CN113620813B - Preparation method of N, N-dimethyl-1, 3-propanediamine - Google Patents

Preparation method of N, N-dimethyl-1, 3-propanediamine Download PDF

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CN113620813B
CN113620813B CN202110929550.1A CN202110929550A CN113620813B CN 113620813 B CN113620813 B CN 113620813B CN 202110929550 A CN202110929550 A CN 202110929550A CN 113620813 B CN113620813 B CN 113620813B
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hydrogenation
nitrate
dimethylamine
acrylonitrile
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CN113620813A (en
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史文涛
王聪
冯传密
崔艳杰
吴昊
崔志国
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China Tianchen Engineering Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a preparation method of N, N-dimethyl-1, 3-propylene diamine, which comprises the following steps: mixing acrylonitrile with dimethylamine solution, injecting into a microchannel reactor for addition reaction, mixing reaction liquid with hydrogen, preheating, entering into a continuous hydrogenation reactor filled with Ni-based alloy hydrogenation catalyst for hydrogenation reaction, and then decompressing, rectifying and separating to obtain the required product. The preparation method of the invention utilizes the advantages of continuous reaction, high mass transfer and heat transfer efficiency, narrow residence time distribution, no amplification effect and the like of the microchannel reactor, so that the addition reaction of acrylonitrile and dimethylamine has the characteristics of high efficiency, high conversion rate, few byproducts, the hydrogenation reaction is carried out under extremely mild reaction conditions by using the novel Ni-based alloy catalyst, and simultaneously, the extremely high conversion rate and the product selectivity are obtained, so that the whole reaction system has the advantages of realizing continuous production, convenient operation, high resource utilization rate and the like.

Description

Preparation method of N, N-dimethyl-1, 3-propanediamine
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of N, N-dimethyl-1, 3-propanediamine.
Background
Dimethylaminopropylamine, known collectively as N, N-dimethyl-1, 3-propanediamine (DMAPA), is one of the most important species of lower aliphatic diamine compounds. The compound has polarity and active chemical property, can form hydrogen bonds, has lone pair electrons on N atoms, has nucleophilic capability, and is easy to react with electrophilic compounds. The DMAPA is mainly used in the fields of daily chemicals, pesticides, dyes, oil fields, water treatment, resins, other assistants and the like, and has wider application. Currently, most DMAPA products are used to produce amidobetaines, and the remaining small portion of DMAPA products are used as urethane catalysts, epoxy curing agents and accelerators, as well as to produce dyes and propamocarb, etc.
The preparation method of N, N-dimethyl-1, 3-propylene diamine comprises two preparation methods, wherein one preparation method takes acrolein and dimethylamine as raw materials, as mentioned in patent CN102026956A, the acrolein and dimethylamine react at 4 ℃ and 0-3MPa to obtain N, N, N ', N' -substituted 1, 3-propylene diamine, the obtained mixture reacts with ammonia and hydrogen at 40-400 ℃ in the presence of a catalyst and at 6MPa to obtain N, N-dimethyl-1, 3-propylene diamine, and the yield is 91%.
At present, the main method for industrially producing N, N-dimethyl-1, 3-propanediamine is to prepare dimethyl aminopropionitrile by taking acrylonitrile and dimethylamine as raw materials and carrying out Michael addition, and then, preparing N, N-dimethyl-1, 3-propanediamine by hydrogenation. For example, the patent CN101321722A is prepared by taking acrylonitrile and dimethylamine as raw materials and preparing N, N-dimethyl-1, 3-propanediamine through hydrogenation. The method adopts an intermittent reaction kettle for hydrogenation, the catalyst is Raney-Ni, the hydrogenation pressure is 3Mpa under the condition of caustic alkali aqueous solution, the reaction temperature is 90 ℃, and the final yield of N, N-dimethyl-1, 3-propanediamine is 93%.
The patent CN103333073B takes dimethylamine and acrylonitrile as raw materials, and uses a fixed bed to continuously prepare the dimethylaminopropionitrile, wherein the conversion rate of the acrylonitrile and the selectivity of the dimethylaminopropionitrile are both more than 99 percent. And then the obtained dimethylamino propionitrile intermediate directly enters a second fixed bed reactor for hydrogenation, the hydrogenation pressure is 3-10MPa, and a Raney-Ni catalyst is adopted to be matched with an alcohol solution promoter of 0.1-10% of alkali, so that the yield of the N, N-dimethyl-1, 3-propanediamine is 98%.
Patent CN101321722B provides a process for the preparation of N, N-dimethyl-1, 3-propanediamine on an industrial scale. Firstly, carrying out addition reaction on acrylonitrile and dimethylamine serving as raw materials to prepare 3-dimethylamino propionitrile, wherein the dimethylamine is excessive by 10%, and the reaction is carried out in a bubble column; the excess dimethylamine and water are then evaporated to give a concentrated dimethylaminopropionitrile product at the bottom of the bubble column, which is then transferred to a batch hydrogenation reactor for catalytic hydrogenation to give N, N-dimethyl-1, 3-propanediamine.
The patent CN105198754B adds acrylonitrile and dimethylamine into a synthesis reaction kettle to react, and then removes the dimethylamine by rectification under reduced pressure to prepare N, N-dimethylamino acrylonitrile; adding a hydrogenation catalyst, introducing liquid ammonia and hydrogen into a high-pressure reaction kettle, reacting, settling, performing primary distillation, and rectifying to obtain N, N-dimethyl-1, 3-propylene diamine.
Patent CN1747925a focuses on a process for preparing high purity 3-dimethylaminopropylamine from N, N-dimethylaminopropionitrile using a low pressure process: hydrogen and N, N-dimethylaminopropionitrile are fed to a low pressure reactor containing a reaction medium of a sponge nickel catalyst, at least one group IA alkali metal hydroxide and water, wherein the amount of water is about 0.1 to 10% by weight of the reaction medium and the reaction pressure is 45 to 300 psig. The process yields at least 99% of dimethylaminopropylamine calculated as N, N-dimethylaminopropionitrile.
The above-mentioned patent methods, although providing synthetic preparation methods of DMAPA, still have room for improvement in terms of raw material conversion, product yield, by-product selectivity, and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing N, N-dimethyl-1, 3-propanediamine, which realizes continuous, high conversion and high selectivity of producing N, N-dimethyl-1, 3-propanediamine.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for preparing N, N-dimethyl-1, 3-propanediamine, which comprises the following steps:
(1) Mixing acrylonitrile and dimethylamine solution according to a certain proportion, injecting the mixture into a microchannel reaction device, and carrying out addition reaction under certain temperature and pressure conditions to obtain a first reaction solution containing dimethylaminopropionitrile, wherein the conversion rate of the acrylonitrile is 100%, and the selectivity of the dimethylaminopropionitrile is more than 99.8%;
(2) Mixing the first reaction liquid with hydrogen, preheating, and then entering a continuous hydrogenation reactor filled with a Ni-based alloy hydrogenation catalyst for hydrogenation reaction to obtain a second reaction liquid containing N, N-dimethyl-1, 3-propanediamine, wherein the conversion rate of the dimethylaminopropionitrile is 100%, and the product selectivity is more than 99.8%;
(3) The second reaction liquid is decompressed, rectified and separated to obtain the required product, for example, a stainless steel rectifying tower with the DN40 of 2 meters in height is used, 4 multiplied by 4 stainless steel theta ring packing is filled in the stainless steel rectifying tower, the tower top pressure is 200Pa, the tower top temperature is 50-60 ℃, the tower bottom temperature is 80-90 ℃, the reflux ratio is 2:1, and the purity of the product is over 99.95 percent.
Further, in the step (1), the molar ratio of the acrylonitrile to the dimethylamine is 1:1-2, the addition reaction temperature is 30-120 ℃, the reaction pressure is 1-5bar, and the residence time is 10-60s.
Further, the solvent of the dimethylamine solution in the step (1) is water or alcohol, the alcohol is fatty alcohol with the total carbon number of 1-4, and the concentration of dimethylamine is 10% -40%.
Further, the reaction temperature of the hydrogenation reaction in the step (2) is 10-60 ℃, the reaction pressure is 1-5bar, and the residence time is 10-30min.
Further, the Ni-based alloy hydrogenation catalyst in the step (2) is an amorphous catalyst of Ni-Al-Co, and the preparation method thereof is as follows:
grinding an alloy consisting of nickel, aluminum and cobalt into powder, mixing the powder with an alkali solution, carrying out dealumination treatment, removing an upper alkali solution, washing the powder with deionized water to be neutral to obtain a crude catalyst product, mixing the crude catalyst product with the alkali solution containing a modifier, carrying out hydrothermal aging, filtering and separating to obtain solid particles, drying and baking the solid particles, and reducing the solid particles with hydrogen to obtain the required catalyst.
Further, the mass ratio of Ni, al and Co in the crude product is 100-200:10-30:1-5, the hydrothermal aging temperature is 100-150 ℃ and the time is 2-24h.
Further, the modifier is one or more of ferric nitrate, molybdenum nitrate, cerium nitrate, bismuth nitrate, chromium nitrate, manganese nitrate, titanium nitrate, zirconium nitrate, ruthenium nitrate, palladium nitrate and copper nitrate, and the molar ratio of total metal ions in the modifier to nickel in the Ni-based alloy hydrogenation catalyst is 0.01-0.1:1.
Further, the alkali solution is a mixed aqueous solution of sodium hydroxide and ammonium salt, the concentration of the sodium hydroxide is 0.1-2M, and the molar ratio of the sodium hydroxide to the ammonium salt is 1-5:1.
Further, the ammonium salt is one or more of ammonium nitrate, ammonium sulfate and ammonium chloride.
A production apparatus for carrying out the above production method, comprising a mixer for mixing acrylonitrile with a dimethylamine solution;
the feed inlet of the micro-channel reaction device is communicated with the discharge outlet of the mixer;
the hydrogen is filled in the storage tank, and a feed inlet of the storage tank is communicated with a discharge outlet of the microchannel reaction device;
the feeding port of the hydrogenation reactor is communicated with the discharging port of the storage tank;
the gas-liquid separator is communicated with a discharge port of the hydrogenation reactor;
the feeding port of the decompression separation device is communicated with the liquid phase discharging port of the gas-liquid separator.
Preferably, the microchannel reactor comprises a microchannel reactor and a heat exchanger, wherein the heat exchanger is used for adjusting the reaction temperature of the microchannel reactor.
Compared with the prior art, the preparation method of the N, N-dimethyl-1, 3-propanediamine has the following advantages:
(1) The preparation method disclosed by the invention has the advantages of continuity, high mass and heat transfer efficiency, narrow residence time distribution, no amplification effect and the like by utilizing the microchannel reactor, so that the addition reaction of acrylonitrile and dimethylamine has the characteristics of high efficiency, high conversion rate and few byproducts;
(2) The preparation method of the invention uses the novel Ni-based alloy catalyst to enable hydrogenation reaction to be carried out under extremely mild reaction conditions, and simultaneously, very high conversion rate and product selectivity are obtained;
(3) The preparation method of the invention ensures that the whole reaction system has the advantages of continuous production, convenient operation, high resource utilization rate and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 is a schematic diagram of a connection structure of a production apparatus according to an embodiment of the present invention.
Reference numerals illustrate:
1. dimethylamine feed pump; 2. an acrylonitrile feed pump; 3. a mixer; 4. a microchannel reactor; 5. a heat exchanger; 6. a storage tank; 7. a reaction liquid transfer pump; 8. a hydrogenation reactor; 9. a gas-liquid separator; 10. a decompression separation device.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and drawings.
The invention utilizes the characteristics of extremely high specific surface area and regular laminar flow of the microchannel reactor, can greatly improve the yield and selectivity of the reaction, and can precisely control the heat and concentration distribution of the chemical reaction, so that the chemical conversion can obtain high space-time yield in various modes, meanwhile, the reaction quality can be improved by precisely controlling the proportion of the substrate and the reaction reagent, the chemical reaction is generally carried out in a limited channel of 10-1000um, and even dangerous intermediates are generated, the reaction is kept at a micro level, thereby ensuring that the reaction is very safe. In addition, compared with the traditional batch reaction process, the micro-reactor has the advantages of rapid mixing, high-efficiency heat transfer, narrow residence time distribution, good repeatability, rapid system response, convenience in automatic control, almost no amplification effect, high safety performance and the like.
The preparation method of the N, N-dimethyl-1, 3-propylene diamine comprises the following steps:
(1) Mixing acrylonitrile and dimethylamine solution according to a certain proportion, injecting the mixture into a microchannel reaction device, and carrying out addition reaction under certain temperature and pressure conditions to obtain a first reaction solution containing dimethylaminopropionitrile, wherein the conversion rate of the acrylonitrile is 100%, and the selectivity of the dimethylaminopropionitrile is more than 99.8%;
(2) Mixing the first reaction liquid with hydrogen, preheating, and then entering a continuous hydrogenation reactor 8 filled with a Ni-based alloy hydrogenation catalyst for hydrogenation reaction to obtain a second reaction liquid containing N, N-dimethyl-1, 3-propanediamine, wherein the conversion rate of the dimethylaminopropionitrile is 100%, and the product selectivity is more than 99.8%;
(3) The second reaction liquid is decompressed, rectified and separated to obtain the required product, for example, a stainless steel rectifying tower with the DN40 of 2 meters in height is used, 4 multiplied by 4 stainless steel theta ring packing is filled in the stainless steel rectifying tower, the tower top pressure is 200Pa, the tower top temperature is 50-60 ℃, the tower bottom temperature is 80-90 ℃, the reflux ratio is 2:1, and the purity of the product is over 99.95 percent.
As shown in the figure, the production equipment used in the invention comprises a mixer 3, a microchannel reaction device, a storage tank 6, a hydrogenation reactor 8, a gas-liquid separator 9 and a decompression separation device 10, wherein dimethylamine solution is injected into the mixer 3 through a dimethylamine feed pump 1, acrylonitrile is injected into the mixer 3 through an acrylonitrile feed pump 2, the mixer 3 is used for uniformly mixing acrylonitrile and dimethylamine solution, the feed inlet of the microchannel reaction device is communicated with the discharge outlet of the mixer 3, hydrogen is filled in the storage tank 6, the feed inlet of the storage tank 6 is communicated with the discharge outlet of the microchannel reaction device, the feed inlet of the hydrogenation reactor 8 is communicated with the discharge outlet of the storage tank 6, the mixed solution of the first reaction solution discharged from the storage tank 6 and the hydrogen is injected into the hydrogenation reactor 8 through a reaction solution delivery pump 7, the gas-liquid separator 9 is communicated with the discharge outlet of the hydrogenation reactor 8, the feed inlet of the decompression separation device 10 is communicated with the liquid outlet of the gas-liquid separator 9, the microchannel reaction device comprises a microchannel reactor 4 and a heat exchanger 5, and the heat exchanger 5 is used for regulating the reaction temperature of the microchannel reactor 4.
Example 1
The method is characterized in that an ethanol solution of acrylonitrile and 30% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.05, the reaction temperature is 40 ℃, the pressure is 1bar, and the residence time is 40s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.82%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a fixed bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 60 ℃, the pressure is 3bar, and the residence time of the reaction solution is 30min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 120:20:5. The crude product is put into an alkali solution containing ferric nitrate, wherein the molar ratio of iron to nickel is 0.05:1, then the mixture is subjected to hydrothermal aging at 100 ℃ for 12 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium sulfate, wherein the concentration of the sodium hydroxide is 1mol/L, and the molar ratio of the sodium to the ammonium is 2:1. The final hydroconversion was 100% and DMAPA selectivity was 99.83%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 2
The method is characterized in that a methanol solution of acrylonitrile and 35% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.1, the reaction temperature is 60 ℃, the pressure is 1.5bar, and the residence time is 30s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.80%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a trickle bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 40 ℃, the pressure is 4bar, and the residence time of the reaction solution is 30min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 150:15:2. The crude product is put into an alkali solution containing molybdenum nitrate, wherein the molar ratio of molybdenum to nickel is 0.03:1, then the mixture is subjected to hydrothermal aging at 100 ℃ for 24 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium nitrate, wherein the concentration of the sodium hydroxide is 1.5mol/L, and the molar ratio of sodium to ammonium is 2.5:1. The final hydroconversion was 100% and DMAPA selectivity was 99.81%. Finally, obtaining the DMAPA pure product with the purity of 99.96 percent through vacuum rectification.
Example 3
The method is characterized in that an isopropanol solution of acrylonitrile and 40% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.2, the reaction temperature is 80 ℃, the pressure is 2bar, and the residence time is 20s. The reaction product was collected from the outlet of the microchannel reactor for analysis, with an acrylonitrile conversion of 100% and a dimethylaminopropionitrile selectivity of 99.85%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a circulation hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature was 55℃and the pressure was 4bar, and the reaction mixture was left for 25 minutes. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 200:25:1. The crude product is put into an alkali solution containing manganese nitrate, wherein the molar ratio of manganese to nickel is 0.1:1, then the mixture is subjected to hydrothermal aging at 120 ℃ for 20 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium sulfate, wherein the concentration of the sodium hydroxide is 2mol/L, and the molar ratio of the sodium to the ammonium is 3:1. The final hydroconversion was 100% and DMAPA selectivity was 99.85%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 4
The method is characterized in that an acrylonitrile and 20% dimethylamine tertiary butanol solution is used as raw materials, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction liquid is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.3, the reaction temperature is 100 ℃, the pressure is 5bar, and the residence time is 10s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.9%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a fixed bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 30 ℃, the pressure is 2bar, and the residence time of the reaction solution is 30min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 250:25:5. Putting the crude product into an alkali solution containing cerium nitrate and bismuth nitrate, wherein the molar ratio of cerium to bismuth is 1:1, the molar ratio of (cerium+bismuth) to nickel is 0.1:1, then carrying out hydrothermal aging at 150 ℃ for 10 hours, filtering and separating to obtain solid particles, and then carrying out drying, roasting and hydrogen reduction to obtain the Ni-based alloy hydrogenation catalyst. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium chloride, wherein the concentration of the sodium hydroxide is 1.5mol/L, and the molar ratio of the sodium to the ammonium is 2:1. The final hydroconversion was 100% and DMAPA selectivity was 99.86%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 5
The method comprises the steps of taking an ethanol solution of acrylonitrile and 35% dimethylamine as raw materials, and carrying out an addition reaction by a micro-channel reaction device to obtain an addition reaction solution, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.3, the reaction temperature is 120 ℃, the pressure is 5bar, and the residence time is 50s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.88%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a circulation hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 40 ℃, the pressure is 5bar, and the residence time of the reaction solution is 10min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 200:30:5. Putting the crude product into an alkali solution containing titanium nitrate and zirconium nitrate, wherein the molar ratio of titanium to zirconium is 1:1, wherein the molar ratio of (titanium+zirconium) to nickel is 0.1:1, then carrying out hydrothermal aging at 110 ℃ for 24 hours, filtering and separating to obtain solid particles, and then carrying out drying, roasting and hydrogen reduction to obtain the Ni-based alloy hydrogenation catalyst. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium sulfate, wherein the concentration of the sodium hydroxide is 0.5mol/L, and the molar ratio of sodium to ammonium is 5:1. The final hydroconversion was 100% and DMAPA selectivity was 99.9%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 6
The method is characterized in that a methanol solution of acrylonitrile and 40% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.1, the reaction temperature is 40 ℃, the pressure is 1.5bar, and the residence time is 60s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.9%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a fixed bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 20 ℃, the pressure is 4bar, and the residence time of the reaction solution is 10min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 200:10:1. The crude product is put into an alkali solution containing chromium nitrate, wherein the molar ratio of chromium to nickel is 0.04:1, then the mixture is subjected to hydrothermal aging at 100 ℃ for 2 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium sulfate, wherein the concentration of the sodium hydroxide is 0.1mol/L, and the molar ratio of sodium to ammonium is 1:1. The final hydroconversion was 100% and DMAPA selectivity was 99.9%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 7
The method is characterized in that an ethanol solution of acrylonitrile and 30% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.1, the reaction temperature is 30 ℃, the pressure is 1bar, and the residence time is 10s. The reaction product was collected from the outlet of the microchannel reactor for analysis, the conversion of acrylonitrile was 100%, and the selectivity of dimethylaminopropionitrile was 99.9%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a fixed bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 10 ℃, the pressure is 1bar, and the residence time of the reaction solution is 30min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 200:10:5. The crude product is put into an alkali solution containing copper nitrate, wherein the molar ratio of copper to nickel is 0.01:1, then the mixture is subjected to hydrothermal aging at 100 ℃ for 2 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium nitrate, wherein the concentration of the sodium hydroxide is 0.5mol/L, and the molar ratio of sodium to ammonium is 1:1. The final hydroconversion was 100% and DMAPA selectivity was 99.8%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 8
The method is characterized in that an ethanol solution of acrylonitrile and 10% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.3, the reaction temperature is 100 ℃, the pressure is 1bar, and the residence time is 60s. The reaction product was collected from the outlet of the microchannel reactor for analysis, with an acrylonitrile conversion of 100% and a dimethylaminopropionitrile selectivity of 99.85%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a trickle bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature is 60 ℃, the pressure is 5bar, and the residence time of the reaction solution is 30min. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 100:30:1. The crude product is put into an alkali solution containing ruthenium nitrate, wherein the molar ratio of ruthenium to nickel is 0.01:1, then the mixture is subjected to hydrothermal aging at 100 ℃ for 24 hours, then solid particles are obtained through filtration and separation, and then the Ni-based alloy hydrogenation catalyst is obtained after drying, roasting and hydrogen reduction. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium nitrate, wherein the concentration of the sodium hydroxide is 1.5mol/L, and the molar ratio of sodium to ammonium is 1:1. The final hydroconversion was 100% and DMAPA selectivity was 99.81%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Example 9
The method is characterized in that an isopropanol solution of acrylonitrile and 30% dimethylamine is used as a raw material, an addition reaction is carried out through a micro-channel reaction device, and an addition reaction solution is obtained, wherein the molar ratio of the acrylonitrile to the dimethylamine is 1:1.2, the reaction temperature is 60 ℃, the pressure is 1bar, and the residence time is 50s. The reaction product was collected from the outlet of the microchannel reactor for analysis, with an acrylonitrile conversion of 100% and a dimethylaminopropionitrile selectivity of 99.85%. The addition reaction liquid and hydrogen are mixed and preheated and then enter a trickle bed hydrogenation reactor, and a Ni-based alloy hydrogenation catalyst is arranged in the reactor. The hydrogenation reaction temperature was 40℃and the pressure was 2.5bar, and the reaction mixture was allowed to remain for 30 minutes. The preparation method of the hydrogenation catalyst comprises the following steps: and (3) grinding the alloy consisting of nickel, aluminum and cobalt into powder, dissolving and dealuminating the alloy by using alkali solution, removing the alkali solution on the upper layer, and washing the alloy to be neutral by using deionized water to obtain a crude product of the Ni-based alloy hydrogenation catalyst, wherein the mass ratio of Ni to Al to Co is 200:30:5. Putting the crude product into an alkali solution containing ruthenium nitrate and palladium nitrate, wherein the molar ratio of ruthenium to palladium is 1:1, the molar ratio of (ruthenium+palladium) to nickel is 0.01:1, then carrying out hydrothermal aging at 100 ℃ for 24 hours, filtering and separating to obtain solid particles, and then carrying out drying roasting hydrogen reduction to obtain the Ni-based alloy hydrogenation catalyst. The alkali liquor is a mixed aqueous solution of sodium hydroxide and ammonium nitrate, wherein the concentration of the sodium hydroxide is 1.5mol/L, and the molar ratio of sodium to ammonium is 1:1. The final hydroconversion was 100% and DMAPA selectivity was 99.92%. Finally, obtaining the DMAPA pure product with the purity of 99.95 percent through vacuum rectification.
Comparative example 1
The difference from example 1 was that a batch tank reactor was used for the addition reaction, the residence time was 5min, and the other steps were the same as in example 1. After the reaction is finished, the reaction product is collected from the outlet of the kettle-type reactor for analysis, the conversion rate of acrylonitrile is 98.1 percent, and the selectivity of dimethylaminopropionitrile is 95.3 percent.
As can be seen from comparative example 1, the addition reaction using the microchannel reactor has higher reaction efficiency, shorter residence time and higher product yield than the conventional batch-tank reactor.
Comparative example 2
The difference from example 1 is that the catalyst used in the hydrogenation reaction is an N211 Raney nickel catalyst, the other steps being the same as in example 1, the catalyst having a Ni content of about 90% and the remainder being aluminum. The final hydroconversion was 100% and DMAPA selectivity was 96.9%.
Comparative example 3
The difference from example 1 is that the catalyst used in the hydrogenation reaction is an N311 raney nickel catalyst, the other steps being the same as in example 1, the catalyst having a Ni content of about 85% and the balance being aluminum. The hydrogenation reaction temperature is 60 ℃, the pressure is 3bar, and the residence time of the reaction solution is 30min. The final hydroconversion was 100% and DMAPA selectivity 89.47%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (6)

1. A method for preparing N, N-dimethyl-1, 3-propanediamine, which is characterized by comprising the following steps:
(1) Mixing acrylonitrile with dimethylamine solution, and injecting the mixture into a microchannel reaction device for addition reaction to obtain a first reaction solution;
(2) Mixing the first reaction liquid with hydrogen, preheating, and then entering a continuous hydrogenation reactor filled with a Ni-based alloy hydrogenation catalyst for hydrogenation reaction to obtain a second reaction liquid;
(3) The second reaction liquid is decompressed, rectified and separated to obtain the required product,
the Ni-based alloy hydrogenation catalyst in the step (2) is an amorphous catalyst of Ni-Al-Co, and the preparation method is as follows:
grinding the alloy consisting of nickel, aluminum and cobalt into powder, mixing with alkali solution for dealumination treatment, removing upper alkali solution, washing with deionized water to neutrality to obtain a crude catalyst product, mixing the crude catalyst product with alkali solution containing a modifier, carrying out hydrothermal aging, filtering and separating to obtain solid particles, drying and baking the solid particles, reducing with hydrogen to obtain the required catalyst,
the mass ratio of Ni, al and Co in the crude product is 100-200:10-30:1-5, the hydrothermal aging temperature is 100-150 ℃ and the time is 2-24 hours,
the modifier is one or more of ferric nitrate, molybdenum nitrate, cerium nitrate, bismuth nitrate, chromium nitrate, manganese nitrate, titanium nitrate, zirconium nitrate, ruthenium nitrate, palladium nitrate and copper nitrate, the molar ratio of total metal ions in the modifier to nickel in the Ni-based alloy hydrogenation catalyst is 0.01-0.1:1,
the production equipment used in the preparation method comprises a mixer, wherein the mixer is used for mixing acrylonitrile with dimethylamine solution;
the feed inlet of the micro-channel reaction device is communicated with the discharge outlet of the mixer;
the hydrogen is filled in the storage tank, and a feed inlet of the storage tank is communicated with a discharge outlet of the microchannel reaction device;
the feeding port of the hydrogenation reactor is communicated with the discharging port of the storage tank;
the gas-liquid separator is communicated with a discharge port of the hydrogenation reactor;
the feed inlet of the decompression separation device is communicated with the liquid phase discharge outlet of the gas-liquid separator;
the microchannel reaction device comprises a microchannel reactor and a heat exchanger, wherein the heat exchanger is used for adjusting the reaction temperature of the microchannel reactor.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the molar ratio of the acrylonitrile to the dimethylamine is 1:1-2, the addition reaction temperature is 30-120 ℃, the reaction pressure is 1-5bar, and the residence time is 10-60s.
3. The method of manufacturing according to claim 1, characterized in that: the solvent of the dimethylamine solution in the step (1) is water or alcohol, the alcohol is fatty alcohol with the total carbon number of 1-4, and the concentration of dimethylamine is 10% -40%.
4. The method of manufacturing according to claim 1, characterized in that: the reaction temperature of the hydrogenation reaction in the step (2) is 10-60 ℃, the reaction pressure is 1-5bar, and the residence time is 10-30min.
5. The method of manufacturing according to claim 1, characterized in that: the alkali solution is a mixed aqueous solution of sodium hydroxide and ammonium salt, the concentration of the sodium hydroxide is 0.1-2M, and the molar ratio of the sodium hydroxide to the ammonium salt is 1-5:1.
6. The method of manufacturing according to claim 5, wherein: the ammonium salt is one or more of ammonium nitrate, ammonium sulfate and ammonium chloride.
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CN115974701A (en) * 2023-02-06 2023-04-18 大庆华理生物技术股份有限公司 Dehydration method of N, N-2-methyl-1,3-propane diamine
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