Preparation method and continuous production device of long-chain diamine

Abstract

The invention provides a preparation method and a continuous production device of long-chain diamine. The preparation method of the long-chain diamine comprises the following steps: respectively flowing a raw material solution and hydrogen through a hydrogenation reactor loaded with a supported nickel-based catalyst, and reacting to obtain diamine, wherein the raw material solution contains dinitrile and a solvent; the reaction temperature is 80-130 DEG C; the volume space velocity of the hydrogen is 20-4000 h <-1 >; the volume space velocity of the raw material solution is 0.1-9h <-1 >. By adopting the preparation method of the long-chain diamine provided by the invention, continuous preparation of the diamine with high purity and high conversion rate can be realized.

Description

Technical Field

[0001] The invention relates to a preparation method and a continuous production device of long-chain diamine. Background Art

[0002] Long-chain diamines (straight-chain diamines with 8-20 carbon atoms) are often used to prepare long-chain polyamide materials, such as decanediamine (with 10 carbon atoms) for preparing nylon 1010, nylon 1012, nylon 10T, etc., and dodecanediamine can be used to prepare nylon 1210, nylon 1212, nylon 12T, etc. In addition to the good mechanical properties, wear resistance, lubricity, solvent resistance and molding processability of ordinary nylon, long-chain polyamides also have the characteristics of low water absorption, good dimensional stability, good toughness and softness, excellent wear resistance, and excellent electrochemical properties. Therefore, long-chain polyamides are widely used in automobile brake pipes, oil pipes, bearings, anti-vibration parts, etc. in the automotive field, high-voltage circuit breakers, relay switches, transformers, wire and cable protection materials, etc. in the electrical and electronic fields, and can be used in toothbrush filaments, medical and food packaging materials, clothing, etc. in the civilian field. Due to its wide range of applications and long-term market prospects, the production technology of long-chain diamines has attracted widespread attention from academia and the business community.

[0003] Hu Guosheng's project at North University of China (Pan Yu. Research on the synthesis process and application of decanediamine [D]. Supervisor: Hu Guosheng. North University of China, 2014. Xing Ke. Research on the reaction of preparing diamines from long-chain dibasic acids [D]. North University of China, 2015.) used a kettle reactor to explore the process of hydrogenating decanedinitrile and dodecanedinitrile to prepare decanediamine and dodecanediamine. Among them, sebacate is used as a raw material, the amount of ethanol used is 1.1:1 relative to the mass ratio of sebacate, the potassium hydroxide is 0.6% relative to the mass of sebacate, the catalyst is Raney nickel, the mass ratio is 15% of the mass of sebacate, the hydrogen pressure is 2.1MPa, the stirring speed is 600r / min, the temperature is controlled at 70-95°C, the product is subjected to reduced pressure distillation, and the yield of dodecanediamine is 92%; dodecanedinitrile is used as a raw material, 1.1 times the mass ratio of ethanol is used, 0.8% potassium hydroxide is used as an inhibitor relative to the mass of dodecanedinitrile, the catalyst is Raney nickel, the mass ratio is 15% of the mass of dodecanedinitrile, the hydrogen pressure is 2.1MPa, the stirring speed is 800r / min, the temperature is controlled at 110°C, the catalyst is subsequently filtered to remove the catalyst, the ethanol is distilled to remove the ethanol, the product is subjected to reduced pressure distillation, and the yield of dodecanedinitrile is 92%.

[0004] The research group of Zhu Weihong / Lu Zhongjie from East China University of Science and Technology adopted a kettle reactor, with sebacate as raw material, 10% Raney nickel relative to the mass of sebacate as catalyst, 0.5%-1% potassium hydroxide relative to the mass of sebacate as inhibitor, reaction temperature of 70-90°C, reaction pressure of 2.5MPa, stirring speed of 1000r / min, and ethanol in a 1:1 ratio relative to the mass of sebacate. Subsequently, the catalyst was removed by filtration, and the ethanol was removed by distillation. The product was subjected to reduced pressure distillation to obtain decanediamine with a molar yield of greater than 96.5% and a purity of greater than 99%.

[0005] The Chinese patent (CN101068775B) uses a bath slurry bed reactor, 1,8-octanedionitrile as the raw material, Raney nickel as the catalyst, a small amount of water as the solvent, tetramethylammonium hydroxide as the inhibitor, and reacts at 75°C under a hydrogen pressure of 2.76MPa to obtain 1,8-octanediamine with a purity of 96.6%. The conversion rate of suberonitrile is 100%.

[0006] Chinese patent (CN111875501A) discloses a multi-stage continuous kettle reactor, which uses Raney nickel as a catalyst, ethanol as a solvent, 2.3MPa hydrogen pressure, and 90°C to catalytically hydrogenate sebacate, and can obtain decanediamine with a molar yield of 98.2%.

[0007] A Chinese patent (CN106748806A) discloses the use of a modified supported Ni-Co-Pd catalyst, aliphatic dinitriles and hydrogen as raw materials, dialkoxymethane as solvent, and the subsequent use of a fluidized bed reactor to achieve the preparation of suberonitrile, sebacate, dodecanedinitrile, tetradecanedinitrile, hexadecanedinitrile, and octadecanedinitrile, with a product purity of >98%.

[0008] Based on the above background technology, diamine synthesis mostly adopts kettle reactor, and intermittent production realizes diamine preparation process. In the subsequent separation and purification process, the catalyst Raney nickel or skeleton nickel is removed by filtering, however, Raney nickel is easy to spontaneously combust when encountering air, and the filtering separation process has certain safety hazards. At the same time, the reaction solution contains a large amount of flammable and explosive organic solvent ethanol, which will increase the risk of combustion and explosion. Therefore, the entry of oxygen should be strictly avoided in the catalyst separation section, which increases the difficulty of operation and safety requirements. At the same time, most technologies adopt single-pot intermittent process for production, and operations such as feeding, transfer, and distillation all need to be carried out manually, which will not only cause product quality fluctuations, but also have the disadvantages of large production labor intensity, high risk of on-site operation, and many waste discharges. In addition, it is difficult to increase the production capacity of single-pot intermittent production, and it is impossible to meet the current demand for production in various industries. Summary of the invention

[0009] The technical problem to be solved by the present invention is: to overcome the shortcomings of the prior art, to provide a preparation method and a continuous production device for long-chain diamines, to realize the continuous production of long-chain diamines, and to eliminate the catalyst filtration and separation process, which can effectively solve the problems mentioned in the above background technology, such as high production intensity, large fluctuations in product quality, high risks in on-site operations, high waste emissions, and difficulty in increasing production capacity.

[0010] To achieve the above objectives, the present invention adopts the following technical solutions.

[0011] The present invention provides a method for preparing a long-chain diamine, comprising the following steps: a raw material solution and hydrogen gas are respectively passed through a hydrogenation reactor carrying a supported nickel-based catalyst to react to obtain the diamine; wherein:

[0012] The raw material solution contains dinitrile and solvent;

[0013] The reaction temperature is 80-130°C;

[0014] The volume space velocity of the hydrogen is 20-4000h -1 ;

[0015] The volume space velocity of the raw material solution is 0.1-9h -1 .

[0016] In the present invention, the volume space velocity ratio of the raw material solution and the hydrogen is preferably 0.1:(5-200), more preferably 0.1:(5-100); for example 0.1:25.

[0017] In the present invention, the reaction temperature is preferably 85-105°C, such as 90°C or 100°C.

[0018] In the present invention, the reaction pressure is preferably 1-15 MPa, more preferably 2-10 MPa, such as 3 MPa or 9 MPa.

[0019] In the present invention, the volume space velocity of the hydrogen is preferably 25-1000h -1 , preferably 25-100h -1 , for example 40h -1 , 43h -1 or 50h -1 .

[0020] In the present invention, the volume space velocity of the raw material solution is preferably 0.1-5h -1 , more preferably 0.1-1h -1 , for example 0.5h -1 .

[0021] In the present invention, the volume space velocity refers to the volume flow rate (m 3 / h) and catalyst volume (m 3 ) ratio.

[0022] In the present invention, the raw material solution is preferably obtained by mixing the solvent with the dinitrile.

[0023] Preferably, the dinitrile is in liquid state during the mixing.

[0024] In the present invention, the supported nickel-based catalyst at least comprises nickel and a carrier, and preferably comprises nickel, a modified metal and a carrier.

[0025] Wherein, in the supported nickel-based catalyst, the weight content of nickel is preferably 30%-80%, and the weight content of the modified metal is preferably 2%-12%, and the rest is the carrier.

[0026] Among them, in the supported nickel-based catalyst, the modified metal is preferably one or more of Li, Na, K, Be, Mg, Ca, Cu, Co, Zr, Mo, Zn, Cd, Ru, Rh, Pd and Pt, such as magnesium and sodium, chromium and sodium.

[0027] Wherein, the carrier of the supported nickel-based catalyst is preferably selected from one or more of alumina, silicon oxide, diatomaceous earth, activated carbon, molecular sieve and zeolite.

[0028] In the present invention, the nickel in the supported nickel-based catalyst preferably exists in the form of metallic nickel and nickel oxide.

[0029] More preferably, the carrier is silicon oxide and / or diatomaceous earth.

[0030] In a more preferred embodiment of the present invention, the supported nickel-based catalyst contains nickel, magnesium, sodium and a carrier.

[0031] Preferably, the weight content of the nickel is 30%-80%, the weight content of the magnesium and the sodium is 2%-12%, and the rest is the carrier.

[0032] Preferably, the weight content of magnesium is 2%-10%, and the weight content of sodium is 1%-5%.

[0033] In the present invention, when the supported nickel-based catalyst contains magnesium, the magnesium is preferably present in the form of magnesium oxide. When the supported nickel-based catalyst contains sodium, the sodium is preferably present in the form of sodium oxide. When the supported nickel-based catalyst contains chromium, the chromium is preferably present in the form of metallic chromium and chromium oxide.

[0034] In the present invention, the supported nickel-based catalyst can be prepared by conventional methods in the art, preferably by coprecipitation. Specifically, the supported nickel-based catalyst is prepared by mixing a raw metal salt solution and a carrier and coprecipitating.

[0035] Wherein, the metal salt preferably includes one or more of nickel nitrate, magnesium nitrate, chromium nitrate and sodium carbonate.

[0036] In a preferred embodiment of the present invention, the supported nickel-based catalyst is prepared by mixing nickel nitrate, magnesium nitrate and sodium carbonate with water, and then adding a carrier, such as silicon oxide and / or diatomaceous earth, for co-precipitation.

[0037] In another preferred embodiment of the present invention, the supported nickel-based catalyst is prepared by mixing nickel nitrate, chromium nitrate and sodium carbonate with water, and then adding a carrier, such as silicon oxide and / or diatomaceous earth, for co-precipitation.

[0038] In the present invention, the hydrogenation reactor is preferably a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor or a microreactor.

[0039] In the present invention, the heating mode of the hydrogenation reactor is preferably electric heating, steam jacket heating or thermal oil heating.

[0040] In the present invention, after the supported nickel-based catalyst is loaded into the hydrogenation reactor, preferably, nitrogen is first used to replace the air in the hydrogenation reactor, and then hydrogen is used to replace the nitrogen in the hydrogenation reactor.

[0041] In the present invention, the chemical formula of the dinitrile is NC(CH2) n CN, n is preferably any integer between 6 and 18, such as sebacate, undecanedinitrile, dodecanedinitrile, tridecanedinitrile, tetradecanedinitrile, pentadecedinitrile, and hexadecanedinitrile.

[0042] In the present invention, the solvent is preferably selected from one or more organic solvents of ester compounds, organic acid compounds, alcohol compounds, ketone compounds, ether compounds, sulfoxide compounds, halogenated alkanes, hydrocarbon compounds and ammonia solutions.

[0043] Wherein, the hydrocarbon compound is preferably an alkane compound;

[0044] In the present invention, the solvent is preferably selected from one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, formic acid, acetic acid, propionic acid, butyric acid, methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, acetone, cyclohexanone, tetrahydrofuran, dioxane, ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, monochloroalkanes, dichloroalkanes, trichloroalkanes, tetrachloroalkanes, benzene, toluene, ethylbenzene, xylene, cyclopentane, cyclohexane, saturated alkanes with 5-20 carbon atoms, trimethylamine, triethylamine, ammonia water and liquid ammonia. Wherein, the saturated alkanes with 5-20 carbon atoms are, for example, one or more of pentane, hexane, heptane, octane, decane, n-undecane, n-dodecane, n-tridecane and n-hexadecane.

[0045] In the present invention, the mass ratio of the solvent to the dinitrile is preferably (0.01-20):(1-20), more preferably (1-10):(1-10), for example 2:1 or 9:1.

[0046] In the present invention, the raw material solution preferably further contains an inhibitor, which is preferably one or more of sodium hydroxide, potassium hydroxide, ammonia water and liquid ammonia.

[0047] In a preferred embodiment of the present invention, the solvent is one or more of ethers, alcohols or alkane compounds, and the inhibitor is one or more of sodium hydroxide, potassium hydroxide, ammonia water and liquid ammonia.

[0048] In the present invention, in the raw material solution, the inhibitor concentration is measured by mass fraction, and any concentration falls within the scope of patent protection of the present invention.

[0049] When the raw material solution further contains an inhibitor, the raw material solution is preferably prepared by first mixing the solvent with the inhibitor and then mixing with the dinitrile.

[0050] In the present invention, the raw material solution and hydrogen are preferably preheated before flowing through the hydrogenation reactor.

[0051] Wherein, the preheating is preferably preheating to the reaction temperature.

[0052] In the present invention, the reaction preferably further includes a heat exchange step.

[0053] In the present invention, the reaction preferably further comprises a purification step; the purification preferably comprises distillation and / or rectification.

[0054] In the present invention, the reaction preferably further includes a separation step.

[0055] Wherein, the separation pressure is preferably 0-15MPa; for example, 0.5MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa or 14MPa.

[0056] The separation product obtained by the separation preferably includes one or more of unreacted gas, solvent and inhibitor. The unreacted gas includes hydrogen that does not participate in the reaction.

[0057] The separated product obtained by the separation is preferably re-entered into the hydrogenation reactor for recycling. When the separated product contains an inhibitor, the inhibitor can be re-entered into the reaction for recycling by distillation.

[0058] In the present invention, the dinitrile is preferably first heated to a liquid state in a dinitrile storage tank with a jacket and then used to prepare the raw material solution.

[0059] Wherein, the pressure resistance of the binary nitrile storage tank is preferably 0.1-2MPa.

[0060] Wherein, the pressure resistance of the jacket of the binary nitrile storage tank is preferably 0.1-1 MPa.

[0061] In a preferred embodiment of the present invention, the heating medium in the jacket of the jacketed binary nitrile storage tank is steam or heat transfer oil.

[0062] In the present invention, the reaction may be followed by a purification step; the purification preferably includes distillation and / or rectification.

[0063] In the present invention, the reaction product of the reaction is a solution containing diamine. The solution containing diamine is subjected to the separation to remove unreacted gas, solvent and inhibitor to obtain crude diamine. The purity of the crude diamine is >60%, preferably >96%, for example 96%-98.99%.

[0064] Furthermore, the crude diamine is refined to obtain refined diamine, wherein the purity of the refined diamine is preferably >99%, such as 99%-99.99%.

[0065] The present invention also provides a continuous production device for the above-mentioned long-chain diamine, which comprises a raw material solution storage tank, a hydrogen storage tank, a preheater, a hydrogenation reactor and a product storage tank, wherein the outlets of the raw material solution storage tank and the hydrogen storage tank are respectively connected to the inlet of the preheater, the outlet of the preheater is connected to the inlet of the hydrogenation reactor, and the outlet of the hydrogenation reactor is connected to the inlet of the product storage tank;

[0066] The preheater preheats the raw material solution from the raw material solution storage tank and the hydrogen from the hydrogen storage tank; and the hydrogenation reactor carries a supported nickel-based catalyst.

[0067] Wherein, the raw material solution storage tank is used to store the raw material solution.

[0068] In the present invention, the hydrogenation reactor is preferably one or more of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor and a microreactor.

[0069] Wherein, the fixed bed reactor is preferably one of an adiabatic fixed bed reactor, a tubular fixed bed reactor or an autothermal fixed bed reactor.

[0070] In the present invention, the heating mode of the hydrogenation reactor is one or more of electric heating, steam jacket heating and thermal oil heating.

[0071] In the present invention, the preheater is preferably selected from a coil preheater and / or a shell-and-tube preheater.

[0072] In the present invention, a heat exchanger is preferably provided between the hydrogenation reactor and the product storage tank.

[0073] In the present invention, the continuous production device of long-chain diamines preferably also includes a separation device, which is used to separate crude long-chain diamines. The separation device includes a product inlet, a first outlet, and a second outlet. The first outlet is used to discharge unreacted hydrogen, and the second outlet is used to output the crude long-chain diamines.

[0074] In the present invention, the continuous production device of the long-chain diamines preferably further comprises a distillation and / or rectification device, and the inlet of the distillation and / or rectification device is connected to the outlet of the separation device.

[0075] Preferably, the number of the separation devices is more than one, for example, one, two, three or four.

[0076] Preferably, when the number of the separation devices is more than 2, the more than 2 separation devices are connected to the product storage tank in series or in parallel.

[0077] Preferably, the separation device is a pressure tank or a pressure kettle, the internal pressure of which can be set to different values ​​for separating different target impurities.

[0078] Preferably, the outlet of the separation device is connected to the inlet of the preheater through a circulation pump, and the separation product re-enters the hydrogenation reactor for recycling under the action of the circulation pump.

[0079] The positive and progressive effects of the present invention are:

[0080] The invention develops a preparation method and a continuous production device for long-chain diamines. The preparation method for the long-chain diamines adopts a hydrogenation reactor and a supported nickel-based catalyst. Under specific temperature, pressure and volume space velocity conditions, the continuous preparation of diamines with high purity and high conversion rate can be achieved. The content of diamines in the prepared crude diamines is greater than 60%, the conversion rate of dinitrile is above 79%, and the content of secondary amines, the main by-product, is less than 21%.

[0081] The preparation method and continuous production device effectively avoid catalyst separation, and continuous production can greatly reduce the uncertainty caused by manual operation and improve the stability of product quality.

[0082] In summary, the present invention is a safe, reliable, simple and easy-to-use technology for continuous production of long-chain diamines, which is easy to scale up and has great potential for industrial promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 This is a schematic diagram of a continuous production device for long-chain diamines.

[0084] The following are the descriptions of the reference numerals:

[0085] 1-raw solution storage tank, 2-hydrogen storage tank, 3-preheater, 4-hydrogenation reactor, 5-heat exchanger, 6-product storage tank, 7-separation device, 8-circulation pump. DETAILED DESCRIPTION

[0086] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0087] The preparation methods of the catalysts used in the following Examples 1-20 and Comparative Examples 1 and 2 are as follows:

[0088] Catalyst A: At room temperature, 1820g of nickel nitrate and 142g of magnesium nitrate were dissolved in 10L of water, and 1050g of sodium carbonate solvent was added to 10L of water. Under vigorous stirring, the nickel-containing solution was added dropwise to the sodium carbonate solution, and 200g of diatomaceous earth was added. After the addition was completed, the mixture was stirred for 3h and filtered. The resulting filter cake was dispersed in 5L of 0.25% NaOH solution, stirred for 2h, filtered, and the filter cake was dried to obtain catalyst powder. The catalyst was granulated to obtain a crude catalyst, which was heated and activated under H2 atmosphere before use.

[0089] Catalyst B: At room temperature, 1820g of nickel nitrate was dissolved in 10L of water. Separately, 1050g of sodium carbonate solvent was mixed with 10L of water. Under vigorous stirring, the solution containing nickel was added dropwise to the sodium carbonate solution. 200g of diatomaceous earth was added. After the addition was completed, the mixture was stirred for 3h and filtered. The resulting filter cake was dispersed in 5L of 0.25% NaOH solution. The mixture was stirred for 2h and filtered. The filter cake was dried to obtain catalyst powder. The catalyst was granulated to obtain a crude catalyst, which was activated by heating under H2 atmosphere before use.

[0090] The production apparatus used in the following Examples 1-20 and Comparative Examples 1 and 2 is as follows:

[0091] A continuous production device for the above-mentioned long-chain diamine, such as Figure 1 As shown, it includes a raw material solution storage tank 1, a preheater 3, a hydrogenation reactor 4, a heat exchanger 5, a product storage tank 6 and a separation device 7 connected in sequence by pipelines; wherein the raw material solution storage tank 1 is used to store the raw material solution. The preheater 3 is a coil preheater, and the preheater 3 is also connected to a hydrogen storage tank 2. The preheater 3 preheats the raw material solution from the raw material solution storage tank 1 and the hydrogen from the hydrogen storage tank 2. The hydrogenation reactor 4 is a fixed bed reactor, and the heating mode of the fixed bed reactor is steam jacket heating. The reaction product is first treated by the heat exchanger 5 and then stored in the product storage tank 6. The separation device 7 is used to separate the unreacted gas, solvent or inhibitor in the product. The separation device 7 is a pressure tank, and the number of pressure tanks is 1. The pressure in the pressure tank can be set to different values, which is suitable for separating different target impurities. The outlet of the separation device 7 is also connected to the inlet of the preheater 3 through a circulating pump 8, which is used to re-enter the hydrogenation reactor 4 for recycling under the action of the circulating pump 8.

[0092] Example 1

[0093] 100 g of sebacinonitrile was dissolved in 900 mL of ethanol containing 6% ammonia, and the solution was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 80 ° C. The pressure of the fixed bed reactor was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated in a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 60.8%, the conversion rate of sebacatenitrile is 79.9%, and the main by-product secondary amine accounts for 10.9%.

[0094] The purity of decanediamine is the mass percentage of decanediamine in the crude decanediamine; the conversion rate of decanonitrile is the mass percentage of decanonitrile participating in the reaction to the mass percentage of decanonitrile added to the raw material solution; the proportion of the main by-product secondary amine is the mass percentage of the by-product secondary amine in the crude decanediamine.

[0095] Example 2

[0096] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia, and the raw material solution was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 90° C. The pressure of the fixed bed reactor was set at 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 96.4%, the conversion rate of decanonitrile is 99.3%, and the main by-product secondary amine accounts for 0.7%. The crude decanediamine is distilled to obtain refined decanediamine with a purity of 99.7%.

[0097] Example 3

[0098] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia, and the solution was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure of the fixed bed reactor was set to 3.0 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank 7 to obtain crude decanediamine. The separated hydrogen passes through a pipeline and re-enters the hydrogenation reactor under the action of a circulating pump 8 for recycling. According to gas phase detection, the purity of crude decanediamine is 96.1%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 1.3%. The crude decanediamine is distilled to obtain refined decanediamine, and the purity of refined decanediamine is 99.6%.

[0099] Example 4

[0100] 100 g of sebacinonitrile was dissolved in 900 mL of a methanol solution containing 2% KOH to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 90° C. The reactor pressure was set at 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 92.6%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 3%. The crude decanediamine is distilled to obtain refined decanediamine, and the purity of refined decanediamine is 99.5%.

[0101] Example 5

[0102] 100 g of sebacinonitrile was dissolved in 900 mL of a methanol solution containing 2% KOH to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure of the fixed bed reactor was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 90.2%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 4.2%.

[0103] Example 6

[0104] 100 g of sebacinonitrile was dissolved in 900 mL of triethylamine solution, and the solution was added to the raw material storage tank 1. The raw material solution was fed into the fixed bed reactor through the preheater via a feed pump. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 110 ° C. The pressure of the fixed bed reactor was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 65.9%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 7.5%.

[0105] Example 7

[0106] 100 g of sebacinonitrile was dispersed in 900 mL of aqueous ammonia solution containing concentrated ammonia. The raw material solution was fed into a fixed bed reactor through a feed pump. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 130 ° C. The pressure was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 74.4%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 9.4%.

[0107] Example 8

[0108] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia, and the raw material solution was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst B particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure was set to 3.0 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 78.9%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 20.8%.

[0109] Example 9

[0110] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst B particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 96.5%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 3.6%.

[0111] Example 10

[0112] 100 g of sebacinonitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was pumped into a fixed bed reactor through a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure was set to 9.0 MPa. The raw material solution was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of decanediamine is 97.1%, the conversion rate of decanonitrile is 100%, and the main by-product secondary amine accounts for 1.7%. The crude decanediamine is distilled to obtain refined decanediamine with a purity of 99.8%.

[0113] Embodiment 11

[0114] 100 g of sebacinonitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, and the raw material solution was added to a raw material storage tank, and the raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles, and the temperature of the fixed bed reactor was set at 100 ° C, the pressure was set to 3 MPa, and the raw material solution was heated at 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of decanediamine is 94.1%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 5.2%.

[0115] Example 12

[0116] 108 g of undecane dinitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure was set to 9 MPa. The raw material solution was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h -1 ) passes through the reactor, and the hydrogen in the hydrogen storage tank flows through the fixed bed reactor at a flow rate of 150mL / min. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the 11-carbon diamine product can be collected in the product storage tank. The solution containing the 11-carbon diamine product is separated by a pressure tank to obtain crude 11-carbon diamine. According to gas phase detection, the purity of dodecanediamine is 97.5%, the conversion rate of 11-carbon dinitrile is 100%, and the main by-product secondary amine accounts for 1.1%. The crude 11-carbon diamine is distilled to obtain refined 11-carbon diamine with a purity of 99.7%.

[0117] Example 13

[0118] 116 g of dodecanedinitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank, and the raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 100 ° C, the pressure was set to 9.0 MPa, and the raw material solution was heated at 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the dodecanediamine product can be collected in the product storage tank. The solution containing dodecanediamine is separated by a pressure tank to obtain crude dodecanediamine. According to gas phase detection, the purity of crude dodecanediamine is 98.2%, the conversion rate of dodecanedinitrile is 100%, and the main by-product secondary amine accounts for 1.2%. The crude dodecanediamine is distilled to obtain refined dodecanediamine, and the purity of refined dodecanediamine is 99.8%.

[0119] Embodiment 14

[0120] 124 g of tridecanedinitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 100 ° C, the pressure was set to 9 MPa, and the raw material solution was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 120 mL / min (volume space velocity was 40 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the tridecane diamine product can be collected in the product storage tank. The solution containing the tridecane diamine is separated by a pressure tank to obtain the crude tridecane diamine. According to gas phase detection, the purity of the crude tridecane diamine is 97.5%, the conversion rate of tridecane dinitrile is 100%, the main by-product secondary amine accounts for 1.7%, and the crude tridecane diamine is distilled to obtain refined tridecane diamine with a purity of 99.7%.

[0121] Embodiment 15

[0122] 132 g of tetradecanitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank, and the raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles, the temperature of the fixed bed reactor was set to 100 ° C, the reactor pressure was set to 3 MPa, and the raw material solution was heated at 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was 130 mL / min (volume space velocity was 43 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the tetradecane diamine product can be collected in the product storage tank. The solution containing the tetradecane diamine is separated by a pressure tank to obtain the crude tetradecane diamine. According to gas phase detection, the purity of the crude tetradecane diamine is 98.3%, the conversion rate of tetradecane dinitrile is 100%, and the main by-product secondary amine accounts for 0.7%. The crude tetradecane diamine is distilled to obtain refined tetradecane diamine with a purity of 99.8%.

[0123] Example 16

[0124] 140 g of pentadecanedinitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C, the pressure was set at 3.0 MPa, and the raw material solution was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was 130 mL / min (volume space velocity was 43 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the 15-carbon diamine product can be collected in the product storage tank. The solution containing the 15-carbon diamine is separated by a pressure tank to obtain the crude 15-carbon diamine. According to gas phase detection, the purity of the crude 15-carbon diamine is 97.0%, the conversion rate of the 15-carbon dinitrile is 100%, and the main by-product secondary amine accounts for 1.6%. The crude 15-carbon diamine is distilled to obtain refined 15-carbon diamine with a purity of 99.6%.

[0125] Embodiment 17

[0126] 149 g of hexadecane dinitrile was dissolved in 200 g of liquid ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 100 ° C. The pressure was set to 3 MPa. The raw material solution was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h-1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was 130 mL / min (volume space velocity was 43 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the hexadecanediamine product can be collected in the product storage tank. The solution containing the hexadecanediamine is separated by a pressure tank to obtain the crude hexadecanediamine. According to gas phase detection, the purity of the crude hexadecanediamine is 96.4%, the conversion rate of hexadecanedinitrile is 100%, and the main by-product secondary amine accounts for 1.9%. The crude hexadecanediamine is distilled to obtain refined hexadecanediamine with a purity of 99.7%.

[0127] Embodiment 18

[0128] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 100 ° C, the pressure was set to 3.0 MPa, and the mixed liquid was heated at a rate of 0.3 mL / min (volume space velocity was 0.1 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing decanediamine is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 96.1%, the conversion rate of decanonitrile is 100%, and the main by-product secondary amine accounts for 1.3%. The crude decanediamine is distilled to obtain refined decanediamine with a purity of 99.7%.

[0129] Embodiment 19

[0130] 50 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set at 100 ° C. The pressure was set to 3 MPa. The raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 75 mL / min (volume space velocity was 25 h -1) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 98.1%, the conversion rate of sebacatenitrile is 100%, and the main by-product secondary amine accounts for 0.7%. The crude decanediamine is distilled to obtain refined decanediamine with a purity of 99.9%.

[0131] Embodiment 20

[0132] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 130° C., the pressure was set to 3.0 MPa, and the raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, the solution containing the decanediamine product can be collected in the product storage tank. The solution containing the decanediamine product is separated by a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of crude decanediamine is 91%, the main by-product secondary amine accounts for 7.2%, and the conversion rate of sebacate is 100%.

[0133] Comparative Example 1

[0134] The raw materials and preparation method are the same as those in Example 3, except that when reacting in a fixed bed reactor, the raw material solution is heated at 30 mL / min (volume space velocity is 10 h -1 ) passed through the reactor, and the hydrogen in the hydrogen storage tank was 15000mL / min (volume space velocity was 5000h -1 ) flowed through the fixed bed reactor. According to gas phase detection, the purity of the crude decanediamine obtained was 20.9%, and the conversion rate of decanitrile was 21%.

[0135] Comparative Example 2

[0136] 100 g of sebacinonitrile was dissolved in 900 mL of methanol containing 12% ammonia to form a raw material solution, which was added to a raw material storage tank. The raw material solution was fed into a fixed bed reactor through a feed pump and a preheater. The fixed bed reactor was filled with 180 mL of catalyst A particles. The temperature of the fixed bed reactor was set to 50° C., the pressure was set to 3 MPa, and the raw material solution was heated at a rate of 1.5 mL / min (volume space velocity was 0.5 h -1) passed through the reactor, and the hydrogen in the hydrogen storage tank was heated at 150 mL / min (volume space velocity of 50 h -1 ) flows through the fixed bed reactor. There is no need to filter and separate the catalyst. After the liquid flowing out of the fixed bed reactor is treated by a heat exchanger, a solution containing the decanediamine product can be collected in a product storage tank. The solution containing the decanediamine product is separated in a pressure tank to obtain crude decanediamine. According to gas phase detection, the purity of the crude decanediamine is 56%, and the conversion rate of sebaconitrile is 56%.

Claims

1. A method for preparing a long-chain diamine, characterized in that: The method comprises the following steps: a raw material solution and hydrogen gas are respectively passed through a hydrogenation reactor carrying a supported nickel-based catalyst to react and obtain diamine; wherein, The raw material solution contains dinitrile and solvent; The reaction temperature is 80-130°C; The volume space velocity of the hydrogen is 20-4000h -1 ; The volume space velocity of the raw material solution is 0.1-9h -1 .

2. The method for preparing a long-chain diamine according to claim 1, characterized in that: The volume space velocity ratio of the raw material solution to the hydrogen is 0.1:(5-200), preferably 0.1:(5-100); And / or, the reaction temperature is 85-105°C; And / or, the reaction pressure is 1-15 MPa, preferably 2-10 MPa; And / or, the volume space velocity of the hydrogen is 25-1000h -1 , preferably 25-100h -1 ; And / or, the raw material solution is obtained by mixing the solvent with the dinitrile; preferably, the dinitrile is in liquid state during the mixing.

3. The method for preparing a long-chain diamine according to claim 1, characterized in that: The supported nickel-based catalyst contains nickel, a modified metal and a carrier; preferably, in the supported nickel-based catalyst, the weight content of nickel is 30%-80%, and the weight content of the modified metal is 2%-12%, and the rest is a carrier; preferably, the modified metal is one or more of Li, Na, K, Be, Mg, Ca, Cu, Co, Zr, Mo, Zn, Cd, Ru, Rh, Pd and Pt; preferably, the carrier of the supported nickel-based catalyst is selected from one or more of alumina, silicon oxide, diatomaceous earth, activated carbon, molecular sieve and zeolite; And / or, the nickel in the supported nickel-based catalyst exists in the form of metallic nickel and nickel oxide.

4. The method for preparing a long-chain diamine according to claim 3, characterized in that: The supported nickel-based catalyst contains nickel, magnesium, sodium and a carrier; wherein the weight content of the nickel is 30%-80%, the total weight content of the magnesium and the sodium is 2%-12%, and the rest is the carrier; Preferably, the weight content of magnesium is 2%-10%, and the weight content of sodium is 1%-5%; And / or, the carrier is silicon oxide and / or diatomaceous earth; and / or, when the supported nickel-based catalyst contains magnesium, the magnesium is present in the form of magnesium oxide; and / or, when the supported nickel-based catalyst contains sodium, the sodium is present in the form of sodium oxide; And / or, when the supported nickel-based catalyst contains chromium, the chromium exists in the form of metallic chromium and chromium oxide.

5. The method for preparing a long-chain diamine according to claim 1, characterized in that: The supported nickel-based catalyst is prepared by mixing a raw metal salt solution and a carrier and co-precipitating the mixture; Preferably, the metal salt comprises one or more of nickel nitrate, magnesium nitrate, chromium nitrate and sodium carbonate; Preferably, the supported nickel-based catalyst is prepared by mixing nickel nitrate, magnesium nitrate and sodium carbonate with water, and then adding silicon oxide and / or diatomaceous earth for co-precipitation; Preferably, the supported nickel-based catalyst is prepared by mixing nickel nitrate, chromium nitrate and sodium carbonate with water, and then adding silicon oxide and / or diatomaceous earth for co-precipitation; And / or, the hydrogenation reactor is a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor or a microreactor; And / or, the heating mode of the hydrogenation reactor is electric heating, steam jacket heating or thermal oil heating.

6. The method for preparing a long-chain diamine according to claim 1, characterized in that: The chemical formula of the dinitrile is NC(CH2) n CN, n is any integer between 6 and 18; And / or, the solvent is selected from one or more organic solvents of ester compounds, organic acid compounds, alcohol compounds, ketone compounds, ether compounds, sulfoxide compounds, halogenated alkanes, hydrocarbon compounds and ammonia solutions; wherein the hydrocarbon compound is preferably an alkane compound; And / or, the mass ratio of the solvent to the dinitrile is (0.01-20):(1-20), preferably (1-10):(1-10); And / or, the raw material solution further contains an inhibitor; the inhibitor is preferably one or more of sodium hydroxide, potassium hydroxide, ammonia water and liquid ammonia; And / or, the raw material solution is prepared by first mixing the solvent with the inhibitor and then mixing with the dinitrile.

7. The method for preparing a long-chain diamine according to claim 1, characterized in that: The raw material solution and hydrogen are preheated before flowing through the hydrogenation reactor; the preheating is preferably preheated to the reaction temperature; And / or, the reaction further includes a heat exchange step; And / or, the reaction further includes a refining step; the refining preferably includes distillation and / or rectification.

8. The method for preparing a long-chain diamine according to claim 1, characterized in that: The reaction further includes a separation step; Preferably, the separation pressure is 0-15MPa; Preferably, the separation product obtained by the separation includes one or more of unreacted gas, solvent and inhibitor; Preferably, the separated product obtained by the separation re-enters the hydrogenation reactor for recycling.

9. A continuous production device for preparing long-chain diamines, characterized in that: It comprises a raw material solution storage tank, a hydrogen storage tank, a preheater, a hydrogenation reactor and a product storage tank, wherein the outlets of the raw material solution storage tank and the hydrogen storage tank are respectively connected to the inlet of the preheater, the outlet of the preheater is connected to the inlet of the hydrogenation reactor, and the outlet of the hydrogenation reactor is connected to the inlet of the product storage tank; The preheater preheats the raw material solution from the raw material solution storage tank and the hydrogen from the hydrogen storage tank; and the hydrogenation reactor carries a supported nickel-based catalyst.

10. The continuous production device for preparing long-chain diamines according to claim 9, characterized in that: The hydrogenation reactor is selected from one or more of a fixed bed reactor, a fluidized bed reactor, a slurry bed reactor and a microreactor; and / or, the heating mode of the hydrogenation reactor is selected from one or more of electric heating, steam jacket heating and thermal oil heating; And / or, the preheater is selected from a coil preheater and / or a shell and tube heat exchanger; And / or, a heat exchanger is provided between the hydrogenation reactor and the product storage tank; And / or, the continuous production device of long-chain diamines further comprises a separation device, the separation device is used to separate the crude long-chain diamine, the separation device comprises a product inlet, a first outlet, and a second outlet, the first outlet is used to discharge unreacted hydrogen, and the second outlet is used to output the crude long-chain diamine; Preferably, the number of the separation devices is more than one; more preferably, when the number of the separation devices is more than two, the more than two separation devices are connected to the product storage tank in series or in parallel; Preferably, the separation device is a pressure tank or a pressure kettle, the pressure inside of which is set to different values ​​for separating different target impurities; Preferably, the outlet of the separation device is connected to the inlet of the preheater through a circulation pump, and the separation product re-enters the hydrogenation reactor for recycling under the action of the circulation pump.

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