Supported catalyst and application thereof in selective hydrogenation of quinoline compounds
阅读说明：本技术 一种负载型催化剂及其在喹啉类化合物选择加氢中的应用 (Supported catalyst and application thereof in selective hydrogenation of quinoline compounds ) 是由 魏海生 高照华 宋华兴 陈乐乐 颜晓瑞 任万忠 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种负载型催化剂,催化剂载体为磷酸盐,活性组分为Pt、Pd、Au、Rh、Ru、I r、N i中的一种或数种,采用浸渍法制备催化剂,活性组分在催化剂中的质量分数为0.01％-10％。本发明将上述负载型催化剂用于喹啉类化合物选择加氢反应具备高活性、高选择性以及高稳定性,解决了喹啉选择加氢反应的多相催化剂所存在的反应条件苛刻,催化剂制备方法复杂等问题。与现有的喹啉类化合物选择加氢的工业合成路线相比较,本发明所提供催化剂具有反应条件温和,操作简单,成本节约等显著优点。(The invention discloses a supported catalyst, wherein a catalyst carrier is phosphate, an active component is one or more of Pt, Pd, Au, Rh, Ru, I r and N i, the catalyst is prepared by adopting an impregnation method, and the mass fraction of the active component in the catalyst is 0.01-10%. The supported catalyst has high activity, high selectivity and high stability when being used for the selective hydrogenation reaction of the quinoline compound, and solves the problems of harsh reaction conditions, complex preparation method of the catalyst and the like of a heterogeneous catalyst for the selective hydrogenation reaction of the quinoline. Compared with the existing industrial synthetic route of selective hydrogenation of quinoline compounds, the catalyst provided by the invention has the remarkable advantages of mild reaction conditions, simplicity in operation, cost saving and the like.)
1. A load type catalyst is characterized in that a catalyst carrier is phosphate, an active component is one or more of Pt, Pd, Au, Rh, Ru, Ir and Ni, the catalyst is prepared by adopting an impregnation method, and the mass fraction of the active component in the catalyst is 0.01-10%.
2. The supported catalyst of claim 1, wherein the phosphate is one or more of yttrium phosphate, lithium phosphate, iron phosphate, magnesium phosphate, cobalt phosphate, copper phosphate, tripotassium phosphate, boron phosphate, aluminum phosphate, and calcium phosphate.
3. A supported catalyst according to claim 1 or 2 wherein the precursor of the active component is a nitrate or halide of the corresponding active component metal.
4. The supported catalyst according to claim 1 or 2, wherein the phosphate has a specific surface area of 10 to 500m2/g。
5. A supported catalyst according to claim 1 or 2, characterized in that its preparation comprises the following steps:
drying the phosphate carrier to remove adsorption water, cooling to room temperature, adding an impregnation liquid containing active components, continuously stirring uniformly, drying at room temperature, and roasting at 50-300 ℃ for 1-24h to obtain the supported catalyst.
6. The use of the supported catalyst according to any one of claims 1 to 5 in selective hydrogenation of quinoline compounds, wherein the quinoline compound is mixed with a solvent, and the mixed reaction solution is subjected to selective hydrogenation with hydrogen under the action of the supported catalyst to produce a hydrogenated quinoline compound; the reaction temperature of the selective hydrogenation reaction is 20-180 ℃, and the reaction pressure is 0.1-10 MPa.
7. The use of claim 6, wherein the supported catalyst is subjected to reduction treatment before being used in the reaction, wherein the reduction temperature is 50-600 ℃ and the reduction time is 0.5-6 h.
8. The use according to claim 6, wherein the reaction temperature of the selective hydrogenation reaction is 20 to 80 ℃ and the reaction pressure is 0.1 to 0.8 MPa.
9. The use according to claim 6,
the quinoline compound is quinoline, isoquinoline or substituted quinoline; the substituent on the benzene ring or pyridine ring of the substituted quinoline is one or more of halogen, vinyl, aldehyde group, hydroxyl, alkyl and phenyl;
the solvent is one or more of water, methanol, ethanol, toluene, N-dimethylformamide, tetrahydrofuran and cyclohexane.
10. The use according to any one of claims 6 to 9, wherein the mass ratio of the quinolines to the supported catalyst is (1-1000): 1.
Technical Field
The invention belongs to the field of chemical engineering, and particularly relates to a supported catalyst and application thereof in selective hydrogenation of quinoline compounds.
Background
The synthesis of functionalized 1,2,3, 4-tetrahydroquinoline (py-THQ) attracts people's attention because of its important application value in the synthesis research of medicines, alkaloids, pesticides and dyes. At present, the industrial synthesis method of the 1,2,3, 4-tetrahydroquinoline compound mainly comprises chemical synthesis and quinoline catalytic hydrogenation, wherein the reaction process for preparing the 1,2,3, 4-tetrahydroquinoline by the quinoline catalytic hydrogenation method is simple, the raw material cost is low, and the method is a relatively environment-friendly production way. However, the quinoline hydrogenation reaction still has the problems of harsh reaction conditions, low catalytic activity and the like, and meanwhile, the quinoline compound has a toxic effect on the catalyst, so that the improvement of the stability of the catalyst becomes a big problem. Therefore, it is highly desirable to find a supported heterogeneous catalyst with high activity, high selectivity and high stability.
For a long time, people have developed high-activity and high-selectivity catalysts for hydrogenation reaction of quinoline compounds, and the activity and selectivity of the catalysts are different due to different materials and preparation methods.
Document 1(j.am. chem. soc.2012,134,17592-17598) is prepared by using TiO with high specific surface area2Supported nano Au catalyst, due to quinoline in the gold catalytic hydrogenation reaction on H2The activation plays a promoting role, so that the catalyst is in H of 2MPa at 60 DEG C2Under the conditions of (1), 6-chloroquinoline is selectively converted into 6-chlorotetrahydroquinoline within 3h and no dehalogenation phenomenon occurs. Meanwhile, the catalyst has wide applicability, and quinoline compounds or heterocyclic nitrogen compounds substituted by different structures (vinyl, hydroxyl, carbonyl and the like) have better conversion rate and selectivity.
Document 2(j.am.chem.soc.2017,139,9419-9422) adds amine groups (-NH) to the framework of MOF materials2) Limit the active metal Ru because of Ru3+And metal-free amine groups (-NH) on the organic skeleton2) Strong coordination between the two, and obtaining the Ru active site with dispersed atoms. The catalyst can be used for preparing the catalyst with the H of 3.5MPa at the temperature of 100 DEG C2Under the conditions, quinoline is selectively converted into 1,2,3, 4-tetrahydroquinoline within 4h, and the conversion rate and the selectivity are more than 99 percent.
Document 3(Journal of catalysis.2018,359,101-111) with CeO2The nano-rod is used as a carrier to load Pt nano-particles, because of CeO2The rich oxygen vacancies on the surface make Pt have higher electron density, and the Pt and NR-CeO are added2Strong metal carrier interaction (EMSI) between the quinoline and the metal carrier, so that the quinoline is in 2MPa H2Under the condition of (1), the conversion is carried out in 3h with high selectivity to 1,2,3, 4-tetrahydroquinoline without excessive hydrogenation.
The patent (CN 107824209B) discloses a noble metal catalyst supported by carbide, which can obtain better quinoline hydrogenation activity and selectivity under the reaction conditions of 100 ℃ and 2MPa, but the preparation process of the catalyst is complex and the reaction conditions are harsh.
In summary, although the currently studied catalysts have better activity and selectivity for selective hydrogenation of quinoline compounds, the problems of harsh reaction conditions and low catalytic activity still exist, and the development of catalysts with high activity and high selectivity under mild conditions is urgently needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a supported catalyst and application thereof in selective hydrogenation of quinoline compounds. Compared with the existing industrial synthetic route of selective hydrogenation of quinoline compounds, the catalyst provided by the invention has the remarkable advantages of mild reaction conditions, simplicity in operation, cost saving and the like.
The specific technical scheme is as follows:
the invention aims to provide a supported catalyst, wherein a catalyst carrier is phosphate, an active component is one or more of Pt, Pd, Au, Rh, Ru, Ir and Ni, the catalyst is prepared by adopting an impregnation method, and the mass fraction of the active component in the catalyst is 0.01-10%.
Further, the phosphate is one or more of yttrium phosphate, lithium phosphate, iron phosphate, magnesium phosphate, cobalt phosphate, copper phosphate, tripotassium phosphate, boron phosphate, aluminum phosphate and calcium phosphate.
Further, the precursor of the active component is nitrate or halide of the corresponding active component metal.
Further, the specific surface area of the phosphate is 10-500m2/g。
Further, the preparation method of the supported catalyst comprises the following steps:
drying the phosphate carrier to remove adsorption water, cooling to room temperature, adding an impregnation liquid containing active components, continuously stirring uniformly, drying at room temperature, and roasting at 50-300 ℃ for 1-24h to obtain the supported catalyst.
Wherein the room temperature is 25 +/-5 ℃.
The invention also aims to provide the application of the supported catalyst in selective hydrogenation of quinoline compounds.
The application method comprises the following steps: and mixing the quinoline compound with a solvent, and carrying out selective hydrogenation reaction on the mixed reaction liquid and hydrogen under the action of the supported catalyst to generate the hydrogenated quinoline compound.
The catalyst of the present invention may be reused for several times without obvious decrease in activity and selectivity, and may be separated from the reaction solution easily.
Furthermore, the reaction temperature of the selective hydrogenation reaction is 20-180 ℃, and the reaction pressure is 0.1-10 MPa.
Still further, the reaction temperature of the selective hydrogenation reaction is preferably 20 to 80 ℃, and the reaction pressure is preferably 0.1 to 0.8 MPa.
Furthermore, the supported catalyst needs to be subjected to reduction treatment before reaction, wherein the reduction temperature is 50-600 ℃, and the reduction time is 0.5-6 h.
Further, the quinoline compound is quinoline, isoquinoline or substituted quinoline.
Furthermore, the substituent on the benzene ring or pyridine ring of the substituted quinoline is one or more of halogen, vinyl, aldehyde group, hydroxyl, alkyl and phenyl.
Further, the solvent is one or more of water, methanol, ethanol, toluene, DMF (N, N-dimethylformamide), tetrahydrofuran and cyclohexane.
Still further, the solvent is one or more of water, ethanol and toluene.
Furthermore, in the selective hydrogenation reaction, the mass ratio of the quinoline compound to the supported catalyst is (1-1000): 1.
The invention has the following beneficial effects:
aiming at the problems of harsh reaction conditions, complex catalyst preparation method and the like of a heterogeneous catalyst for quinoline selective hydrogenation reaction in the prior art, the invention provides a supported catalyst with high activity, high selectivity and high stability under mild conditions, and the supported catalyst is applied to the quinoline selective hydrogenation reaction. The supported catalyst of the invention can be recycled for multiple times, the activity and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
1. Preparing a supported catalyst:
taking 1g of YPO4Drying at 120 deg.C for 10h, cooling to room temperature, adding 1mL HAuCl prepared in advance4Dropwise addition of the solution to YPO4Continuously stirring to make the color uniform, drying at room temperature for 12h after water is evaporated to dryness, and then roasting at 120 deg.C for 3h to obtain solid particles.
0.05g of the solid particles are weighed out in H2Reducing for 1h at 500 ℃ in the atmosphere to obtain Au/YPO with the Au mass fraction of 0.01 percent4A catalyst.
2. Selective hydrogenation reaction:
adding the catalyst reduced in the step 1 into a high-pressure reaction kettle containing 0.5mmol of quinoline and 5mL of absolute ethyl alcohol, and reacting with H2The air in the kettle was vented, the pressure was increased to 0.1MPa, and the reaction was carried out at 20 ℃ for 0.5h, the results are shown in Table 1.
Example 2
1. Preparing a supported catalyst:
1g of Li is taken3PO4Drying at 120 deg.C for 10H, cooling to room temperature, and adding 1mL of pre-prepared H2PtCl6Dropwise addition of the solution to Li3PO4Continuously stirring to make the color uniform, drying at room temperature for 12h after water is evaporated to dryness, and then roasting at 200 deg.C for 3h to obtain solid particles.
0.05g of the solid particles are weighed out in H2Reducing for 1h at 250 ℃ in the atmosphere to obtain Pt/Li with the Pt mass fraction of 0.1 percent3PO4A catalyst.
2. Selective hydrogenation reaction:
the catalyst reduced in step 1 was added to an autoclave containing 0.5mmol of quinoline and 5mL of toluene, and reacted with H2The air in the kettle was vented, the pressure was increased to 0.3MPa, and the reaction was carried out at 50 ℃ for 0.5h, the results are shown in Table 1.
Example 3
1. Preparing a supported catalyst:
1g of Mg is taken3(PO4)2Drying at 100 deg.C for 10h, cooling to room temperature, adding 1mL of prepared RhCl3Dropwise addition of the solution to Mg3(PO4)2Continuously stirring to make the color uniform, drying at room temperature for 12h after water is evaporated to dryness, and then roasting at 250 deg.C for 24h to obtain solid particles.
0.01g of the solid particles are weighed out in H2Reducing for 1h at 600 ℃ in atmosphere to obtain Rh/Mg with the Rh mass fraction of 1.5 percent3(PO4)2A catalyst.
2. Selective hydrogenation reaction:
adding the reduced catalyst in the step 1Adding into a high-pressure reaction kettle containing 0.5mmol of quinoline and 5ml of DMF, and reacting with H2The air in the kettle was vented, the pressure was increased to 0.8MPa, and the reaction was carried out at 80 ℃ for 0.5h, the results are shown in Table 1.
Example 4
1. Preparing a supported catalyst:
weighing 1g of Co3(PO4)2Drying at 100 deg.C for 10h, cooling to room temperature, and adding 1mL of prepared Pd (NO)3)2Dropwise addition of the solution to Co3(PO4)2Continuously stirring to make the color uniform, drying at room temperature for 12h after water is evaporated to dryness, and then roasting at 300 deg.C for 3h to obtain solid particles.
0.005g of the solid particles are weighed out in H2Reducing for 1h at 100 ℃ under the atmosphere to obtain Pd/Co with the Pd mass fraction of 3.5 percent3(PO4)2A catalyst.
2. Selective hydrogenation reaction:
adding the catalyst reduced in the step 1 into a high-pressure reaction kettle containing 5.0mmol of quinoline and 5mL of absolute ethyl alcohol, and reacting with H2The air in the kettle was vented, the pressure was increased to 0.5MPa, and the reaction was carried out at 40 ℃ for 0.5h, the results are shown in Table 1.
Example 5
1. Preparing a supported catalyst:
1g of Ca is taken3(PO4)2Drying at 120 ℃ for 2h, cooling to room temperature, and adding 1mL of pre-prepared RuCl3Dropwise addition of the solution to Ca3(PO4)2Continuously stirring to make the color uniform, drying at room temperature for 12h after water is evaporated to dryness, and then roasting at 50 deg.C for 3h to obtain solid particles.
0.05g of the solid particles are weighed out in H2Reducing for 1h at 150 ℃ in atmosphere to obtain Ru/Ca with the Ru mass fraction of 5%3(PO4)2A catalyst.
2. Selective hydrogenation reaction:
the reduced catalyst of step 1 was added to an autoclave containing 1.0mmol quinoline and 5mL water, and reacted with H2Discharging the air in the kettle, pressurizing to 0.6MPa, at 7The reaction was carried out at 0 ℃ for 0.5h, and the results are shown in Table 1.
TABLE 1 Selective hydrogenation of quinolines by Supported catalysts in examples 1-5
Example 6
Examination of the Ru/Ca obtained in example 5 having better reactivity3(PO4)2The catalytic performance of the catalyst on different substrates and the reaction conditions are as in example 5, and the difference is only the variety of the substrates. The results are shown in Table 2.
The results show that the catalyst has high activity and selectivity on different substrates and good substrate universality.
TABLE 2 Selective hydrogenation results of the supported catalyst obtained in example 5 on different quinolines
Example 7
Ru/Ca obtained in example 53(PO4)2The catalyst is taken as an example, and the cycling stability of the supported catalyst in the selective hydrogenation of quinoline is examined. The procedure for selective hydrogenation was the same as in example 5. The results are shown in Table 3.
The results show that the catalyst has good cycle stability.
Table 3 catalyst cycle performance results in example 7
Number of cycles
Conversion (%)
Selectivity (%)
1
98
99
2
95
99
3
97
98
4
95
98
5
97
98
6
95
97
7
97
98
8
96
97
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.