CN113416140A - Method for preparing 2-methyl pentanediamine - Google Patents
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Abstract
The invention provides a brand-new method for preparing 2-methylpentamethylenediamine, which uses Ir loaded by Ni-Al hydrotalcite as a catalyst, a fixed bed as a reactor, ammonium formate as a hydrogen source and an ammonia source for reaction, and converts acetaldehyde and methacrylonitrile into 2-methylpentamethylenediamine by a one-pot method in the presence of a solvent and under a certain temperature condition. The method for preparing 2-methyl pentanediamine provided by the invention has the advantages of mild reaction conditions, simple operation process, far higher selectivity of a target product than that of a traditional preparation method, less three wastes, easy product separation, realization of continuous production and potential for industrial application; meanwhile, the preparation process of the used catalyst is simple.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 2-methyl pentanediamine.
Background
2-methyl pentanediamine is an important organic diamine and an organic synthesis intermediate, and the downstream application of the 2-methyl pentanediamine is very wide, for example, the 2-methyl pyridine can be used for preparing 2-methyl pyridine, and the 2-methyl pyridine is an important intermediate for synthesizing nicotinic acid and nicotinamide; another important application of 2-methylpentanediamine is as a chain extender for the production of polyurethanes, spandex, and high modulus aramids, and furthermore 2-methylpentanediamine may also be used as a monomer moiety in place of hexamethylenediamine for the preparation of nylon 66.
The prior method for preparing 2-methyl pentanediamine mainly uses modified doped Raney nickel as a catalyst, directly hydrogenates raw material 2-methyl glutaronitrile to obtain 2-methyl pentanediamine and simultaneously produces 3-methyl piperidine as a byproduct (related documents and patents have appl. Catal. A: Gen.2009,352:193-201, US4885391A, CN101990532A, CN 107365257A, CN111377820A and the like). The reported methods generally have the defect of low selectivity of 2-methyl pentanediamine, the selectivity of the 2-methyl pentanediamine is only 60-74%, and meanwhile, heavy components are by-produced to generate a great amount of three wastes; in addition, the low selectivity of the target product also causes separation difficulties. Therefore, the development of a novel preparation method of the 2-methylpentamethylenediamine is of great significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing 2-methyl pentanediamine, which solves the defect of low selectivity of the 2-methyl pentanediamine in the prior art, and converts raw materials of methacrylonitrile and acetaldehyde into the 2-methyl pentanediamine by a one-pot method.
In order to achieve the above object, the present invention adopts the following technical solutions:
the method for preparing 2-methylpentanediamine is characterized in that acetaldehyde and methacrylonitrile are converted into 2-methylpentanediamine by a one-pot method in the presence of a solvent and under a certain temperature condition by using Ir loaded on Ni-Al hydrotalcite as a catalyst and ammonium formate as a hydrogen source and an ammonia source for reaction. The reaction is shown as follows:
in a specific embodiment, the method comprises the steps of: under a certain temperature and an inert gas atmosphere, filling an Ir catalyst loaded by a Ni-Al hydrotalcite carrier into a fixed bed, dissolving acetaldehyde, methacrylonitrile and ammonium formate into a solvent to form a mixed solution, and then enabling the mixed solution to pass through a catalyst bed layer at a certain airspeed to enable raw materials acetaldehyde and methacrylonitrile to react to generate 2-methylpentamethylenediamine.
In a specific embodiment, the Ni-Al hydrotalcite-supported Ir catalyst adopts Ni-Al hydrotalcite as a carrier and Ir as an active component, and the precursor of the active component is selected from iridium acetate (Ir (OAc)3) Ammonium chloroiridate ((NH)4)2IrCl6) Sodium chloroiridate hexahydrate (Na)2IrCl6.6H2O) and IrCl (IrCl)3) At least one of the above, preferably sodium chloroiridate hexahydrate.
In a specific embodiment, in the Ni-Al hydrotalcite carrier, the molar ratio of Ni to Al is 1-4: 1, preferably 2-3: 1; the mass content of Ir in the supported Ir catalyst accounts for 0.1-1 wt% of the total weight of the catalyst, and preferably 0.4-0.6 wt%.
In a specific embodiment, the method for preparing the supported Ir catalyst comprises the steps of:
(1) preparing a Ni-Al hydrotalcite carrier by adopting a coprecipitation method: ni (NO)3)2.6H2O and Al (NO)3)3.9H2Dissolving O in water to obtain a nitrate solution, slowly dropwise adding the nitrate solution into a urea solution, keeping the mixed solution alkaline in the dropwise adding process, continuously stirring at the temperature of 60-80 ℃ for 24 hours after the dropwise adding is finished to form carrier slurry, then forming, granulating, and roasting at the temperature of 600-800 ℃ for 4-6 hours to obtain a Ni-Al hydrotalcite carrier;
(2) preparing an Ir catalyst loaded with Ni-Al hydrotalcite by an impregnation method: dissolving the active component precursor (one of iridium acetate, ammonium chloroiridate, sodium chloroiridate hexahydrate and iridium trichloride) in water to form an impregnation liquid, then adding the Ni-Al hydrotalcite carrier, stirring at 80-100 ℃ until the water is completely evaporated to dryness, drying at 100-120 ℃ for 4-6 h, and then roasting at 600-800 ℃ for 2-4 h to prepare the Ir-loaded catalyst.
In a specific embodiment, the reaction temperature for preparing 2-methylpentamethylenediamine is 30-80 ℃, preferably 40-60 ℃.
In a specific embodiment, the molar ratio of methacrylonitrile to acetaldehyde is 1:1 to 6, preferably 1:3 to 4.
In a specific embodiment, the solvent is selected from one or more of methanol, ethanol, isopropanol, preferably ethanol.
In a specific embodiment, the mass ratio of the solvent to the methacrylonitrile is 2 to 10:1, preferably 4 to 6: 1.
In a particular embodiment, the molar ratio of ammonium formate to methacrylonitrile is from 1 to 3:1, preferably from 1.5 to 2: 1.
In a specific embodiment, the liquid phase volume space velocity of the mixed solution formed by the ammonium formate, the methacrylonitrile, the acetaldehyde and the solvent is 0.1-1.0 h-1Preferably 0.4 to 0.6h-1。
Compared with the prior art, the technical scheme of the invention has the following positive effects:
1) the method for preparing the 2-methyl pentanediamine is a brand new synthesis process route, the selectivity of the 2-methyl pentanediamine is far higher than that of the traditional preparation method, the conversion rate of methacrylonitrile is more than 99 percent, and the selectivity of the 2-methyl pentanediamine relative to methacrylonitrile is more than 95 percent.
2) The method for preparing 2-methyl pentanediamine of the invention generates less three wastes and the product is easy to separate; meanwhile, the preparation and reaction operation processes of the catalyst are simple, the reaction conditions are mild, and compared with the traditional intermittent process, the method is a continuous process and has the potential of industrial application.
Drawings
FIG. 1 is a GC spectrum of the product 2-methylpentamethylenediamine of the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A method for preparing 2-methyl pentanediamine compound uses Ir catalyst loaded by Ni-Al hydrotalcite, a fixed bed is a reactor, ammonium formate is used as a hydrogen source and an ammonia source for reaction, and acetaldehyde and methacrylonitrile are converted into 2-methyl pentanediamine by a one-pot method under a certain temperature condition in the presence of a solvent.
The specific reaction steps are for example: under a certain temperature and an inert gas atmosphere, filling an Ir catalyst loaded by Ni-Al hydrotalcite into a fixed bed, dissolving acetaldehyde, methacrylonitrile and ammonium formate into a solvent to form a mixed solution, and then enabling the mixed solution to pass through a catalyst bed layer at a certain airspeed to enable raw materials acetaldehyde and methacrylonitrile to react to generate 2-methylpentamethylenediamine.
The one-pot reaction is shown as the following formula:
in the one-pot reaction, the feed molar ratio of methacrylonitrile to acetaldehyde as the raw material is 1:1 to 6, and examples thereof include, but are not limited to, 1:1, 1:2, 1:3, 1:4, 1:5, and 1:6, and preferably 1:3 to 4.
The solvent of the present invention is, for example, one or more selected from methanol, ethanol and isopropanol, and ethanol is preferred. Specifically, the amount of the solvent added in the reaction of the present invention is 2 to 10 times of the mass of methacrylonitrile, for example, but not limited to, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, and preferably 4 to 6 times.
As the hydrogen source and the ammonia source of the present invention, ammonium formate is added in a ratio of 1 to 3:1, for example, but not limited to, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, preferably 1.5 to 2:1, based on the molar ratio of ammonium formate to methacrylonitrile.
Preparation 2-In the method for preparing the methylpentanediamine, the liquid phase volume space velocity of a mixed solution formed by ammonium formate, methacrylonitrile, acetaldehyde and a solvent is 0.1-1.0 h-1For example, including but not limited to 0.1h-1、0.2h-1、0.3h-1、0.4h-1、0.5h-1、0.6h-1、0.7h-1、0.8h-1、0.9h-1、1.0h-1Preferably 0.4 to 0.6h-1。
In the method for preparing 2-methylpentamethylenediamine according to the present invention, the reaction is carried out in both air atmosphere and inert gas atmosphere, and is not particularly limited; preferably, it is carried out under an inert gas atmosphere. The inert gas may be argon or nitrogen, and the present invention is not particularly limited.
Meanwhile, in the method for preparing 2-methylpentamethylenediamine, the reaction temperature is 30-80 ℃, for example, but not limited to, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, preferably 40-60 ℃.
The pressure of the reaction system of the present invention is not particularly limited, and may be, for example, normal pressure, slight positive pressure or high pressure, for example, 1 to 10barG (gauge pressure), or, for example, 0 pressure at the start of the reaction, and the system is maintained in a slight positive pressure state by the generation of gas after the reaction.
Therefore, the method for preparing the 2-methyl pentanediamine has the advantages of low reaction temperature and pressure, mild reaction conditions, high selectivity of the reaction product, large boiling point difference between the reaction product and the raw materials, easy separation and purification, continuous reaction and suitability for industrial production, and the reaction product can be obtained by a one-pot method.
Particularly, according to the method for preparing 2-methylpentamethylenediamine provided by the invention, the conversion rate of methacrylonitrile is more than 99%, and the selectivity of 2-methylpentamethylenediamine relative to methacrylonitrile is more than 95%, which is much higher than the level of 60% -74% in the prior art, so that a very good effect is obtained.
The method for preparing 2-methylpentanediamine uses supported Ir as a catalyst, the catalyst adopts Ni-Al hydrotalcite as a carrier, Ir as an active component, and a precursor of the active component is selected fromIridium trichloride (IrCl)3) Iridium acetate (Ir (OAc)3) Ammonium chloroiridate ((NH)4)2IrCl6) And sodium chloroiridate hexahydrate (Na)2IrCl6.6H2O), preferably sodium chloroiridate hexahydrate.
The molar ratio of Ni to Al of the Ni-Al hydrotalcite carrier is 1-4: 1, and examples include but are not limited to 1: 1. 2: 1. 3: 1. 4:1, preferably 2-3: 1; the amount of Ir in the supported Ir catalyst is 0.1 to 1 wt% based on the total weight of the catalyst, including, but not limited to, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, preferably 0.4 to 0.6 wt%.
The supported Ir can be used as the catalyst by adopting a conventional preparation method in the field of catalyst preparation, for example, a Ni-Al hydrotalcite carrier is prepared first, and then an Ir active component is supported on the Ni-Al hydrotalcite carrier. For the reaction of the invention, as long as the active component and the carrier of the catalyst are the components and the contents, if the active component is loaded too little, the catalytic activity is poor, and if the active component is loaded too much, the reaction speed is too high, the selectivity of the target product is reduced. There is no particular limitation on the preparation process of the catalyst, wherein the preparation method of the Ni — Al hydrotalcite support is, for example, a coprecipitation method, the supporting method of the active component is, for example, an impregnation method, and, for example, a specific catalyst preparation process includes the following steps:
(1) preparing a Ni-Al hydrotalcite carrier by adopting a coprecipitation method: ni (NO)3)2.6H2O and Al (NO)3)3.9H2Dissolving O in water to obtain a nitrate solution, slowly dropwise adding the nitrate solution into a urea solution, keeping the mixed solution alkaline in the dropwise adding process, continuously stirring at the temperature of 60-80 ℃ for 24 hours after the dropwise adding is finished to form carrier slurry, then forming, granulating, and roasting at the temperature of 600-800 ℃ for 4-6 hours to obtain a Ni-Al hydrotalcite carrier;
(2) preparing an Ir catalyst loaded with Ni-Al hydrotalcite by an impregnation method: IrCl is added4Dissolving the mixture in water to form an immersion liquid, adding the Ni-Al hydrotalcite carrier, and stirring the mixture at the temperature of 80-100 DEG CAnd (3) completely evaporating water to dryness, drying for 4-6 h at 100-120 ℃, and then roasting for 2-4 h at 600-800 ℃ to obtain the supported Ir catalyst.
The method for preparing 2-methyl pentanediamine by methacrylonitrile and acetaldehyde in one-pot method provided by the invention has the following possible catalytic mechanism: the Ni-Al hydrotalcite-loaded Ir catalyst has an alkaline active center and can catalyze acetaldehyde and methacrylonitrile to generate Michael addition reaction to generate a 2-methyl-5-aldehyde valeronitrile intermediate; under the synergistic action of Ir catalyst loaded by Ni-Al hydrotalcite, ammonium formate is used as hydrogen source and ammonia source, aldehyde group of 2-methyl-5-aldehyde valeronitrile is subjected to reductive amination, and cyano group is reduced at the same time to generate 2-methyl pentanediamine.
Possible reaction sequences are as follows:
the present invention is described in more detail by the following examples, which are not intended to limit the invention in any way.
The main reagent sources of the embodiment and the comparative example of the invention are as follows:
methacrylonitrile, purity > 98%, japan asahi chemical chemistry;
acetaldehyde, ammonium formate, urea, AR, alatin reagent;
the purity of iridium acetate, ammonium chloroiridate, sodium chloroiridate hexahydrate and iridium trichloride is more than 99 percent, and the method is developed to reach the chemical industry;
methanol, ethanol, isopropanol, AR, chemical industry of Xilonga;
Ni(NO3)2.6H2O、Al(NO3)3.9H2o, AR, alatin reagent.
The gas chromatography test conditions adopted by the invention are as follows:
the instrument model is as follows: agilent 7890B;
a chromatographic column: HP-5;
solvent: dmf (hplc);
sample introduction volume: 0.5 mu L;
sample inlet temperature: 280 ℃;
the split ratio is as follows: 30: 1;
hydrogen flow rate: 40 mL/min;
tail-blow flow: 25 mL/min;
air flow rate: 400 mL/min;
temperature rising procedure: the initial column temperature is 40 ℃, the temperature is kept for 5min, the temperature is raised to 100 ℃ at the speed of 10 ℃/min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is kept for 5 min.
Examples 1 to 9 and comparative examples 1 to 4: preparation of Ni-Al hydrotalcite-loaded Ir catalyst
The preparation method of the Ni-Al hydrotalcite carrier by adopting a coprecipitation method comprises the following specific steps: mixing Ni (NO)3)2.6H2O and Al (NO)3)3.9H2Dissolving O in water according to the molar ratio of 1-4: 1 to obtain a nitrate solution, slowly dropwise adding the nitrate solution into a urea solution, keeping the mixed solution alkaline in the dropwise adding process, continuously stirring at the temperature of 60 ℃ for 24 hours after dropwise adding is finished to form carrier slurry, then molding, granulating, and roasting at the temperature of 600-800 ℃ for 4-6 hours to obtain a Ni-Al hydrotalcite carrier;
the Ni-Al hydrotalcite-loaded Ir catalyst is prepared by an impregnation method, and comprises the following specific steps: dissolving an active component precursor in water to form an impregnation solution, adding the Ni-Al hydrotalcite carrier, stirring at 80-100 ℃ until all water is evaporated to dryness, drying at 100-120 ℃ for 4-6 h, and roasting at 600-800 ℃ for 2-4 h to obtain the Ir-loaded catalyst.
Specific process conditions of examples 1 to 9 and comparative examples 1 to 4 are shown in Table 1, in which the masses of Ni and Al represent Ni (NO) respectively3)2.6H2O and Al (NO)3)3.9H2The mass of O. The catalysts prepared in examples 1 to 9 were named as catalysts # 1 to # 9, and the catalysts prepared in comparative examples 1 to 4 were named as catalysts # 10 to # 13.
TABLE 1 preparation conditions of Supported Ir catalysts
Examples 10 to 18 and comparative examples 5 to 10
The 13 types of catalysts (respectively named as No. 1-13 catalysts in sequence) prepared in the examples 1-9 and the comparative examples 1-4 are selected for preparing the 2-methylpentamethylenediamine, and the method comprises the following steps: a fixed bed reactor from top to bottom is adopted, and the fixed bed reactor is a stainless steel tube with the inner diameter of 4cm and the length of 100 cm. The catalyst loading was 30g and released to 100ml with ceramic. The 1# to 13# catalysts are respectively filled into a fixed bed reactor, and are activated for 2 hours at 400 ℃ in a hydrogen atmosphere. And (5) purging with nitrogen to reduce the temperature, cooling the fixed bed to below 40 ℃, and stopping purging with nitrogen. The fixed bed reactor is adjusted to the temperature required by the reaction, Methacrylonitrile (MAN), acetaldehyde and ammonium formate are dissolved in a solvent according to a certain proportion, and then the solution passes through a catalyst bed layer according to a certain volume space velocity, and the specific reaction conditions are shown in Table 2.
TABLE 2 reaction conditions and reaction results for the preparation of 2-methylpyridine
After the continuous stable reaction for 12 hours, a sample was taken and the composition of the reaction solution was analyzed by gas chromatography to calculate the conversion of methacrylonitrile and the selectivity of 2-methylpentamethylenediamine with respect to methacrylonitrile, and the results are shown in Table 2.
As can be seen from the data in the table, in the preparation process of the present invention, the conversion of methacrylonitrile is higher than 99% on average, while the selectivity of 2-methylpentamethylenediamine with respect to methacrylonitrile is higher than 95.3%. From the results of comparative examples 5 to 8, it can be seen that the ratio of Ni/Al and the amount of Ir loaded in the catalyst both affect the selectivity of 2-methylpentanediamine, and that both the ratio of Ni/Al and the amount of Ir loaded outside the range of the present invention cause the selectivity of the target product to decrease. As can be seen from the results of comparative examples 9 to 10, the reaction temperature outside the range of the present invention also leads to a significant decrease in the selectivity of the target product.
Distilling the reaction liquid to remove light components, and then rectifying to obtain a pure product of 2-methyl pentanediamine, wherein a GC spectrogram of the pure product is shown in figure 1, wherein the retention time of the 2-methyl pentanediamine is 13.48min, and the retention time of the 2.93min is a solvent peak.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A method for preparing 2-methyl pentanediamine is characterized in that Ir loaded by Ni-Al hydrotalcite is used as a catalyst, ammonium formate is used as a hydrogen source and an ammonia source for reaction, and acetaldehyde and methacrylonitrile are converted into the 2-methyl pentanediamine in a one-pot method in the presence of a solvent and under a certain temperature condition; preferably, under a certain temperature and an inert gas atmosphere, the Ir catalyst loaded on Ni-Al hydrotalcite is filled into a fixed bed, acetaldehyde, methacrylonitrile and ammonium formate are dissolved in a solvent to form a mixed solution, and then the mixed solution passes through a catalyst bed layer at a certain space velocity, so that raw materials of acetaldehyde and methacrylonitrile react to generate 2-methylpentamethylenediamine.
2. The method according to claim 1, wherein the Ni-Al hydrotalcite-supported Ir catalyst has a Ni-Al hydrotalcite-supported carrier, an active component Ir, and an active component precursor selected from at least any one of iridium acetate, ammonium chloroiridate, sodium chloroiridate hexahydrate, and iridium trichloride, preferably sodium chloroiridate hexahydrate.
3. The method according to claim 2, wherein the molar ratio of Ni to Al in the Ni-Al hydrotalcite support is 1 to 4:1, preferably 2 to 3: 1; the mass content of Ir in the Ni-Al hydrotalcite-loaded Ir catalyst accounts for 0.1-1 wt% of the total weight of the catalyst, and preferably 0.4-0.6 wt%.
4. The method according to any one of claims 1 to 3, wherein the preparation method of the Ni-Al hydrotalcite-supported Ir catalyst comprises the preparation of a Ni-Al hydrotalcite carrier and the loading of an active component, wherein the preparation method of the Ni-Al hydrotalcite carrier is a coprecipitation method, and the loading method of the active component is an impregnation method; preferably, the preparation method of the Ni-Al hydrotalcite-supported Ir catalyst comprises the following steps:
(1) preparing a Ni-Al hydrotalcite carrier by adopting a coprecipitation method: ni (NO)3).6H2O and Al (NO)3).9H2Dissolving O in water to obtain a nitrate solution, slowly dropwise adding the nitrate solution into a urea solution, keeping the mixed solution alkaline in the dropwise adding process, continuously stirring at the temperature of 60-80 ℃ for 24 hours after the dropwise adding is finished to form carrier slurry, then forming, granulating, and roasting at the temperature of 600-800 ℃ for 4-6 hours to obtain a Ni-Al hydrotalcite carrier;
(2) dissolving the active component precursor in water to form an impregnation solution, adding the Ni-Al hydrotalcite carrier, stirring at 80-100 ℃ until all water is evaporated, drying at 100-120 ℃ for 4-6 h, and roasting at 600-800 ℃ for 2-4 h to obtain the Ir-loaded catalyst.
5. The method according to claim 1, wherein the reaction temperature for preparing 2-methylpentanediamine is 30-80 ℃, preferably 40-60 ℃.
6. The method according to claim 1, wherein the molar ratio of methacrylonitrile to acetaldehyde is 1:1 to 6, preferably 1:3 to 4.
7. The method according to claim 1, wherein the solvent is selected from one or more of methanol, ethanol and isopropanol, preferably ethanol.
8. The process according to claim 1, wherein the mass ratio of the solvent to the methacrylonitrile is 2 to 10:1, preferably 4 to 6: 1.
9. The process according to claim 1, characterized in that the molar ratio between ammonium formate and methacrylonitrile is comprised between 1 and 3:1, preferably between 1.5 and 2: 1.
10. The method according to claim 1, wherein the liquid phase volume space velocity of the mixed solution of ammonium formate, methacrylonitrile, acetaldehyde and solvent is 0.1-1.0 h-1Preferably 0.4 to 0.6h-1。
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