CN111068669A - Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof - Google Patents

Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof Download PDF

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CN111068669A
CN111068669A CN202010037567.1A CN202010037567A CN111068669A CN 111068669 A CN111068669 A CN 111068669A CN 202010037567 A CN202010037567 A CN 202010037567A CN 111068669 A CN111068669 A CN 111068669A
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heterogeneous catalyst
titanium dioxide
selective hydrogenation
quinoline
catalyst
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CN111068669B (en
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魏中哲
周强
王建国
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Zhejiang University of Technology ZJUT
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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    • B01J23/462—Ruthenium
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    • B01J23/50—Silver
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/24—Oxygen atoms attached in position 8
    • C07D215/26—Alcohols; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof, wherein the heterogeneous catalyst comprises 1-10 wt% of noble metal particles and 9-90 wt% of titanium dioxide with oxygen vacancies, and the noble metal particles are loaded on the titanium dioxide with oxygen vacancies. Compared with the common titanium dioxide supported noble metal catalyst, the heterogeneous catalyst of the invention is applied to the selective hydrogenation reaction of the catalytic quinoline compound, because the noble metal in the heterogeneous catalyst of the invention and the oxygen vacancy of the titanium dioxide act together, electrons are transferred, so that the noble metal is rich in charge, thereby improving the catalytic activity of the heterogeneous catalyst.

Description

Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof
Technical Field
The invention relates to the field of catalysts, and particularly relates to a heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof.
Background
The synthesis of functionalized 1,2,3, 4-tetrahydroquinoline (py-THQ) is receiving increasing attention due to its great utility in the production of pharmaceuticals, alkaloids, pesticides and other fine chemicals. High reaction temperatures are required for the hydrogenation of N-heteroaromatics catalyzed by transition metal and metal-free catalysts: (>120 ℃ and a long reaction time: (>24 h) Because they have a low H2And (4) activating capacity. The noble metal (such as Ir, Ru, Rh, Pd and Pt) catalytic system has higher catalytic activity for the hydrogenation reaction of quinoline compounds. However, both heterogeneous and homogeneous catalysts generally have poor substrate applicability in the presence of other reducible functional groups (Cl, OH, CHO, etc.), resulting in reduced chemoselectivity. In addition, strong adsorption of quinoline and hydrogenated quinoline may lead to catalyst poisoning. Therefore, the development of a quinoline compound hydrogenation catalyst with high activity and high selectivity is of great significance.
For a long time, efforts have been made to develop a catalyst with high activity, high selectivity and high stability for selective hydrogenation of quinoline compounds to prepare 1,2,3, 4-tetrahydroquinoline compounds. TiO 22As a common metal oxide, it has attracted much attention as a carrier due to its strong interaction with metals. For example, using high specific surface area TiO2The supported nano Au catalyst can be used for preparing a catalyst at 60 ℃ and 2MPa H2Under the reaction conditions of (1), 6-chloroquinoline is quantitatively converted into 6-chlorotetrahydroquinoline within 3h, and no dehalogenation reaction occurs (j.am. chem. soc. 2012, 134, 17592.). The catalytic systemThe substrate universality is very good, and better yield can be obtained for quinoline substrates substituted by some reducible groups (acetyl, vinyl and the like) or other nitrogen-containing aromatic compounds (such as isoquinoline, 7, 8-benzoquinoline, acridine and the like). At the same time, rutile phase TiO2The supported nano gold catalyst can also be used for completing the selective hydrogenation of quinoline compounds by taking formic acid as a hydrogen source at 130 ℃ (Adv. Synth. Catal. 2015, 357, 753). However, these catalysts are either complicated to prepare or the reaction conditions are severe.
The defect of the metal oxide is one of important factors influencing the performance of the metal oxide, the oxygen vacancy is one of the most important defects of the metal oxide, the electronic structure regulation and the influence research on the metal are less, and the invention is to use the oxygen vacancy TiO2The strong interaction with noble metals is applied to heterogeneous catalytic reactions.
Disclosure of Invention
In view of the above technical problems in the prior art, an object of the present invention is to provide a heterogeneous catalyst for selective hydrogenation of quinoline compounds, which is synthesized by a specific method and contains noble metal particles, and which is stable to air, water and heat, and exhibits excellent catalytic activity and selectivity when applied to selective hydrogenation of quinoline, and an application thereof.
The heterogeneous catalyst for the selective hydrogenation reaction of the quinoline compounds is characterized by comprising 1-10 wt% of noble metal particles and 9-90 wt% of titanium dioxide with oxygen vacancies, wherein the noble metal particles are loaded on the titanium dioxide with the oxygen vacancies.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in that the preparation method of the titanium dioxide with oxygen vacancies comprises the following steps: calcining titanium dioxide serving as a raw material at 600-1200 ℃ for 0.5-6 h in an inert gas atmosphere to obtain the titanium dioxide with oxygen vacancies.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in thatCharacterized in that in the method for preparing the titanium dioxide with oxygen vacancy, the titanium dioxide raw material is TiO2(B) And the inert gas is nitrogen.
The heterogeneous catalyst for selective hydrogenation of quinoline compounds is characterized in that the preparation method of the heterogeneous catalyst comprises the following steps:
1) adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) and (2) placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst.
The heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds is characterized in that the noble metal particles are Au, Ag, Rh, Os, Ir, Ru, Pt or Pd particles; the particle size of the noble metal particles is 1 to 50nm, preferably 1 to 15 nm.
The heterogeneous catalyst for the selective hydrogenation reaction of the quinoline compounds is characterized in that in the step 2), the roasting temperature is 200-600 ℃, and preferably 250-500 ℃.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds are mixed with a solvent, and the mixed reaction liquid and hydrogen carry out selective hydrogenation reaction under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 0-150 ℃, and the reaction pressure is 0.1-10 MPa; the solvent is water, ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the quinoline compounds are quinoline or substituted quinoline, the number of substituent groups on benzene rings or pyridine rings of the substituted quinoline is one or more, and the substituent groups on the benzene rings or the pyridine rings of the substituted quinoline are halogen, C1-C3 alkoxy, hydroxyl or phenyl.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the mass of the heterogeneous catalyst is 0.1-10% of the mass of the quinoline compounds.
The application of the heterogeneous catalyst in selective hydrogenation reaction of quinoline compounds is characterized in that the temperature for performing the selective hydrogenation reaction is 20-80 ℃, the pressure is 0.1-2 MPa, and the solvent is water or ethanol.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. in the preparation process of the catalyst carrier, TiO is selected as titanium dioxide2(B) And TiO 22(B) Has a flaky multi-layer structure which is unstable at high temperature and in which O is desorbed during high-temperature calcination in an inert atmosphere to form oxygen vacancies. In the catalyst prepared by the invention, due to the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancies, the contact surface between the noble metal particles and the titanium dioxide carrier is increased, the dissociation of hydrogen is promoted, and the contact surface is not easy to be attached by quinoline, so that the coordination bond formed by the nitrogen atom in the quinoline and the catalyst is inhibited, the catalytic activity is reduced, and the poisoning phenomenon of the catalyst can be effectively avoided.
2. In the heterogeneous catalyst, due to the strong interaction between the noble metal particles and the titanium dioxide carrier with oxygen vacancies and the effectiveness of hydrogen reduction (namely, the hydrogen effectively reduces the ionic noble metal into a simple substance), the noble metal particles of the heterogeneous catalyst prepared by the method have uniform size and good dispersity, and the average diameter of the noble metal particles can reach 1-10 nm. The heterogeneous catalyst is stable to air, water and heat, the catalytic quinoline hydrogenation activity is not reduced after the heterogeneous catalyst exists in the air for 5 months, and the metal valence state is kept unchanged.
3. Compared with the common titanium dioxide supported noble metal catalyst, when the heterogeneous catalyst is applied to the selective hydrogenation reaction of the catalytic quinoline compound, the noble metal in the heterogeneous catalyst and the oxygen vacancy of the titanium dioxide act together to cause the shift of electrons, so that the noble metal is rich in charges (the electron-rich noble metal particles are more beneficial to the dispersion of the electron-rich noble metal particles on the catalyst carrier, and are more beneficial to the exposure of metal active sites and the improvement of catalytic activity), and the catalytic activity of the heterogeneous catalyst is improved. Taking the example of preparing 1,2,3, 4-tetrahydroquinoline by catalyzing the hydrogenation reaction of quinoline, the conversion rate of quinoline can reach 100%, and the selectivity of 1,2,3, 4-tetrahydroquinoline can reach more than 95%.
Drawings
FIG. 1 is a HRTEM image of the catalyst obtained in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 based on TiO2-xHeterogeneous catalyst loaded with Ru
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 0.15ml of previously prepared RuCl was added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Ru catalyst.
Example 2 based on TiO2-xPd-supported heterogeneous catalyst
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 0.15ml of previously prepared PdCl were then added3Aqueous solution (PdCl)3The concentration of the aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that PdCl is added3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Pd after later-stage calcination are closely and uniformly combined.
The prepared solid mixture is placed in a tube furnace and calcined for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Pd catalyst.
Example 3 TiO-based2-xHeterogeneous catalyst loaded with Au
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 0.15ml of HAuCl prepared beforehand was added4·4H2O aqueous solution (HAuCl)4Concentration of 4H2O aqueous solution 10 mg/mL), and stirring and mixing the mixture uniformly to give HAuCl4·4H2O adsorption on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and Au after later-stage calcination are closely and uniformly combined.
The prepared solid mixture is placed in a tube furnace and calcined for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Au catalyst.
Example 4 based on TiO2-xPt-supported heterogeneous catalyst
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 0.15ml of previously prepared H2PtCI6·6H2O aqueous solution (H)2PtCI6·6H2The concentration of the O aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that H is added2PtCI6·6H2O adsorption on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Pt are closely and uniformly combined after the later-stage calcination.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Pt catalyst.
Example 5 based on TiO2-xAg-supported heterogeneous catalyst
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
The TiO prepared above was then added to a 100mL beaker2-x0.2g of material, 0.15ml of pre-prepared AgNO was added3Aqueous solution (AgNO)3The concentration of the aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that AgNO is mixed3Adsorbing on TiO2-xOn the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ag after the later calcination are closely and uniformly combined.
Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2-xA supported Ag catalyst.
Example 6 example 1 TiO2-xCharacterization of the Supported Ru catalyst
The TiO obtained in example 1 was examined by high-resolution transmission electron microscope (HRTEM)2-xThe supported Ru catalyst was characterized, and the characterization results are shown in FIG. 1, which confirmed that the catalyst was composed of titanium dioxide nano-metal Ru. Ru nano particles are uniformly distributed on TiO2-xOn the material, Ru and twoThe titanium oxide was in intimate contact, indicating that there was a significant interaction between the Ru and the titanium dioxide. The average grain diameter of the Ru nano particles is 1.8 nm by counting 150 nanometer Ru metal particles.
Example 7 preparation of tetrahydroquinoline by hydrogenation of quinoline using the heterogeneous catalyst prepared in example 1
After charging 118. mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 1 and 10mL of methylene chloride into a 50 mL stainless steel autoclave, and evacuating the inside of the stainless steel autoclave with hydrogen 3 times (i.e., the inside of the stainless steel autoclave was replaced with air by hydrogen and the inside of the stainless steel autoclave was evacuated, which is equivalent to the following example), charging hydrogen to 1MPa and sealing, heating in a 60 ℃ water bath, magnetically stirring, and carrying out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 98% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 97%.
EXAMPLE 8 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 2
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 2 and 10mL of tetrahydrofuran were charged into a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, hydrogen was charged to 1MPa and sealed, and the mixture was heated in a water bath at 80 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of quinoline to be 99% and the selectivity of 1,2,3, 4-tetrahydroquinoline to be 90%.
Example 9 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 3
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 3 and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a 60 ℃ water bath, magnetically stirred, subjected to selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the obtained quinoline by detection to be 98% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 95%.
EXAMPLE 10 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 4
Mu.l of quinoline, 10 mg of the heterogeneous catalyst prepared in example 4 and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, the autoclave was charged with hydrogen to 1MPa and sealed, heated in a 60 ℃ water bath, magnetically stirred, subjected to selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of quinoline is 99% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 96%.
EXAMPLE 11 preparation of tetrahydroquinoline by hydrogenation of quinoline over the heterogeneous catalyst prepared in example 5
Mu.l of quinoline, 10 mg of the catalyst of example 5 and 10mL of N, N-dimethylformamide were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen in the stainless steel autoclave, charging hydrogen to 1MPa and sealing were carried out, and the mixture was heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating by detection that the conversion rate of quinoline is 90% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 95%.
Examples 8-11 demonstrate that titania with vacancies supporting noble metals all have good activity and selectivity for the hydrogenation of quinoline.
EXAMPLE 12 preparation of tetrahydroquinoline by catalytic hydrogenation of quinoline after 5 months' storage with the catalyst prepared in example 3
After the heterogeneous catalyst prepared in example 3 is placed in a cool and shady environment at room temperature and a relative humidity of 70% -80% for 5 months, the catalytic activity of the heterogeneous catalyst is verified according to the following steps: mu.l of quinoline, 10 mg of the catalyst prepared in example 3 after leaving to stand for 5 months, and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after the inside of the stainless steel autoclave was purged with hydrogen 3 times, the inside was charged with hydrogen to 1MPa and sealed, and the mixture was heated in a water bath at 60 ℃ and magnetically stirred to carry out a selective hydrogenation reaction for 3 hours. After the reaction was stopped, the residual hydrogen in the stainless steel autoclave was carefully discharged, and the reaction solution was taken out. And (3) separating the heterogeneous catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 96% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 92%. By comparing example 14 with example 10, it can be seen that the catalyst obtained in example 3 is very stable and very inert to both air and moisture.
Examples 13 to 20
Examples 14 to 21 are examples in which the heterogeneous catalyst prepared in example 1 was used to catalyze the hydrogenation of quinoline compounds to produce functional hydrides, the procedure of examples 14 to 21 was the same as in example 7, and the molar charge of the reaction substrate, the volume of the solvent added, and the amount of the catalyst added were the same as in example 7. Table 1 shows the reaction conditions and the corresponding reaction results for each example.
TABLE 1
Figure DEST_PATH_IMAGE002
As can be seen from examples 13-20, the catalysts have very good versatility and the different substituents are well preserved during the reaction, i.e., Ru/TiO2-xThe catalyst is a high-activity and high-selectivity catalyst in the catalytic hydrogenation of quinoline compounds.
Comparative example 1 is based on TiO2(B) Ru-supported heterogeneous catalyst for quinoline hydrogenation
0.2g TiO was added to a 100mL beaker2（B）Then 0.15ml of previously prepared RuCl was added3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on TiO2(B) On the material. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. Putting the prepared solid mixture into a tubular furnace, calcining for 1h at the temperature of 300 ℃ in the atmosphere of hydrogen to obtain TiO2(B) A supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of TiO prepared as described above2(B) The supported Ru catalyst and 10mL of ethanol were added to a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen, charging hydrogen to 1MPa and sealing were performed, and the mixture was heated in a 60 ℃ water bath, magnetically stirred, and reacted for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of quinoline to be 20% and the selectivity of 1,2,3, 4-tetrahydroquinoline to be 85%.
Comparative example 2 preparation of tetrahydroquinoline by hydrogenation of quinoline based on a catalyst with titanium dioxide P25 supporting Ru
Preparing a catalyst: 250.2 g of titanium dioxide P are added to a 100ml beaker, followed by 0.15ml of the previously prepared RuCl3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbed on titanium dioxide P25. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. The solid mixture obtained above was placed in a tube furnace and calcined at 300 ℃ for 1 hour under a hydrogen atmosphere to obtain a P25-supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of the Ru catalyst supported on P25 prepared above and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of evacuation with hydrogen, hydrogen was charged to 1MPa and sealed, and the mixture was heated in a 60 ℃ water bath, magnetically stirred and reacted for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of the quinoline is 25% and the selectivity of the 1,2,3, 4-tetrahydroquinoline is 96%.
As can be seen from comparative examples 1 and 2, TiO alone2(B) Or when the titanium dioxide P25 is a carrier loaded with the nano metal Ru, the catalytic activity of the catalyst is lower than that of the catalyst prepared in example 3, and the oxygen vacancy of the titanium dioxide plays an important role.
Comparative example 3 is based on TiO2-xNaBH for loading Ru4Reduced heterogeneous catalyst
0.4g of TiO was taken2(B) Calcining for 1h at 600 ℃ in nitrogen atmosphere to obtain titanium dioxide material with oxygen vacancies, and marking the titanium dioxide material as TiO2-xA material.
Taking the prepared TiO2-xAdding 0.2g of the material into 50 mL of deionized water, performing ultrasonic treatment for 10 min, and adding 0.15mL of pre-prepared RuCl3Aqueous solution (RuCl)3The concentration of the aqueous solution is 10 mg/mL), after ultrasonic treatment is carried out for 10 min, 5mL of freshly prepared sodium borohydride aqueous solution is added for continuous ultrasonic treatment (the concentration of the sodium borohydride aqueous solution is 1 mg/mL), and Ru is subjected to ultrasonic treatment3+Reducing the Ru into a simple substance, then carrying out suction filtration, washing filter residue for multiple times, and drying to obtain TiO2-xA supported Ru catalyst.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of TiO prepared as described above2-xThe supported Ru catalyst and 10mL of ethanol were added to a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen, charging hydrogen to 1MPa and sealing were performed, and the mixture was heated in a 60 ℃ water bath, magnetically stirred, and reacted for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and detecting and calculating to obtain that the conversion rate of quinoline is 55% and the selectivity of 1,2,3, 4-tetrahydroquinoline is 95%.
As can be seen from the comparison of the reaction results of comparative example 3 and example 7, the reduction mode and the catalyst activity are closeAnd (4) relationship. High temperature calcination of Ru in a hydrogen atmosphere3+The catalyst prepared by reducing the Ru into the simple substance has higher catalytic activity.
Comparative example 4 commercial activated carbon-supported Ru-based catalyst for hydrogenation of quinoline to tetrahydroquinoline
Preparing a catalyst: adding 0.2g commercial activated carbon (coconut shell activated carbon, 200-300 mesh, available from Jiuding chemical technology Co., Ltd.) into 50 mL deionized water, adding 0.15mL of pre-prepared RuCl3Aqueous solution (RuCl)3Concentration of aqueous solution is 10 mg/mL), stirring and mixing evenly to ensure that RuCl is generated3Adsorbing on activated carbon. And then heating and stirring at the temperature of 70 ℃ until the deionized water in the beaker is completely volatilized to obtain a solid mixture, wherein the solid obtained by the method can ensure that the titanium dioxide and the Ru which are calcined at the later stage are closely and uniformly combined. And (3) putting the prepared solid mixture into a tubular furnace, and calcining the solid mixture for 1h at the temperature of 300 ℃ in a hydrogen atmosphere to obtain the Ru catalyst supported by the active carbon.
The catalytic reaction process comprises the following steps: mu.l of quinoline, 10 mg of the commercial activated carbon Ru-supported catalyst prepared above and 10mL of ethanol were placed in a 50 mL stainless steel autoclave, and after 3 times of charging and discharging with hydrogen, charging and sealing were carried out, heating in a water bath at 80 ℃ with magnetic stirring, and reaction was carried out for 3 hours. After the reaction was stopped, the residual hydrogen was carefully removed, and the reaction solution was taken out. And separating the catalyst from the reaction liquid by adopting a centrifugal method, detecting the reaction liquid by using gas chromatography, and calculating the conversion rate of the quinoline to be 18% and the selectivity of the 1,2,3, 4-tetrahydroquinoline to be 43%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (10)

1. The heterogeneous catalyst for the selective hydrogenation reaction of quinoline compounds is characterized by comprising 1-10 wt% of noble metal particles and 9-90 wt% of titanium dioxide with oxygen vacancies, wherein the noble metal particles are loaded on the titanium dioxide with the oxygen vacancies.
2. The heterogeneous catalyst for selective hydrogenation of quinolines according to claim 1, wherein said titanium dioxide having oxygen vacancies is prepared by the process comprising: calcining titanium dioxide serving as a raw material at 600-1200 ℃ for 0.5-6 h in an inert gas atmosphere to obtain the titanium dioxide with oxygen vacancies.
3. The heterogeneous catalyst for selective hydrogenation of quinolines according to claim 2, wherein in said process for preparing titanium dioxide having oxygen vacancies, the titanium dioxide starting material is TiO2(B) And the inert gas is nitrogen.
4. The heterogeneous catalyst for selective hydrogenation of quinolines according to claim 1, characterized in that said heterogeneous catalyst is prepared by a method comprising the following steps:
1) adding the titanium dioxide with the oxygen vacancy into an aqueous solution of a noble metal precursor, stirring and mixing uniformly to enable the noble metal precursor to be adsorbed on the titanium dioxide, and then heating and stirring at 60-80 ℃ until the moisture is completely volatilized to obtain a solid mixture;
2) and (2) placing the solid mixture obtained in the step 1) in a tubular furnace, and roasting in an atmosphere of introducing hydrogen to reduce the precious metal precursor loaded on the titanium dioxide into precious metal particles, thus obtaining the heterogeneous catalyst.
5. The heterogeneous catalyst for selective hydrogenation of quinolines according to claim 1, wherein the noble metal particles are Au, Ag, Rh, Os, Ir, Ru, Pt or Pd particles; the particle size of the noble metal particles is 1 to 50nm, preferably 1 to 15 nm.
6. The heterogeneous catalyst for selective hydrogenation of quinoline compounds as claimed in claim 4, wherein in step 2), the calcination temperature is 200-600 ℃, preferably 250-500 ℃.
7. The application of the heterogeneous catalyst in selective hydrogenation of quinoline compounds according to claim 1, wherein the quinoline compounds are mixed with a solvent, and the mixed reaction solution is subjected to selective hydrogenation with hydrogen under the action of the heterogeneous catalyst to generate hydrogenated quinoline compounds; wherein the reaction temperature is 0-150 ℃, and the reaction pressure is 0.1-10 MPa; the solvent is water, ethanol, dichloromethane, tetrahydrofuran, ethyl acetate, dioxane, N-dimethylformamide, N-hexane or toluene.
8. The application of the heterogeneous catalyst in selective hydrogenation of quinoline compounds as claimed in claim 7, wherein the quinoline compounds are quinoline or substituted quinoline, the number of substituents on the benzene ring or pyridine ring of the substituted quinoline is one or more, and the substituents on the benzene ring or pyridine ring of the substituted quinoline are halogen, C1-C3 alkoxy, hydroxyl or phenyl.
9. The application of the heterogeneous catalyst in selective hydrogenation of quinoline compounds according to claim 7, wherein the mass of the heterogeneous catalyst is 0.1-10% of the mass of the quinoline compounds.
10. The application of the heterogeneous catalyst in selective hydrogenation of quinoline compounds according to claim 7, wherein the selective hydrogenation is carried out at a temperature of 20-80 ℃ and a pressure of 0.1-2 MPa, and the solvent is water or ethanol.
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CN115739068A (en) * 2022-11-18 2023-03-07 南京大学盐城环保技术与工程研究院 Supported catalyst, preparation method thereof and photocatalytic treatment device using supported catalyst

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