CN113501761A - Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method - Google Patents
Method for continuously producing N, N-diethyl-1, 3-propane diamine by one-step method Download PDFInfo
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Abstract
The invention provides a method for continuously producing N, N-diethyl-1, 3-propanediamine by one-step method, which adopts a tubular fixed bed reactor, wherein the lower end of the tubular fixed bed reactor is filled with ion exchange resin as a catalyst, and the upper end is filled with a metal monoatomic catalyst immobilized on mesoporous oxide, so that acrylonitrile and diethylamine react to prepare the N, N-diethyl-1, 3-propanediamine, and the product is subjected to atmospheric distillation to remove light components, and vacuum distillation and separation to obtain the product. The method has the advantages of high reaction conversion rate, high reaction selectivity, reduction of risks of excessive hydrogenation and deamination in reaction, greatly prolonged service life of the catalyst, reduction of catalyst replacement frequency, simplification of the process, and great reduction of process cost and safety risk in comparison with the conventional catalyst.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a production method of N, N-diethyl-1, 3-propanediamine.
Background
N, N-diethyl-1, 3-propane diamine is an important organic chemical raw material, is one of low-grade aliphatic diamine compounds, has a tertiary amine and primary amine structure, has active hydrogen, has active chemical properties, can form hydrogen bonds, has lone pair electrons on an N atom, has strong nucleophilic ability, is used as an important organic raw material intermediate in production, is mainly used in the fields of epoxy curing agents, polyurethane catalysts, surfactants and the like, and has a larger application space.
N, N-diethyl-1, 3-propanediamine is generally synthesized by first subjecting acrylonitrile and diethylamine to Michael addition to obtain diethylaminopropionitrile as an intermediate product, and then subjecting the diethylaminopropionitrile to hydrogenation reduction with hydrogen to obtain N, N-diethyl-1, 3-propanediamine as a target product, which is generally synthesized in two steps in two batch reactors. For the addition reaction, this step requires a relatively high conversion, usually above 99%. Because the raw material acrylonitrile belongs to a high-toxicity chemical product, and the residual acrylonitrile can generate strong toxic action on a hydrogenation reaction catalyst, the reaction time is usually greatly prolonged in production, the acrylonitrile is completely converted, the reaction efficiency is low, or acid/alkali and a polar solvent are added to promote the reaction process, but the three wastes are more, and the acid/alkali and the polar solvent which are used as the addition reaction catalyst easily generate toxic action on the hydrogenation step catalyst. For hydrogenation reduction reaction, a raney catalyst is usually used for catalytic reaction, but the selectivity of the process is usually low, more excessive hydrogenation and deamination byproducts are generated while products are generated, and the main catalyst framework structure is usually collapsed while modification is performed by adding an alkaline auxiliary agent, so that the service life of the catalyst is influenced, and the reaction safety risk is high.
U.S. Pat. No. 4,4885391, U.S. Pat. No. 5,621,0316761 and other publications disclose methods for hydrogenating dimethylaminopropionitrile to produce dimethylaminopropylamine using Raney nickel or Raney cobalt, which are similar to the reaction for preparing diethylaminopropylamine, but have low reaction selectivity, and the production of primary amine still has partially decomposed and polymerized products, and the batch production in a reaction kettle results in the production of a plurality of refined products, and the separation module takes out excessive by-products, and the single kettle has low reaction efficiency, and the catalyst has the risks of leakage, spontaneous combustion and the like.
The patent publications CN108383756A and CN102050734A report that the corresponding nitrile ethylation product is obtained by nitrile ethylation through addition of polyamine and acrylonitrile, the reaction conversion rate is high, the reaction rate is high, but a basic auxiliary agent needs to be introduced for reaction, and the long-time operation of the catalyst cannot be ensured.
The publication CN103333073A reports that N, N-dimethyl-1, 3-propanediamine is produced by a continuous method, but two sets of fixed beds are required to run simultaneously, one set of fixed bed carries out addition reaction, and inert fillers are adopted to fill a reaction tube, so that the reaction rate is slow, and the production efficiency is low; a fixed bed is used for addition reaction, Raney nickel is used as a catalyst, an alcohol solution of alkali is required to be added as an auxiliary agent for reaction, but the introduction of a large amount of alkali can cause the collapse of pore channels of the catalyst, the reaction life is influenced, and meanwhile, the risk of additional waste water and pipeline blockage can be caused.
In summary, the prior art usually requires batch operation in two reactors, the efficiency is low, and for the addition reaction, the reaction time of pure acrylonitrile and diethylamine system is long, the reaction efficiency is low, and the addition of acid/alkali as catalyst results in more three wastes and the catalyst can cause toxic effect on the hydrogenation reaction. In addition, for the hydrogenation reduction reaction, a raney catalyst is usually used for the reaction, but the reaction usually has low selectivity, more excessive hydrogenation and deamination byproducts are generated during the reaction, and the addition of an alkaline auxiliary agent may cause the collapse of the skeleton structure of the main catalyst, affect the service life of the catalyst, generate more waste water and be difficult to treat, and have high reaction safety risk.
Therefore, in order to improve the reaction efficiency, avoid the introduction of new acid/base auxiliary agents during the addition reaction, and improve the product selectivity and catalyst life, a new preparation method of N, N-diethyl-1, 3-propanediamine needs to be developed.
Disclosure of Invention
Aiming at the defects of the existing reaction, the method adopts a one-step method to continuously produce the N, N-diethyl-1, 3 propane diamine, accelerates the addition reaction rate under the condition of not introducing acid/alkali, and enables the addition reaction to be completed at the front end of a reactor; meanwhile, the selectivity of hydrogenation reaction is improved, the catalyst framework collapse caused by the introduction of an alkaline auxiliary agent is avoided, the service life of the catalyst is not influenced, and meanwhile, a Raney catalyst is replaced, so that the process risk is avoided, and the process is safer and more economical.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for continuously producing N, N-diethyl-1, 3-propanediamine by one-step method adopts a tubular fixed bed reactor, the lower end of the tubular fixed bed reactor is filled with ion exchange resin as a catalyst, and the upper end of the tubular fixed bed reactor is filled with a metal monoatomic catalyst immobilized on mesoporous oxide, so that the N, N-diethyl-1, 3-propanediamine is prepared by acrylonitrile and diethylamine reaction and hydrogen reaction, light components of the product are removed by normal pressure rectification, and the product with the purity of 99 percent is obtained by reduced pressure rectification separation.
The invention utilizes a fixed bed tubular reactor to carry out continuous reaction, synthesizes N, N-diethyl-1, 3-propane diamine by a one-step method, the lower end of the tubular reactor is filled with ion exchange resin, and the upper end is filled with a metal monatomic catalyst which is fixedly loaded on mesoporous oxide, so that acrylonitrile and diethylamine can directly generate an intermediate product at the front end of the reactor and then are hydrogenated to obtain the product N, N-diethyl-1, 3-propane diamine. The process passes through the tubular reactor in a mode of entering and exiting, so that the reactor is constantly in a full liquid state, and the liquid retention time is increased. In the ionic resin section, the polarization of acrylonitrile double bonds is promoted by taking the pretreated ionic resin as a catalyst, the reaction process is accelerated, the intermediate product can be quickly obtained by addition in the ionic resin section during the reaction, the toxic action of other solvents introduced into the system on the catalyst at the upper end is avoided, and the solvent rectification step and the generation of three wastes are reduced. In the metal monatomic catalyst section, the intermediate product and hydrogen are added to obtain a product, and the utilization rate of active components of the monatomic catalyst is greatly improved through the unique electronic geometric structure of the monatomic catalyst, so that the reaction efficiency is greatly accelerated; the characteristic of atom isolation is utilized to enable the compound to have a single active site; the catalyst acidity and alkalinity is modulated by modulating the carrier and utilizing the synergistic effect of the metal monoatomic atoms and the carrier, side reactions are selectively inhibited, and a large amount of byproducts generated by excessive hydrogenation and deamination are avoided; compared with the conventional Raney metal catalyst, the catalyst does not need to be modified by adding an auxiliary agent, so that the structural collapse of the catalyst caused by the introduction of alkali is avoided, the service life of the catalyst is greatly prolonged, the replacement frequency of the catalyst is reduced, the process is simplified, and the process cost and the safety risk are greatly reduced.
As a preferred method, a one-step process for the continuous production of N, N-diethyl-1, 3-propanediamine comprises the steps of: the pretreated ion exchange resin is filled at the lower end of the reactor, and the metal monatomic catalyst immobilized on the mesoporous oxide is filled at the upper end of the reactor. Respectively replacing a reaction system by using nitrogen and hydrogen, activating the catalyst for 10-24 hours by introducing the hydrogen under the conditions of 100-250 ℃, preferably 100-200 ℃ and 2-4MPa, respectively replacing the reactor by using the nitrogen and the hydrogen after the activation is finished, stamping the reactor by using the hydrogen for 2-8MPa, setting the temperature to be 60-120 ℃, enabling the temperature in a bed to meet the requirement, inputting acrylonitrile, diethylamine and the hydrogen with a certain molar ratio into the reactor according to a certain space velocity, enabling the diethylamine and the acrylonitrile to carry out addition reaction in an ionic resin section, then carrying out hydrogenation reaction in a metal monatomic catalyst section, carrying out normal-pressure rectification on a product to remove light components, and carrying out reduced-pressure rectification separation to obtain a product with the purity of 99%.
In the invention, the ion resin is acidic ion exchange resin, preferably styrene macroporous ion exchange resin, because polystyrene resin has better adsorption property on organic pigments of a reaction part, high reaction activity can be provided, and the color number of the reaction liquid can be reduced; and the macroporous resin has low crosslinking degree, larger internal porosity and more flow channels, so that the reaction exchange rate is high, and the diffusion of the reaction intermediate product diethylaminopropionitrile is better than that of gel resin.
The particle size of the ionic resin is 1.2-2.5mm, preferably 2-2.5mm, and the larger particle size can reduce the pressure difference loss of a material circulation reactor, reduce the reaction energy consumption and prolong the service life of the ionic resin.
The ionic resin is required to be pretreated before the reaction, and the ionic resin is firstly soaked in 80%, 60%, 40% and 20% of salt solution for 1-3h in sequence to complete the pre-swelling process of the resin. The purpose is to slow down the swelling speed and prevent the resin from swelling. Then the resin is put into a reflux device containing 2 to 6 weight percent of hydrochloric acid solution and stirred for 6 to 8 hours at the temperature of between 30 and 60 ℃, and the cleaning and transformation processes of the resin are completed. The transformed resin was placed in an oven. Heating to 60-80 ℃ at the speed of 0.5-2 ℃/min in a nitrogen atmosphere, avoiding resin sintering caused by overhigh temperature, drying for 4-6 hours, placing the resin in an ammonia water solution containing 300-500ppm ferric chloride and 100-300ppm tetraammine dichloride copper metal complex, wherein the mass ratio of the resin to the ammonia water solution containing 300-500ppm ferric chloride and 100-300ppm tetraammine dichloride copper metal complex is 1:3-5, and stirring for 6-10 hours at the temperature of 50-70 ℃ under the condition of a reflux device. A novel functional group is introduced by adding a bimetallic ion complex, so that on one hand, the acidity of the ion exchange resin is adjusted, the phenomenon that the acidity of the ion exchange resin is too strong to cause temperature runaway at the initial stage of reaction is avoided, on the other hand, the introduction of iron ions can inhibit the polymerization of acrylonitrile in the reaction process to a certain extent, and finally, the washing liquid is washed for many times by deionized water until the washing liquid is neutral, and the standard pH of the washing liquid is 6.5-8.5.
In the invention, the reaction needs to be subjected to a catalyst activation process before the reaction starts, and the activation temperature is 100-250 ℃ under a hydrogen atmosphere, preferably 100-200 ℃. The catalyst needs to be activated before the reaction is started, because a part of slight carbon deposit blocks the catalyst pore channels and reduces the activity of the catalyst after the catalyst is prepared and placed for a long time.
In the invention, the reaction process conditions are as follows: the reaction temperature is 60-150 ℃, preferably 80-120 ℃; the reaction pressure is 4-8MPa, preferably 5-6 MPa; the feed molar ratio of acrylonitrile, diethylamine and hydrogen is 1:0.8-1.3:2-15, preferably 1:1.1-1.2: 3-5; the volume space velocity of acrylonitrile is 0.5-15h-1Preferably 2-6h-1。
The acrylonitrile purity should be above 99% high purity acrylonitrile.
In the invention, the mesoporous oxide is one or more of zirconium dioxide, titanium dioxide, aluminum oxide and silicon dioxide.
The load metal of the single-atom catalyst is one or more of Fe, Co, Pd, Nd, Rh, Ru, Ce, Zn, Ni and Mo. The metal loading is 2 to 6 wt%, preferably 3 to 5 wt%.
The monatomic catalyst is a spherical, strip-shaped or cloverleaf catalyst, the diameter is 2-8mm, preferably 2-4mm, and the bed bulk density is 0.5-10g/ml, preferably 0.8-4 g/ml.
The preparation method of the metal monatomic catalyst immobilized on the mesoporous oxide comprises the following steps:
(1) preparation of the support
Dissolving a template agent in a solvent, adjusting the pH value to 7-8 after stirring, adding a carrier precursor solution, stirring, drying and calcining to remove the template agent, wherein the calcining temperature rise rate is preferably 1-5 ℃/min, preferably 0.5-2 ℃/min, so as to obtain a corresponding mesoporous oxide carrier;
(2) preparation of monatomic catalyst
Dissolving the mesoporous oxide carrier prepared in the step (1) in water, dropwise adding a metal salt solution, preferably at a speed of 1-5ml/min, simultaneously adding a precipitant solution, adjusting the corresponding pH to 7-8, refluxing, stirring, filtering, drying, and roasting to obtain a corresponding metal monatomic catalyst precursor; and (3) carrying out aftertreatment on the precursor in a mixed atmosphere of carbon monoxide and methyl iodide to obtain a monatomic dispersed noble metal catalyst, drying, roasting and forming to obtain the catalyst.
As a preferable embodiment, the preparation method of the metal monatomic catalyst supported on the mesoporous oxide comprises the steps of:
(1) preparation of the support
Dissolving a certain amount of template agent in a solvent at the temperature of 30-60 ℃, stirring for 3-5h in a reflux device in a constant-temperature water bath at the temperature of 30-60 ℃, respectively dropwise adding a certain amount of acetic acid or hydrochloric acid to adjust the pH value to 7-8, subsequently dropwise adding a plurality of carrier precursor solutions, continuously stirring for 2-3h, drying for 3-5h at the temperature of 50-70 ℃ to evaporate the solvent, then taking out a sample, and placing the sample in a muffle furnace to be calcined for 5-10h at the temperature of 300-600 ℃, preferably 350-550 ℃ to remove the template agent, wherein the heating rate is 1-5 ℃/min. And fully grinding the calcined sample to obtain the corresponding mesoporous oxide carrier.
(2) Preparation of monatomic catalyst
The monoatomic catalyst is prepared by a post-treatment dispersion method. Preparing a metal salt solution with a certain concentration in a beaker, simultaneously placing the mesoporous oxide carrier prepared in the step (1) in a 500ml round-bottom flask, adding a certain volume of deionized water, stirring and dissolving to prepare a carrier emulsion with a certain concentration, dropwise adding the prepared corresponding metal salt solution at a certain speed, simultaneously adding a precipitator solution, controlling the load capacity of the precipitator solution, stirring and refluxing for 8-12 hours in a reflux device at 60-80 ℃ after dropwise adding, drying the product at a constant temperature of 60-80 ℃ for 8-12 hours after suction filtration, placing the product in a drying oven, calcining for 10-15 hours at 300-600 ℃ in a muffle furnace under the condition of nitrogen atmosphere, and raising the temperature at 1-5 ℃/min. Then calcining for 3-5h at 300-600 ℃ under the hydrogen atmosphere condition, wherein the heating rate is 1-5 ℃/min. Obtaining the corresponding monatomic catalyst precursor. The precursor is treated for 4-6h at the temperature of 200-250 ℃ under the mixed atmosphere of carbon monoxide and methyl iodide (the molar ratio is 1.5-2:1), the obtained monoatomic dispersion noble metal catalyst is calcined for 10-15h at the temperature of 300-600 ℃ in a muffle furnace under the atmosphere of nitrogen and hydrogen, and the heating rate is 1-5 ℃/min. And fully grinding the calcined sample, and forming to obtain the corresponding metal monatomic catalyst loaded on the mesoporous oxide.
The template agent in the step (1) is one or two of hexadecyl trimethyl ammonium bromide or hexadecyl triethyl ammonium bromide.
The solvent in step (1) of the present invention may be any suitable solvent known in the art, such as ethanol, isopropanol, methanol, ethers, etc., preferably ethanol, in order to better disperse the templating agent in the system.
In the step (1), the carrier precursor solution is an organic salt solution containing carrier elements (such as zirconium, titanium, aluminum and silicon), preferably one or more of zirconium n-propoxide, titanium n-propoxide, aluminum n-propoxide and silicon ester solutions, wherein the mass ratio of the carrier precursor to the template agent is 2-10, preferably 3-6; the concentration ranges from 40 to 50 wt%.
The calcination temperature for removing the template in the step (1) is 300-600 ℃, preferably 350-550 ℃.
The precipitant in step (2) of the present invention is one or more of aqueous solutions of sodium hydroxide, lithium hydroxide, urea and sodium carbonate, wherein the mass ratio of the precipitant to the supported metal salt is 0.8-3, preferably 1-2; the concentration range is 40-70%.
The carrier emulsion described in the step (2) of the present invention has a pH ranging from 7 to 8 and a concentration ranging from 10 to 30% by weight.
The salt solution of the metal in the step (2) of the present invention may be one or more of nitrate, acetate and chloride of the metal, and the concentration thereof is in the range of 20 to 70 wt%, preferably 30 to 50 wt%.
The dropping rate of the salt solution of the metal in the step (2) of the present invention is in the range of 0.2 to 5ml/min, preferably 0.5 to 3.5ml/min, and the dropping rate of the precipitant is in the range of 0.5 to 6ml/min, preferably 1 to 4 ml/min.
Compared with the prior art, the invention has the following positive effects:
the invention adopts a tubular reactor to continuously produce the N, N-diethyl-1, 3-propanediamine by a one-step method, the lower end of the tubular reactor is filled with ion exchange resin, and the upper end of the tubular reactor is filled with a metal monatomic catalyst which is fixedly loaded on mesoporous oxide, so that acrylonitrile and diethylamine can directly generate an intermediate product at the front end of the reactor and then are hydrogenated to obtain the N, N-diethyl-1, 3-propanediamine. The reactor is in a full liquid state by adopting a mode of bottom inlet and top outlet. In the ionic resin section, the polarization of acrylonitrile double bonds is promoted by taking the pretreated ionic resin as a catalyst, the reaction process is accelerated, an intermediate product can be generated at the front end of the reactor, the reaction conversion rate reaches over 99 percent, and the toxic effect of other solvents introduced into the system on the catalyst at the upper end is avoided. In the metal monatomic catalyst section, the metal monatomic catalyst immobilized on the mesoporous oxide has a single active site by utilizing the characteristic of atom isolation, and simultaneously, the synergistic effect of the metal component and the mesoporous oxide carrier is utilized to improve the reaction selectivity and reduce the risks of excessive hydrogenation and deamination of the reaction.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Placing 5g of hexadecyl trimethyl ammonium bromide into a three-neck flask containing 200ml of ethanol, stirring for 3 hours in a constant-temperature water bath at the condition of a reflux device at 30 ℃, adding 20 wt% of acetic acid solution to adjust the pH value to 7, then dropwise adding 30g of 50 wt% of zirconium n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after dropwise adding, and drying for 5 hours at 70 ℃ to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 5 hours at the temperature of 350 ℃ so as to remove the template agent, wherein the heating rate is 1 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous ZrO2And (3) a carrier. Dissolving 25g of the prepared carrier powder in 100ml of deionized water to obtain a carrier emulsion, placing the carrier emulsion in a three-neck flask, and dropwise adding 70% of the carrier emulsion into the three-neck flask at the rate of 0.5ml/minWhile adding 10.95g of 40% sodium hydroxide solution dropwise at the rate of 0.7ml/min, and stirring the mixture in a reflux device at 70 ℃ for 8 hours. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 10 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 2 ℃/min. Then, the mixture is reduced and calcined for 5h at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monoatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 6h at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 1.5:1 to obtain a monoatomic dispersed Fe catalyst, and then placing the monoatomic dispersed Fe catalyst in a muffle furnace to be reduced and calcined for 10h at 500 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 2 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite (serving as a binder and not counting the total amount of the catalyst), and forming to obtain [ Fe ] with the loading capacity of 5%]-ZrO2A monatomic catalyst.
Example 2
Placing 4.8g of hexadecyltriethylammonium bromide into a three-neck flask containing 100ml of ethanol, stirring in a constant-temperature water bath for 5 hours at 40 ℃ under the condition of a reflux device, adding a 20 wt% acetic acid solution to adjust the pH to 7.5, then dropwise adding 36g of a 40% titanium n-propoxide solution into the three-neck flask at the rate of 1ml/min, continuously stirring for 3 hours after the dropwise adding is finished, and drying at 60 ℃ for 5 hours to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 10h at 500 ℃ to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous TiO2And (3) a carrier. 32g of the prepared carrier powder is dissolved in 150ml of deionized water to obtain a carrier emulsion, the carrier emulsion is placed in a three-neck flask, and 20% praseodymium nitrate (Pr (NO) is dropwise added into the three-neck flask at the rate of 5ml/min3)3) 7.42g of the solution, 3.7g of 40 percent sodium hydroxide solution is added dropwise at the same time at the speed of 2.5ml/min, and the stirring is continued for 12 hours at the temperature of 60 ℃ in a reflux device after the dropwise addition. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 15 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 2 ℃/min. Then, the mixture is reduced and calcined for 5h at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. To obtain a phasePlacing the precursor into a tubular furnace, treating for 4h at 200 ℃ in the mixed atmosphere of carbon monoxide and methyl iodide with the molar ratio of 1.5:1 to obtain the monoatomic dispersed Pr catalyst, and then placing the Pr catalyst into a muffle furnace to be reduced and calcined for 15h at 500 ℃ under the atmosphere of nitrogen and hydrogen, wherein the heating rate is 2 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain the [ Pr with the loading capacity of 2%]-TiO2A monatomic catalyst.
Example 3
6.1g of hexadecyltrimethylammonium bromide was placed in a three-necked flask containing 250ml of ethanol, stirred in a thermostatic water bath at 60 ℃ for 4 hours under the condition of a reflux device, 10 wt% of dilute hydrochloric acid solution was added to adjust the pH to 8, then 97.6g of 50% silicone ester solution was added dropwise to the three-necked flask at a rate of 1ml/min, and after the dropwise addition was completed, stirring was continued for 3 hours, followed by drying at 50 ℃ for 5 hours to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 5 hours at the temperature of 600 ℃ to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain the corresponding mesoporous SiO2And (3) a carrier. 21g of the prepared carrier powder is dissolved in 80ml of deionized water to obtain a carrier emulsion, the carrier emulsion is placed in a three-neck flask, 9.21g of 60% cobalt nitrate solution is dropwise added into the three-neck flask at the speed of 3ml/min, 18.41g of 60% urea solution is dropwise added at the speed of 5.9ml/min, and the mixture is continuously stirred in a reflux device for 10 hours at the temperature of 80 ℃ after the dropwise addition. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 10 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 2 ℃/min. Then, the mixture is reduced and calcined for 5h at 300 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 6h at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 2:1 to obtain a monatomic dispersed Co catalyst, and then placing the monatomic dispersed Co catalyst in a muffle furnace, and carrying out reduction calcination for 15h at 400 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 2 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain the [ Co ] with the loading of 6%]-SiO2A monatomic catalyst.
Example 4
Placing 6.2g of hexadecyl trimethyl ammonium bromide into a three-neck flask containing 150ml of ethanol, stirring for 3 hours in a constant-temperature water bath at the condition of a reflux device at 50 ℃, adding 10% dilute hydrochloric acid solution to adjust the pH to 7, then dropwise adding 124g of 50% zirconium n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after dropwise adding, and drying for 3 hours at 70 ℃ to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 8 hours at the temperature of 400 ℃ so as to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous ZrO2And (3) a carrier. 15g of the prepared carrier powder is dissolved in 100ml of deionized water to obtain carrier emulsion, the carrier emulsion is placed in a three-neck flask, 3.49g of 50% cerium nitrate solution is dropwise added into the three-neck flask at the speed of 2ml/min, 7.48g of 70% sodium hydroxide solution is dropwise added at the speed of 4.4ml/min, and the mixture is continuously stirred in a reflux device at the temperature of 70 ℃ for 12 hours after the dropwise addition. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 10 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 4 ℃/min. Then, the mixture is reduced and calcined for 5h at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monoatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 6h at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 1.8:1 to obtain a monoatomic dispersed Ce catalyst, and then placing the monoatomic dispersed Ce catalyst in a muffle furnace to be subjected to reduction calcination for 12h at 400 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 1 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain [ Ce ] with the loading of 5%]-ZrO2A monatomic catalyst.
Example 5
Placing 5g of hexadecyl trimethyl ammonium bromide into a three-neck flask containing 400ml of ethanol, stirring for 3 hours in a constant-temperature water bath under the condition of a 40 ℃ reflux device, adding 10% dilute hydrochloric acid solution to adjust the pH to 7.5, then dropwise adding 30g of 50% aluminum n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after dropwise adding, and drying for 4 hours at 70 ℃ to evaporate the solvent. Then the sample is placed in a muffle furnace to be calcined for 7 hours at the temperature of 350 ℃ so as to remove the template agent, and the heating rate is 2 DEG CAnd/min. Fully grinding the calcined sample to obtain corresponding mesoporous Al2O3And (3) a carrier. Taking 12g of prepared carrier powder, dissolving the carrier powder in 100ml of deionized water to obtain carrier emulsion, placing the carrier emulsion in a three-neck flask, dropwise adding 3.77g of 60% ruthenium nitrate solution into the three-neck flask at the speed of 1ml/min, dropwise adding 14.69g of 40% sodium hydroxide solution at the speed of 3.9ml/min, and continuously stirring for 5 hours in a reflux device at the temperature of 60 ℃ after the dropwise adding. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 10 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 3 ℃/min. Then, the mixture is reduced and calcined for 5h at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monoatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 5h at 240 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 2:1 to obtain a monoatomic dispersed Ru catalyst, and then placing the monoatomic dispersed Ru catalyst in a muffle furnace to perform reduction calcination for 10h at 500 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 2 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain [ Ru with the load of 6%]-Al2O3A monatomic catalyst.
Example 6
Placing 3.4g of hexadecyl trimethyl ammonium bromide into a three-neck flask containing 250ml of ethanol, stirring for 3 hours in a constant-temperature water bath at the condition of a reflux device at 30 ℃, adding a 10% acetic acid solution to adjust the pH value to 7, then dropwise adding 40.8g of a 50% titanium n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after dropwise adding, and drying for 4 hours at 50 ℃ to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 5 hours at the temperature of 600 ℃ to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous TiO2And (3) a carrier. 13g of the prepared carrier powder was dissolved in 120ml of deionized water to obtain a carrier emulsion, the carrier emulsion was placed in a three-necked flask, and 20% rhodium nitrate (Rh (NO) (NO: 1) was added dropwise to the three-necked flask at a rate of 1ml/min3)3) 3.64g of the solution, 3.64g of 60 percent sodium hydroxide solution is added dropwise at the same time at the rate of 1ml/min, and the solution is stirred continuously for 5 hours at the temperature of 70 ℃ in a reflux device after the dropwise addition. Then the mixture is filtered and post-positionedDrying in an oven at constant temperature of 80 ℃ for 8 hours. Calcining the mixture for 10 hours in a muffle furnace at the temperature of 300 ℃ under the nitrogen atmosphere condition, wherein the heating rate is 3 ℃/min. Then, the mixture is reduced and calcined for 3h at the temperature of 600 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monoatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 4h at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 1.5:1 to obtain a monoatomic dispersed Rh catalyst, and then placing the monoatomic dispersed Rh catalyst in a muffle furnace to perform reduction calcination for 12h at 400 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 3 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain the [ Rh ] with the loading capacity of 2%]-TiO2A monatomic catalyst.
Example 7
Placing 5.9g of hexadecyl trimethyl ammonium bromide into a three-neck flask containing 200ml of ethanol, stirring for 3 hours in a constant-temperature water bath at the condition of a reflux device at 30 ℃, adding a 10% acetic acid solution to adjust the pH value to 7, then dropwise adding 35.4g of a 50% titanium n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after dropwise adding, and drying for 5 hours at 70 ℃ to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 5 hours at the temperature of 350 ℃ so as to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous TiO2And (3) a carrier. 29g of the prepared carrier powder is dissolved in 100ml of deionized water to obtain carrier emulsion, the carrier emulsion is placed in a three-neck flask, 7.12g of 35 percent cerium nitrate solution is dropwise added into the three-neck flask at the speed of 1ml/min, 18.23g of 40 percent urea solution is dropwise added at the speed of 2.6ml/min, and the mixture is continuously stirred for 5 hours in a reflux device at the temperature of 70 ℃ after the dropwise addition. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 12 hours in a muffle furnace at 500 ℃ under the nitrogen atmosphere, wherein the heating rate is 1 ℃/min. Then, the mixture is reduced and calcined for 4 hours at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monoatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 5 hours at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 1.5:1 to obtain a monoatomic dispersed Ce catalyst, placing the monoatomic dispersed Ce catalyst in a muffle furnace at 500 ℃ in a nitrogen and hydrogen atmosphereReducing and calcining for 15h, wherein the heating rate is 4 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain [ Ce ] with the loading of 4%]-TiO2A monatomic catalyst.
Example 8
Placing 7.1g of hexadecyltriethylammonium bromide into a three-neck flask containing 100ml of ethanol, stirring for 3 hours in a constant-temperature water bath at the condition of a reflux device at 50 ℃, adding a 10% acetic acid solution to adjust the pH value to 7, then dropwise adding 71g of a 50% aluminum n-propoxide solution into the three-neck flask at the speed of 1ml/min, continuously stirring for 3 hours after the dropwise adding is finished, and drying for 5 hours at 70 ℃ to evaporate the solvent. And then placing the sample in a muffle furnace to be calcined for 5 hours at the temperature of 350 ℃ so as to remove the template agent, wherein the heating rate is 2 ℃/min. Fully grinding the calcined sample to obtain corresponding mesoporous Al2O3And (3) a carrier. 24g of the prepared carrier powder was dissolved in 140ml of deionized water to obtain a carrier emulsion, the carrier emulsion was placed in a three-necked flask, and 20% neodymium nitrate (Nd (NO) (NO: 1) was added dropwise to the three-necked flask at a rate of 1ml/min3)3) 13.75g of the solution, 7.79g of 60 percent sodium hydroxide solution is added dropwise at the same time at the rate of 0.57ml/min, and the solution is stirred continuously for 8 hours at the temperature of 70 ℃ in a reflux device after the dropwise addition. Then the mixture is filtered and put into an oven to be dried for 8 hours at the constant temperature of 80 ℃. Calcining the mixture for 10 hours at 600 ℃ in a muffle furnace under the nitrogen atmosphere, wherein the heating rate is 2 ℃/min. Then, the mixture is reduced and calcined for 5h at 500 ℃ under the hydrogen atmosphere condition, and the heating rate is 2 ℃/min. Obtaining a corresponding monatomic catalyst precursor, placing the precursor in a tubular furnace, treating for 4h at 250 ℃ in a mixed atmosphere of carbon monoxide and methyl iodide with a molar ratio of 1.5:1 to obtain a monatomic dispersed Nd catalyst, and then placing the monatomic dispersed Nd catalyst in a muffle furnace to perform reduction calcination for 10h at 500 ℃ in a nitrogen and hydrogen atmosphere, wherein the heating rate is 5 ℃/min. Taking 15g of calcined sample, fully grinding, adding 5g of pseudo-boehmite, and forming to obtain the [ Nd ] with the load of 5%]-TiO2A monatomic catalyst.
Reaction of catalyst for production of DEAPA:
soaking 50g of styrene macroporous acidic ion exchange resin in 100ml of saturated salt water with different concentrations of 80%, 60%, 40% and 20%Soaking for 2h, placing the resin in a reflux device containing 3 wt% hydrochloric acid solution, stirring at 50 ℃ for 6h, filtering, placing in an oven, heating to 60 ℃ at the speed of 2 ℃/min under the nitrogen atmosphere, and drying for 8 h. The resin was then placed in 200g of an aqueous ammonia solution containing 500ppm of ferric chloride and 300ppm of tetraammine copper dichloride complex and stirred at 50 ℃ for 6h under reflux conditions. Finally, the reactor was washed with deionized water to pH 7, 50g of the pretreated ion exchange resin was packed in the lower end of the reactor, and 50g of the mesoporous oxide supported metal monatomic catalyst prepared in examples 1 to 8 was packed in the upper end of the reactor, the volume of which was about 100ml (36X 8 mm). Firstly, nitrogen and hydrogen are respectively used for replacing a system pipeline, and after replacement is finished, hydrogen is used for activating the catalyst of the tubular reactor for 12 hours under the conditions of 150 ℃ and 0.5 MPa. After the activation, hydrogen is pressed to 5MPa, the set temperature is 100 ℃, the temperature in the bed reaches the requirement, and diethylamine, acrylonitrile and hydrogen are mixed according to the molar ratio of 1.02:1:2.5 for 2h-1The volume space velocity (measured by acrylonitrile) of (A) is input into a reactor, gas-liquid-solid three-phase reaction is carried out under the conditions of 100 ℃ and 5MPa, and sampling is carried out for chromatographic analysis (Agilent GC 7890A), wherein the chromatogram is provided with a FID detector, a DB-5 model chromatographic column is selected as the chromatographic column, the detection method is shown in Table 1, and the analysis result is shown in Table 2.
Comparative examples 1 to 2
50g of the pretreated ion exchange resin (pretreatment procedure as above) was packed in the lower end of the reactor, and 50g of commercially available Raney nickel (comparative example 1, Gray) and Raney cobalt (comparative example 2, Gray) catalysts were packed in the upper end of the reactor, respectively, the reactor volume being about 100ml (36 x 8 mm). Firstly, nitrogen and hydrogen are respectively used for replacing a system pipeline, and after replacement is finished, hydrogen is used for activating the catalyst of the tubular reactor for 12 hours under the conditions of 150 ℃ and 0.5 MPa. After the activation, hydrogen is pressed to 5MPa, the set temperature is 100 ℃, the temperature in the bed reaches the requirement, and diethylamine, acrylonitrile and hydrogen are mixed according to the molar ratio of 1.02:1:2.5 for 2h-1The volume space velocity of (A) is inputted into a reactor, gas-liquid-solid three-phase reaction is carried out under the conditions of 100 ℃ and 5MPa, samples are taken and analyzed by chromatography (Agilent GC 7890A), the detection method is shown in Table 1, and the analysis result is shown in Table 2.
Example 9
50g of the untreated styrenic macroporous acidic ion exchange resin was packed in the lower end of the reactor, and 50g of the catalyst prepared in example 2 was packed in the upper end of the reactor, the volume of which was about 100ml (36 × 8 mm). Firstly, nitrogen and hydrogen are respectively used for replacing a system pipeline, and after replacement is finished, hydrogen is used for activating the catalyst of the tubular reactor for 12 hours under the conditions of 150 ℃ and 0.5 MPa. After the activation, hydrogen is pressed to 5MPa, the set temperature is 100 ℃, the temperature in the bed reaches the requirement, and diethylamine, acrylonitrile and hydrogen are mixed according to the molar ratio of 1.02:1:2.5 for 2h-1The volume space velocity of (A) is inputted into a reactor, gas-liquid-solid three-phase reaction is carried out under the conditions of 100 ℃ and 5MPa, samples are taken and analyzed by chromatography (Agilent GC 7890A), the detection method is shown in Table 1, and the analysis result is shown in Table 2.
TABLE 1 detection methods
| Initial temperature of column box: | 50℃ |
| stage one heating rate: | 5℃/min |
| stage one target temperature | 80℃ |
| Stage-keeping time: | 0min |
| temperature rise rate in stage two: | 15℃/min |
| stage two target temperature | 300℃ |
| Stage two retention time: | 15min |
| sample injector temperature: | 300℃ |
| detector temperature: | 300℃ |
| Detector hydrogen flow rate: | 30ml/min |
| carrier gas: | Nitrogen |
| sample introduction pressure of a chromatographic column: | 13.781psi |
| total flow rate: | 43.3ml/min |
| column box flow rate: | 3ml/min |
| the split ratio is as follows: | 30:1 |
| flow splitting: | 39ml/min |
| sample introduction amount: | 0.2μl |
TABLE 2 analysis results of examples 1 to 9 and comparative examples 1 to 2
As can be seen from Table 2: compared with the comparative example, the activity and the selectivity of the catalyst prepared by the method are obviously improved compared with the comparative example, and meanwhile, the catalyst which is continuously operated for more than 500 hours basically has no obvious inactivation phenomenon and is obviously superior to the Raney series catalyst of the comparative example.
Examples 10 to 15
The catalyst prepared according to example 6 was prepared by first filling 50g of the pretreated ion exchange resin (same procedure as above) in the lower end of the reactor and 50g of the metal monatomic catalyst immobilized on the mesoporous oxide in the upper end of the reactor, the volume of which was about 100ml (36 × 8 mm). Firstly, nitrogen and hydrogen are respectively used for replacing a system pipeline, and after replacement is finished, hydrogen is used for activating the catalyst of the tubular reactor for 12 hours under the conditions of 150 ℃ and 0.5 MPa. Diethylamine, acrylonitrile and hydrogen are mixed according to the molar ratio of 1.02:1:2.5 for 2h-1The volume airspeed of (A) is input into a reactor, gas-liquid-solid three-phase reaction is carried out under the conditions of certain temperature and pressure, sampling is carried out, chromatographic analysis (Agilent GC 7890A) is carried out, a FID detector is arranged on the chromatogram, a DB-5 model chromatographic column is selected for the chromatographic column to change the reaction temperature, the pressure and the airspeed, and the result is shown in a table 3:
TABLE 3 examples 10 to 15
The above-mentioned embodiments and experimental examples are provided to illustrate the present invention and the technical concept and features, and are intended to enable the understanding of the present technology, to be read and executed, and not to limit the present invention, and any modification and change made within the spirit and scope of the appended claims are intended to fall within the scope of the present invention.
Claims (10)
1. A one-step method for continuously producing N, N-diethyl-1, 3-propanediamine is characterized in that a tubular fixed bed reactor is adopted, ion exchange resin is filled at the lower end of the tubular fixed bed reactor to serve as a catalyst, a metal monatomic catalyst immobilized on mesoporous oxide is filled at the upper end of the tubular fixed bed reactor, acrylonitrile, diethylamine and hydrogen react to prepare the N, N-diethyl-1, 3-propanediamine, light components of the product are removed through normal pressure rectification, and the product is obtained through reduced pressure rectification separation.
2. The method according to claim 1, wherein the ion exchange resin is an acidic ion exchange resin, preferably a styrenic macroporous ion exchange resin, having a particle size of between 1.2 and 2.5mm, preferably between 2 and 2.5 mm.
3. The method of claim 1 or 2, wherein the reaction is preceded by a pretreatment of the ion exchange resin, which is first sequentially soaked with saturated saline solutions of different concentrations to complete a pre-swelling process of the resin, after being washed and transformed by hydrochloric acid solution, the transformed ion exchange resin is modified by ammonia water solution containing ferric chloride and tetraammine copper dichloride metal complex, and finally washed to be neutral, and the washing solution is standard pH 6.5-8.5, preferably using 300-500ppm ferric chloride and 100-300ppm copper metal dichloride ammonia water solution modified ion exchange resin, the ion exchange resin and containing 300-500ppm ferric chloride and 100-300ppm copper metal dichloride ammonia water solution mass ratio of 1: 3-5.
4. The method as claimed in any one of claims 1 to 3, wherein the reaction is subjected to a catalyst activation process before the reaction is started, wherein the activation temperature is 100-250 ℃, preferably 100-200 ℃ and the activation time is 10-24h under a hydrogen atmosphere.
5. The method according to any one of claims 1 to 4, characterized in thatCharacterized in that the reaction process conditions are as follows: the reaction temperature is 60-150 ℃, preferably 80-120 ℃; the reaction pressure is 4-8MPa, preferably 5-6 MPa; the feed molar ratio of acrylonitrile, diethylamine and hydrogen is 1:0.8-1.3:2-15, preferably 1:1.1-1.2: 3-5; the volume space velocity of acrylonitrile is 0.5-15h-1Preferably 2-6h-1。
6. The method according to any one of claims 1 to 5, wherein the mesoporous oxide is one or more of zirconium dioxide, titanium dioxide, aluminum oxide, silicon dioxide; and/or the load metal is one or more of Fe, Co, Pd, Nd, Rh, Ru, Ce, Zn, Ni and Mo; and/or, the metal loading is from 2 to 6 wt%, preferably from 3 to 5 wt%.
7. The method according to any one of claims 1 to 6, wherein the method for preparing the metal monoatomic catalyst supported on the mesoporous oxide comprises the following steps:
(1) preparation of the support
Dissolving a template agent in a solvent, adjusting the pH value to 7-8 after stirring, adding a carrier precursor solution, stirring, drying and calcining to remove the template agent, wherein preferably the calcining temperature rise rate is 0.5-2 ℃/min, so as to obtain a corresponding mesoporous oxide carrier;
(2) preparation of monatomic catalyst
Dissolving the mesoporous oxide carrier prepared in the step (1) in water, dropwise adding a metal salt solution, preferably at a rate of 0.5-3.5ml/min, simultaneously adding a precipitant, preferably at a rate of 1-4ml/min, refluxing, stirring, filtering, drying and roasting to obtain a corresponding metal monatomic catalyst precursor; and (3) carrying out aftertreatment on the precursor in a mixed atmosphere of carbon monoxide and methyl iodide to obtain a monatomic dispersed noble metal catalyst, drying, roasting and forming to obtain the catalyst.
8. The method of claim 7, wherein the template agent in step (1) is one or more of cetyltrimethylammonium bromide or cetyltriethylammonium bromide; and/or, the calcination temperature for removing the template agent is 300-600 ℃, preferably 350-550 ℃.
9. The method according to claim 7 or 8, wherein the carrier precursor solution in step (1) is an organic salt solution containing carrier elements (such as zirconium, titanium, aluminum, silicon), preferably one or more of zirconium n-propoxide, titanium n-propoxide, aluminum n-propoxide, silicon ester solutions, wherein the ratio of carrier precursor to templating agent mass is 2-10, preferably 3-6; the concentration ranges from 40 to 50 wt%.
10. The method according to claim 10, wherein the precipitant in step (2) is one or more of sodium hydroxide, lithium hydroxide, urea, and sodium carbonate in aqueous solution, and the mass ratio of precipitant to metal salt is 0.8-3, preferably 1-2; the concentration range of the precipitant solution is 40-70 wt%; and/or, the metal salt solution in the step (2) is one or more of nitrate, acetate and chloride of metal, and the concentration of the metal salt solution is 20-70 wt%, and preferably 30-50 wt%.
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| CN113813944A (en) * | 2021-10-22 | 2021-12-21 | 上海科技大学 | Monoatomic rhodium catalyst and preparation method and application thereof |
| CN115414942A (en) * | 2022-09-23 | 2022-12-02 | 中国石油化工股份有限公司 | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine as well as preparation method and application thereof |
| CN118580151A (en) * | 2024-08-02 | 2024-09-03 | 江苏万盛大伟化学有限公司 | Preparation method of aliphatic diamine compound |
| CN118580151B (en) * | 2024-08-02 | 2024-10-29 | 江苏万盛大伟化学有限公司 | Preparation method of aliphatic diamine compound |
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