C, 140°C, 150°C, 170°C, 180°C or a range consisting of any two thereof; a hydrogen pressure of 3MPa to 8MPa, for example, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa or a range consisting of any two thereof; a reaction time of 60min to 300min, for example, 60min, 80min, 100min, 120min, 150min, 180min, 200min, 230min, 250min, 280min, 300min or a range consisting of any two thereof, which is beneficial to improving the conversion rate of IDAN and the selectivity of DETA, and improving the yield of DETA.

[0038] Specifically, in the preparation process of DETA, the amount of hydrogen added satisfies the above hydrogen pressure (ie, hydrogen is charged into the reactor and the hydrogen is pressurized to a preset hydrogen pressure). In specific implementation, hydrogen can be fed continuously.

[0039] Specifically, IDAN can be obtained by pre-treating an iminodiacetonitrile raw material (IDAN raw material), wherein the pre-treating process includes: extracting the iminodiacetonitrile raw material with an extractant to obtain iminodiacetonitrile; wherein the extractant includes water and a first organic solvent. By pre-treating the IDAN raw material and extracting it with the extractant, impurities such as sulfuric acid and sulfate in the IDAN can be removed, thereby facilitating the subsequent hydrogenation reaction of the IDAN.

[0040] In the embodiments of the present invention, the IDAN raw material can be obtained by conventional methods in the art, such as commercially available or homemade by conventional methods in the art.

[0041] Due to factors such as the preparation process of IDAN, commercially available or homemade IDAN raw materials (or crude IDAN, or crude IDAN) by conventional methods in the art usually have residual trace amounts of impurities such as sulfuric acid and sulfates, which is not conducive to being directly used as a raw material for hydrogenation reaction. The crude IDAN is pretreated (or purified or impurity-removed) to remove trace amounts of impurities such as sulfuric acid and sulfates, and the purified IDAN is used as a raw material to carry out the above-mentioned hydrogenation reaction in a reaction liquid system containing components such as a solvent, a hydrogenation catalyst, and a catalyst protective agent to generate DETA. That is, in the above-mentioned hydrogenation reaction, the IDAN used (hereinafter referred to as purified IDAN) is the IDAN obtained by purifying the crude IDAN only through the above-mentioned pretreatment process.

[0042] Specifically, the main acidic substances in the crude IDAN product are residual trace impurities such as sulfuric acid and sulfates that are insoluble in organic solvents. By using the above-mentioned extractant for extraction and phase separation during the extraction process, the impurity components such as sulfuric acid and sulfates in the crude IDAN product can be removed to obtain purified IDAN. The purified IDAN can be directly used in the above-mentioned hydrogenation reaction to ensure the conversion rate of IDAN and the selectivity and yield of DETA.

[0043] Specifically, the first organic solvent may include one or more of dioxane, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, n-butanol, ethyl acetate, and butyl acetate.

[0044] In some embodiments, the mass ratio of IDAN to the extractant (i.e., the mass fraction of IDAN in the extractant) can be 5% to 20%, for example, 5%, 8%, 10%, 13%, 15%, 18%, 20% or a range consisting of any two thereof.

[0045] In some embodiments, the process of extracting crude IDAN with an extractant may include: mixing crude IDAN and an extractant, then adding an inorganic salt thereto to promote phase separation, then taking out an organic phase (upper layer liquid) to obtain an IDAN raw material solution containing purified IDAN (i.e., purified IDAN exists in the IDAN raw material solution). The inorganic salt can reduce the solubility of water in the first organic solvent, which is more conducive to phase separation. The inorganic salt may specifically include a water-soluble inorganic salt, such as lithium hydroxide.

[0046] In specific implementation, the crude IDAN product and the extractant can be mixed, stirred and shaken to mix evenly, and then lithium hydroxide is added thereto to promote phase separation (the upper liquid is the organic phase, and the lower liquid is the aqueous phase). After phase separation, the organic phase is taken out using a separatory funnel or other instrument; the organic phase is filtered 2 to 4 times (e.g., 3 times) to remove impurities, and an IDAN raw material solution containing purified IDAN is obtained. Subsequently, the IDAN raw material solution can be directly used and added to the above-mentioned reaction liquid system to react IDAN with hydrogen to generate DETA.

[0047] According to the research and analysis of the inventors, the purified IDAN is easily decomposed at high temperature to produce cyano groups (CN - ), which is easy to complex with hydrogenation catalysts such as Raney cobalt, causing the loss of hydrogenation catalysts, and will be adsorbed in the catalyst pores, affecting the catalyst activity, and further affecting the conversion rate of IDAN and the selectivity of DETA. In the embodiment of the present invention, under the above-mentioned DETA preparation system, by introducing the above-mentioned weak complex as a catalyst protector, the ability of the organic group in the catalyst protector to complex with the metal element is worse than that of CN - (For example, the carbonyl complexing ability of nickel carbonyl is poorer than that of CN - ), while CN generated by IDAN - The coordination is strong and can be exchanged with the organic groups in the catalyst protector to generate corresponding complexes (usually liquid products), thus avoiding CN - It has an adverse effect on the hydrogenation catalyst, thereby ensuring the catalyst activity.

[0048] Specifically, the above-mentioned hydrogenation reaction process may include a first reaction stage and a second reaction stage. The first reaction stage is a continuous feeding stage of IDAN (specifically, it may be a continuous feeding stage of IDAN raw material liquid), and the second reaction stage is a reaction stage after the continuous feeding of IDAN is completed. That is, in the first reaction stage, IDAN (IDAN raw material liquid) is continuously added to the reaction liquid system until the feeding of IDAN (IDAN raw material liquid) is completed (that is, after all IDAN (IDAN raw material liquid) is added to the reaction liquid system), and the preset reaction conditions are maintained for a preset time (i.e., the second reaction stage), and then the reaction is terminated to obtain DETA.

[0049] Specifically, the feed space velocity of the IDAN raw material solution (i.e., the space velocity of the IDAN raw material solution during the process of adding the IDAN raw material solution to the reaction liquid system) can be 1 to 5 g / min, for example, 1 g / min, 2 g / min, 3 g / min, 4 g / min, 5 g / min or a range consisting of any two of them.

[0050] In a specific implementation, components such as a solvent, a hydrogenation catalyst, a catalyst protective agent, and an auxiliary agent can be added to a reactor to form a reaction liquid system; then the reactor is closed, and the air in the reactor is replaced with an inert gas (for example, an inert gas of 0.5 MPa to 0.7 MPa (such as about 0.6 MPa)), and the air can be replaced 2 to 5 times (such as 3 times), and then the inert gas in the reactor is replaced with hydrogen (for example, hydrogen of 0.8 to 1.2 MPa (such as about 1 MPa)), and the air can be replaced 2 to 5 times (such as 3 times); and then hydrogen is filled into the reactor. and pressurize the hydrogen to a preset reaction pressure, start the reactor to heat it to the reaction temperature, add IDAN into the reactor by pumping at a preset space velocity, and specifically add IDAN raw material liquid thereto to carry out a hydrogenation reaction (first carry out the first reaction stage, and after the IDAN feeding is completed, keep it for a preset time (i.e., carry out the second reaction stage)), after the hydrogenation reaction is completed, after the temperature in the reactor drops to room temperature, filter the reaction liquid in the reactor to obtain a filtrate containing DETA, and then further separate and purify DETA as needed.

[0051] For example, the filtrate containing DETA generally contains piperazine in addition to DETA. In specific implementation, DETA and piperazine can be separated by reduced pressure distillation or the like as needed.

[0052] Specifically, piperazine is generally produced as a by-product in the above-mentioned preparation process of DETA, that is, after the hydrogenation reaction is completed, the reaction liquid in the reactor contains piperazine, and after filtering the reaction liquid, the filtrate containing DETA also contains piperazine. After obtaining the filtrate containing DETA, parameters such as the conversion rate of IDAN, the yield (selectivity) of DETA, and the yield (selectivity) of piperazine can be analyzed by gas chromatography analysis or the like.

[0053] In the embodiment of the present invention, through the above-mentioned preparation process of DETA, the conversion rate of IDAN (which can basically reach 100%) and the selectivity of DETA (not less than 80%, especially reaching more than 85%, or even more than 90%) can be improved, and the selectivity of by-products such as piperazine can be reduced (the selectivity of piperazine is less than 7%, generally 3% to 7%).

[0054] In the embodiment of the present invention, through the preparation process of DETA, the catalytic activity of the hydrogenation catalyst can be maintained, the deactivation of the hydrogenation catalyst can be avoided, the service life of the hydrogenation catalyst can be increased, and the stable and continuous production of DETA can be facilitated.

[0055] Specifically, the hydrogenation catalyst can be reused multiple times (i.e., the hydrogenation catalyst can be applied multiple times according to the above-mentioned preparation process of DETA), that is, after the hydrogenation catalyst is subjected to the above-mentioned hydrogenation reaction once, it can be separated from the reaction liquid and then used as a hydrogenation catalyst again for the above-mentioned hydrogenation reaction, and so on, and reused multiple times. After multiple reuses, the hydrogenation catalyst can still maintain a relatively high catalytic activity, for example, after five reuses, it can still maintain a relatively high conversion rate of IDAN (more than 50%, especially more than 87%) and a relatively high selectivity of DETA (more than 85%, even more than 90%).

[0056] The present invention is further described below through specific embodiments.

[0057] Unless otherwise specified, in the following examples or comparative examples, the IDAN (i.e., IDAN raw material), dioxane, lithium hydroxide, and Raney nickel (Raney cobalt catalyst) used are from Inokai Technology Co., Ltd., and the others are common commercially available raw materials.

[0058] In the following examples and comparative examples, the conditions for gas chromatography analysis are: using Agilent 7890 and DB-5 (30 mm*0.25 mm*0.25 μm), the injector temperature is 280°C, and the detector temperature is 300°C. The heating program is as follows: the initial column temperature is 50°C, maintained for 2 min; the temperature is increased to 80°C at 5°C / min, maintained for 0 min; the temperature is increased to 300°C at 15°C / min, maintained for 15 min; the content of each component is determined by the normalization method, and the IDAN conversion rate, DETA yield and piperazine yield are measured.

[0059] Example 1

[0060] S1. Pretreatment of crude IDAN (IDAN raw material)

[0061] 100 g of crude IDAN, 240 g of water and 350 g of dioxane (first organic solvent) were mixed, stirred and shaken thoroughly, and 5 g of lithium hydroxide was added thereto to promote phase separation; after phase separation, the upper liquid (organic phase) was taken out using a separatory funnel, and the upper liquid was filtered three times to remove impurities to obtain an IDAN raw material solution.

[0062] S2. Hydrogenation reaction

[0063] 10 g of Raney cobalt was added to the reactor, and 200 g of dioxane (the second organic solvent), 1.5 g of LiOH, and 0.5 g of carbonyl nickel were added; the reactor was closed, the air in the reactor was replaced with 0.6 MPa nitrogen for three times, and the nitrogen in the reactor was replaced with 1 MPa hydrogen for three times, the hydrogen was pressurized to 5 MPa, the heating was turned on, and the reaction temperature was heated to 130° C., and 200 g of IDAN raw material liquid (the mass concentration of IDAN was 15% wt) was continuously pumped into the reactor at an air velocity of 3 g / min to carry out the first stage reaction. After the feeding was completed, it was kept for 30 minutes (i.e., the second stage reaction) to terminate the reaction; when the temperature in the reactor dropped to room temperature, the reaction liquid in the reactor was filtered to obtain a filtrate containing DETA; wherein the filtration was nitrogen filtration in the reactor, and the obtained liquid (filtrate containing DETA) was discharged from the reactor through a bottom tube, and the solid (mainly Raney nickel) was retained in the reactor for subsequent application cycles;

[0064] The filtrate containing DETA was analyzed by gas chromatography, and the results showed that the IDAN conversion rate of the first batch (i.e., the first use of the hydrogenation catalyst) was 100%, the DETA yield was 93%, and the piperazine yield was 5%.

[0065] (3) Raney cobalt was used for 5 times (i.e., Raney cobalt was used as a hydrogenation catalyst, and after performing step S2 once, the Raney cobalt separated from the reaction liquid of step S2 was used as a hydrogenation catalyst to repeat step S2 (i.e., the second time), and so on, until it was used for 5 times, wherein, as mentioned in step S2, 0.5 g of carbonyl nickel was added to each batch as a catalyst protective agent), and the IDAN conversion rate of the fifth batch (i.e., the fifth time of hydrogenation catalyst application) was measured to be 100%, the DETA yield was 92.5%, and the piperazine yield was 5%.

[0066] Embodiment 2 to Embodiment 8: The difference from Embodiment 1 is that the conditions such as the first organic solvent in step S1, the second organic solvent in step S2, the type and amount of the catalyst protecting agent are different, see Table 1 for details. Except for the differences shown in Table 1, the other steps and conditions are the same.

[0067] Comparative Example 1

[0068] S1. Preprocessing of Rough IDAN

[0069] 100 g of crude IDAN and 590 g of dioxane were mixed, stirred and shaken thoroughly, and filtered three times to remove impurities to obtain an IDAN raw material solution.

[0070] S2, hydrogenation reaction: The difference from step S2 (hydrogenation reaction) in Example 1 is that the second solvent is tetrahydrofuran, and the other conditions are the same as in Example 1.

[0071] Comparative Example 2

[0072] S1. Pretreatment of crude IDAN: the same as step S1 in Example 1 (pretreatment of crude IDAN).

[0073] S2, hydrogenation reaction The difference from step S2 (hydrogenation reaction) in Example 1 is that no catalyst protective agent is added, and the second organic solvent used is tetrahydrofuran (i.e., in Comparative Example 2, 10 g of Raney cobalt, 200 g of tetrahydrofuran and 1.5 g of LiOH are added to the reactor, and then the reactor is closed to carry out the subsequent process)

[0074] The conditions such as the type and amount of the first organic solvent, the second organic solvent, and the catalyst protecting agent in each embodiment and comparative example, as well as the reaction results (IDAN conversion rate, DETA selectivity, and piperazine selectivity of the first and fifth batches) are shown in Table 1.

[0075] Table 1 Preparation conditions and reaction results of DETA

[0076]

[0077] As can be seen from Table 1, in Examples 1 to 8, after the IDAN raw material is extracted with water and an organic solvent, the IDAN is subjected to a hydrogenation reaction, and a catalyst protector is introduced into the hydrogenation reaction system, which can improve the conversion rate of IDAN and the yield of DETA, reduce the yield of piperazine, and at the same time increase the service life of the hydrogenation catalyst.

[0078] Among them, relative to Comparative Example 1 (pretreatment of IDAN raw material with an organic solvent), Examples 4 to 9 use water and organic solvents as extractants to pretreat the IDAN raw material, which can significantly improve the conversion rate of IDAN and the yield of DETA, while reducing the yield of piperazine and increasing the service life of the hydrogenation catalyst.

[0079] Among them, compared with Comparative Example 2 (no catalyst protectant was added during the hydrogenation reaction), Examples 4 to 9 introduced a catalyst protectant during the hydrogenation reaction, which can significantly improve the service life of the hydrogenation catalyst. Even when the fifth batch is applied, a high IDAN conversion rate and DETA yield can still be maintained, while reducing the yield of piperazine.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A N 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The following steps are involved: The iminodiacetonitrile is reacted with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protective agent to generate N 1 -(2-aminoethyl)-1,2-ethylenediamine; wherein the catalyst protecting agent comprises one or more of carbonyl nickel, carbonyl iron, tetraamine nickel, and tetraamine cobalt.

2. The N according to claim 1 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The hydrogenation catalyst comprises one or more of Raney nickel, Raney cobalt and a supported catalyst; Preferably, the supported catalyst includes a carrier and an active component supported on the carrier, the carrier includes one or more of aluminum oxide, silicon oxide, zinc oxide, titanium oxide, magnesium oxide, activated carbon, diatomaceous earth, and silica gel, and the active component includes one or more of sodium element, potassium element, titanium element, manganese element, iron element, cobalt element, copper element, molybdenum element, nickel element, ruthenium element, rhodium element, palladium element, and platinum element.

3. N according to claim 1 or 2 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The mass ratio of the hydrogenation catalyst to the iminodiacetonitrile is 5% to 40%.

4. N according to claim 1 or 2 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The mass ratio of the catalyst protecting agent to the hydrogenation catalyst is 1% to 10%.

5. N according to claim 1 or 2 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The reaction liquid system further includes an auxiliary agent, and the auxiliary agent includes a metal oxide and / or a metal hydroxide; Preferably, the metal element in the metal oxide includes an alkali metal and / or an alkaline earth metal, and the metal element in the metal hydroxide includes an alkali metal and / or an alkaline earth metal.

6. The N according to claim 5 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The mass ratio of the auxiliary agent to the hydrogenation catalyst is 10% to 20%.

7. The N according to claim 5 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The alkali metal includes lithium and / or potassium; And / or, the alkaline earth metal includes calcium.

8. N according to claim 1 or 2 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The solvent includes one or more of dioxane, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, n-butanol, ethyl acetate, and butyl acetate.

9. The N according to claim 1 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The reaction conditions are as follows: reaction temperature is 80° C. to 180° C., hydrogen pressure is 3 MPa to 8 MPa, and reaction time is 60 min to 300 min.

10. The N according to claim 1 1 -(2-aminoethyl)-1,2-ethylenediamine preparation method, characterized in that, The iminodiacetonitrile is obtained by pre-treating an iminodiacetonitrile raw material, wherein the pre-treating process comprises: extracting the iminodiacetonitrile raw material with an extractant to obtain the iminodiacetonitrile; wherein the extractant comprises water and a first organic solvent; Preferably, the pretreatment process comprises: extracting the iminodiacetonitrile raw material with an extractant to obtain a raw material liquid containing the iminodiacetonitrile; The process of reacting iminodiacetonitrile with hydrogen in a reaction liquid system containing a solvent, a hydrogenation catalyst and a catalyst protective agent comprises: adding a raw material liquid containing the iminodiacetonitrile to the reaction liquid system, and reacting the iminodiacetonitrile with hydrogen to generate N 1 -(2-aminoethyl)-1,2-ethylenediamine, generating the N 1 -(2-aminoethyl)-1,2-ethylenediamine; wherein, during the process of adding the raw material liquid containing the iminodiacetonitrile into the reaction liquid system, the space velocity of the raw material liquid containing the iminodiacetonitrile is 1 to 5 g / min.

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