CN115121269A - Nickel-based catalyst for hydrogenation of aromatic ring and preparation method and application thereof - Google Patents

Nickel-based catalyst for hydrogenation of aromatic ring and preparation method and application thereof Download PDF

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CN115121269A
CN115121269A CN202210927395.4A CN202210927395A CN115121269A CN 115121269 A CN115121269 A CN 115121269A CN 202210927395 A CN202210927395 A CN 202210927395A CN 115121269 A CN115121269 A CN 115121269A
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acid
nickel
catalyst
hydrogenation
aromatic ring
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柳翔
段成杰
朱佳政
李坤
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Nanjing Tech University
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    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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    • C07D209/04—Indoles; Hydrogenated indoles
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
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    • 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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    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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
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    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Abstract

The invention discloses a nickel-based catalyst for hydrogenation of aromatic ring compounds, and a preparation method and application thereof. The catalyst of the invention takes nano nickel as an active center, hydroxyapatite HAP as a carrier and organic acid as a ligand to carry out complexing modification in the preparation process, and adopts a complexing impregnation method to coordinate Ni of different organic acids 2+ The catalyst is loaded on HAP, dried and reduced by hydrogen to prepare the catalyst, and the catalyst is applied to catalyzing aromatic ring compound hydrogenation to prepare cyclohexane compounds or heterocyclic compounds. The preparation method is simple, and the obtained catalyst has the characteristics of good metal nickel dispersibility, high catalytic activity and selectivity, wide substrate application range and relatively mild hydrogenation reaction temperature and pressure of the aromatic ring compound, and has good industrial application prospect.

Description

Nickel-based catalyst for aromatic ring hydrogenation and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a nickel-based catalyst for aromatic ring hydrogenation, and a preparation method and application thereof.
Background
The aromatic ring catalytic hydrogenation is one of basic reactions in the chemical field, is an important method for synthesizing alicyclic compounds, and has wide application in the fields of medicine and natural product synthesis, coal petroleum and lignin refining, organic matter liquid hydrogen storage and the like. Conventional aromatic ring hydrogenation processes based on solid metal catalysts or metal complex catalysts generally require harsh reaction conditions such as high temperature, high pressure, and the like. In the past decades, precious metal catalysts such as supported nano Pt (j.am. chem.soc.2018, 140, 11325), Pd (eur.j.org.chem.2020, 5514), Ru (ACS sustamable chem.eng.2020, 8, 15740), Rh (j.catal.2017, 354, 113) have made great progress in improving the aromatic ring hydrogenation efficiency, and hydroconversion can be achieved at relatively low temperature or pressure. However, due to scarcity of precious metal resources and continuously rising price, the production cost is continuously increased, and the finding of a high-efficiency non-precious metal catalyst with abundant reserves and low price for aromatic ring hydrogenation reaction to replace a precious metal hydrogenation catalyst has important industrial value.
The currently developed Ni-based or Co-based non-noble metal aromatic ring hydrogenation catalyst still needs to be carried out under higher reaction pressure or temperature, and the catalytic performance still needs to be improved. SiO prepared by pyrolysis of Co-pyromellitic acid-piperazine coordination polymers generated in situ as reported by M.Beller et al 2 Nano Co-loaded catalyst (Co-PMA-PZ MOF @ SiO) 2 ) Can be used for the hydroconversion of various aromatic hydrocarbon compounds, but the reaction needs to be carried out at 135 ℃ and 50bar H 2 Carried out under conditions (ACS cat.2019, 9, 8581). Sunreh et al disclose two nano nickel catalysts for aromatic ring hydrogenation, namely a nano nickel-based polyhedral catalyst (CN103357410A) and a bimetallic sea urchin type catalyst (CN 104475107A). The hydrogenation reaction conditions are respectively 100-150 ℃, 4-7 MPa H 2 And 130-180 ℃ and 2-7 MPa H 2 The reaction pressure is high and the substrate applicability is narrow. Meanwhile, for the carrier-free nano nickel-based catalyst, agglomeration is easy to occur in the actual reaction, and the stability of the catalyst is poor. Chinese patent CN103084180B discloses a supported superfine amorphous metallic nickel catalyst for catalyzing full hydrogenation of aromatic rings and a preparation method thereof. The superfine amorphous metal nickel catalyst prepared from nickel carbonyl can be used for catalytic hydrogenation of heavy benzol, but the reaction needs to be carried out at 180 ℃ and 5MPa H 2 The method is carried out under the condition, and the applicability of the substrate is narrow; and the preparation of the catalyst also needs high pressure H of 2-8 MPa 2 To complete the process.
The catalytic performance of the metal catalyst is closely related to the dispersion degree of the metal active center. In many reactions, the improvement of the metal dispersion degree is beneficial to the improvement of the catalytic performance, and meanwhile, the metal utilization rate can be increased, and the catalyst cost is effectively reduced. In the research on the preparation of inexpensive metal catalysts, in recent years, the coordination pyrolysis method developed by m.beller (Science2017, 358, 326; nat. catal.2022, 5, 20) and r.kempe (nat. catal.2019, 2, 71) and the like has been attracting attention. The method utilizes a metal complex or a metal complex generated in situ as a precursor, and carries out high-temperature pyrolysis in an inert atmosphere to prepare the Ni, Co and Fe nano metal catalyst with high metal dispersion degree, high activity and good selectivity. The complexation of the metal with the ligand and the formation of a barrier between metal ions by the ligand or promote the formation of smaller sized metal nanoparticles. The cheap metal catalyst prepared by the coordination pyrolysis method has excellent performance in reactions such as liquid-phase catalytic hydrogenation, reductive amination and hydrodeoxygenation, and has high catalytic activity and wide substrate applicability. These studies may provide new ideas for the preparation of high performance nickel-based catalysts and their application in aromatic ring selective hydrogenation.
Disclosure of Invention
Aiming at the problems that the non-noble metal catalyst in the prior art is low in catalytic activity, high in reaction temperature and/or pressure required for catalyzing the hydrogenation reaction of aromatic ring compounds, narrow in applicability of the aromatic ring compounds and the like, the invention mainly aims to provide the nickel-based catalyst for the hydrogenation of the aromatic ring.
It is still another object of the present invention to provide a method for preparing the above nickel-based catalyst.
It is another object of the present invention to provide use of the above nickel-based catalyst.
The invention is realized by the following steps that a nickel-based catalyst for aromatic ring hydrogenation has a chemical general formula of xNi/HAP (yL); wherein the content of the first and second substances,
ni is active metal nickel;
x is the load of Ni, and the value of x is 1.0-10.0 wt%;
HAP is hydroxyapatite, Ca/P is 1.5-1.67: 1;
l is an organic acid ligand, y is the molar ratio of L to Ni, and the numerical value is 0-5.0.
Preferably, the particle size of the active metal nickel is 1-10 nm, the average particle size is 4.2-5.8 nm, and the active metal nickel is small in size and uniform in dispersion, so that the hydrogenation reaction is facilitated.
The invention further discloses a preparation method of the nickel-based catalyst for aromatic ring hydrogenation, which comprises the following steps:
(1) dissolving nickel salt and organic acid in deionized water, adding hydroxyapatite, stirring and evaporating to dryness under the heating condition of 80-100 ℃, and drying to obtain a catalyst precursor;
(2) grinding and sieving the catalyst precursor, and placing the catalyst precursor in 10 vol% H 2 And reducing the mixture for 30-120 min at 600-800 ℃ in an/Ar mixed atmosphere to obtain the nickel-based catalyst with the nickel loading of 1-10 wt%.
Preferably, in step (1), the nickel salt is nickel nitrate hexahydrate; the organic acid is selected from any one of malonic acid, succinic acid, glutaric acid, adipic acid, DL-malic acid, tartaric acid, citric acid, mucic acid, gluconic acid, propionic acid, n-butyric acid, n-valeric acid, n-caproic acid, DL-aspartic acid, L-alanine, L-lysine and ethylenediamine tetraacetic acid.
Preferably, in the step (1), the molar ratio of the nickel salt to the organic acid is 1: 0 to 5.0;
in the step (1), the mass-to-volume ratio of the nickel salt, the deionized water and the hydroxyapatite is 50-550.5 mg: 10mL of: 1.0 g.
Preferably, in the step (1), the molar ratio of calcium to phosphorus in the hydroxyapatite is 1.5-1.67: 1.
the invention further discloses application of the nickel-based catalyst in catalyzing hydrogenation of aromatic ring compounds to prepare cyclohexane compounds or heterocyclic compounds.
Preferably, the aromatic ring compound is selected from any one of toluene, o-methylbenzene, m-methylbenzene, p-methylbenzene, phenol, anisole, phenethylamine, pyridine, quinoline, pyrrole, indole, methyl 3-furyl formate, naphthalene, N-dimethylaniline, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoate, methyl phenylacetate, methyl phenylpropionate, methyl o-methylbenzoate, methyl m-methylbenzoate, methyl p-methylbenzoate, ethyl p-methoxybenzoate, dimethyl phthalate, dimethyl terephthalate, methyl 2-naphthoate, dioctyl phthalate, and dioctyl terephthalate.
Preferably, the specific process for catalyzing the hydrogenation of the aromatic ring compound is as follows: mixing a nickel-based catalyst, a solvent and an aromatic ring compound, and reacting for 3-12 hours at the temperature of 110-150 ℃ and under the hydrogen pressure of 0.5-2.0 Mpa; wherein the solvent is any one of n-hexane, cyclohexane, n-heptane, ethanol, water and acetonitrile.
Preferably, the molar ratio of the active metal nickel to the aromatic ring compound in the nickel-based catalyst is 1: 25 to 100.
The invention overcomes the defects of the prior art and provides a nickel-based catalyst for aromatic ring hydrogenation and a preparation method and application thereof. The invention adopts an organic acid complexing impregnation method to prepare the nickel-based catalyst for efficiently hydrogenating the aromatic ring, and utilizes an organic acid ligand and Ni 2+ The complexing effect of the catalyst and the electrostatic effect of the organic acid and the hydroxyapatite HAP as the carrier disperse and stabilize the Ni nano particles as the active components, obtain the high-dispersion and small-size Ni nano particles, improve the dissociation capability of the catalyst on hydrogen and improve the hydrogenation performance of the catalyst.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects: the nickel-based catalyst has the characteristics of simple preparation method, high catalytic activity, good selectivity and the like, and has the advantages that in the reaction of catalyzing aromatic ring compounds to prepare cyclohexane or heterocyclic compounds, the yield of target products can reach more than 98%, the reaction conditions are relatively mild, the reaction temperature and pressure are relatively low, and the nickel-based catalyst has good industrial application prospect.
Drawings
FIG. 1 is a TEM image of a 5 wt% Ni/HAP (1.0TA) catalyst obtained in example 3 of the present invention;
FIG. 2 is a particle size distribution diagram of supported nano Ni of 5 wt% Ni/HAP (1.0TA) catalyst obtained in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1 preparation of catalysts with different nickel loadings
(1) Respectively dissolving 50mg, 260.8mg and 550.5mg of nickel nitrate hexahydrate in 10mL of deionized water, adding 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) after dissolution, stirring and evaporating under the heating condition of 80 ℃, and drying in an oven at 100 ℃ for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 Reducing the mixture in an Ar mixed atmosphere at 600 ℃ for 30min to obtain the Ni/HAP catalyst with Ni loading of 1 wt%, 5 wt% and 10 wt%.
Example 2 Effect of different Nickel Supported catalysts on hydrogenation Performance
When the 1 wt% Ni/HAP, 5 wt% Ni/HAP and 10 wt% Ni/HAP catalysts prepared in example 1 are used in the catalytic reaction of preparing methyl cyclohexanecarboxylate by hydrogenating methyl benzoate, 2 mol% Ni of the catalysts are respectively added, 5mL of n-hexane and 1mmol of methyl benzoate are mixed in a high-pressure reaction kettle, and H is carried out at 1.0MPa 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results obtained are shown in Table 1.
TABLE 1 results of the experiment
Catalyst and process for preparing same Conversion (%) Yield (%)
1wt％Ni/HAP 32 32
5wt％Ni/HAP 60 60
10wt％Ni/HAP 47 47
As can be seen from Table 1, when the Ni loading is 5 wt%, the hydrogenation activity of the benzene ring of methyl benzoate is higher than that when the Ni loading is 1 wt% or 10 wt%, and the yield of 60% of the product can be obtained.
Example 3 Effect of different solvents on hydrogenation Activity
The 5 wt% Ni/HAP catalyst prepared in example 1 was used for methyl benzoate hydrogenation in different solvents. 23.5mg of 5 wt% Ni/HAP catalyst, 5mL of solvent and 1mmol of methyl benzoate were mixed in a high pressure reactor at 1.0MPa H 2 And reacting at 130 ℃ for 5 hours, wherein the solvent is one of water, ethanol, acetonitrile, cyclohexane, n-hexane and n-heptane. The yield was analyzed by gas chromatography, and the results obtained are shown in Table 2.
TABLE 2 results of the experiment
Solvent(s) Conversion (%) Yield (%)
Water (I) 1 1
Ethanol 0 0
Acetonitrile 0 0
N-hexane 60 60
N-heptane 62 57
Cyclohexane 53 51
As can be seen from Table 2, the reaction has the best hydrogenation activity when n-hexane is used as the solvent.
Example 4
(1) 260.8mg of nickel nitrate hexahydrate and 134.5mg of tartaric acid (the molar ratio is 1: 1) are dissolved in 10mL of deionized water, 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) is added after dissolution, the mixture is stirred and evaporated to dryness under the heating condition of 80 ℃, and the mixture is placed in an oven at 100 ℃ for drying for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 Reducing the mixture in a mixed Ar atmosphere at 600 ℃ for 30min to obtain the 5wt percent Ni/HAP (1.0TA) catalyst which is complexly impregnated by tartaric acid.
The transmission electron microscope of the obtained 5 wt% Ni/HAP (1.0TA) catalyst is shown in FIG. 1, and it can be seen from FIG. 1 that Ni is uniformly distributed on the surface of HAP in the form of nanoparticles.
The supported nano Ni particle size distribution of the resulting 5 wt% Ni/HAP (1.0TA) catalyst is shown in FIG. 2, and it can be seen from FIG. 2 that the average particle size of the Ni nanoparticles is 4.2 nm.
Example 5
The 5 wt% Ni/HAP (1.0TA) catalyst prepared in example 4 was used in the catalytic reaction of methyl benzoate hydrogenation to prepare methyl cyclohexanecarboxylate, 23.5mg of the above catalyst, 5mL of n-hexane and 1mmol of methyl benzoate were mixed in a high pressure reactor at 1.0MPa H 2 At 130 ℃ for 5 hours, the yield was analyzed by gas chromatography, the conversion of methyl benzoate was 83% and the selectivity of methyl cyclohexanecarboxylate was 83%. Compared with a 5 wt% Ni/HAP catalyst without tartaric acid complex, the catalytic activity of the catalyst is obviously improved.
EXAMPLE 6 preparation of Ni catalyst from monocarboxylic organic acids of different chain lengths
(1) Respectively dissolving 260.8mg of nickel nitrate hexahydrate and organic acids (propionic acid, n-butyric acid and n-caproic acid) with equal molar ratio in 10mL of deionized water, adding 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) after dissolution, stirring and evaporating to dryness under the heating condition of 80 ℃, and drying in an oven at 100 ℃ for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 And reducing the mixture for 30min at 600 ℃ in an/Ar mixed atmosphere to respectively obtain the nickel-based catalyst in which propionic acid, n-butyric acid and n-caproic acid are complexly impregnated.
Example 7 Effect of Ni catalysts prepared from different chain Length Monocarboxy organic acids on hydrogenation Performance
The catalysts prepared in example 6 were used in the catalytic hydrogenation of methyl benzoate, respectively. Mixing 23.5mg of one of the above catalysts, 5mL of n-hexane and 1mmol of methyl benzoate in a high pressure reactor at 1.0MPa H 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results are shown in Table 3.
TABLE 3 results of the experiment
Organic acids Carbon chain length Conversion (%) Yield (%)
Propionic acid 3 44 44
N-butyric acid 4 56 56
Hexanoic acid 6 65 65
As can be seen from Table 3, the yield of methyl cyclohexanecarboxylate shows a tendency to increase with increasing chain length of the monocarboxylic organic acid, with the highest hydrogenation performance of the six carbon n-hexanoic acid complex impregnated 5 wt% Ni/HAP (1.0 HA).
Example 8 preparation of Ni catalyst from Dicarboxyl organic acids of different chain lengths
(1) 260.8mg of nickel nitrate hexahydrate and organic acid (malonic acid, succinic acid, glutaric acid and adipic acid) with equal molar ratio are dissolved in 10mL of deionized water, 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) is added after the nickel nitrate hexahydrate and the organic acid are dissolved, the mixture is stirred and evaporated to dryness under the heating condition of 80 ℃, and the mixture is placed in an oven with the temperature of 100 ℃ for drying for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 Reducing for 30min at 600 ℃ in a mixed atmosphere of/Ar to respectively obtain the nickel-based catalyst which is impregnated by the complex of malonic acid, succinic acid, glutaric acid and adipic acid.
Example 9 influence of Ni catalysts prepared from Dicarboxyl organic acids of different chain lengths on hydrogenation Performance
The catalysts prepared in example 8 were used for the catalytic hydrogenation of methyl benzoate, respectively. Mixing 23.5mg of one of the above catalysts, 5mL of n-hexane and 1mmol of methyl benzoate in a high pressure reactor at 1.0MPa H 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results are shown in Table 4.
TABLE 4 results of the experiment
Organic acids Carbon chain length Conversion (%) Yield (%)
Malonic acid 3 69 69
Succinic acid 4 79 79
Glutaric acid 5 67 67
Adipic acid 6 45 45
As can be seen from Table 4, as the carbon chain length of the dicarboxy organic acid increases, the conversion of methyl benzoate shows a tendency to increase first and then decrease. Among them, succinic acid complex impregnated 5 wt% Ni/HAP (1.0SA) catalyst with a carbon chain length of 4 showed the best catalytic performance. Comparing tables 2 and 3, it can be seen that although n-hexanoic acid has higher activity than n-butanoic acid, succinic acid has higher hydrogenation activity than Ni catalyst prepared from adipic acid when there are two carboxyl groups on the same carbon chain.
Example 10 preparation of Ni catalyst from organic acids containing varying amounts of hydroxyl groups
(1) 260.8mg of nickel nitrate hexahydrate and organic acids (succinic acid, malic acid, tartaric acid, adipic acid, mucic acid and gluconic acid) with equal molar ratio are dissolved in 10mL of deionized water, 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) is added after the dissolution, the mixture is stirred and evaporated to dryness under the heating condition of 80 ℃, and the mixture is placed in an oven with 100 ℃ for drying for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 Reducing for 30min at 600 ℃ in a mixed atmosphere of/Ar to respectively obtain the nickel-based catalyst which is impregnated by succinic acid, malic acid, tartaric acid, adipic acid, muconic acid and gluconic acid in a complex manner.
Example 11 influence of Ni catalysts prepared from organic acids having different numbers of hydroxyl groups on hydrogenation Performance
The catalysts prepared in example 10 were used for the catalytic hydrogenation of methyl benzoate, respectively. Taking 23.5mg of one of the catalysts, 5mL of n-hexane and 1mmol of methyl benzoate in a high-pressure reaction kettleMixing at 1.0MPa H 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results are shown in Table 5.
TABLE 5 results of the experiment
Organic acids Carbon chain length Number of hydroxyl group Conversion (%) Yield (%)
Succinic acid 4 0 79 79
Malic acid 4 1 81 81
Tartaric acid 4 2 83 83
Adipic acid 6 0 45 45
Mucic acid 6 4 56 56
Gluconic acid 6 5 76 76
As can be seen from Table 5, the hydrogenation activity of the catalyst increased with the number of hydroxyl groups on the carbon chain as compared with succinic acid, malic acid and tartaric acid having the same carbon chain length of 4, and when the remaining two carbons of the tetracarboxylate were substituted with hydroxyl groups, the 5 wt% Ni/HAP (1.0TA) obtained with tartaric acid having a hydroxyl group number of 2 had the best catalytic performance. In carboxylic acids with a carbon chain length of 6, the same law can also be observed, i.e. an increase in activity with increasing hydroxyl number, although the catalytic activity is relatively poor.
EXAMPLE 12 preparation of Ni catalyst with different amounts of Carboxylic organic acid
(1) 260.8mg of nickel nitrate hexahydrate and organic acids (propionic acid, L-alanine, succinic acid, DL-aspartic acid, n-hexanoic acid and L-lysine) with equal molar ratio are dissolved in 10mL of deionized water, 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.67: 1) is added after the nickel nitrate hexahydrate and the organic acids are dissolved, the mixture is stirred and evaporated to dryness under the heating condition of 80 ℃, and the mixture is placed in an oven with 100 ℃ for drying for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 Reducing in mixed atmosphere of/Ar at 600 deg.C for 30min to obtain propionic acid, L-alanine, succinic acid, DL-TianmenNickel-based catalyst impregnated by complexing aspartic acid, n-hexanoic acid and L-lysine.
Example 13 influence of Ni catalysts prepared with organic acids containing different amounts of carboxyl groups on hydrogenation Performance
The catalysts prepared in example 12 were used for the catalytic hydrogenation of methyl benzoate, respectively. Mixing 23.5mg of one of the above catalysts, 5mL of n-hexane and 1mmol of methyl benzoate in a high pressure reactor at 1.0MPa H 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results are shown in Table 6.
TABLE 6 results of the experiment
Organic acids Number of carbon chain Number of amino groups Conversion (%) Yield (%)
Propionic acid 3 0 44 44
L-alanine 3 1 63 63
Succinic acid 4 0 79 79
DL-aspartic acid 4 1 70 70
Hexanoic acid 6 0 65 65
L-lysine 6 2 68 68
As can be seen from Table 7, the amino group has a certain promoting effect on propionic acid as a three-carbon carboxylic acid and n-hexanoic acid as a six-carbon carboxylic acid, but the excessive amino substitution cannot improve the hydrogenation activity for succinic acid.
EXAMPLE 14 Effect of different tartaric acid additions on the hydrogenation Performance of the catalyst
(1) Dissolving 67.3mg, 134.5mg, 269.0mg and 672.6mg of tartaric acid and 260.8mg of nickel nitrate hexahydrate (molar ratio is 0.5: 1, 1: 1, 2: 1, 5: 1 respectively) in 10mL of deionized water, adding 1g of hydroxyapatite (molar ratio of calcium to phosphorus is 1.67: 1) after dissolution, stirring and drying by distillation under the heating condition of 80 ℃, and drying in an oven at 100 ℃ for 5 hours;
(2) grinding the solid obtained after drying in the step (1)After sieving, the mixture was placed in 10 vol% H 2 Reducing the mixture in a mixed gas/Ar atmosphere at 600 ℃ for 30min to obtain 5 wt% Ni/HAP (yTA) catalysts which are complexly impregnated by tartaric acid with different molar ratios.
The prepared catalyst is used in the catalytic reaction of preparing the methyl cyclohexanecarboxylate by hydrogenating the methyl benzoate, 23.5mg of the catalyst, 5mL of n-hexane and 1mmol of methyl benzoate are mixed in a high-pressure reaction kettle, and H are respectively carried out under 1.0MPa 2 The reaction was carried out at 130 ℃ for 5 hours, and the yield was analyzed by gas chromatography, and the results are shown in Table 7.
TABLE 7 results of the experiment
Tartaric acid/Ni (molar ratio) Conversion (%) Yield (%)
0.5 64 64
1 83 83
2 19 19
5 15 15
As can be seen from table 8, the hydrogenation activity of the 5 wt% Ni/hap (yta) catalyst increased and then decreased with the addition of tartaric acid when the molar ratio of nickel to tartaric acid was 1: 1, the catalyst has the best catalytic performance.
Example 15
The tartaric acid complex impregnated 5 wt% Ni/HAP (1.0TA) catalyst prepared in example 4 was applied to hydrogenation of different aromatic ring compounds. Wherein the dosage of the aromatic ring compound or heterocyclic compound is 1mmol, the solvent is 5mL n-hexane, and the H is 1.0-2.5 MPa 2 And reacting at 80-130 ℃ in a high-pressure reaction kettle for 7-12 hours, and analyzing the yield by gas chromatography, wherein the obtained results are shown in Table 8.
Table 8 analysis results
Figure BDA0003780142820000111
Figure BDA0003780142820000121
Figure BDA0003780142820000131
Figure BDA0003780142820000141
Example 16
(1) Respectively dissolving 50mg, 260.8mg and 550.5mg of nickel nitrate hexahydrate in 10mL of deionized water, adding 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.5: 1) after dissolution, stirring and evaporating to dryness under the heating condition of 100 ℃, and drying in an oven at 100 ℃ for 5 hours;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 And reducing the mixture at 800 ℃ for 120min in a mixed Ar atmosphere to obtain the Ni/HAP catalyst with the loading amounts of 1 wt%, 5 wt% and 10 wt%.
Example 17
(1) 260.8mg of nickel nitrate hexahydrate and organic acid (propionic acid, L-alanine, succinic acid, DL-aspartic acid, n-hexanoic acid and L-lysine) are dissolved in 10mL of deionized water together, 1g of hydroxyapatite (the molar ratio of calcium to phosphorus is 1.5: 1) is added after the dissolution, the mixture is stirred and evaporated to dryness under the heating condition of 100 ℃, and the mixture is placed in a 100 ℃ oven for drying for 5 hours; the molar ratio of nickel nitrate hexahydrate to organic acid is 1: 5.0;
(2) grinding and sieving the solid obtained after drying in the step (1), and placing the solid in 10 vol% H 2 And reducing the mixture for 120min at 800 ℃ in an Ar mixed atmosphere to respectively obtain the nickel-based catalyst in which propionic acid, L-alanine, succinic acid, DL-aspartic acid, n-hexanoic acid and L-lysine are subjected to complex impregnation.
Example 18
The prepared 5 wt% Ni/HAP (1.0TA) catalyst is used in the catalytic reaction of preparing the methyl cyclohexanecarboxylate by hydrogenating the methyl benzoate, 23.5mg of the catalyst is taken, 5mL of n-hexane and methyl benzoate (the molar ratio of active metal nickel to the methyl benzoate in the nickel-based catalyst is 1: 25) are mixed in a high-pressure reaction kettle, and H are carried out under 0.5MPa 2 After 3 hours at 110 ℃, the yield was analyzed by gas chromatography, the conversion of methyl benzoate was 80%, and the selectivity of methyl cyclohexanecarboxylate was 80%. Compared with 5 wt% Ni/HAP catalyst without tartaric acid complexation, the catalytic activity of the catalyst is obviously improved.
Example 19
The prepared 5 wt% Ni/HAP (1.0TA) catalyst is used in the catalytic reaction of preparing the methyl cyclohexanecarboxylate by hydrogenating the methyl benzoate, 23.5mg of the catalyst is taken, 5mL of n-hexane and methyl benzoate (the molar ratio of active metal nickel to the methyl benzoate in the nickel-based catalyst is 1: 100) are mixed in a high-pressure reaction kettle, and H are carried out under 2.0MPa 2 After 12 hours at 150 ℃, the yield was analyzed by gas chromatography, the conversion of methyl benzoate was 81%, and the selectivity of methyl cyclohexanecarboxylate was 81%. Compared with a 5 wt% Ni/HAP catalyst without tartaric acid complex, the catalytic activity of the catalyst is obviously improved.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Claims (10)

1. A nickel-based catalyst for hydrogenation of aromatic rings, which is characterized in that the chemical general formula of the catalyst is xNi/HAP (yL); wherein the content of the first and second substances,
ni is active metal nickel;
x is the load of Ni, and the value of x is 1.0-10.0 wt%;
HAP is hydroxyapatite, Ca/P is 1.5-1.67: 1;
l is an organic acid ligand, y is the molar ratio of L to Ni, and the numerical value is 0-5.0.
2. The nickel-based catalyst according to claim 1, wherein the active metal nickel has a particle size of 1 to 10nm and an average particle size of 4.2 to 5.8 nm.
3. A method for preparing a nickel-based catalyst for hydrogenation of aromatic rings, comprising the steps of:
(1) dissolving nickel salt and organic acid in deionized water, adding hydroxyapatite, stirring and evaporating to dryness under the heating condition of 80-100 ℃, and drying to obtain a catalyst precursor;
(2) grinding and sieving the catalyst precursor, and placing the catalyst precursor into 10 vol% H 2 And reducing the mixture for 30-120 min at 600-800 ℃ in an/Ar mixed atmosphere to obtain the nickel-based catalyst with the nickel loading of 1-10 wt%.
4. The method according to claim 3, wherein in the step (1), the nickel salt is nickel nitrate hexahydrate; the organic acid is any one of malonic acid, succinic acid, glutaric acid, adipic acid, DL-malic acid, tartaric acid, citric acid, mucic acid, gluconic acid, propionic acid, n-butyric acid, n-valeric acid, n-caproic acid, DL-aspartic acid, L-alanine, L-lysine and ethylenediamine tetraacetic acid.
5. The method according to claim 3, wherein in the step (1), the molar ratio of the nickel salt to the organic acid is 1: 0 to 5.0;
in the step (1), the mass-to-volume ratio of the nickel salt, the deionized water and the hydroxyapatite is 50-550.5 mg: 10mL of: 1.0 g.
6. The preparation method according to claim 3, wherein in the step (1), the molar ratio of calcium to phosphorus in the hydroxyapatite is 1.5-1.67: 1.
7. use of the nickel-based catalyst of claim 1 or claim 2 in catalyzing the hydrogenation of aromatic ring compounds to produce cyclohexanes or heterocycles.
8. The use according to claim 8, wherein the aromatic ring compound is selected from any one of toluene, o-methylbenzene, m-methylbenzene, p-methylbenzene, phenol, anisole, phenethylamine, pyridine, quinoline, pyrrole, indole, methyl 3-furyl formate, naphthalene, N-dimethylaniline, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoate, methyl phenylacetate, methyl phenylpropionate, methyl o-methylbenzoate, methyl m-methylbenzoate, methyl p-methylbenzoate, ethyl p-methoxybenzoate, dimethyl phthalate, dimethyl terephthalate, methyl 2-naphthoate, dioctyl phthalate, and dioctyl terephthalate.
9. The use according to claim 7, wherein the catalytic aromatic ring compound hydrogenation specific process is: mixing a nickel-based catalyst, a solvent and an aromatic ring compound, and reacting for 3-12 hours at the temperature of 110-150 ℃ and under the hydrogen pressure of 0.5-2.0 Mpa; wherein the solvent is any one of n-hexane, cyclohexane, n-heptane, ethanol, water and acetonitrile.
10. The use according to claim 9, wherein the molar ratio of the active metal nickel in the nickel-based catalyst to the aromatic ring compound is 1: 25 to 100.
CN202210927395.4A 2022-08-03 2022-08-03 Nickel-based catalyst for hydrogenation of aromatic ring and preparation method and application thereof Pending CN115121269A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103357410A (en) * 2013-08-05 2013-10-23 上海中科高等研究院 Nanometer nickel-based polyhedron catalyst used for aromatic ring hydrogenation, preparation method thereof and application thereof
CN106967018A (en) * 2017-04-21 2017-07-21 中国科学技术大学 Application and a kind of preparation method of tetrahydrofurfuryl alcohol of a kind of phosphorus ash stone material in catalytic hydrogenation
US20190374934A1 (en) * 2016-12-22 2019-12-12 IFP Energies Nouvelles Method for the hydrogenation of aromatics using a nickel-based catalyst
CN112742422A (en) * 2021-01-20 2021-05-04 烟台大学 Supported catalyst and application thereof in selective hydrogenation of quinoline compounds
CN114588940A (en) * 2022-01-28 2022-06-07 南京工业大学 Nickel-based catalyst for hydrogenation of phenolic compounds and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103357410A (en) * 2013-08-05 2013-10-23 上海中科高等研究院 Nanometer nickel-based polyhedron catalyst used for aromatic ring hydrogenation, preparation method thereof and application thereof
US20190374934A1 (en) * 2016-12-22 2019-12-12 IFP Energies Nouvelles Method for the hydrogenation of aromatics using a nickel-based catalyst
CN106967018A (en) * 2017-04-21 2017-07-21 中国科学技术大学 Application and a kind of preparation method of tetrahydrofurfuryl alcohol of a kind of phosphorus ash stone material in catalytic hydrogenation
CN112742422A (en) * 2021-01-20 2021-05-04 烟台大学 Supported catalyst and application thereof in selective hydrogenation of quinoline compounds
CN114588940A (en) * 2022-01-28 2022-06-07 南京工业大学 Nickel-based catalyst for hydrogenation of phenolic compounds and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王迎军: "《生物医用陶瓷材料》", 广州：华南理工大学出版社, pages: 27 - 28 *

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