CN102658125A - 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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- CN102658125A CN102658125A CN2012101233067A CN201210123306A CN102658125A CN 102658125 A CN102658125 A CN 102658125A CN 2012101233067 A CN2012101233067 A CN 2012101233067A CN 201210123306 A CN201210123306 A CN 201210123306A CN 102658125 A CN102658125 A CN 102658125A
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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 system para-aminophenol.
Background technology
Para-aminophenol (being called for short PAP) is a kind of broad-spectrum organic synthesis intermediate.The traditional mode of production route is the chlorobenzene route, chlorobenzene through nitrated obtain paranitrochlorobenzene, again through hydrolysis obtain p-nitrophenol, after para-aminophenol is produced in 3 step such as reducing process (iron powder, akali sulphide or hydrogen) chemical reaction and a series of separation process.
With nitrobenzene is the route of raw material, and at first nitrobenzene generates para hydroxybenzene amine through zinc powder, electrolysis or catalytic hydrogenating reduction, can generate para-aminophenol without being separated in directly to reset through Bamberge under the acid condition.Wherein, because nitrobenzene is 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 through productive rate, the selectivity of zinc powder electronation.Nitrobenzene catalytic hydrogenating reduction method is the nineteen seventies novel technique at first developed of the U.S..
Nitrobenzene catalytic hydrogenating reduction method is the novel technique of nineteen seventies exploitation.Nitrobenzene catalytic hydrogenation system para-aminophenol is a complicated competitive reaction.At first nitrobenzene reduces under the effect of catalyst and generates the intermediate product hydroxyanilines, and hydroxyanilines is reset in sour environment and generated end product para-aminophenol (PAP) then.In this process, part of hydroxyl aniline also further hydrogenation generate accessory substance aniline.Therefore,, just must require catalyst system therefor to have the activity of appropriateness to be beneficial to reaction and generate hydroxyanilines, simultaneously again under suitable condition, the intermediate hydroxyanilines transformed rapidly to target product PAP in order to improve the yield of PAP.For improving the ultimate yield of PAP, U.S. Pat 4264529 has been used the Pt/ aluminium oxide catalyst in the preparation process, because Pt/ aluminium oxide carrier in the presence of acid medium is easy to dissolving, so catalyst loss is serious.With platinum sulfide or molybdenum sulfide/C catalyst, used sulfuric acid concentration is had relatively high expectations to consersion unit up to 50% in the disclosed para-aminophenol synthetic method of US3953509.The disclosed para-aminophenol synthetic method of US6403833 and CN1075489C has been used nickel/ZSM-5 or Pt/ nylon, though catalytic stability is better, the selectivity of PAP is relatively poor.Among the CN1562465A Pt is loaded on the bifunctional acidic carrier, exist the problem that carrier is run off by acid leach solution, catalyst life is unstable.CN1061808A need not use under the situation of expensive catalyst, and electroreduction nitrobenzene generates para-aminophenol in acid medium, and this method shortcoming is the hard to bear corrosion of electrode material.
Summary of the invention
The present invention provides a kind of Catalysts and its preparation method that has high stability, high activity and optionally be used for nitrobenzene catalytic hydrogenation system para-aminophenol for fear of the weak point that prior art exists, to improve the yield of PAP.
Its characteristics of catalyst of the present invention are, are carrier with the active carbon, and Pt is a major catalyst, MoS
2Be co-catalyst, the content of said catalyst activity component Pt is 0.1-6%; Co-catalyst MoS
2Constituent content be 1-5%; Surplus is a carrier active carbon.
Catalyst of the present invention, its preparation methods steps is following:
(1) Pt/C Preparation of catalysts
Active carbon behind the nitric acid purifying is immersed in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%; The proportioning of said chloroplatinic acid aqueous solution and active carbon is V (a chloroplatinic acid aqueous solution volume): m (active carbon)=1: 2-1: 4ml/g; At 40-60 ℃ of following constant temperature 4-6h, be cooled to 20 ℃; The preparation saturated aqueous sodium carbonate is with maceration extract furnishing alkalescence; Drip excess hydrazine hydrate while stirring, in water-bath, be incubated 1-4h then, make the chloroplatinic acid reduction fully; Cross and filter solid phase components, be washed till no chlorion, get the Pt/C catalyst behind the placement vacuum desiccator inner drying with deionized water;
(2) co-catalyst MoS
2Be adsorbed on the Pt/C
The four thio ammonium molybdate crystal is dissolved in deionized water; The Pt/C catalyst that adds gained in the step (1); The weight portion proportioning of said four thio ammonium molybdate crystal and Pt/C catalyst is 1: 3-1: 5, stir 1-3h, static placement 4-8h at the immersion condition lower magnetic force; Dry under 60-90 ℃, get catalyst precursor ATTM-Pt/C (I);
With ATTM-Pt/C (I) quartz ampoule of packing into, place the tubular type kiln roasting, temperature is 350-550 ℃, the feeding flow is 0.15m
3/ h hydrogen is reduction 1-4h down; After treating that quartz ampoule cools off fully, obtain black powder MoS
2-Pt/C catalyst.
Active carbon according to the invention is a coconut husk carrier charcoal, and granularity is the 200-320 order, and specific surface is 1000-1300m
2/ g.
The alkaline range of the maceration extract in the step of the present invention (1) is pH=7.0-10.0.
Compared with present technology, beneficial effect of the present invention is embodied in:
Catalysts and its preparation method of the present invention is following:
The present invention adds MoS
2Make the MoS of co-catalyst
2-Pt/C catalyst has good catalytic performance, and activity of such catalysts and selectivity obviously improve, and through after repeatedly recycling, the yield of PAP is still more than 83%.
Reaction temperature of the present invention is between 70-100 ℃, and preference temperature is 86-88 ℃, and it is best that inhale the hydrogen effect this moment.The most frequently used active carbon be carrier to process the 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%.
The specific embodiment
Embodiment 1
It is 15-20ml that the active carbon of 40-60g behind the nitric acid purifying is immersed in volume, and volumetric concentration is in the chloroplatinic acid aqueous solution of 4-8%, at 50 ℃ of constant temperature 4-6h, is cooled to 20 ℃; The preparation saturated aqueous sodium carbonate is with maceration extract furnishing alkalescence; Drip excess hydrazine hydrate while stirring, in water-bath, be incubated 1-4h then, make the chloroplatinic acid reduction fully; Cross and filter solid phase components, be washed till no chlorion, place the vacuum desiccator inner drying and get Pt/C catalyst 40-60g with deionized water, subsequent use; 8-12g four thio ammonium molybdate crystal (ATTM) is dissolved in deionized water, adds subsequent use Pt/C, stir 1-3h at the immersion condition lower magnetic force, static placement 4-8h, dry under 60-90 ℃, get catalyst precursor ATTM-Pt/C (I); With ATTM-Pt/C (I) quartz ampoule of packing into, place the tubular type kiln roasting, temperature is 350-550 ℃, the feeding flow is 0.15m
3/ h hydrogen is reduction 1-4h down; After treating that quartz ampoule cools off fully, obtain black powder MoS
2-Pt/C catalyst 37-56g.
Embodiment 2
In the 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 the displacement apparatus, and inspection air-tightness.About heat temperature raising to 87 ℃, keep constant temperature, logical H
2Stop heating behind the question response 5h, logical N
2Purge, be cooled to room temperature, reclaim catalyst.Analyzing the yield of knowing para-aminophenol through GC-MS is 86%.
Embodiment 3
Use the catalyst among the 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. the catalyst of a nitrobenzene catalytic hydrogenation system para-aminophenol is characterized in that, this catalyst is carrier with the active carbon, and Pt is a major catalyst, MoS
2Be co-catalyst, the content of said catalyst activity component Pt is 0.1-6%; Co-catalyst MoS
2Constituent content be 1-5%; Surplus is a carrier active carbon.
2. the catalyst of the said a kind of nitrobenzene catalytic hydrogenation system para-aminophenol of claim 1, its preparation methods steps is following: (1) Pt/C Preparation of catalysts
Active carbon behind the nitric acid purifying is immersed in the chloroplatinic acid aqueous solution that volumetric concentration is 4-8%; The proportioning of said chloroplatinic acid aqueous solution and active carbon is V (a chloroplatinic acid aqueous solution volume): m (active carbon)=1: 2-1: 4ml/g; At 40-60 ℃ of following constant temperature 4-6h, be cooled to 20 ℃; The preparation saturated aqueous sodium carbonate is with maceration extract furnishing alkalescence; Drip excess hydrazine hydrate while stirring, in water-bath, be incubated 1-4h then, make the chloroplatinic acid reduction fully; Cross and filter solid phase components, solid phase is washed till no chlorion, get the Pt/C catalyst behind the placement vacuum desiccator inner drying with deionized water;
(2) co-catalyst MoS
2Be adsorbed on the Pt/C
The four thio ammonium molybdate crystal is dissolved in deionized water; The Pt/C catalyst that adds gained in the step (1); The weight proportion of said four thio ammonium molybdate crystal and Pt/C catalyst is 1: 3-1: 5, stir 1-3h, static placement 4-8h at the immersion condition lower magnetic force; Dry under 60-90 ℃, get catalyst precursor ATTM-Pt/C (I);
With ATTM-Pt/C (I) quartz ampoule of packing into, place the tubular type kiln roasting, temperature is 350-550 ℃, the feeding flow is 0.15m
3/ h hydrogen is reduction 1-4h down; After treating that quartz ampoule cools off fully, obtain black powder MoS
2-Pt/C catalyst.
3. by the method for preparing catalyst of the described a kind of nitrobenzene catalytic hydrogenation system para-aminophenol of claim 2, it is characterized in that used active carbon is a coconut husk carrier charcoal, granularity is the 200-320 order, and specific surface is 1000-1300m
2/ g.
4. by the method for preparing catalyst of the described a kind of nitrobenzene catalytic hydrogenation system para-aminophenol of claim 2, the alkaline range that it is characterized in that the maceration extract in the step (1) is pH=7.0-10.0.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113240A (en) * | 2013-03-11 | 2013-05-22 | 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 |
| CN107983370A (en) * | 2017-11-06 | 2018-05-04 | 青岛科技大学 | A kind of MoS2Application of the micro-flowers in catalysis manufacturing process of aniline through nitrobenzene hydrogenation reaction |
| CN112138650A (en) * | 2020-09-17 | 2020-12-29 | 张国良 | Method for preparing special catalyst for producing p-aminophenol by nitrobenzene hydrogenation |
| CN112657542A (en) * | 2020-12-28 | 2021-04-16 | 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113240A (en) * | 2013-03-11 | 2013-05-22 | 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 |
| CN107983370A (en) * | 2017-11-06 | 2018-05-04 | 青岛科技大学 | A kind of MoS2Application of the micro-flowers in catalysis manufacturing process of aniline through nitrobenzene hydrogenation reaction |
| 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 |
| CN112657542A (en) * | 2020-12-28 | 2021-04-16 | 常州大学 | Method for preparing p-aminophenol from nitrobenzene |
| 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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