CN102658125B - Catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and preparation method thereof - Google Patents
Catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and preparation method thereof Download PDFInfo
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- CN102658125B CN102658125B CN201210123306.7A CN201210123306A CN102658125B CN 102658125 B CN102658125 B CN 102658125B CN 201210123306 A CN201210123306 A CN 201210123306A CN 102658125 B CN102658125 B CN 102658125B
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- aminophenol
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Abstract
The invention relates to a novel catalytic agent for preparing p-aminophenol by using nitrobenzene catalytic hydrogenation and a preparation method thereof. The catalytic agent enables active carbon to serve as a carrier, enables Pt to serve as a main catalytic agent and enables MoS2 to serve as an auxiliary catalytic agent. The preparation step of the catalytic agent comprises (1) preparing Pt/C catalytic agent, namely enabling the Pt to be loaded on the activated carbon through an infusion process; and (2) restoring the auxiliary catalytic agent MoS2 through steeping and roasting under certain H2, loading on the Pt/C, and finally obtaining the catalytic agent for preparing the p-aminophenol. The catalytic agent for synthesizing the p-aminophenol is high in productivity and high in selectivity, and the catalytic agent is good in stability. After 23 times of circulation, the catalytic agent keeps good activity, yield coefficient of the p-aminophenol is above 83%, and the catalytic agent has good industrial application prospect.
Description
Technical field
The present invention relates to catalyst technical field, specifically a kind of Catalysts and its preparation method by nitrobenzene para-aminophenol processed.
Background technology
Para-aminophenol (being called for short PAP) is a kind of broad-spectrum organic synthesis intermediate.Traditional mode of production route is chlorobenzene route, and chlorobenzene is through nitratedly obtaining paranitrochlorobenzene, obtaining p-nitrophenol, produce para-aminophenol finally by the 3 step chemical reactions such as reducing process (iron powder, akali sulphide or hydrogen) and a series of separation process again through hydrolysis.
Route taking nitrobenzene as raw material, first nitrobenzene, through zinc powder, electrolysis or catalytic hydrogenating reduction, generates para hydroxybenzene amine, can directly reset and generate para-aminophenol through Bamberge without being separated under acid condition.Wherein, because nitrobenzene is through the productive rate of zinc powder electronation, selective low and that electrode life is low, electrochemical reactor amplifies difficulty etc. is former thereby make this preparation method be difficult to carry out suitability for industrialized production.By Catalytic Hydrogenation of Nitrobenzene reducing process is the nineteen seventies novel technique first developed of the U.S..
By Catalytic Hydrogenation of Nitrobenzene reducing process is the novel technique of nineteen seventies exploitation.By Catalytic Hydrogenation of Nitrobenzene para-aminophenol processed is a complicated competitive reaction.First nitrobenzene reduces and generates intermediate product hydroxyanilines under the effect of catalyst, and then hydroxyanilines is reset and generated end product para-aminophenol (PAP) in sour environment.In this process, part of hydroxyl aniline also further hydrogenation generate accessory substance aniline.Therefore, in order to improve the yield of PAP, just must require used catalyst to have appropriate activity to be beneficial to reaction and generate hydroxyanilines, under suitable condition again, intermediate hydroxyanilines be transformed rapidly simultaneously to target product PAP.For improving the ultimate yield of PAP, US Patent No. 4264529 has been used Pt/ aluminium oxide catalyst in preparation process, because Pt/ aluminium oxide carrier under acid medium exists is easy to dissolve, so catalyst loss is serious.In the disclosed para-aminophenol synthetic method of US3953509, with platinum sulfide or molybdenum sulfide/C catalyst, sulfuric acid concentration used, up to 50%, is had relatively high expectations to consersion unit.The disclosed para-aminophenol synthetic method of US6403833 and CN1075489C has been used nickel/ZSM-5 or Pt/ nylon, although catalytic stability is better, PAP's is selectively poor.In CN1562465A, Pt is loaded on bifunctional acidic carrier, exist the problem that carrier is run off by acid leach solution, catalyst life is unstable.CN1061808A is not in the situation that needing to use expensive catalyst, and in acid medium, electroreduction nitrobenzene generates para-aminophenol, and this method shortcoming is the hard to bear corrosion of electrode material.
Summary of the invention
The weak point that the present invention exists for fear of prior art, provides a kind of and has high stability, high activity and optionally for the Catalysts and its preparation method of By Catalytic Hydrogenation of Nitrobenzene para-aminophenol processed, to improve the yield of PAP.
Its feature of catalyst of the present invention is, taking active carbon as carrier, Pt is major catalyst, MoS
2for co-catalyst, the content of described catalyst activity component Pt is 0.1-6%; Co-catalyst MoS
2constituent content be 1-5%; Surplus is carrier active carbon.
Catalyst of the present invention, its preparation methods steps is as follows:
(1) preparation of Pt/C catalyst
Active carbon after nitric acid purifying is immersed in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%, the proportioning of described chloroplatinic acid aqueous solution and active carbon is V (chloroplatinic acid aqueous solution volume): m (active carbon)=1: 2-1: 4ml/g, constant temperature 4-6h at 40-60 DEG C, is cooled to 20 DEG C; Preparation saturated aqueous sodium carbonate, by maceration extract furnishing alkalescence; Drip while stirring excess hydrazine hydrate, then in water-bath, be incubated 1-4h, make chloroplatinic acid reduction completely; Filter to obtain solid phase components, be washed till without chlorion by deionized water, place after vacuum desiccator inner drying to obtain Pt/C catalyst;
(2) co-catalyst MoS
2be adsorbed on Pt/C
Four thio ammonium molybdate crystal is dissolved in to deionized water, add the Pt/C catalyst of gained in step (1), the weight portion proportioning of described four thio ammonium molybdate crystal and Pt/C catalyst is 1: 3-1: 5, stir 1-3h at immersion condition lower magnetic force, static placement 4-8h, dry at 60-90 DEG C, obtain catalyst precursor ATTM-Pt/C (I);
Pack ATTM-Pt/C (I) into quartz ampoule, be placed in tubular type kiln roasting, temperature is 350-550 DEG C, and passing into flow is 0.15m
3under/h hydrogen, reduce 1-4h; After quartz ampoule is completely cooling, obtain black powder MoS
2-Pt/C catalyst.
Active carbon of the present invention is coconut husk carrier charcoal, and granularity is 200-320 order, and specific surface is 1000-1300m
2/ g.
The alkaline range of the maceration extract in step of the present invention (1) is pH=7.0-10.0.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Catalysts and its preparation method of the present invention is as follows:
The present invention adds MoS
2make the MoS of co-catalyst
2-Pt/C catalyst has good catalytic performance, and the activity and selectivity of catalyst obviously improves, and after repeatedly recycling, the yield of PAP is still more than 83%.
Reaction temperature of the present invention is between 70-100 DEG C, and preference temperature is 86-88 DEG C, now inhales hydrogen effect best.The most frequently used active carbon be carrier to make platinum load capacity be 0.1%～6% Pt/C catalyst, the load capacity of Pt should be controlled in the scope of 2.5%-3%.
Detailed description of the invention
Embodiment 1
It is 15-20ml that active carbon by 40-60g after nitric acid purifying is immersed in volume, in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%, at 50 DEG C of constant temperature 4-6h, is cooled to 20 DEG C; Preparation saturated aqueous sodium carbonate, by maceration extract furnishing alkalescence; Drip while stirring excess hydrazine hydrate, then in water-bath, be incubated 1-4h, make chloroplatinic acid reduction completely; Filter to obtain solid phase components, be washed till without chlorion by deionized water, place vacuum desiccator inner drying and obtain Pt/C catalyst 40-60g, for subsequent use; 8-12g four thio ammonium molybdate crystal (ATTM) is dissolved in to deionized water, adds Pt/C for subsequent use, stir 1-3h at immersion condition lower magnetic force, static placement 4-8h, dry at 60-90 DEG C, obtain catalyst precursor ATTM-Pt/C (I); Pack ATTM-Pt/C (I) into quartz ampoule, be placed in tubular type kiln roasting, temperature is 350-550 DEG C, and passing into flow is 0.15m
3under/h hydrogen, reduce 1-4h; After quartz ampoule is completely cooling, obtain black powder MoS
2-Pt/C catalyst 37-56g.
Embodiment 2
In normal pressure stirred reactor, add 100ml distilled water, mass fraction is 98% concentrated sulfuric acid 10ml, 0.05ml methyl-sulfoxide, 0.3g MoS
2-Pt/C catalyst, 20ml nitrobenzene.Logical N
2, the air in displacement apparatus, and check air-tightness.Be heated to 87 DEG C of left and right, keep constant temperature, logical H
2.After question response 5h, stop heating, logical N
2purge, be cooled to room temperature, reclaim catalyst.Analyze and know that the yield of para-aminophenol is 86% through GC-MS.
Embodiment 3
Use the catalyst in embodiment 2, reaction condition is the same, and after 22 circulations, the yield of measuring para-aminophenol in the 23rd secondary response liquid is 83%.
Claims (4)
1. a catalyst for By Catalytic Hydrogenation of Nitrobenzene para-aminophenol processed, this catalyst is taking active carbon as carrier, and Pt is major catalyst, MoS
2for co-catalyst, it is characterized in that, the content of described catalyst activity component Pt is 0.1-6%; Co-catalyst MoS
2constituent content be 1-5%; Surplus is carrier active carbon;
Its preparation methods steps is as follows:
(1) preparation of Pt/C catalyst
Active carbon after nitric acid purifying is immersed in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%, the proportioning of described chloroplatinic acid aqueous solution and active carbon is chloroplatinic acid aqueous solution volume V: active carbon m=1:2-1:4mL/g, constant temperature 4-6h at 40-60 DEG C, is cooled to 20 DEG C; Preparation saturated aqueous sodium carbonate, by maceration extract furnishing alkalescence; Drip while stirring excess hydrazine hydrate, then in water-bath, be incubated 1-4h, make chloroplatinic acid reduction completely; Filter to obtain solid phase components, solid phase is washed till without chlorion by deionized water, place after vacuum desiccator inner drying to obtain Pt/C catalyst;
(2) co-catalyst MoS
2be adsorbed on Pt/C
Four thio ammonium molybdate crystal is dissolved in to deionized water, add the Pt/C catalyst of gained in step (1), the weight proportion of described four thio ammonium molybdate crystal and Pt/C catalyst is 1:3-1:5, stir 1-3h at immersion condition lower magnetic force, static placement 4-8h, dry at 60-90 DEG C, obtain catalyst precursor ATTM-Pt/C (I);
Pack ATTM-Pt/C (I) into quartz ampoule, be placed in tubular type kiln roasting, temperature is 350-550 DEG C, and passing into flow is 0.15m
3under/h hydrogen, reduce 1-4h; After quartz ampoule is completely cooling, obtain black powder MoS
2-Pt/C catalyst.
2. a method for preparing catalyst for By Catalytic Hydrogenation of Nitrobenzene para-aminophenol processed described in claim 1, its spy is that step is as follows:
(1) preparation of Pt/C catalyst
Active carbon after nitric acid purifying is immersed in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%, the proportioning of described chloroplatinic acid aqueous solution and active carbon is chloroplatinic acid aqueous solution volume V: active carbon m=1:2-1:4mL/g, constant temperature 4-6h at 40-60 DEG C, is cooled to 20 DEG C; Preparation saturated aqueous sodium carbonate, by maceration extract furnishing alkalescence; Drip while stirring excess hydrazine hydrate, then in water-bath, be incubated 1-4h, make chloroplatinic acid reduction completely; Filter to obtain solid phase components, solid phase is washed till without chlorion by deionized water, place after vacuum desiccator inner drying to obtain Pt/C catalyst;
(2) co-catalyst MoS
2be adsorbed on Pt/C
Four thio ammonium molybdate crystal is dissolved in to deionized water, add the Pt/C catalyst of gained in step (1), the weight proportion of described four thio ammonium molybdate crystal and Pt/C catalyst is 1:3-1:5, stir 1-3h at immersion condition lower magnetic force, static placement 4-8h, dry at 60-90 DEG C, obtain catalyst precursor ATTM-Pt/C (I);
Pack ATTM-Pt/C (I) into quartz ampoule, be placed in tubular type kiln roasting, temperature is 350-550 DEG C, and passing into flow is 0.15m
3under/h hydrogen, reduce 1-4h; After quartz ampoule is completely cooling, obtain black powder MoS
2-Pt/C catalyst.
3. the method for preparing catalyst of By Catalytic Hydrogenation of Nitrobenzene according to claim 2 para-aminophenol processed, is characterized in that active carbon used is coconut husk carrier charcoal, and granularity is 200-320 order, and specific surface is 1000-1300m
2/ g.
4. by the method for preparing catalyst of By Catalytic Hydrogenation of Nitrobenzene claimed in claim 2 para-aminophenol processed, the alkaline range that it is characterized in that the maceration extract in step (1) is pH=7.0-10.0.
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| CN103113240B (en) * | 2013-03-11 | 2014-06-25 | 河北工业大学 | Process for directly synthesizing p-aminophenol through hydrogenation of nitrobenzene |
| CN103357407A (en) * | 2013-07-29 | 2013-10-23 | 西安凯立化工有限公司 | Preparation method and application of catalyst for one-step preparation of p-aminophenol from nitrobenzene |
| CN107983370B (en) * | 2017-11-06 | 2020-09-15 | 青岛科技大学 | MoS2Application of micro-flower in catalyzing reaction for preparing aniline by hydrogenating nitrobenzene |
| CN112138650A (en) * | 2020-09-17 | 2020-12-29 | 张国良 | Method for preparing special catalyst for producing p-aminophenol by nitrobenzene hydrogenation |
| CN112657542B (en) * | 2020-12-28 | 2023-09-22 | 常州大学 | Method for preparing p-aminophenol from nitrobenzene |
| CN112812025A (en) * | 2021-01-13 | 2021-05-18 | 江苏普洛德化学科技有限公司 | Preparation process of p-aminophenol |
| CN114931946A (en) * | 2022-07-04 | 2022-08-23 | 上海大学 | Pt/C composite catalyst and preparation method and application thereof |
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| CN102124081A (en) * | 2008-06-18 | 2011-07-13 | 雪佛龙美国公司 | System and method for pretreatment of solid carbonaceous material |
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| CN102124081A (en) * | 2008-06-18 | 2011-07-13 | 雪佛龙美国公司 | System and method for pretreatment of solid carbonaceous material |
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| MoS2/C催化剂上硝基苯催化加氢的反应研究;刘银等;《应用化工》;20100531;第39卷(第5期);第658页-第661页 * |
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