CN112657542A - Method for preparing p-aminophenol from nitrobenzene - Google Patents
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Abstract
The invention discloses a method for preparing p-aminophenol by nitrobenzene, which mainly comprises the following steps: mainly uses Pt as a main active component and uses Mg, Cr and Ni as auxiliary agents in the presence of CO2/H2O system, hydrogen reduction reaction is carried out in a high-pressure reaction kettle for 4-7 hours at the reaction temperature of 100-150 ℃, and H is added in the reaction kettle2CO under the pressure of 0.5-2 MPa2The pressure is 4-6 MPa; after the reaction is finished, the filtered catalyst can be dried for continuous use, and ammonia can be treated by the catalystThe selectivity of the base phenol can reach more than 85 percent. This reaction, with CO2/H2The O system replaces the traditional sulfuric acid system, solves the problems of environmental pollution and post-treatment of sulfuric acid, avoids the corrosion of sulfuric acid to equipment, and can adjust the acidity of the carrier and solve the problem of CO by using the catalyst with the HZSM-5 molecular sieve as the carrier2/H2The O system has insufficient acidity and the catalyst has good stability.
Description
Technical Field
The invention belongs to the field of catalytic hydrogenation, and relates to a method for preparing p-aminophenol from nitrobenzene.
Background
para-Aminophenol (p-amino phenol, PAP for short) is an important organic intermediate and chemical raw material, and has wide application in the industries of medicine, rubber, dye and the like. In the pharmaceutical industry, p-aminophenol is mainly used for producing drugs such as paracetamol and the like, can be used for synthesizing paracetamol (p-acetaminophenol), clofibrate (ethyl p-chlorophenoxymethylpropionate), paracetamol (p-acetamino acetylsalicylate), vitamins, compound nicotinamide, clofibrate, 6-hydroxyquinoline, and saligenin and the like, and is a very important medical intermediate; in the dye industry, PAP can be used as an intermediate of similar dyes, and p-aminophenol can also be used for producing various dyes such as disperse materials, acid dyes, direct dyes, sulfur dyes, fur dyes and the like in the dye industry; in the rubber industry, PAP is mainly used for producing p-phenylenediamine anti-aging agents, and has the advantages of no toxicity, low pollution, high efficiency and the like.
At present, the synthesis of p-aminophenol mainly comprises the following methods: the p-nitrophenol method comprises an electrolytic reduction method, a catalytic hydrogenation reduction method and a chromium powder reduction method; phenols including phenol nitrosation, phenol halogenation ammonification and phenol coupling; p-nitrochlorobenzene process; the paranitrobenzene method comprises an electrolytic reduction method, a metal reduction method and a catalytic hydrogenation reduction method. The chromium powder reduction method using nitrophenol as a raw material is the earliest process route for producing PAP, but the method has high cost and serious pollution; the method which takes phenol and p-nitrochlorobenzene as raw materials has long process flow and low yield; the nitrobenzene electrolytic reduction process has large investment in equipment and needs to consume a large amount of electricity; the catalytic hydrogenation method of nitrophenol is more expensive than nitrobenzene in raw material, so that the catalytic hydrogenation method of nitrobenzene as raw material for preparing p-aminophenol has more industrial development value.
The invention patent CN103570563A discloses a process for preparing p-aminophenol by directly hydrogenating nitrobenzene, which comprises the following steps: adding a nitrogen-doped carbon-protected acid-resistant hydrogenation catalyst into a nitrobenzene-containing sulfuric acid solution, and adding an organic solvent; with N2After replacing the air in the high-pressure reaction kettle, introducing H2The reaction temperature is 80-200 ℃, the reaction time is 1-10 hours, and the selectivity of the p-aminophenol can reach 100%. The catalyst after the reaction can be recycled, and no waste slag and liquid are discharged in the production process. But the reaction process still has the problem of sulfuric acid corrosion; the invention patent CN103357407A discloses a preparation method and application of a catalyst for preparing p-aminophenol by a nitrobenzene one-step method, wherein the method comprises the following steps: pretreatment of activated carbon, loading of platinum salt, loading of vanadate and reduction of a catalyst; the mass percentage of platinum in the catalyst is 0.5-5%, and the mass percentage of vanadium is 0.05-2%. . According to the invention, a certain amount of metal vanadium is added into the Pt/C catalyst, so that the poisoning effect of sulfide in a nitrobenzene raw material on platinum is reduced, the service life of the catalyst is prolonged, the catalytic activity and selectivity of the catalyst are improved, the prepared catalyst is stable in performance and good in repeatability, the catalyst can be used for catalyzing nitrobenzene to prepare p-aminophenol in one step, the purity requirement on the raw material nitrobenzene is reduced, and the catalytic cost is reduced. The invention patent CN103553943A discloses a method for preparing p-aminophenol by hydrogenation of nitrobenzene, using pressurized CO2/H2C acid formed in O promotes intermediate N-phenylhydroxylamine formed in nitrobenzene hydrogenation reaction to generate Bamberger rearrangement to generate p-aminophenol, and CO is released after the reaction is finished2The system is self-neutralized, thus fundamentally avoiding the pollution to the environment caused by the production of salt wastewater by adding alkali for neutralization in the traditional reaction process, but the yield of the aminophenol is not high.
Disclosure of Invention
The invention aims to provide a method for preparing p-aminophenol from nitrobenzene, and the methodThe method is carried out based on a catalyst, the catalyst takes Pt as an active component, takes Mg, Cr and Ni as auxiliary agents, and is loaded on solid acid prepared on an HZSM-5 type molecular sieve to prepare the hydrogenation catalyst, and the solid acid in the hydrogenation catalyst can also be mixed with CO2/H2The O systems together provide the desired acid for the Bamberger rearrangement in the reaction.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing p-aminophenol from nitrobenzene comprises the following steps: adding nitrobenzene, a solid acid catalyst, a surfactant and water into the batch reaction autoclave, wherein the weight ratio of the nitrobenzene to the water is 1: 10-40, and the weight ratio of the solid acid catalyst to the nitrobenzene is 1: 20-50, sealing the high-pressure reaction kettle, and introducing CO2Replacing air in the kettle for 3-5 times, and introducing CO2The pressure is 4-6 MPa, so that CO is formed2/H2Heating the O system to 100-150 ℃, starting stirring at 700rpm/min, and introducing H into the kettle after the temperature is stable2The pressure is increased to 4.5-6.5 MPa, and the reaction is carried out for 4-7 hours;
the carrier of the solid acid catalyst is an HZSM-5 type molecular sieve, and the HZSM-5 type molecular sieve is loaded with Pt, Mg, Ni and Cr.
Furthermore, the mass content of Pt in the solid acid catalyst is 2-5%, and the total mass content of Mg, Cr and Ni is 0.5-2% of the catalyst.
Further, the silicon-aluminum ratio of the HZSM-5 type molecular sieve is 25-110.
Further, the solid acid catalyst is prepared by the following method: firstly, putting HZSM-5 type molecular sieve powder into a muffle furnace to be roasted for 4-6 h at 500-700 ℃, taking out the HZSM-5 type molecular sieve powder, soaking the HZSM-5 type molecular sieve powder for 0.5-3 h in dilute sulfuric acid with the concentration of 3-8 mol/L, drying the powder after soaking, then putting the powder into the muffle furnace to be roasted for 4-6 h at 300-500 ℃ to obtain acid modified HZSM-5 type molecular sieve powder, adding the acid modified HZSM-5 type molecular sieve powder into a mixed solution of Pt salt, Mg salt, Ni salt and Cr salt, controlling the added HZSM-5 type molecular sieve powder to be soaked in equal volume, putting the soaked substance into an oven to be dried, then putting the powder into the muffle furnace to be roasted for 2-4 h at 400-600 ℃, finally taking out the powder to be put into a tubular furnace to be roasted at 400-600 DEG CUnder the condition of introducing H2And reducing for 3-5 h to prepare the solid acid catalyst.
Further, the Pt salt is potassium chloroplatinate, and the Mg salt, the Ni salt and the Cr salt are respectively magnesium nitrate, chromium nitrate and nickel nitrate.
Further, the surfactant is cetyl trimethyl ammonium bromide, and the mass ratio of the cetyl ammonium bromide to the nitrobenzene is 1: 100.
Furthermore, the mass ratio of the dilute sulfuric acid to the roasted HZSM-5 type molecular sieve powder is 1: 9-11.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional sulfuric acid process, the method avoids the corrosion of sulfuric acid to equipment and the pollution to the environment, improves the solubility of organic matters in the water phase based on the surfactant, ensures that the water phase is fully contacted with the organic phase, simultaneously ensures that the liquid phase and the gas phase carry out phase transfer catalytic reaction, accelerates the reaction rate, simultaneously improves the selectivity of the aminophenol, and solves the problem of CO due to the addition of the HZSM-5 molecular sieve catalyst loaded with the main active component Pt and the auxiliary agents Mg, Ni and Cr2/H2The O system has the defects of insufficient acidity and low selectivity, and the preparation process is simple and has high efficiency.
Drawings
FIG. 1 is a SEM representation of the pure support HZSM-5 of the examples;
FIG. 2 is a SEM representation of the sulfuric acid loaded carrier in the examples;
FIG. 3 is a SEM representation result of the carrier loaded with Pt in the example;
FIG. 4 is a SEM representation of the sulfuric acid and Pt loaded carrier of the examples.
As can be seen from the 4 figures of the SEM, when only sulfuric acid and Pt are loaded alone, the effect of loading on the carrier is comparatively random dispersion, but when the carrier is loaded with both sulfuric acid and the active component Pt, the effect of loading is remarkably better than that of loading sulfuric acid and Pt alone, which can be comparatively uniformly loaded on the surface of the carrier.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
Firstly, weighing 1g of HZSM-5 molecular sieve, putting the HZSM-5 molecular sieve into a muffle furnace, and roasting for 6 hours at 500 ℃. Then soaking the mixture in dilute sulfuric acid (0.5mol/ml, the mass ratio of the dilute sulfuric acid to the carrier is 1:10, the same below) for 1 hour, drying the mixture, and then roasting the dried mixture in a muffle furnace at the temperature of 400 ℃ for 5 hours.
Second, 0.1397gH is weighed2PtCl6·6H2Dissolving O (0.05263 g in terms of metal Pt) in water to prepare impregnation liquid, and soaking 1g of HZSM-5 molecular sieve treated in the first step in the impregnation liquid for half an hour by adopting an equal-volume impregnation method.
And thirdly, putting the impregnated substance in the second step into an oven to be dried at 100 ℃.
And fourthly, putting the substance prepared in the third step into a muffle furnace and burning for 3 hours at the temperature of 500 ℃.
And fifthly, putting the material sintered in the fourth step into a tubular furnace, introducing hydrogen at 500 ℃ for reduction for 4 hours, and preparing the catalyst for preparing p-aminophenol from nitrobenzene.
The catalyst has HZSM-5 molecular sieve as carrier and Pt supported in 5%
Example 2
The procedure is as in example 1.
The catalyst has HZSM-5 molecular sieve as carrier and Pt supported in 5%
Example 3
Firstly, 1g of HZSM-5 molecular sieve is weighed and put into a muffle furnace to be roasted for 4 hours at the temperature of 700 ℃. Then soaking the mixture in dilute sulfuric acid for 1 hour, and then putting the mixture into a muffle furnace for roasting for 6 hours at 300 ℃.
Secondly, 0.1106gH are weighed2PtCl6·6H2Dissolving O (0.04167 g in terms of metal Pt) in water to prepare impregnation liquid, and soaking 1g of HZSM-5 molecular sieve serving as a carrier in the impregnation liquid for half an hour by adopting an isometric impregnation method.
And thirdly, putting the impregnated substance in the second step into an oven to be dried at 100 ℃.
And fourthly, putting the substance prepared in the third step into a muffle furnace to be burnt for 2 hours at the temperature of 600 ℃.
And fifthly, putting the material sintered in the fourth step into a tubular furnace, introducing hydrogen for reduction for 3 hours at the temperature of 600 ℃, and preparing the catalyst for preparing p-aminophenol from nitrobenzene.
The catalyst has HZSM-5 molecular sieve as carrier and Pt supported in 4%
Example 4
Firstly, 1g of HZSM-5 molecular sieve is weighed and put into a muffle furnace to be roasted for 5 hours at the temperature of 600 ℃. Then soaking the mixture in dilute sulfuric acid for 1 hour, and then putting the mixture into a muffle furnace for roasting for 4 hours at 500 ℃.
Secondly, 0.08211gH are weighed2PtCl6·6H2Dissolving O (0.03093 g in terms of metal Pt) in water to prepare impregnation liquid, and soaking 1g of HZSM-5 molecular sieve serving as a carrier in the impregnation liquid for half an hour by adopting an isometric impregnation method.
And thirdly, putting the impregnated substance in the second step into an oven to be dried at 100 ℃.
And fourthly, putting the substance prepared in the third step into a muffle furnace to be sintered for 4 hours at the temperature of 400 ℃.
And fifthly, putting the material sintered in the fourth step into a tubular furnace, introducing hydrogen at 400 ℃ for reduction for 5 hours, and preparing the catalyst for preparing p-aminophenol from nitrobenzene.
The catalyst has HZSM-5 molecular sieve as carrier and Pt supported in 3%
Example 5
The procedure is as in example 4, wherein 0.05418gH is weighed in the second step2PtCl6·6H2O (0.02041 g in terms of metal Pt).
The catalyst has HZSM-5 molecular sieve as carrier and Pt supported in 2%
Example 6
The procedure is as in example 4, wherein the second step requires weighing 0.1397gH2PtCl6·6H2O (0.05263 g in terms of Pt metal) and 0.2266gMg (NO)3)2·6H2O (0.02148 g in terms of metal Mg) was dissolved in water to prepare an immersion liquid.
The catalyst has HZSM-5 molecular sieve as carrier, Pt metal loading 5% and Mg metal loading 2%.
Example 7
The procedure is as in example 4, wherein the second step requires weighing 0.1397gH2PtCl6·6H2O (0.05263 g in terms of Pt) and 0.08183gCr (NO)3)2·6H2O (0.01063 g in terms of metal Cr) is dissolved in water to prepare an immersion liquid,
the carrier in the catalyst is HZSM-5 molecular sieve (silica-alumina ratio is 45), the load capacity of metal Pt is 5%, and the load capacity of metal Cr is 1%.
Example 8
The procedure is as in example 4, wherein the second step requires weighing 0.1397gH2PtCl6·6H2O (0.05263 g in terms of metal Pt) and 0.0407gNi (NO)3)2·6H2O (0.00529 g in terms of metallic Ni) was dissolved in water to prepare an immersion liquid.
The catalyst has HZSM-5 molecular sieve as carrier, Pt supported in 5% and Ni supported in 0.5%.
Example 9
In the first step, 0.1397gH is weighed2PtCl6·6H2O (0.05263 g in terms of Pt) and 0.0407g Ni (NO)3)2·6H2O (0.00529 g in terms of metallic Ni) was dissolved in water to prepare an immersion liquid. 1g of HZSM-5 molecular sieve is used as a carrier and is soaked in the soaking solution for half an hour by adopting an isometric soaking method.
And secondly, putting the impregnated substance in the second step into an oven to be dried at 100 ℃.
And thirdly, putting the substance prepared in the third step into a muffle furnace and sintering for 4 hours at the temperature of 400 ℃.
And fourthly, putting the material sintered in the fourth step into a tubular furnace, introducing hydrogen at 400 ℃ for reduction for 5 hours, and preparing the catalyst for preparing p-aminophenol from nitrobenzene.
The catalyst has HZSM-5 molecular sieve as carrier, Pt supported in 5% and Ni supported in 0.5%.
Example 10
The procedure is as in example 4, wherein the first step requires the immersion of dilute phosphoric acid.
The carrier in the catalyst is HZSM-5 molecular sieve (silica-alumina ratio is 80), and the load capacity of metal Pt is 3%.
Example 11
The procedure is as in example 4, wherein the second step is carried out by weighing.
The carrier in the catalyst is HZSM-5 molecular sieve (silica-alumina ratio is 80), and the load capacity of metal Pt is 3%.
Examples 10 to 20 examples of preparation of p-aminophenol from nitrobenzene
Example 10
0.08g of the catalyst of example 1, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially raised to 100 ℃. Continuously introducing CO2To 4MPa, then introducing H2To 4.5 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result showed 11.71% conversion of nitrobenzene and 57.33% selectivity to aminophenol.
Example 11
0.05g of the catalyst of example 2, 25ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially raised to 140 ℃. Introducing CO2The pressure is adjusted to 5MPa, then H is introduced2To 6 MPa. The reaction was carried out for 4h at 700rpm with a magnetic stirrer. The reaction result showed that the conversion of nitrobenzene was 3.16% and the selectivity to aminophenol was 73.58%.
Example 12
0.05g of the catalyst of example 3, 60ml of distilled water, 2g of nitrobenzene and 0.02g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially increased to 120 ℃. Continuously introducing CO2To 5.5MPa, then introducing H2To 6 MPa. The reaction was carried out for 7h at 700rpm with a magnetic stirrer. The reaction result is that the conversion rate of nitrobenzene is 15.24 percent, and the selectivity of p-aminophenol is 77.76％。
Example 13
0.08g of the catalyst of example 4, 64ml of distilled water, 1.6g of nitrobenzene and 0.016g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially increased to 110 ℃. Continuously introducing CO2To 4MPa, then introducing H2To 6 MPa. The reaction was carried out for 5h at 700rpm with a magnetic stirrer. The reaction result showed 43.67% conversion of nitrobenzene and 84.04% selectivity to aminophenol.
Example 14
0.05g of the catalyst of example 5, 30ml of distilled water, 2g of nitrobenzene and 0.02g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially increased to 110 ℃. Continuously introducing CO2To 6MPa, then introducing H2To 6.5 MPa. The reaction was carried out for 4h at 700rpm with a magnetic stirrer. The reaction result showed that the conversion of nitrobenzene was 6.47% and the selectivity to aminophenol was 62.81%.
Example 15
0.1g of the catalyst of example 6, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially raised to 130 ℃. Continuously introducing CO2To 4MPa, then introducing H2To 6 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result was 60.87% conversion of nitrobenzene and 82.8% selectivity to aminophenol.
Example 16
0.05g of the catalyst from example 7, 40ml of distilled water, 2.4g of nitrobenzene and 0.024g of DMSO were placed in an autoclave in this order and charged with CO2Replacing air in the kettle for 3 times, and introducing 2MPa CO2The temperature was initially raised to 150 ℃. Introducing CO2The pressure is adjusted to 4MPa, then H is introduced2To 5 MPa. The reaction was carried out for 7h at 700rpm with a magnetic stirrer. The reaction result showed 57.41% conversion of nitrobenzene and 85.63% selectivity to aminophenol.
Example 17
0.08g of the catalyst of example 8, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2Heating to 100 deg.C, and introducing CO2To 4 MPa. Then introducing H2To 4.5 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result shows that the conversion rate of nitrobenzene is 12.11 percent, and the selectivity of p-aminophenol is 90 percent.
Example 18
0.08g of the catalyst of example 9, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2Heating to 100 deg.C, and introducing CO2To 4 MPa. Then introducing H2To 4.5 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result showed 4.6% conversion of nitrobenzene and 88.2% selectivity to aminophenol.
Example 19
0.08g of the catalyst of example 2, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2Heating to 100 deg.C, and introducing CO2To 4 MPa. Then introducing H2To 4.5 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result showed 5.57% conversion of nitrobenzene and 76.86% selectivity to aminophenol.
Example 20
0.08g of the catalyst of example 8, 50ml of distilled water, 2.5g of nitrobenzene and 0.025g of DMSO were placed in an autoclave in this order, and CO was introduced2Replacing air in the kettle for 3 times, and introducing 2MPa CO2Heating to 140 deg.C, and introducing CO2To 4 MPa. Then introducing H2To 6 MPa. The reaction was carried out for 6h at 700rpm with a magnetic stirrer. The reaction result showed that the conversion of nitrobenzene was 73.5% and the selectivity to aminophenol was 80.37%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Claims (7)
1. A method for preparing p-aminophenol by using nitrobenzene is characterized in that: the method comprises the following steps: adding nitrobenzene, a solid acid catalyst, a surfactant and water into a batch reaction autoclave, wherein the weight ratio of the nitrobenzene to the water is 1: 10-40, the weight ratio of the solid acid catalyst to the nitrobenzene is 1: 20-50, sealing the autoclave, and introducing CO2Replacing air in the kettle for 3-5 times, and introducing CO2The pressure is 4-6 MPa, so that CO is formed2/H2Heating the O system to 100-150 ℃, starting stirring at 700rpm/min, and introducing H into the kettle after the temperature is stable2The pressure is increased to 4.5-6.5 MPa, and the reaction is carried out for 4-7 hours;
the carrier of the solid acid catalyst is an HZSM-5 type molecular sieve, and the HZSM-5 type molecular sieve is loaded with Pt, Mg, Ni and Cr.
2. The process for preparing p-aminophenol from nitrobenzene according to claim 1, wherein: the mass content of Pt in the solid acid catalyst is 2-5%, and the total mass content of Mg, Cr and Ni is 0.5-2% of the catalyst.
3. The process for preparing p-aminophenol from nitrobenzene according to claim 1, wherein: the silicon-aluminum ratio of the HZSM-5 type molecular sieve is 25-110.
4. The process for preparing p-aminophenol from nitrobenzene according to claim 1, wherein: the solid acid catalyst is prepared by the following method: firstly, putting HZSM-5 type molecular sieve powder into a muffle furnace to be roasted for 4-6H at 500-700 ℃, taking out the HZSM-5 type molecular sieve powder, soaking the HZSM-5 type molecular sieve powder for 0.5-3H in dilute sulfuric acid with the concentration of 3-8 mol/L, drying the HZSM-5 type molecular sieve powder after soaking, then putting the HZSM-5 type molecular sieve powder into the muffle furnace to be roasted for 4-6H at 300-500 ℃ to obtain acid modified HZSM-5 type molecular sieve powder, adding the acid modified HZSM-5 type molecular sieve powder into a mixed solution of Pt salt, Mg salt, Ni salt and Cr salt, controlling the added HZSM-5 type molecular sieve powder to be soaked in equal volume, putting the soaked substance into an oven to be dried, then putting the HZSM-5 type molecular sieve powder into the muffle furnace to be roasted for 2-4H at 400-600 ℃, finally taking2And reducing for 3-5 h to prepare the solid acid catalyst.
5. The process for preparing p-aminophenol from nitrobenzene according to claim 1, wherein: the surfactant is cetyl trimethyl ammonium bromide, and the mass ratio of the cetyl ammonium bromide to the nitrobenzene is 1: 100.
6. The process for preparing p-aminophenol from nitrobenzene according to claim 4, wherein: the Pt salt is potassium chloroplatinate or chloroplatinic acid, and the Mg salt, the Ni salt and the Cr salt are respectively magnesium nitrate, chromium nitrate and nickel nitrate.
7. The process for preparing p-aminophenol from nitrobenzene according to claim 4, wherein: the mass ratio of the dilute sulfuric acid to the roasted HZSM-5 type molecular sieve powder is 1: 9-11.
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| CN113663720A (en) * | 2021-09-10 | 2021-11-19 | 湖南大学 | Preparation method and application of nickel modified molecular sieve catalyst for regenerating rich amine |
| CN115770608A (en) * | 2022-11-03 | 2023-03-10 | 浙江新和成股份有限公司 | Amination catalyst for synthesizing amine compound from olefin, and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221769A (en) * | 1989-12-27 | 1993-06-22 | Mitsui Toatsu Chemicals Inc. | Production of p-acetylaminophenol from p-aminophenyl acetate |
| US6403833B1 (en) * | 2001-01-30 | 2002-06-11 | Council Of Scientific And Industrial Research | Single step hydrogenation of nitrobenzene to p-aminophenol |
| JP2002226443A (en) * | 2001-01-31 | 2002-08-14 | Council Scient Ind Res | Method for hydrogenating nitrobenzene into p- aminophenol in one step |
| CN1562465A (en) * | 2004-03-22 | 2005-01-12 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN101402059A (en) * | 2008-10-10 | 2009-04-08 | 广东海洋大学 | Process for producing shell powder supported solid acid biodiesel catalyst |
| CN101722032A (en) * | 2009-12-10 | 2010-06-09 | 复旦大学 | Catalyst for synthesizing p-aminophenol by hydrogenation reduction of nitrobenzene and preparation method thereof |
| CN102658125A (en) * | 2012-04-24 | 2012-09-12 | 安徽理工大学 | Catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and preparation method thereof |
| CN102827006A (en) * | 2012-09-20 | 2012-12-19 | 台州职业技术学院 | Method for preparing catalytically nitrified aromatic compound with fixed bed reactor |
| CN103553943A (en) * | 2013-11-17 | 2014-02-05 | 大连理工大学 | Method for preparing para amino phenol by virtue of nitrobenzene hydrogenation |
-
2020
- 2020-12-28 CN CN202011575572.4A patent/CN112657542B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221769A (en) * | 1989-12-27 | 1993-06-22 | Mitsui Toatsu Chemicals Inc. | Production of p-acetylaminophenol from p-aminophenyl acetate |
| US6403833B1 (en) * | 2001-01-30 | 2002-06-11 | Council Of Scientific And Industrial Research | Single step hydrogenation of nitrobenzene to p-aminophenol |
| JP2002226443A (en) * | 2001-01-31 | 2002-08-14 | Council Scient Ind Res | Method for hydrogenating nitrobenzene into p- aminophenol in one step |
| CN1562465A (en) * | 2004-03-22 | 2005-01-12 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN101402059A (en) * | 2008-10-10 | 2009-04-08 | 广东海洋大学 | Process for producing shell powder supported solid acid biodiesel catalyst |
| CN101722032A (en) * | 2009-12-10 | 2010-06-09 | 复旦大学 | Catalyst for synthesizing p-aminophenol by hydrogenation reduction of nitrobenzene and preparation method thereof |
| CN102658125A (en) * | 2012-04-24 | 2012-09-12 | 安徽理工大学 | Catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and preparation method thereof |
| CN102827006A (en) * | 2012-09-20 | 2012-12-19 | 台州职业技术学院 | Method for preparing catalytically nitrified aromatic compound with fixed bed reactor |
| CN103553943A (en) * | 2013-11-17 | 2014-02-05 | 大连理工大学 | Method for preparing para amino phenol by virtue of nitrobenzene hydrogenation |
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| CN113663720A (en) * | 2021-09-10 | 2021-11-19 | 湖南大学 | Preparation method and application of nickel modified molecular sieve catalyst for regenerating rich amine |
| CN113663720B (en) * | 2021-09-10 | 2023-01-03 | 湖南大学 | Preparation method and application of nickel modified molecular sieve catalyst for regenerating rich amine |
| CN115770608A (en) * | 2022-11-03 | 2023-03-10 | 浙江新和成股份有限公司 | Amination catalyst for synthesizing amine compound from olefin, and preparation method and application thereof |
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