CN114805225B - Hydrogenation method of methyl quinoxaline - Google Patents
Hydrogenation method of methyl quinoxaline Download PDFInfo
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- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a hydrogenation method of methylquinoxaline. The method comprises the following steps of taking methylquinoxaline and hydrogen as raw materials, carrying out hydrogenation reaction in the presence of a catalyst to obtain a hydrogenation product of the methylquinoxaline, wherein the catalyst is selected from one or a combination of two of molybdenum carbide and tungsten carbide, the catalyst is an unsupported catalyst, the catalyst is a crystal with a layered structure, and the crystal is a hexagonal close-packed structure. The catalyst of the invention can realize the hydrogenation reaction of the methylquinoxaline under mild reaction conditions at lower temperature, has high conversion rate of raw materials which can reach 100 percent, and can obtain high-quality percentage of perhydrogenated products.
Description
Technical Field
The invention relates to a hydrogenation method of methylquinoxaline.
Background
At present, hydrogen energy storage and transportation are mainly carried out in the form of high-pressure hydrogen and liquid hydrogen. Wherein the high-pressure hydrogen has low hydrogen storage density and poor safety performance; the liquid hydrogen has large energy consumption for hydrogen storage, and the safety performance is not high enough because the hydrogen needs to be discharged for pressure relief. The liquid organic hydrogen storage can realize hydrogen storage and transportation at normal temperature and normal pressure, is safer and more convenient, and is an important development direction of hydrogen storage and transportation.
The nitrogen-containing fused heterocyclic aromatic compound is taken as a hydrogen storage material, and has attracted extensive attention due to a mild hydrogenation and dehydrogenation process. Among them, methylquinoxaline has high mass hydrogen storage density and low hydrogenation temperature, and is a preferable hydrogen storage and discharge material. However, the hydrogenation of methylquinoxaline generally employs noble metal catalysts such as Ru, Pt, Pd, etc. In the hydrogenation process of the pure noble metal catalyst, the catalyst has poor toxicity resistance and is easy to permanently poison and deactivate. In the actual hydrogenation process, certain impurities may exist in the industrially adopted methylquinoxaline, and the impurities are easily adsorbed on the active sites of the noble metal catalyst and can also aggravate the inactivation of the catalyst. In addition, the cost of noble metal catalysts is high. Chinese patent CN113753850A discloses that monomethylquinoxaline is subjected to hydrogenation reaction in the presence of alumina or carbon-supported noble metal catalyst, but the cost of the catalyst is still high, and the hydrogenation catalytic efficiency needs to be further improved.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides an improved methyl quinoxaline hydrogenation method, which has the advantages of high hydrogenation efficiency, mild hydrogenation conditions and low cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a hydrogenation method of methylquinoxaline takes methylquinoxaline and hydrogen as raw materials, and carries out hydrogenation reaction in the presence of a catalyst to obtain a hydrogenation product of the methylquinoxaline, wherein the catalyst is selected from one or a combination of two of molybdenum carbide and tungsten carbide, the catalyst is an unsupported catalyst, the catalyst is a crystal with a layered structure, and the crystal is a hexagonal close-packed structure.
In some embodiments of the invention, the specific surface area of the catalyst is 40 to 60 m 2 A/g, preferably 45 to 55 m 2 (iv)/g, more preferably 55 m 2 /g。
In some embodiments of the invention, the lamellar structure has a lamella length of 20 to 40nm, preferably 20 to 28 nm.
In some embodiments of the invention, the methylquinoxaline is selected from the group consisting of 2-methylquinoxaline, 5-methylquinoxaline, and 6-methylquinoxaline, in combination with one or more.
In some embodiments of the present invention, the mass ratio of the methylquinoxaline to the catalyst is 4 to 10: 1.
In some embodiments of the invention, the temperature of the hydrogenation reaction is 80-190 ℃ and the hydrogen pressure is 5-10 MPa.
In some embodiments of the invention, the temperature of the hydrogenation reaction is 100 to 170 ℃ and the hydrogen pressure is 8 to 10 MPa.
Preferably, the temperature of the hydrogenation reaction is 120 ℃, and the hydrogen pressure is 8 MPa.
In some embodiments of the invention, the time of the hydrogenation reaction is 5 to 10 hours.
In some embodiments of the present invention, the hydrogenation product of methylquinoxaline comprises a perhydrogenation product of methylquinoxaline and a tetrahydrogenation product of methylquinoxaline, the mass of the perhydrogenation product of methylquinoxaline constituting more than 85% of the mass of the hydrogenation product of methylquinoxaline.
Preferably, the mass of the perhydrogenated product of the methylquinoxaline accounts for 92% or more of the mass of the hydrogenated product of the methylquinoxaline. Further preferably, the mass of the perhydrogenated product of the methylquinoxaline accounts for 95% or more of the mass of the hydrogenated product of the methylquinoxaline. Particularly preferably, the mass of the perhydrogenated product of the methylquinoxaline accounts for 98% or more of the mass of the hydrogenated product of the methylquinoxaline.
In some embodiments of the present invention, the hydrogenation product of methylquinoxaline comprises a perhydrogenation product of methylquinoxaline, a hexahydrogenation product of methylquinoxaline, and a tetrahydrogenation product of methylquinoxaline, the mass of the perhydrogenation product of methylquinoxaline constituting more than 62% of the mass of the hydrogenation product of methylquinoxaline.
Preferably, the mass of the perhydrogenated product of the methylquinoxaline accounts for 65% or more of the mass of the hydrogenated product of the methylquinoxaline. Further preferably, the mass of the perhydrogenated product of methylquinoxaline accounts for 95% or more of the mass of the hydrogenated product of methylquinoxaline.
The inventors found through research that when one or two of unsupported tungsten carbide or molybdenum carbide is/are used as a catalyst for the hydrogenation reaction of the methylquinoxaline, and the catalyst is controlled to be a crystal with a layered structure, and the unit cell configuration of the crystal is a hexagonal close-packed structure, the high-efficiency hydrogenation reaction of the methylquinoxaline can be realized under mild hydrogenation reaction conditions. The catalyst is adopted to carry out hydrogenation reaction, the conversion rate of raw materials is high, a high-quality percentage perhydrogenation product can be obtained, and industrial-grade methylquinoxaline with certain impurity content can be used as a hydrogenation raw material to stably carry out hydrogenation reaction.
In some embodiments of the present invention, the method for hydrogenating methylquinoxaline specifically comprises the steps of: mixing the catalyst and the methylquinoxaline, adding an organic solvent to obtain a reaction mixture, placing the reaction mixture in a reaction kettle, and carrying out hydrogenation reaction at the temperature of 80-180 ℃ and the hydrogen pressure of 5-10 MPa.
In some embodiments of the invention, the organic solvent is selected from the group consisting of 1, 4-dioxane, cyclohexane and methylcyclohexane.
In some embodiments of the present invention, the mass ratio of the organic solvent to the methylquinoxaline is 1.5 to 4: 1.
In some embodiments of the present invention, the hydrogenation process of the methylquinoxaline further comprises reducing the temperature and pressure after the hydrogenation reaction is completed, and separating the catalyst and the hydrogenation product of the methylquinoxaline.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst can realize the hydrogenation reaction of the methylquinoxaline under mild reaction conditions at lower temperature, has high conversion rate of raw materials which can reach 100 percent, and can obtain a high-quality percentage of fully hydrogenated products.
(2) The catalyst can be recycled for multiple times when used for hydrogenation reaction of analytically pure methylquinoxaline, and the activity of the catalyst can not be obviously reduced after the catalyst is used for multiple times; the catalyst can be suitable for hydrogenation reaction of industrial-grade methylquinoxaline containing certain impurities, the activity of the catalyst cannot be obviously reduced, and the catalyst has strong anti-toxicity stability.
(3) The mass percentage of the perhydrogenated product in the hydrogenated product of methylquinoxaline can be further increased by controlling the temperature and hydrogen pressure of the hydrogenation reaction. The mass percentage of the perhydrogenated product in the hydrogenated product of methylquinoxaline can be as high as 98%.
(4) The catalyst is non-supported, is simple to prepare, is non-noble metal, and is low in cost.
Drawings
FIG. 1 is a TEM spectrum of the molybdenum carbide catalyst of example 1.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
This example provides a hydrogenation process for 2-methylquinoxaline:
wherein the catalyst is non-supported molybdenum carbide which is a crystal with a layered structure, the length of a lamella of the layered structure is 20nm, and the specific surface area is 50 m 2 And/g, the unit cell structure of the crystal is a hexagonal close-packed structure. The TEM image of the catalyst is shown in FIG. 1, and the catalyst is seen to be a layered structure. The 2-methylquinoxaline is analytically pure.
10g of molybdenum carbide catalyst, 50g of 2-methylquinoxaline and 100g of 1, 4-dioxane which is an organic solvent are weighed. Firstly, mixing a molybdenum carbide catalyst and 2-methylquinoxaline, uniformly stirring, adding 1, 4-dioxane, and placing in a reaction kettle for hydrogenation reaction. The conditions of the hydrogenation reaction are as follows: the heating temperature is 120 ℃, the hydrogen pressure is 8MPa, and the reaction time is 7 h. After the reaction is finished, reducing the temperature and relieving the pressure, separating the hydrogenation product of the 2-methylquinoxaline from the molybdenum carbide catalyst, and collecting the hydrogenation product of the 2-methylquinoxaline for later use.
Examples 2 to 5
Examples 2 to 5 provide a hydrogenation method of methylquinoxaline, which is substantially the same as example 1 except that: the length of the lamella of the catalyst molybdenum carbide and the specific surface area are changed, the type of the methylquinoxaline is changed, or the industrial methylquinoxaline is selected as the raw material, and the specific formula is shown in the following table 1.
The on-line sampling method was used to analyze and detect the sampled organic materials using a gas chromatograph-mass spectrometer, and the species and content of the hydrogenation products of the methylquinoxalines in examples 1 to 5 were analyzed, and the conversion rate of the hydrogenation reaction was calculated, and the results are shown in table 2 below, in which 4H product means tetrahydro product, and 6H product means hexahydro product.
As can be seen from Table 2 above, the molybdenum carbide catalyst of the present invention can achieve hydrogenation of 2-methylquinoxaline, 5-methylquinoxaline or 6-methylquinoxaline with high conversion, and the mass percentage of the perhydrogenated product in the hydrogenated product can be as high as 98%. In addition, the molybdenum carbide catalyst can be used for hydrogenation of industrial pure methylquinoxaline, and the catalyst is not easy to be poisoned by impurities and has good stability.
Example 6
This example provides a hydrogenation process for 2-methylquinoxaline:
wherein the catalyst is non-supported tungsten carbide which is a crystal with a layered structure, the length of a lamella of the layered structure is 20nm, and the specific surface area is 50 m 2 The unit cell structure of the crystal is a hexagonal close-packed structure. The 2-methylquinoxaline is analytically pure.
10g of tungsten carbide catalyst, 50g of 2-methylquinoxaline and 100g of 1, 4-dioxane, an organic solvent, are weighed out. Firstly, mixing a tungsten carbide catalyst and 2-methylquinoxaline, uniformly stirring, adding 1, 4-dioxane, and placing in a reaction kettle for hydrogenation reaction. The conditions of the hydrogenation reaction are as follows: the heating temperature is 150 ℃, the hydrogen pressure is 8MPa, and the reaction time is 7 h. After the reaction is finished, reducing the temperature and relieving the pressure, separating the hydrogenation product of the 2-methylquinoxaline from the tungsten carbide catalyst, and collecting the hydrogenation product of the 2-methylquinoxaline for later use.
Examples 7 to 10
Examples 7 to 10 provide a hydrogenation process of methylquinoxaline, which is substantially the same as example 6 except that: the length of the lamella and the specific surface area of the tungsten carbide catalyst are changed, the type of the methylquinoxaline is changed, or the industrial methylquinoxaline is selected as the raw material, and the specific formula is shown in the following table 3.
The on-line sampling method was used to analyze and detect the sampled organic substances using a gas chromatograph-mass spectrometer, and the species and content of the hydrogenation products of the methylquinoxalines in examples 6 to 10 were analyzed, and the conversion rate of the hydrogenation reaction was calculated, and the results are shown in table 4 below, in which 4H product means tetrahydro product, and 6H product means hexahydro product.
As can be seen from the above Table 4, the tungsten carbide catalyst of the present invention can achieve hydrogenation of 2-methylquinoxaline, 5-methylquinoxaline or 6-methylquinoxaline with high conversion rate, and the mass percentage of the perhydrogenated product in the hydrogenated product can be as high as 96%. In addition, the tungsten carbide catalyst can be used for hydrogenation of industrial pure methylquinoxaline, and the catalyst is not easy to be poisoned by impurities and has good stability.
Examples 11 to 15
Examples 11-15 provide a hydrogenation process for 2-methylquinoxaline, which is essentially the same as example 1, i.e., using a molybdenum carbide catalyst, except that: the temperature and hydrogen pressure of the hydrogenation reaction were varied. The specific conditions of examples 11 to 15, as well as the conversion of the hydrogenation reaction, the kind and the mass percentage of the hydrogenated product are shown in Table 5 below.
Example 16
Example 16 provides a hydrogenation process of 2-methylquinoxaline, which is substantially the same as example 1 except that: the temperature of the hydrogenation reaction is 190 ℃, and the hydrogen pressure is 5 MPa. As a result, the conversion rate of the hydrogenation reaction was 100%, the mass percentage of the perhydrogenated product in the hydrogenated product of 2-methylquinoxaline was 85%, and the other products were ring-cleavage products.
It is understood from examples 11 to 16 that increasing the hydrogenation temperature within a certain range while keeping the hydrogen pressure constant contributes to increasing the conversion of the hydrogenation and the mass percentage of the perhydrogenated product in the hydrogenated product. However, when the temperature is too high, ring breakage of the hydrogenated product may occur, and the mass percentage of the perhydrogenated product may be decreased.
Comparative example 1
Comparative example 1 provides a hydrogenation process for 4, 6-dimethyldibenzothiophene, which is essentially the same as in example 1, except that: 2-methylquinoxaline is replaced by 4, 6-dimethyldibenzothiophene. The detection shows that the conversion rate of the hydrogenation reaction is 32%, the hydrogenated products have ring breakage, and the hydrogenated products specifically comprise hexahydroproducts, toluene and methylcyclohexane.
Comparative example 2
Comparative example 2 provides a process for the hydrogenation of 2-methylthiophene, which is essentially the same as in example 1, except that: 2-methylquinoxaline is replaced by 2-methylthiophene. As can be seen from the detection, the hydrogenation reaction can not be actually carried out, and any hydrogenation product is not obtained.
Comparative example 3
Comparative example 3 provides a process for the hydrogenation of benzofuran which is essentially the same as in example 1 except that: 2-methylquinoxaline is replaced by benzofuran. As can be seen by detection, the conversion rate of the hydrogenation reaction is 17%, and the hydrogenation product has a dihydro product, no perhydrogenation product and no ring-breaking product.
As can be seen from comparative examples 1 to 3, the tungsten carbide and molybdenum carbide catalysts of the present invention either fail to catalyze the hydrogenation of mono-heterocyclic ring, hetero-fused ring or multi-ring containing oxygen or sulfur, or, although they do, have low conversion, ring breakage of hydrogenation products, low content of perhydrogenated products, etc. The inventor finds that the catalyst is suitable for the hydrogenation reaction of the methylquinoxaline, can efficiently obtain a perhydrogenated hydrogenation product, and further can be used for the hydrogenation reaction of the specific methylquinoxaline.
Comparative example 4
Comparative example 4 provides a hydrogenation process of 2-methylquinoxaline, which is substantially the same as example 1 except that: replacing the catalyst with Ni/Al with the load mass percent of 20% 2 O 3 A catalyst. According to detection, the conversion rate of the hydrogenation reaction is 95%, the hydrogenation product comprises a hexahydroproduct and a large amount of ring-broken products, and the perhydrogenation product is not detected. In the hydrogenation process of the supported nickel catalyst, the selectivity of a target product is poor, only the benzene ring part of the 2-methylquinoxaline can be hydrogenated, the heterocyclic ring part is easy to break, and a byproduct is generated.
Comparative example 5
Comparative example 5 provides a hydrogenation process of 2-methylquinoxaline, which is substantially the same as example 1 except that: the molybdenum carbide catalyst is loaded on the alumina carrier by the mass percent of 40%. According to detection, the conversion rate of the hydrogenation reaction is 48%, and the hydrogenation reaction products comprise a perhydrogenated product, a hexahydrogenated product and a tetrahydrogenated product, wherein the perhydrogenated product accounts for 33% by mass. It can be seen that when the catalyst is supported, the conversion of the hydrogenation reaction is reduced and the formation of perhydrogenated products is not favored.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (9)
1. MethylquinoxalineThe hydrogenation method of the quinoline takes the methylquinoxaline and hydrogen as raw materials, and carries out hydrogenation reaction in the presence of a catalyst to obtain a hydrogenation product of the methylquinoxaline, and is characterized in that: the catalyst is selected from one or the combination of two of molybdenum carbide and tungsten carbide, the catalyst is an unsupported catalyst, the catalyst is a crystal with a layered structure, and the crystal is a hexagonal close-packed structure; the specific surface area of the catalyst is 40-60 m 2 (ii)/g; the length of the lamellar layer of the lamellar structure is 20-40 nm.
2. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the methylquinoxaline is selected from one or more of 2-methylquinoxaline, 5-methylquinoxaline and 6-methylquinoxaline; and/or the mass ratio of the methylquinoxaline to the catalyst is 4-10: 1.
3. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the temperature of the hydrogenation reaction is 80-190 ℃, and the hydrogen pressure is 5-10 MPa; and/or the hydrogenation reaction time is 5-10 hours.
4. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the temperature of the hydrogenation reaction is 100-170 ℃, and the hydrogen pressure is 8-10 MPa.
5. The method for hydrogenating a methylquinoxaline according to claim 1, wherein: the hydrogenation product of the methylquinoxaline includes a perhydrogenation product of the methylquinoxaline and a tetrahydrogenation product of the methylquinoxaline, and the mass of the perhydrogenation product of the methylquinoxaline accounts for 85% or more of the mass of the hydrogenation product of the methylquinoxaline.
6. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the hydrogenation product of the methylquinoxaline includes a perhydrogenation product of the methylquinoxaline, a hexahydrogenation product of the methylquinoxaline and a tetrahydrogenation product of the methylquinoxaline, the mass of the perhydrogenation product of the methylquinoxaline constituting 62% or more of the mass of the hydrogenation product of the methylquinoxaline.
7. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the hydrogenation method of the methylquinoxaline specifically comprises the following steps: mixing the catalyst and the methylquinoxaline, adding an organic solvent to obtain a reaction mixture, placing the reaction mixture in a reaction kettle, and carrying out hydrogenation reaction at the temperature of 80-180 ℃ and the hydrogen pressure of 5-10 MPa.
8. The hydrogenation process of methylquinoxaline according to claim 7, characterized in that: the organic solvent is selected from one or more of 1, 4-dioxane, cyclohexane and methylcyclohexane; and/or the mass ratio of the organic solvent to the methylquinoxaline is 1.5-4: 1.
9. The hydrogenation process of methylquinoxaline according to claim 1, characterized in that: the hydrogenation method of methylquinoxaline further comprises reducing the temperature and pressure after the hydrogenation reaction is completed, and separating the catalyst and the hydrogenation product of the methylquinoxaline.
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