Method and device for continuous amination hydrogenation of acrylonitrile in pipeline reactor

Abstract

The invention belongs to the field of fine chemical engineering, and particularly relates to a method and a device for continuous amination hydrogenation of acrylonitrile in a pipeline reactor, the method comprises the following steps: S1, continuous addition reaction of acrylonitrile and chain organic amine in a first pipeline reactor; s2, the reaction liquid obtained in the step S1 directly flows into a second channelization reactor for a continuous hydrogenation reaction; and S3, carrying out reduced pressure distillation on the reaction liquid obtained in the step S2. The two-step series-connection type channelization reactor has the advantages of being easy to operate, capable of achieving continuous production, good in heat dissipation effect, safe, controllable and high in production efficiency.

Description

Technical Field

[0001] This invention relates to a method and apparatus for continuous amination and hydrogenation of acrylonitrile in a pipelined reactor. Background Technology

[0002] Acrylonitrile (molecular formula C3H3N, molecular weight 53.06, boiling point 77.3℃) is an important organic chemical raw material, playing a significant role in synthetic fibers, synthetic resins, and other polymer materials, and has broad application prospects. Furthermore, acrylonitrile polymers and their derivatives are also widely used in building materials and daily necessities.

[0003] 1,3-Propanediamine derivatives (R,R҆:-(CH2)nCH3) are a class of widely used organic chemical raw materials and fine chemical intermediates. N,N-Dimethyl-1,3-Propanediamine, abbreviated as DMAPA, belongs to the lower aliphatic diamine class and is an important chemical intermediate widely used in the preparation of detergents, surfactants, textiles, lubricant additives, gasoline additives, preservatives, humectants, and foaming agents. 3-Diethylaminopropylamine, with the molecular formula C7H... 18 N2 can be used as a solvent, extractant, and intermediate in organic synthesis. It can also be used as a curing agent for epoxy resins, in small castings, laminates, and adhesives.

[0004] The synthesis of 1,3-propanediamine derivatives can be achieved by first reacting acrylonitrile with an amine via Michael addition to generate the corresponding aminopropionitrile, followed by hydrogenation. For example, in the industrial synthesis of N,N-dimethyl-1,3-propanediamine, acrylonitrile undergoes an addition reaction with dimethylamine to prepare dimethylaminopropionitrile, which is then hydrogenated to obtain N,N-dimethyl-1,3-propanediamine. Patent CN113620813A summarizes methods for synthesizing N,N-dimethyl-1,3-propanediamine using different reaction devices such as fixed-bed reactors, bubble-cap reactors, and reaction vessels. However, batch reactors are difficult to use for continuous production due to low levels of automation and complex processes; microchannel reactors are costly and difficult to scale up industrially; while fixed-bed reactors have limited heat transfer, easily leading to localized overheating and increasing process risk. Furthermore, the catalyst in fixed-bed reactors is prone to deactivation, requiring shutdown and catalyst replacement.

[0005] The Michael addition reaction of acrylonitrile with amines and the hydrogenation reaction of aminopropionitrile are characterized by high and rapid exothermic reactions. Especially for the hydrogenation reaction, inaccurate temperature control can lead to runaway temperatures and the risk of hydrogen explosion. Furthermore, batch processes may result in acrylonitrile leaks, posing a health hazard to operators. Therefore, developing continuous, safe, efficient, high-yield, simple-to-operate, and low-cost processes is crucial for the amination and hydrogenation of acrylonitrile to prepare 1,3-propanediamine derivatives. Summary of the Invention

[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a method and apparatus for continuous amination and hydrogenation of acrylonitrile in a pipelined reactor.

[0007] To address the aforementioned technical problems, this invention uses acrylonitrile and amine as raw materials. First, an addition reaction is carried out in a first-stage tubular reactor to obtain aminopropionitrile. Then, the reaction solution is directly injected into a second-stage tubular reactor coated with a Ni-Cu catalyst for a hydrogenation reaction to obtain the corresponding 1,3-propanediamine derivative. The synthetic reaction formula is as follows:

[0008]

[0009] The first aspect of this invention provides a method for continuous amination and hydrogenation of acrylonitrile in a pipelined reactor, comprising the following steps:

[0010] S1. Acrylonitrile and chain organic amines undergo a continuous addition reaction in the first tubular reactor;

[0011] S2. The reaction liquid from step S1 is directly fed into the second pipeline reactor for continuous hydrogenation reaction.

[0012] S3. The corresponding 1,3-propanediamine derivative can be obtained by vacuum distillation of the reaction solution from step S2.

[0013] Preferably, in step S1, the chain-like organic amine secondary amine has the general structural formula R-NH-R', where R and R' are -(CH2)nCH3.

[0014] Preferably, in step S1, the molar ratio of acrylonitrile to chain organic amine is 0.9–1:1–1.2, more preferably 1:1.05–1.1; the addition temperature is 10–50°C, more preferably 20–40°C; the reaction pressure is 0.2–0.6 MPa, more preferably 0.2–0.4 MPa; and the reaction time is 1–6 min, more preferably 2–4 min.

[0015] Preferably, in step S2, the second pipeline reactor is coated with a Ni-Cu catalyst coating with a coating thickness of 1-5 mm and a molar ratio of Ni to Cu of 1-20:1, more preferably 5-12:1.

[0016] Preferably, the Ni-Cu catalyst coating is applied by electroplating; the electroplating solution comprises: metal salts containing Ni and Cu, pH buffer, and additives; the current density used for electroplating is 1–5 A / dm³. 2The electroplating temperature is 50–80℃, and the electroplating time is 20–120 min. The electrolyte is prepared by adding the components to water and stirring with ultrasound or magnetic force to obtain a homogeneous solution. The current density used for electroplating is 1–5 A / dm² (preferably 2.5–3.5 A / dm²). 2 The electroplating temperature is 50-80℃ (preferably 60-70℃), and the electroplating time is 20-120 min (preferably 30-60 min).

[0017] Preferably, Ni and Cu are derived from any one or more of metal sulfates, aminosulfonates, chlorides, and citrates. Ni and Cu can exist as simple metal ions or complex ions, and the sources of Ni and Cu can be any one of metal sulfates, aminosulfonates, chlorides, and citrates, with nickel sulfate and copper sulfate being preferred. The complexing agent can be trisodium citrate.

[0018] Preferably, the pH buffer is any one of boric acid, disodium hydrogen phosphate, acetic acid, or an acetate, with boric acid being the most preferred.

[0019] Preferably, the additive is one or more of saccharin, sodium saccharin, or sodium dodecyl sulfate, with sodium dodecyl sulfate and sodium saccharin being more preferred.

[0020] Preferably, in step S2, the mass flow rate ratio of hydrogen to acrylonitrile in the hydrogenation reaction is 0.075–0.11:1, the reaction temperature is 60–120°C, preferably 70–90°C; the reaction pressure is 1.0–6.0 MPa, preferably 2.0–4.0 MPa; and the residence time is 0.5–4 h, preferably 1.5–2 h.

[0021] Under optimal conditions, the conversion rate of acrylonitrile is above 99.5%, the product yield is above 99.0%, and the product purity is above 99.5%.

[0022] A second aspect of the present invention provides an apparatus for continuous amination hydrogenation of acrylonitrile, the apparatus being used to perform the reaction as described above in the method of continuous amination hydrogenation of acrylonitrile in a tubular reactor, comprising a first tubular reactor and a second tubular reactor connected in series.

[0023] The first pipelined reactor is used for a continuous addition reaction of acrylonitrile with chain organic amines;

[0024] The second pipelined reactor is used for continuous hydrogenation reaction by directly allowing the reaction liquid from the first pipelined reactor to flow into the second pipelined reactor, wherein a hydrogen inlet is provided between the first pipelined reactor and the second pipelined reactor.

[0025] Compared with the prior art, the technical solution of the present invention has the following technical effects:

[0026] (1) The pipeline reactor can precisely control the temperature. The first step of acrylonitrile amination reaction has the characteristics of large and fast heat release. It has the advantages of precise temperature control and avoiding the reaction runaway caused by excessively high reaction temperature. At the same time, the heat released in this step can be recovered for the second step hydrogenation reaction, which not only improves the safety of the reaction process, but also saves energy consumption.

[0027] (2) A two-step series pipeline reactor is adopted. After the acrylonitrile and amine addition reaction in the first step, the acrylonitrile directly enters the second pipeline reactor. There is no need to store or pre-treat the first reaction liquid. The reaction operation is simple, and a continuous process can be realized. The production efficiency is high and the degree of automation is high.

[0028] (3) The pipeline reactor makes it easy to control the hydrogenation reaction pressure, increase gas-liquid mass transfer, promote the hydrogenation reaction, and improve the reaction efficiency.

[0029] (4) The pipeline reactor adopts Ni-Cu catalyst coating, which increases the contact area between the catalyst and the reaction liquid, and the catalyst can be reused, thereby improving the conversion rate of reactants and the selectivity of products.

[0030] (5) The product post-processing is simple. High-purity products can be obtained through simple vacuum distillation, simplifying the operation process. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the process flow for a method of continuous amination and hydrogenation of acrylonitrile in a pipelined reactor according to the present invention. Detailed Implementation

[0032] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto:

[0033] Example 1-1:

[0034] A method for the continuous preparation of N,N-dimethyl-1,3-propanediamine by hydrogenation following the addition reaction of acrylonitrile and dimethylamine in a pipelined reactor, such as... Figure 1 As shown, it includes the following steps:

[0035] (1) The second pipeline reactor 2 is immersed in an electroplating solution containing nickel sulfate, copper sulfate, trisodium citrate, boric acid, sodium dodecyl sulfate and sodium saccharin, at a flow rate of 3.0 A / dm 2 A 3 mm thick Ni-Cu alloy film was obtained by electroplating at 65℃ for 45 min using a current density of 180 g / L nickel sulfate, 20.6 g / L copper sulfate, 80 g / L trisodium citrate, 15 g / L boric acid, 0.1 g / L sodium dodecyl sulfate, and 0.7 g / L sodium saccharin in the electroplating solution.

[0036] (2) Acrylonitrile and dimethylamine were injected into the first pipeline reactor 1 (inner diameter 4 mm, pipe length 10 m) at a molar ratio of 1:1.1 via metering pump 1 and metering pump 2. The flow rates of acrylonitrile and dimethylamine were 11.92 g / min and 11.14 g / min, respectively. The reaction temperature was set to 20 °C. The reaction pressure was adjusted to 0.2 MPa via back pressure valve 1 after the first pipeline reactor 1. The reaction residence time was 4 min.

[0037] (3) The reaction liquid at the outlet of the first pipeline reactor 1 flows directly into the second pipeline reactor 2 (inner diameter 30 mm, pipe length 20 m) after passing through a one-way valve. At the same time, hydrogen is injected into the second pipeline reactor 2 for hydrogenation reaction. The hydrogen pumping rate is 0.484 L / min (0.99 g / min), the reaction temperature is 80 °C, the reaction residence time is 110 min, and the reaction pressure is adjusted to stabilize at 3 MPa by the back pressure valve 2 after the second pipeline reactor 2.

[0038] (4) The reaction liquid flows into the collection tank and is purified by vacuum distillation to obtain the product N,N-dimethyl-1,3-propanediamine. A small amount of liquid is taken through sampling valve 1 for gas phase analysis. The conversion rate of acrylonitrile is 99.8% and the yield of N,N-dimethyl-1,3-propanediamine is higher than 99.0%. The purity of the N,N-dimethyl-1,3-propanediamine product obtained after vacuum distillation purification is ≥99.5%.

[0039] Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-2

[0040] The steps of Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-2 are the same as those of Example 1-1, except that the thickness of the Ni-Cu alloy film on the inner wall of the second tubular reactor 2 is changed. This yields Examples 1-2 to 1-5, as well as Comparative Examples 1-1 and 1-2. The conversion rate of the acrylonitrile feedstock and the product yield were measured, and the data are shown in Table 1.

[0041] Table 1. Effect of Ni-Cu alloy film thickness in the second tubular reactor 2 on acrylonitrile selectivity and N,N-dimethyl-1,3-propanediamine (DMAPA) yield.

[0042] Group Ni-Cu alloy film thickness (mm) Acrylonitrile conversion rate (%) DMAPA yield (%) Example 1-1 3 99.8 99.8 Examples 1-2 1 99.7 99.0 Examples 1-3 2 998 99.4 Examples 1-4 4 99.6 99.7 Examples 1-5 5 99.8 99.6 Comparative Example 1-1 0.1 99.6 10.5 Comparative Examples 1-2 8 99.8 99.7

[0043] Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-2

[0044] The steps of Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2-2 differ from those of Example 1-1 only in that the molar ratio of Ni to Cu in the electroplating solution used in the second pipeline reactor 2 is changed, while the concentration of nickel sulfate remains constant and only the concentration of copper sulfate is changed; otherwise, the steps are the same as in Example 1-1. This yields Examples 2-1 to 2-7, as well as Comparative Examples 2-1 and 2-2. The conversion rate of the raw material acrylonitrile and the product yield were measured, and the data are shown in Table 1.

[0045] Table 2. Effect of Ni to Cu molar ratio in electroplating solution on acrylonitrile selectivity and N,N-dimethyl-1,3-propanediamine (DMAPA) yield

[0046] Group Molar ratio of Ni to Cu Acrylonitrile conversion rate (%) DMAPA yield (%) Example 1-1 9：1 99.8 99.8 Example 2-2 6：1 99.7 99.0 Example 2-3 7：1 99.7 99.2 Examples 2-4 8：1 99.8 99.7 Examples 2-5 10：1 99.6 99.7 Examples 2-6 11：1 99.8 99.6 Examples 2-7 12：1 99.6 99.4 Comparative Example 2-1 1：3 99.7 67.5 Comparative Example 2-2 40：1 99.7 88.9

[0047] The purity of the N,N-dimethyl-1,3-propanediamine product obtained in the above case is ≥99.5%.

[0048] Examples 3-1 to 3-5

[0049] The steps in Examples 3-1 to 3-5 are the same as in Example 1-1, except that the type of amine used as the raw material in the first tubular reactor 1 is different. The conversion rate of the acrylonitrile and the product yield were tested, and the following data were obtained (Table 3).

[0050] Table 3. Effects of raw material amine type on acrylonitrile selectivity and product yield

[0051] Group amine Acrylonitrile conversion rate (%) Product yield (%) Example 1-1 dimethylamine 99.8 99.8 Example 3-1 Diethylamine 99.7 99.4 Example 3-2 di-n-propylamine 99.6 99.2 Example 3-3 diisopropylamine 99.5 99.3 Examples 3-4 di-n-butylamine 99.6 99.0 Examples 3-5 diisobutylamine 99.5 99.5

[0052] The purity of the products obtained in the above cases is ≥99.5%.

[0053] Examples 4-1 to 4-6

[0054] The steps of Examples 4-1 to 4-6 differ from those of Example 1-1 only in that the reaction temperature of the first tubular reactors 1 and 2 is changed, and the reactant conversion rate and product yield are detected, resulting in the following data (Table 4).

[0055] Table 4. Effect of reaction temperature on acrylonitrile conversion and N,N-dimethyl-1,3-propanediamine (DMAPA) yield

[0056] Group <![CDATA[Reaction temperature T1 (°C) of the first tubular reactor 1]]> <![CDATA[Reaction temperature T2 (°C) of the first tubular reactor 1]]> Acrylonitrile conversion rate (%) DMAPA yield (%) Example 1-1 20 80 99.8 99.8 Example 4-1 10 60 99.5 99.2 Example 4-2 30 70 99.6 99.7 Example 4-3 40 90 99.5 99.6 Example 4-4 50 100 99.6 99.5 Examples 4-5 20 110 99.8 99.3 Examples 4-6 20 120 99.8 99.0

[0057] The purity of the N,N-dimethyl-1,3-propanediamine product obtained in the above case is ≥99.5%.

[0058] Examples 5-1 to 5-4

[0059] The steps in Examples 5-1 to 5-4 are the same as those in Example 1-1, except that the lengths of the first tubular reactor 1 and the second tubular reactor 2 are changed, and only the residence time of the reaction is changed. The reactant conversion rate and product yield were tested, and the following data were obtained (Table 5).

[0060] Table 5. Effect of reaction residence time on acrylonitrile conversion and N,N-dimethyl-1,3-propanediamine (DMAPA) yield

[0061] Group <![CDATA[L1(m)]]> <![CDATA[L2(m)]]> <![CDATA[τ1(min)]]> <![CDATA[τ2(min)]]> DMAPN yield (%) DMAPA yield (%) Example 1-1 10 20 4 110 99.8 99.8 Example 5-1 15 20 6 110 99.8 99.7 Example 5-2 20 20 8 110 99.7 99.6 Example 5-3 5 20 2 110 99.6 99.6 Example 5-4 10 18 4 99 99.8 99.2 Example 5-5 10 22 4 121 99.8 99.5

[0062] The purity of the N,N-dimethyl-1,3-propanediamine product obtained in the above case is ≥99.5%.

[0063] Examples 6-1 to 6-4

[0064] The steps of Examples 6-1 to 6-4 are the same as those of Example 1-1, except that the reaction pressure is changed by adjusting the back pressure valves after the first pipelined reactor 1 and the second pipelined reactor 2. The reactant conversion rate and product yield were tested and the following data were obtained (Table 6).

[0065] Table 6. Effect of reaction pressure on acrylonitrile conversion and N,N-dimethyl-1,3-propanediamine (DMAPA) yield

[0066] Group <![CDATA[Reaction pressure P1 (MPa) of the first tubular reactor 1]]> <![CDATA[Reaction pressure P1 (MPa) of the first tubular reactor 1]]> Acrylonitrile conversion rate (%) DMAPA yield (%) Example 1-1 0.2 3.0 99.8 99.8 Example 6-1 0.1 2.0 99.6 99.7 Example 6-2 0.3 2.0 99.5 99.6 Example 6-3 0.2 1.5 99.7 99.2 Example 6-4 0.2 2.5 99.7 99.4

[0067] The purity of the N,N-dimethyl-1,3-propanediamine product obtained in the above case is ≥99.5%.

[0068] Examples 7-1 to 7-2 and Comparative Examples 3-1 to 3-2

[0069] The steps of Examples 7-1 to 7-2 and Comparative Examples 3-1 to 3-2 are the same as those of Example 1-1, except that the flow rates of dimethylamine and acrylonitrile are changed, and the length of the tubular reactor is adjusted accordingly to ensure that the residence time of the reaction remains constant. Thus, Examples 7-1 to 7-2, and Comparative Examples 3-1 and 3-2 are obtained. The product yields were measured, and the following data were obtained (Table 7).

[0070] Table 7. Effect of material flow rate ratio on acrylonitrile conversion and N,N-dimethyl-1,3-propanediamine (DMAPA) yield

[0071] Group Flow rate of dimethylamine (g / min) Acrylonitrile flow rate (g / min) The flow rate ratio of dimethylamine to acrylonitrile Acrylonitrile conversion rate (%) DMAPA yield (%) Example 1-1 11.14 11.92 1:1.07 99.7 99.8 Example 7-1 10.10 11.92 1:1.18 99.6 99.6 Example 7-2 12.16 11.92 1.02:1 99.7 99.4 Comparative Example 3-1 9.61 11.92 1:1.24 80.0 85.2 Comparative Example 3-2 13.11 11.92 1.10:1 99.6 90.0

[0072] The purity of the N,N-dimethyl-1,3-propanediamine product obtained in the above case is ≥99.5%.

[0073] Examples 8-1 to 8-2 and Comparative Examples 4-1 to 4-2

[0074] The steps of Examples 8-1 to 8-2 and Comparative Examples 4-1 to 4-2 are the same as those of Example 1-1, except that the flow rates of acrylonitrile and dimethylamine are kept constant, the ratio of hydrogen to acrylonitrile is changed, and the length of the tubular reactor is adjusted accordingly to ensure that the residence time of the reaction remains constant. The rest is identical to Example 1-1. Thus, Examples 8-1 to 8-2, and Comparative Examples 4-1 and 4-2 are obtained. The product yields were measured, and the following data were obtained (Table 5).

[0075] Table 8. Effect of material flow rate ratio on the yield of N,N-dimethyl-1,3-propanediamine (DMAPA)

[0076] Group Hydrogen pumping rate (L / min) The mass ratio of hydrogen to acrylonitrile DMAPA yield (%) Example 1-1 0.484 0.083:1 99.8 Example 8-1 0.455 0.078:1 99.0 Example 8-2 0.513 0.088:1 99.9 Comparative Example 4-1 0.397 0.068:1 76.5 Comparative Example 4-2 0.571 0.098:1 99.8

[0077] The purity of the N,N-dimethyl-1,3-propanediamine obtained in the above case is ≥99.5%.

[0078] Based on the same inventive concept, the present invention provides a second aspect of an apparatus for continuous amination hydrogenation of acrylonitrile, the apparatus being used to carry out the reaction of the above-described continuous amination hydrogenation of acrylonitrile in a tubular reactor, comprising a first tubular reactor 1 and a second tubular reactor 2 connected in series.

[0079] The first pipeline reactor 1 is used for a continuous addition reaction of acrylonitrile with chain organic amines;

[0080] The second pipelined reactor 2 is used for continuous hydrogenation reaction where the reaction liquid from the first pipelined reactor 1 flows directly into the second pipelined reactor 2. A hydrogen inlet is provided between the first pipelined reactor 1 and the second pipelined reactor 2. Figure 1 As shown in the figure, numbers 1-6 and 8-11 are shut-off valves, and 7 is a check valve.

[0081] In summary, the technical solution of the present invention has the following technical effects:

[0082] (1) The pipeline reactor can precisely control the temperature. The first step of acrylonitrile amination reaction has the characteristics of large and fast heat release. It has the advantages of precise temperature control and avoiding the reaction runaway caused by excessively high reaction temperature. At the same time, the heat released in this step can be recovered for the second step hydrogenation reaction, which not only improves the safety of the reaction process, but also saves energy consumption.

[0083] (2) A two-step series pipeline reactor is adopted. After the acrylonitrile and amine addition reaction in the first step, the acrylonitrile directly enters the second pipeline reactor. There is no need to store or pre-treat the first reaction liquid. The reaction operation is simple, and a continuous process can be realized. The production efficiency is high and the degree of automation is high.

[0084] (3) The pipeline reactor makes it easy to control the hydrogenation reaction pressure, increase gas-liquid mass transfer, promote the hydrogenation reaction, and improve the reaction efficiency.

[0085] (4) The pipeline reactor adopts Ni-Cu catalyst coating, which increases the contact area between the catalyst and the reaction liquid, and the catalyst can be reused, thereby improving the conversion rate of reactants and the selectivity of products.

[0086] (5) The product post-processing is simple. High-purity products can be obtained through simple vacuum distillation, simplifying the operation process.

[0087] It is worth noting that in this application, "first" and "second" do not refer to any order, but are used only to distinguish the names.

[0088] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A method for continuous amination hydrogenation of acrylonitrile in a tubular reactor, characterized in that, comprising the following steps: S1, acrylonitrile and chain organic amine are subjected to continuous addition reaction in a first tubular reactor; S2, the reaction solution after step S1 is directly flowed into a second tubular reactor for continuous hydrogenation reaction; S3, the reaction solution after step S2 is subjected to vacuum distillation. In step S1, the chain 2. The method of claim 1, wherein, organic amine is a secondary amine with a general structure of R-NH-R', and R and R' are -(CH2)nCH3. In step S1, the molar ratio of acrylonitrile to chain organic amine is 0.9-1:1-1.2, the addition temperature is 10-50℃, 3. The method of claim 1, wherein, the reaction pressure is 0.2-0.6 MPa, and the reaction time is 1-6 min. In step S2, the second tubular reactor is coated with a Ni-Cu catalyst coating with a thickness of 1-5 mm, and the molar ratio of Ni to Cu is 1-20:

1.

4. The method of claim 1, wherein, The Ni-Cu catalyst coating is coated by electroplating; the electroplating solution composition used for electroplating includes: Ni and Cu, the electroplating temperature is 50-80℃, and the electroplating time is 20-120 min.

5. The method of claim 4, wherein, The source of Ni and Cu is any one or several of metallic sulfate, sulfamate, chloride, and citrate. The pH buffer is any one of boric acid, disodium hydrogen phosphate, acetic acid, or acetate. Metal salt, pH buffer and additives; current density used for plating is 1-5 A / dm 2 , The additive is one or several of saccharin, sodium saccharin, or sodium dodecyl sulfate.

6. The method of claim 4, wherein, In step S2, the mass flow rate ratio of hydrogen to acrylonitrile in the hydrogenation reaction is 0.075-0.11:1, 7. The method of claim 5, wherein, the reaction temperature is 60-120℃, the reaction pressure is 1.0-6.0 MPa, and the residence time is The device is used 8. The method of claim 5, wherein, for the reaction of the method for continuous amination hydrogenation of acrylonitrile in a tubular reactor as claimed in any one of claims 1-9, which includes a first tubular reactor and a second tubular reactor in series, the first tubular reactor is used for continuous addition reaction of acrylonitrile and chain organic amine; 9. The method of any one of claims 1-8, wherein, the second tubular reactor is used for continuous hydrogenation reaction of the reaction solution directly flowed from the first tubular reactor into the second tubular reactor, wherein a hydrogen inlet is provided between the first tubular reactor and the second tubular reactor. ​ ​ 0.5～4h。 10. An apparatus for the continuous amination and hydrogenation of acrylonitrile, characterized in that ​ ​ ​ ​ ​ ​ ​ ​ ​

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