CN112010765A - Method for preparing p-aminophenol by transfer hydrogenation of nitrobenzene - Google Patents
Method for preparing p-aminophenol by transfer hydrogenation of nitrobenzene Download PDFInfo
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Abstract
The invention relates to a method for preparing p-aminophenol by nitrobenzene transfer hydrogenation. The method comprises the following steps: adding a hydrogen source, nitrobenzene and a catalyst into a reactor, and reacting for 2-12 hours at 60-180 ℃ under magnetic stirring to obtain a product p-aminophenol; wherein, the catalyst is a supported metal catalyst and a solid acid catalyst; the hydrogen source is aqueous formic acid solution or isopropanol. The invention avoids using high pressure H2The raw material greatly reduces the danger of the process for preparing the p-aminophenol by hydrogenating the nitrobenzene. The catalyst used has good catalytic performance, the conversion rate of nitrobenzene is up to 80.0 percent, and the yield of p-aminophenol is up to 51.3 percent.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing p-aminophenol by nitrobenzene transfer hydrogenation.
Background
Para-aminophenol is an important chemical raw material and a medical intermediate, and is widely applied to the fields of medicines, dyes, rubber, pesticides, photosensitive materials and the like.
The synthesis process of p-aminophenol mainly includes p-nitrophenol method, p-nitrochlorobenzene method, phenol method, nitrobenzene method, etc. Wherein, the preparation process taking phenol and p-nitrochlorobenzene as raw materials has long flow and low total yield. The nitrobenzene electrolytic reduction method is a relatively environment-friendly process route, but the investment of process equipment is large, and a large amount of electric power is consumed. The iron powder reduction method using p-nitrophenol as a raw material is the earliest process route for producing p-aminophenol, and the process does not need hydrogen and has high safety; however, the method has high cost and serious pollution and is rarely used at present. The catalytic hydrogenation process for synthesizing p-aminophenol by using nitrobenzene (or p-nitrophenol) as raw material has the advantages of short process, less pollution, low energy consumption and the like, and the nitrobenzene has lower price, so that the process has more industrial production value (petrochemical, 2018, 47 (1): 79-85)
However, the hydrogenation of nitrobenzene to p-aminophenol requires hydrogenation in H2In the presence of oxygen. Due to H2And the process is flammable and explosive, and has potential safety hazards in storage, use and recycling, so that the process is potentially dangerous. Catalytic Transfer Hydrogenation (CTH) is an important Hydrogenation reduction method in organic synthesis. Not directly using H in the CTH reaction2But adopts a hydrogen donor as a hydrogen source, so that the method has the advantage of high safety; meanwhile, the CTH reaction is mostly carried out under normal pressure, the reaction temperature is low, the requirement on equipment is not high, and the danger of the reaction is reduced from the viewpoint (Chem Rev,2015, 115: 6621-. Formic acid and isopropanol are important hydrogen donors, are liquid at room temperature, are convenient to store and transport as hydrogen sources and are high in pressure H2It has great advantages in safety and may be used widely in catalytic transfer hydrogenation reaction. If formic acid or isopropanol is used as hydrogen source to catalyze nitrobenzene to transfer and hydrogenate to prepare p-aminophenol, H can be avoided2Greatly reduces the danger of reaction, and has important science at present when people increasingly attach importance to the safety of chemical productionMeaning and application value.
Disclosure of Invention
The invention aims to provide a method for preparing p-aminophenol by nitrobenzene transfer hydrogenation, aiming at the defects in the prior art. The method uses formic acid or isopropanol as hydrogen source to replace H2As raw material, the use of high pressure H is avoided2The raw material greatly reduces the danger of the process for preparing the p-aminophenol by hydrogenating the nitrobenzene.
The technical scheme of the invention is as follows:
a method for preparing p-aminophenol by nitrobenzene transfer hydrogenation comprises the following steps:
adding a hydrogen source, nitrobenzene and a catalyst into a reactor, and reacting for 2-12 hours at 60-180 ℃ under magnetic stirring to obtain a product p-aminophenol;
the catalyst is a supported metal catalyst and a solid acid catalyst, and the molar ratio of the materials is that the hydrogen source is nitrobenzene 1: 0.1-1; wherein the dosage of the metal catalyst is 0.01-0.5 g/ml nitrobenzene; the dosage of the solid acid catalyst is 0.1-5 g/ml nitrobenzene;
the hydrogen source is formic acid aqueous solution or isopropanol; when the hydrogen source is formic acid, an auxiliary agent Cetyl Trimethyl Ammonium Bromide (CTAB) is added, and the dosage of the CTAB is 10-20 mg/ml nitrobenzene;
the supported metal catalyst comprises active metal and carrier, the active metal is one or more of Pd and Pt, and the carrier is gamma-Al2O3、TiO2、CeO2、MgO、SiO2、ZrO2Molecular sieves or activated carbon; the loading amount of the active component is 0.1-10%.
The solid acid catalyst is SO4 2-/ZrO2、SO4 2-/ZrO2-Al2O3、SO4 2-/TiO2、SO4 2-/Fe2O3Acid molecular sieve (HZSM-5, HY, Hbeta) or carbon-based solid acid.
The concentration range of the formic acid aqueous solution is 0.05-2 g/ml.
The preferred molar ratio of the hydrogen source to the nitrobenzene is 1: 0.1-0.5; the preferable dosage of the supported metal catalyst is 0.05-0.2 g/ml nitrobenzene; the preferable dosage of the solid acid catalyst is 0.5-1 g/ml nitrobenzene; the preferable dosage of the active metal load is 0.1-10%.
The preferable reaction temperature is 120-180 ℃.
The preferable reaction time is 4-8 h.
The invention has the substantive characteristics that:
the traditional hydrogenation method is to take nitrobenzene as raw material and react with raw material H in an acid medium2Carrying out reaction; the invention adopts a 'transfer hydrogenation' method to replace H by using formic acid or isopropanol as a hydrogen source2As raw materials, the method realizes the catalytic transfer hydrogenation of nitrobenzene to generate p-aminophenol.
The invention has the beneficial effects that:
(1) the invention uses formic acid or isopropanol as hydrogen source, and utilizes H generated by in-situ decomposition of the formic acid or isopropanol2The nitrobenzene hydrogenation is carried out to prepare the p-aminophenol, thereby avoiding the use of high pressure H2(more than 2 MPa) is used as a raw material, so that the safety of the p-aminophenol synthesis process is greatly improved.
(2) The invention realizes the method for preparing the p-aminophenol by the transfer hydrogenation of the nitrobenzene for the first time, the used catalyst has good catalytic performance, the conversion rate of the nitrobenzene is up to 80.0 percent, and the yield of the p-aminophenol is up to 51.3 percent.
Detailed Description
The following non-limiting examples will provide those of ordinary skill in the art with a more complete understanding of the present invention, but are not intended to limit the invention in any way and that insubstantial modifications and adaptations of the invention may be made by those of ordinary skill in the art in view of the present disclosure. The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The solid acid catalyst is a known material, in particular SO4 2-/ZrO2、SO4 2-/ZrO2-Al2O3、SO4 2-/TiO2、SO4 2-/Fe2O3Acid molecular sieve (HZSM-5, HY, Hbeta) or carbon-based solid acid.
In the supported metal catalyst, the active metal is one or more of Pd and Pt, and the carrier is gamma-Al2O3、TiO2、CeO2、MgO、SiO2、ZrO2Molecular sieves or activated carbon; the loading capacity of the active component is 0.1-10%, and the preparation is an excessive impregnation method.
The following examples employ supported metal catalysts prepared as follows, but are not limited thereto:
firstly, preparing a supported metal catalyst by an excess impregnation method: accurately weigh 0.1g of the carrier into a beaker and disperse in 5ml of deionized water. Accurately weighing 0.015g of PdCl2And 0.01g of KCl in a beaker, and ultrasonically treating for 15min to completely dissolve the mixture to prepare a precursor solution. And dropwise adding the precursor solution into the carrier solution, and stirring vigorously for 12 h.
Step two, catalyst reduction: adding NaBH4The solution is reduced for 1h, and the theoretical loading of the finally obtained catalyst, namely the metal Pd, is 6 wt%.
Example 1
0.8mL of nitrobenzene (7.8mmol), 30mL of formic acid solution with the concentration of 0.52mol/l (15.6mmol) and solid acid SO4 2-/ZrO2(0.5g), cetyltrimethylammonium bromide (CTAB, 0.01g) and reduced 6 wt% Pd/AC catalyst (0.1g) were added to the reactor, which was sealed and N was added2The air in the reaction kettle is evacuated, and the reaction is stopped after the reaction is carried out for 6 hours under the magnetic stirring at the temperature of 150 ℃. The reaction was cooled to room temperature, the reaction mixture was filtered under reduced pressure, and the filtrate was analyzed by liquid chromatography. The analysis showed that the conversion of nitrobenzene was 78.0% and the yield of p-aminophenol was 20%.
Example 2
The other steps were the same as example 1 except that 1.2ml of isopropyl alcohol (15.7mmol) as a hydrogen source was added and CTAB was 0g, and the reaction resulted in a conversion of nitrobenzene of 65.3% and a yield of p-aminophenol of 16.1%.
Example 3
The other steps were the same as example 1 except that Pt/AC was used as the catalyst, and the conversion of nitrobenzene was 65.3% and the yield of p-aminophenol was 19.1%.
Example 4
The other steps were the same as example 1 except that the reaction temperature was 120 deg.c, and the reaction resulted in a nitrobenzene conversion of 60.1% and a p-aminophenol yield of 11.4%.
Example 5
The other steps were the same as example 1 except that the reaction temperature was 180 deg.c, and the conversion of nitrobenzene was 80.0% and the yield of p-aminophenol was 11.7%.
Example 6
The other steps were the same as example 1 except that the reaction time was 4 hours, and the reaction results in a nitrobenzene conversion of 69.2% and a p-aminophenol yield of 12.5%.
Example 7
The other steps were the same as example 1 except that the reaction time was 8 hours, and the reaction results in a nitrobenzene conversion of 85.1% and a p-aminophenol yield of 15.3%.
Example 8
The other steps were the same as example 1 except that 0.4g of solid acid was added, and the reaction resulted in a nitrobenzene conversion of 79.3% and a p-aminophenol yield of 15.1%.
Example 9
The other steps were the same as example 1 except that 1.2g of solid acid was added, and the reaction resulted in a nitrobenzene conversion of 75.5% and a p-aminophenol yield of 25.7%.
Example 10
The other steps were the same as example 1 except that 0.05g of 6 wt% Pd/AC was added, and the reaction results in 80.0% conversion of nitrobenzene and 51.3% yield of p-aminophenol.
Example 11
The other steps were the same as example 1 except that 0.2g of 6 wt% Pd/AC was added, and the reaction results in a nitrobenzene conversion of 85.0% and a p-aminophenol yield of 31.3%.
Example 12
The other steps were the same as example 1 except that the Pd loading of the added Pd/AC was 0.1 wt%, and the reaction resulted in a nitrobenzene conversion of 30.5% and a p-aminophenol yield of 5.0%.
Example 13
The other procedure was the same as in example 1 except that the Pd loading of the added Pd/AC was 10 wt%, and the reaction resulted in a nitrobenzene conversion of 83.2% and a p-aminophenol yield of 21.2%.
Example 14
The other steps are the same as example 1, except that the carrier of the catalyst is TiO2As a result, the conversion of nitrobenzene was 31% and the yield of p-aminophenol was 11%.
Example 15
The other steps are the same as example 1, except that the carrier of the catalyst is CeO2As a result, the conversion of nitrobenzene was 40.7% and the yield of p-aminophenol was 5%.
Example 16
The other procedure was the same as in example 1 except that ZrO was used as the carrier of the catalyst2As a result, the conversion of nitrobenzene was 64% and the yield of p-aminophenol was 18.3%.
Example 17
The other steps are the same as example 1, except that the carrier of the catalyst is SiO2As a result of the reaction, the conversion of nitrobenzene was 45.5% and the yield of p-aminophenol was 10%.
Example 18
The other steps are the same as example 1 except that the catalyst carrier is MgO, and the reaction results in a nitrobenzene conversion of 46.1% and a p-aminophenol yield of 9.3%.
Example 19
The other steps are the same as example 1, except that the carrier of the catalyst is gamma-Al2O3As a result, the conversion of nitrobenzene was 43.1% and the yield of p-aminophenol was 7.3%.
Example 20
The other steps are the same as example 1, except that the carrier of the catalyst is molecular sieve, and the reaction results in a nitrobenzene conversion rate of 40.1% and a p-aminophenol yield of 10.1%.
Example 21
The other procedure was the same as in example 1 except that SO was used as the solid acid4 2-/TiO2As a result, the conversion of nitrobenzene was 68.5% and the yield of p-aminophenol was 15.1%.
Example 22
The other procedure was the same as in example 1 except that SO was used as the solid acid4 2-/ZrO2-Al2O3As a result, the conversion of nitrobenzene was 69.6% and the yield of p-aminophenol was 20.1%.
Example 23
The other procedure was the same as in example 1 except that SO was used as the solid acid4 2-/Fe2O3As a result of the reaction, the conversion of nitrobenzene was 65.3% and the yield of p-aminophenol was 10.1%.
Example 24
The other steps were the same as example 1 except that HZSM-5 was used as the solid acid, and the reaction resulted in a nitrobenzene conversion of 63.2% and a p-aminophenol yield of 9.3%.
Example 25
The other steps were the same as example 1 except that the solid acid added was a carbon-based solid acid, and the reaction resulted in a nitrobenzene conversion of 69.3% and a p-aminophenol yield of 28.1%.
Example 26
The other steps are the same as example 1 except that the hydrogen source, nitrobenzene in a ratio of 2:1 (the amount of nitrobenzene used is kept constant) is added, and the reaction results in a nitrobenzene conversion of 85.0% and a p-aminophenol yield of 25.1%.
Example 27
The other steps are the same as example 1 except that 3:1 of nitrobenzene is added as the hydrogen source (the amount of nitrobenzene is kept constant), and the reaction results in 90.3% conversion of nitrobenzene and 22.5% yield of p-aminophenol.
Example 28
The other steps were the same as example 1 except that the catalyst was reused 3 times, and the reaction resulted in a nitrobenzene conversion of 57.5% and a p-aminophenol yield of 15.5%.
As is clear from the above examples, the reaction performance for preparing p-aminophenol by transfer hydrogenation of nitrobenzene was good, and the reaction was carried out using 7.8mmol of nitrobenzene, 30ml (15.6mmol) of formic acid having a concentration of 0.52mol/l, 6 wt% Pd/AC0.05g, and 0.5g of solid acid SO4 2-/ZrO2And the reaction conversion rate and yield under the experimental conditions of 0.01g CTAB are higher. The supported metal catalyst has higher catalytic activity after reduction, and still has higher catalytic activity after recovery and recycling, the conversion rate of the recoverable nitrobenzene of the metal catalyst is 57.5 percent, and the yield of the p-aminophenol is 15.5 percent.
The invention is not the best known technology.
Claims (7)
1. A method for preparing p-aminophenol by nitrobenzene transfer hydrogenation is characterized by comprising the following steps:
adding a hydrogen source, nitrobenzene and a catalyst into a reactor, and reacting for 2-12 hours at 60-180 ℃ under magnetic stirring to obtain a product p-aminophenol;
the catalyst is a supported metal catalyst and a solid acid catalyst, and the molar ratio of the materials is that the hydrogen source is nitrobenzene 1: 0.1-1; wherein the dosage of the metal catalyst is 0.01-0.5 g/ml nitrobenzene; the dosage of the solid acid catalyst is 0.1-5 g/ml nitrobenzene;
the hydrogen source is formic acid aqueous solution or isopropanol; when the hydrogen source is formic acid, an auxiliary agent Cetyl Trimethyl Ammonium Bromide (CTAB) is added, and the dosage of the CTAB is 10-20 mg/ml nitrobenzene.
2. The method for preparing p-aminophenol through nitrobenzene transfer hydrogenation according to claim 1, wherein said supported metal catalyst comprises an active metal and a carrier, the active metal is one or more of Pd and Pt, the carrier is γ -Al2O3、TiO2、CeO2、MgO、SiO2、ZrO2Molecular sieves or activated carbon; the loading amount of the active component is 0.1-10%.
3. The process for preparing p-aminophenol by transfer hydrogenation of nitrobenzene according to claim 1, wherein said solid acid catalyst is SO4 2-/ZrO2、SO4 2-/ZrO2-Al2O3、SO4 2-/TiO2、SO4 2-/Fe2O3Acid molecular sieve (HZSM-5, HY, Hbeta) or carbon-based solid acid.
4. The method for preparing p-aminophenol through the transfer hydrogenation of nitrobenzene according to claim 1, wherein said aqueous formic acid solution has a concentration ranging from 0.05 to 2 g/ml.
5. The method for preparing p-aminophenol by nitrobenzene transfer hydrogenation according to claim 1, wherein the preferred molar ratio of the feed to nitrobenzene is 1: 0.1-0.5; the preferable dosage of the supported metal catalyst is 0.05-0.2 g/ml nitrobenzene; the preferable dosage of the solid acid catalyst is 0.5-1 g/ml nitrobenzene; the preferable dosage of the active metal load is 0.1-10%.
6. The method for preparing p-aminophenol through nitrobenzene transfer hydrogenation according to claim 1, wherein said preferred reaction temperature is from 120 to 180 ℃.
7. The method for preparing p-aminophenol through nitrobenzene transfer hydrogenation according to claim 1, wherein said preferred reaction time is 4 to 8 hours.
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| CN113429301A (en) * | 2021-06-28 | 2021-09-24 | 河北工业大学 | Method for preparing toluenediamine by dinitrotoluene hydrogenation with isopropanol as hydrogen source |
| CN113860979A (en) * | 2021-11-05 | 2021-12-31 | 大连理工大学 | Method for preparing high value-added chemicals from room-temperature transfer hydrogenation unsaturated compounds by taking aldose as hydrogen source |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113860979B (en) * | 2021-11-05 | 2024-01-26 | 大连理工大学 | Method for preparing high value-added chemicals by transferring hydrogenated unsaturated compounds at room temperature by using aldose as hydrogen source |
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