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CN111135822B - Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound - Google Patents

Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound Download PDF

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CN111135822B
CN111135822B CN201811313905.9A CN201811313905A CN111135822B CN 111135822 B CN111135822 B CN 111135822B CN 201811313905 A CN201811313905 A CN 201811313905A CN 111135822 B CN111135822 B CN 111135822B
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CN111135822A (en
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王爱琴
任煜京
张磊磊
张涛
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Dalian Institute of Chemical Physics of CAS
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    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract

本发明公开了一种负载型高分散贵金属催化剂在芳香硝基化合物选择反应中的应用，该催化剂以VIII族或IB族贵金属中的一种或两种以上为活性组分，以高比表面积的氧化物为载体，采用吸附‑快速热处理的方法得到催化剂，催化剂的活性组分含量为0.05％‑20％。该催化剂对芳香硝基化合物的选择加氢反应表现出优异的活性、选择性和稳定性。相比于传统的芳香硝基化合物选择性加氢的工业合成路线，该发明所提供的反应过程具有绿色友好、操作简单等优点。

Figure 201811313905

The invention discloses the application of a supported high-dispersion noble metal catalyst in the selective reaction of aromatic nitro compounds. The oxide is used as a carrier, and the catalyst is obtained by the method of adsorption-rapid heat treatment, and the active component content of the catalyst is 0.05%-20%. The catalyst exhibits excellent activity, selectivity and stability for the selective hydrogenation of aromatic nitro compounds. Compared with the traditional industrial synthesis route of selective hydrogenation of aromatic nitro compounds, the reaction process provided by the invention has the advantages of green friendliness, simple operation and the like.

Figure 201811313905

Description

Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound
Technical Field
The invention relates to an application of a supported high-dispersion noble metal catalyst in selective hydrogenation reaction of aromatic nitro compounds
Background
The selective hydrogenation of aromatic nitro compounds to obtain corresponding functionalized aniline compounds has important applications in many aspects, such as in the industries of dyes, pigments, medicines, pesticides, and the like. Currently, there are industrially mature techniques for the hydrogenation of simple aromatic nitro compounds, but selective reduction of nitro groups when the substituent is a reducible group remains a challenging issue. Industrially, for the selective hydrogenation of aromatic nitro compounds containing reducible groups, it is customary to employ metered amounts of reducing agents, for example Na2S2O4In order to overcome the disadvantage that the reducing agent is a hydrogen gas and PbO or H is used as the reducing agent, researchers have used a hydrogen gas as the reducing agent3PO2Added to the supported Pt catalyst, although the activity is reduced, the selectivity to the target product is improved, but such a catalyst produces phenylhydroxylamine intermediate product, which may be at a very low level at risk of explosion. Researchers find that the intermediate product can be converted into a target product by respectively adding iron salt or alum salt into the catalytic system, but a large amount of transition metal salt remains in the solution after the reaction, and the subsequent treatment process is complex and is not economical and environment-friendly. Therefore, a heterogeneous catalyst with high activity and high selectivity is urgently needed for the reaction.
Many patents and literature describe supported catalysts for the selective hydrogenation of aromatic nitro compounds, which vary in activity depending on the support and the method of preparation.
Documents 1(Science,2006,313:332) and 2(Journal of the American Chemical Society,2007,129:16230) were adopted with a deposition-precipitation methodPreparing Au/TiO by a precipitation method2The catalyst is applied to nitrobenzene hydrogenation reaction, and the gold catalyst has excellent aniline selectivity and catalytic activity for nitrobenzene compounds. At the same time, the authors have found that the reason for the high selectivity is that the nitro group of the aromatic nitro compound is preferentially adsorbed on Au and TiO2The interface of the support, and thus the nitro group, is preferentially reduced, exhibiting high selectivity.
Document 3(Advanced Synthesis)&Catalysis,2011,353:1260) prepared a porous ionic copolymer supported Pt catalyst by a one-pot method, the supported amount of Pt was 4.9 wt%, and the size of the obtained Pt nanoparticles was 2-4 nm. Under mild conditions for many substituents (R ═ F, Cl, Br, I, CHO, CN, NH)2、CH3CO, OH, etc.) exhibit high activity and selectivity.
Document 4(ACS Catalysis,2013,3:608) prepares an Rh3Ni1 catalyst by a chemical reduction method, and applies the catalyst to a selective hydrogenation reaction of an aromatic nitro compound, and the result shows that the selective reduction activity of the catalyst is good, and the corresponding amine yield of a plurality of substrates can reach 99%.
Document 5(WO 2009071727) prepared a Pt/TiO2 catalyst by impregnation at 3bar P at 40 ℃H2Under the reaction conditions of (1), when the supported amount is 0.2% in the selective hydrogenation reaction of 3-nitrostyrene, the reaction is carried out for 7 hours to obtain 92% yield and the selectivity is 93.1%.
Reference 6(Journal of Physical Chemistry C,2009,113:17803) prepared Au/Al by colloidal deposition2O3The Au nano-particle size in the catalyst is 2.5 nm. In the hydrogenation reaction of 3-nitrostyrene, the reaction conditions are 120 ℃ and 3MPa H2The pressure and the reaction time are 1h, the conversion rate is 100 percent, and the selectivity of the 3-aminostyrene reaches 99 percent. The authors concluded that the reason for the high activity of the catalyst was the small size of the Au nanoparticles and the supported Al containing acid-base sites2O3And the synergistic effect between the two is that the catalyst shows high activity and selectivity.
Disclosure of Invention
The catalyst shows high activity and selectivity in hydrogenation of aromatic nitro compounds, has mild reaction conditions, can be recycled, has good stability and low cost, and has industrial application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
the application of a supported high-dispersion noble metal catalyst in selective reaction of aromatic nitro compounds is characterized in that the active component of the supported high-dispersion noble metal catalyst is common noble metal, a carrier is common oxide, and the mass content of the active component in the catalyst is 0.05-20%.
The preparation process of the supported high-dispersion noble metal catalyst comprises the following steps:
1) dissolving a certain amount of soluble precursor of the noble metal in a certain amount of deionized water, and adding a proper amount of common inorganic and organic reagents to obtain a noble metal precursor complex solution, wherein in order to ensure the formation of the soluble precursor complex solution of the noble metal, the ratio of the common inorganic and organic reagents to the noble metal is 10:1-1000: 1. (ii) a
The concentration of the noble metal in the noble metal precursor solution is 0.1-100 mg/ml;
the noble metal is one or a mixture of more than two of ruthenium, rhodium, palladium, silver, iridium, platinum and gold in any ratio, and the soluble precursor of the noble metal is one or more than two of chloride, nitrate and organic complex of the noble metal; the common inorganic agents are: one or a mixture of more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, wherein the common organic reagent is one or a mixture of more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents in any ratio.
2) The soluble precursor complex solution of the noble metal and the carrier are mixed evenly according to the required proportion, stirred for 10 to 600 minutes, filtered and dried for 8 to 12 hours at the temperature of 60 to 120 ℃ to obtain the noble metal catalyst precursor.
The carrier is one or a mixture of more than two of alumina, silicon oxide, ferric oxide, cerium oxide and titanium oxide in any ratio,
3) the catalyst is subjected to heat treatment before reaction, and is placed in He, Ar and N2、H2、O2And treating at 200-800 deg.c for 10-600 sec in air atmosphere.
The reaction is carried out in a closed high-pressure reaction kettle, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute.
The reaction is carried out in a solvent, the adopted solvent is one or more than two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, pyridine, tetrahydrofuran, dodecane and water, and the concentration of the aromatic nitro compound serving as a reaction substrate in a reaction solution is 0.0001-5 mol/L;
the reaction substrate is aromatic nitro compound
Figure BDA0001855750580000031
The substituent R is one of hydrogen, halogen, vinyl, ethynyl, nitrile group, aldehyde group, phenolic hydroxyl, carbonyl, methyl, isopropyl, methoxyl and other aromatic nitro compound derivatives, and the number of the substituent R is 1-5.
The molar ratio of the active component of the catalyst to the reaction substrate is 1 x 10-4To 1.
The preferred reaction temperature is 20-80 deg.C, the preferred initial pressure of hydrogen in the reaction vessel at room temperature is 0.1-2.5Mp, and the preferred reaction time is 0.5-6 h.
The catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
The activity test method of the catalyst provided by the invention comprises the following steps:
the reactor is a high-pressure reaction kettle, reaction substrates, internal standards and solvents are prepared into reaction liquid with certain concentration, a certain amount of reaction liquid is taken by a pipette for reaction each time, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute. After the reaction was completed, the reaction mixture was cooled to room temperature, and then a sample was taken for gas chromatography.
The invention has the following effects:
1. the selective hydrogenation of aromatic nitro compounds to obtain corresponding functionalized anilines has applications in many fields, such as agriculture, medicine, dyes and high molecular polymers. The invention provides a supported high-dispersion noble metal catalyst which can catalyze to obtain functionalized aniline with high selectivity.
2. The invention provides a supported high-dispersion noble metal catalyst which can be recycled for a plurality of times in the selective hydrogenation reaction of aromatic nitro compounds, and the activity is not obviously reduced.
3. The invention provides a supported high-dispersion noble metal catalyst which is easy to separate from a reaction solution after reaction and is simple and convenient to operate.
In a word, the invention realizes the preparation of the functionalized aniline by the high-efficiency and high-selectivity conversion of the aromatic nitro compound, and compared with the existing industrial catalyst system, the catalyst provided by the invention is green and friendly in the reaction process, saves the cost, and is expected to be applied industrially.
Drawings
FIG. 1 is an electron microscope picture of a supported high-dispersion noble metal Pt-FeOx catalyst prepared by the method of the invention.
FIG. 2 is a diagram of a supported high-dispersion noble metal Pt-CeO2HAADF-STEM pictures of the catalyst.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, but the invention is not limited thereto.
Example 1: 0.054g of chloroplatinic acid is dissolved in 20g of deionized water, 0.5g of 25% ammonia water is added, the mixture is stirred for 3 hours, 1g of ferric oxide is added, the mixture is stirred for 5 hours, filtered and washed, the obtained product is placed in a drying oven at 60 ℃ and dried for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated at 600 ℃ for 10 seconds under the He condition to obtain a 2% Pt/FeOx catalyst which is placed in a dryer for standby. (the catalyst is shown in the picture of an electron microscope in FIG. 1) as shown in FIG. 1: the noble metal in the catalyst of the invention exists in a form of high dispersion even atomic level dispersion, and the dispersion degree of the noble metal is 100 percent.
Example 2: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of cerium dioxide is added, the mixture is stirred for 2 hours, filtered and washed, the mixture is placed in a baking oven at 120 ℃, dried for 12 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated for 120 seconds at 500 ℃ under Ar condition to obtain 1% Pt/CeO2And (5) putting the catalyst in a dryer for later use. (the catalyst is shown in the electron microscope of FIG. 2) as shown in FIG. 1: the noble metal in the catalyst of the invention exists in a form of high dispersion even atomic level dispersion, and the dispersion degree of the noble metal is 100 percent.
Example 3: dissolving 0.054g of chloroplatinic acid in 20g of deionized water, adding 1.5g of ammonium nitrate, stirring for 2h, adding 1g of aluminum oxide, stirring for 1h, filtering, washing, placing in a drying oven at 100 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and adding N2After 240 seconds of treatment at 300 ℃ under the condition, 2 percent Pt/Al is obtained2O3And (5) putting the catalyst in a dryer for later use.
Example 4: dissolving 0.017g of palladium chloride in 20g of deionized water, adding 0.2g of ethanolamine organic reagent, stirring for 3H, adding 1g of ferric oxide, stirring for 4H, filtering, washing, placing in a 90 ℃ oven, drying for 10H to obtain a supported high-dispersion palladium-based catalyst precursor, placing the precursor in a quartz tube, and H2Treating at 350 deg.c for 20 sec to obtain 1% Pd/FeOx catalyst in the drier for further use.
Example 5: 0.021g of chloroauric acid is dissolved in 20g of deionized water, 0.8g of triethyl phosphate organic reagent is added, the mixture is stirred for 1 hour, 1g of cerium oxide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 70 ℃ and dried for 7 hours to obtain a supported high-dispersion gold-based catalyst precursor, the precursor is placed in a quartz tube, the precursor is treated at 550 ℃ for 300 seconds under the air condition to obtain a 1% Au/CeO2 catalyst, and the obtained product is placed in a dryer for later use.
Example 6: dissolving 0.027g of chloroplatinic acid in 10g of deionized water, adding 2g of cysteine organic reagent, stirring for 2h, adding 1g of titanium oxide, stirring for 2, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and treating at 400 ℃ under the He condition for 120 seconds to obtain 1% Pt/TiO2And (5) putting the catalyst in a dryer for later use.
Example 7 (comparative): dissolving 0.027g chloroplatinic acid in 1.5g deionized water, adding 1g alumina, stirring for 0.5H, placing in an oven at 80 deg.C, drying for 8H, placing in a quartz tube, and placing in a quartz tube2After 600 seconds of treatment at 300 ℃ under the condition, 1 percent Pt/Al is obtained2O3And (5) putting the catalyst in a dryer for later use.
Example 8 (comparative): dissolving 0.027g chloroplatinic acid in 1.5g deionized water, adding 1g silicon oxide, stirring for 0.5H, placing in an oven at 80 deg.C, drying for 8H, placing in a quartz tube, and placing in a quartz tube2After 600 seconds of treatment at 300 ℃ under the condition, 1 percent Pt/SiO is obtained2And (5) putting the catalyst in a dryer for later use.
Application example 1:
taking a certain amount of catalyst in a reaction tube, adding 5ml of 0.1M 3-nitrostyrene reaction solution (toluene as a solvent and o-xylene as an internal standard) by a pipette, and reacting under the condition of 3bar H2(initial pressure), 40 ℃.
The specific experimental results are as follows:
results of selective hydrogenation of 3-nitrostyrene over highly dispersed noble metal catalysts loaded with iron monoxide
Figure BDA0001855750580000051
TABLE 2% Pt/CeO2Circulation experiment result of catalyst in selective hydrogenation reaction of 3-nitrostyrene
Figure BDA0001855750580000052
TABLE III results of selective hydrogenation of 1% Pt/FeOx in different reaction substrates
Figure BDA0001855750580000053
Figure BDA0001855750580000061
TABLE four results of selective hydrogenation of 3-nitrostyrene by supported highly dispersed platinum based catalysts prepared by different preparation methods
Figure BDA0001855750580000062
The catalyst shows excellent activity, selectivity and stability for the selective hydrogenation reaction of the aromatic nitro compound. Compared with the traditional industrial synthesis route of selective hydrogenation of aromatic nitro compounds, the reaction process provided by the invention has the advantages of environmental friendliness, simplicity in operation and the like.

Claims (8)

1. The application of the high-dispersion noble metal supported catalyst in the hydrogenation of aromatic nitro compounds is characterized in that: the catalyst is prepared by taking an oxide as a carrier and one or more than two of VIII group or IB group noble metals as active components through adsorption-rapid heat treatment, and is used in the selective hydrogenation reaction of aromatic nitro compounds;
the preparation process of the high dispersion noble metal supported catalyst is as follows,
1) dissolving a soluble precursor of noble metal in deionized water and/or an organic solvent to obtain a noble metal precursor solution, and adding an inorganic and/or organic reagent to obtain a noble metal precursor complex solution;
the concentration of the noble metal in the noble metal precursor solution is 0.1-100 mg/ml;
the volume of the deionized water and/or the organic solvent is 5ml-50 ml;
the mass of the inorganic reagent and/or the organic reagent is 0.0005g-10 g;
the noble metal soluble precursor is one or more than two of noble metal chloride, nitrate, acetylacetone complex and triphenylphosphine complex, and the inorganic reagent is: one or more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents are mixed according to any ratio, the organic reagent is one or more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents are mixed according to any ratio, and in order to ensure the formation of a soluble precursor complex solution of the noble metal, the ratio of the amounts of the inorganic and/or organic reagents and the noble metal is 10:1-1000: 1;
2) uniformly mixing the soluble precursor complex solution of the noble metal and the carrier according to the required proportion, stirring for 10-600 minutes, filtering, and drying at 60-120 ℃ for 8-12 hours to obtain a noble metal catalyst precursor;
3) the catalyst is subjected to heat treatment before reaction, and is placed in He, Ar and N2、H2、O2And reducing at 200-800 deg.c in one or several kinds of air for 10-600 sec.
2. Use according to claim 1, characterized in that: the active component is one or a mixture of more than two of ruthenium, rhodium, palladium, silver, iridium, platinum and gold in any ratio, and the mass content of the active component in the catalyst is 0.05-20%.
3. Use according to claim 1, characterized in that: the carrier oxide is one or a mixture of more than two of aluminum oxide, silicon oxide, ferric oxide, cerium oxide and titanium oxide in any ratio.
4. Use according to claim 1, characterized in that:
the reaction is carried out in a closed high-pressure reaction kettle, the initial pressure of hydrogen in the reaction kettle at room temperature is 0.1-5Mpa, the reaction temperature is 25-120 ℃, and the reaction time is not less than 1 minute.
5. Use according to claim 1 or 4, characterized in that:
the reaction is carried out in a solvent, the adopted solvent is one or more than two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, pyridine, tetrahydrofuran, dodecane and water, and the concentration of the aromatic nitro compound serving as a reaction substrate in a reaction solution is 0.0001-5 mol/L;
the reaction substrate is aromatic nitro compound
Figure 156491DEST_PATH_IMAGE002
The substituent R is one, two, three, four or five of hydrogen, halogen, vinyl, ethynyl, nitrile group, aldehyde group, phenolic hydroxyl, carbonyl, methyl, isopropyl, methoxyl and other aromatic nitro compound derivatives, and the number of the substituent R is 1-5.
6. Use according to claim 1 or 4, characterized in that: the molar ratio of the active component of the catalyst to the reaction substrate is 1 x 10-4To 1.
7. Use according to claim 4, characterized in that: the reaction temperature is 20-80 ℃, the initial pressure of hydrogen in the reaction kettle is 0.1-2.5 Mpa at room temperature, and the reaction time is 0.5-6 h.
8. Use according to claim 1 or 4, characterized in that: the catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
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