CN85103667B - Prepare p-aminophenol technology from the catalytic hydrogenation of oil of mirbane highly selective - Google Patents
Prepare p-aminophenol technology from the catalytic hydrogenation of oil of mirbane highly selectiveInfo
- Publication number
- CN85103667B CN85103667B CN85103667A CN85103667A CN85103667B CN 85103667 B CN85103667 B CN 85103667B CN 85103667 A CN85103667 A CN 85103667A CN 85103667 A CN85103667 A CN 85103667A CN 85103667 B CN85103667 B CN 85103667B
- Authority
- CN
- China
- Prior art keywords
- mirbane
- oil
- aminophenol
- hydrogenation catalyst
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
From oil of mirbane one step reduction system p-aminophenol, process is in oscillation mode reactor or stirring-type reactor, use quaternary ammonium salt surface active agent, as Trimethyllaurylammonium bromide, oil of mirbane is dispersed in the aqueous sulfuric acid, in the presence of hydrogenation catalyst, feed hydrogen, the oil of mirbane highly selective is converted into p-aminophenol.The used hydrogenation catalyst of the present invention is platinum/carbon or platinum+other precious metal/C catalyst that process methyl alcohol or formaldehyde reduction were handled, and typical reaction conditions is: temperature 80-110 ℃, and hydrogen pressure 1.6-2.5kg/cm
2, sulfuric acid concentration is that 14-18% reaches and oil of mirbane volume ratio 3-5: 1, and tensio-active agent add-on 3-5 ‰.Catalyzer add-on (precious metal/oil of mirbane) 0.4-2 ‰, reaction times 1-2 hour, the nitro transformation efficiency was more than 80%, and the p-aminophenol production rate is 80-86%, and p-aminophenol can reach 30: 1 than the selectivity of aniline.
Description
The present invention relates to prepare the organic synthesis technology of numbness amino phenol from the oil of mirbane highly selective.
P-aminophenol is important organic intermediate, is widely used in industry such as dyestuff, rubber, sensitive materials, pharmacy.
The system p-aminophenol is to use the p-nitrophenol reducing process at present, and reaction process is as follows:
Since the raw materials cost height, reacted waste material-iron mud, and environmental pollution is heavy, so limited the production of p-aminophenol.
This century, the '20s began, and people set about studying the technology for preparing the numbness amino phenol from catalytic hydrogenation of nitrobenzene, and reaction process is:
Catalytic hydrogenation of nitrobenzene generates intermediate product N-hydroxyanilines, resets then to be p-aminophenol in acidic medium.Be reflected at acidic mediums such as catalyzer and aqueous sulfuric acid and exist next step to finish, main by product is an aniline.Far away from early stage United States Patent (USP) 2,198,249 and English Patent 856,316 in report is all arranged, but because oil of mirbane solubleness in acidic solution very low (only being 0.8%), for avoiding unreacted oil of mirbane to encase catalyzer, influence speed of response, and the aggravation side reaction, can only adopt and in reactive system, drip oil of mirbane continuously, and the control rate of addition equals speed of response, to prevent from reaction solution to surpass its solubleness.This not only makes complicated operation, and is restive, and speed of response is low, by product is many, and p-aminophenol has only about 3: 1 than the selectivity of aniline.
Early seventies, United States Patent (USP) 3,535,382 adopt nonionogenic tenside nonyl phenol glyceride to come the water of emulsion reaction liquid, oily two-phase, and (water is an aqueous sulfuric acid, liquid phase is an oil of mirbane), adopt once to feed intake, solved the problem that needs to drip continuously oil of mirbane in the reaction process, but still existing aniline byproduct content height, p-aminophenol is than the problem of the selectivity not high (about 10: 1) of aniline.
United States Patent (USP) 3,715,397 employing dimethyl sulfoxide (DMSO) (DMSO) are tensio-active agent, the p-aminophenol production rate is 59.4～85%, but because aqueous sulfuric acid and oil of mirbane volume ratio made the reactor utilization ratio extremely low up to 50: 1, and DMSO content excessive (with the oil of mirbane volume ratio be 2.4: 1), be difficult to reclaim.
United States Patent (USP) 4,415,753 in order to obtain higher selectivity, adopts the double-reactor two-step reaction.The first step is with DMSO, and ethanol, ammoniacal liquor are solvent, at 18～20 ℃, and 10～15kg/cm
2Under the gauge pressure, shortening generates the N-hydroxyanilines; The second step elimination catalyzer, in second reactor, the N-hydroxyanilines is rearranged into p-aminophenol under 70 ℃ of temperature.Owing to adopted two reactors, and need to reclaim problem such as DMSO, increased the complexity of technology.
The objective of the invention is to: to by oil of mirbane, aqueous sulfuric acid, the reaction system that tensio-active agent and hydrogenation catalyst are formed, screen a kind of have greater activity and hydrogenation catalyst optionally, and the tensio-active agent with better dispersing property, to obtain high as far as possible p-aminophenol selectivity, putting before this, select a kind of reactor utilization ratio height, the reaction conditions gentleness, easy and simple to handle, be easy to industrialized oil of mirbane system p-aminophenol technology.
Technological process of the present invention is, in earthquake formula reactor or the stirring-type reactor, utilize tensio-active agent and by stirring or concussion, oil of mirbane is dispersed in acidic medium such as the aqueous sulfuric acid, in the presence of hydrogenation catalyst (precious metal), the oil of mirbane highly selective is reduced to p-aminophenol by hydrogen.
The inventor finds, for above-mentioned specific reaction system, platinum/carbon of handling through formaldehyde or methyl alcohol reduction, platinum-rhodium/carbon, and platinum-ruthenium/carbon, Pt-Pd/c catalyzer etc. good catalytic activity is all arranged, can significantly improve the selectivity and the speed of reaction of reaction.
Preparation of Catalyst of the present invention and treatment process are: special chloroplatinic acid aqueous solution (platinum/C catalyst) or Platinic chloride-Trichlororhodium mixed aqueous solution (platinum-rhodium/C catalyst) or Platinic chloride-ruthenium trichloride mixed aqueous solution (platinum-ruthenium/carbon catalyst), or Platinic chloride-Palladous chloride mixed aqueous solution is immersed on the activated carbon of crossing with purifying treatment such as nitric acid or hydrochloric acid.Between 8～10, add methyl alcohol or formaldehyde with alkali (as sodium hydroxide, yellow soda ash, sodium bicarbonate etc.) regulator solution pH value, under 80-105 ℃, reductase 12～8 hour, contained noble metal amount is 0.5～8%, generally between 2～5% on the activated carbon.To bicomponent catalyst, the ratio of two-pack (platinum is to the ratio of other precious metals) is 2～20: 1.
The inventor also finds, to this reaction system, use quaternary ammonium salt surface active agent, particularly Trimethyllaurylammonium bromide, hexadecyldimethyl benzyl ammonium brometo de amonio etc., can significantly improve the dispersion effect of oil of mirbane, so aqueous sulfuric acid and oil of mirbane volume ratio can be reduced to 3～5: 1, thus can improve plant factor greatly, and simplify the operation.
Oil of mirbane transformation efficiency of the present invention is more than 80%, p-aminophenol production rate 80～86%, and selectivity (p-aminophenol is than aniline) reaches as high as 30: 1 more than 20: 1, and the reaction times is below 3 hours, the shortlyest reaches 0.5 hour.
Because selectivity is good, by product is few in the reaction solution, thus can save with the multiple extraction reaction solution of organic solvent (as benzene, pimelinketone etc.), removing the purification step of variable color quality, can directly crystallization from reaction solution, must white or light yellow crystal.In the long storage brown bottle, there is not obvious variable color.Its fusing point is 184-186 ℃, and through infrared, ultraviolet, determination of elemental analysis, p-aminophenol purity can reach more than 99%.
Temperature of reaction of the present invention is 60-130 ℃, and optimal temperature is 80-110 ℃; Reaction pressure 1-3kg/cm
2Suitable hydrogen pressure is 1.6-2.5kg/cm
2; Sulfuric acid concentration is 10-25%, suitable concentration 14～18%; Tensio-active agent charging capacity (is benchmark with oil of mirbane) is 2～10 ‰, sufficient quantity 3～5 ‰; Catalyzer charging capacity (precious metal is than oil of mirbane) is 0.2～5 ‰, sufficient quantity 0.4～2 ‰; Reaction times is 0.5～1 hour, how at 1～2 hour; Under above-mentioned processing condition, can do heating source with water vapor, and can directly select for use standard equipment-glass-lined reactor to do reactor, be convenient to industrial production.
Embodiment
In oscillation mode reactor, add 12g oil of mirbane, 14% aqueous sulfuric acid 50ml, Trimethyllaurylammonium bromide 46mg, 2% platinum-ruthenium/carbon catalyst (platinum: ruthenium is 5: 1) 0.6g is at hydrogen pressure 2.0kg/cm
2, under the condition that temperature is 95 ± 1 ℃, reacted 1 hour 20 minutes, filter catalyzer, tell unreacted oil of mirbane, add ammoniacal liquor then, make reaction solution pH=4～5, use steam distillation, remove aniline and allochroic organic impurity, behind the decolorizing with activated carbon, add S-WAT, continuation is transferred the pH=7 of reaction solution with ammoniacal liquor, cool off the p-aminophenol white crystal.
The oil of mirbane transformation efficiency of this reaction is 90%, and the p-aminophenol production rate is 86%, and p-aminophenol is 30.1: 1 than the selectivity of aniline.
Embodiment two
The catalyzer of embodiment one gained, add again in the oscillation mode reactor, repeat above-mentioned steps, reacted 1 hour 30 minutes, the oil of mirbane transformation efficiency is 89%, and the p-aminophenol production rate is 83.5%, and p-aminophenol is 25: 1 than the selectivity of aniline.
Embodiment three
In oscillation mode reactor, add 30g oil of mirbane, 18% aqueous sulfuric acid 70ml, cetyl trimethylammonium bromide 62mg, 4% platinum/C catalyst 0.3g is at hydrogen pressure 2.2kg/cm
2, under the condition that temperature is 90 ± 1 ℃, reacting 1 hour 55 minutes, the oil of mirbane transformation efficiency is 85%, and the p-aminophenol production rate is 81%, and p-aminophenol is 21.1:1 than aniline selectivity.
Embodiment four
In oscillation mode reactor, add 12g oil of mirbane, 16% aqueous sulfuric acid 50ml, dodecyl acid methyl brometo de amonio 40mg, 5% platinum/C catalyst 0.4g is at hydrogen pressure 2.0kg/cm
2, under 90 ± 1 ℃ of conditions of temperature, reacted 0.5 hour, oil of mirbane transformation efficiency 92%, p-aminophenol production rate 84%, p-aminophenol is 24: 1 than aniline selectivity.
Claims (3)
1, a kind of from oil of mirbane system p-aminophenol technology, it is characterized in that: in earthquake formula reactor or the stirred autoclave, utilize tensio-active agent and by concussion or stir, oil of mirbane is dispersed in acidic medium such as the aqueous sulfuric acid, containing in the presence of the hydrogenation catalyst of precious metal, feed hydrogen, the oil of mirbane highly selective is converted into p-aminophenol.
2, by claim 1 described technology, it is characterized in that: the precious metal in the hydrogenation catalyst is loaded in that weight percent is 0.5-8% on the activated carbon, and sufficient quantity is 2-5%, and the ratio of platinum and other precious metals is 2-20 in the two-pack hydrogenation catalyst: 1.
3, by the described technology of claim 1-2, it is characterized in that: the sepn process of reaction product is, reaction product with the elimination hydrogenation catalyst, add adjusting PH with base value 4-5, use steam distillation, remove aniline and a small amount of other variable color organic impuritys, and add decolorizing with activated carbon, add S-WAT or V-Brite B is anti-oxidation, with about adjusting PH with base value to 7, promptly separate out the p-aminophenol crystal then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103667A CN85103667B (en) | 1985-05-22 | 1985-05-22 | Prepare p-aminophenol technology from the catalytic hydrogenation of oil of mirbane highly selective |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103667A CN85103667B (en) | 1985-05-22 | 1985-05-22 | Prepare p-aminophenol technology from the catalytic hydrogenation of oil of mirbane highly selective |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103667A CN85103667A (en) | 1986-09-03 |
| CN85103667B true CN85103667B (en) | 1987-07-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85103667A Expired CN85103667B (en) | 1985-05-22 | 1985-05-22 | Prepare p-aminophenol technology from the catalytic hydrogenation of oil of mirbane highly selective |
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| Country | Link |
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| CN (1) | CN85103667B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100428990C (en) * | 2007-03-22 | 2008-10-29 | 南京大学 | Y2 O3 nanometer carrier Ag catalyst, its synthesis and use |
| CN102872862B (en) * | 2012-10-12 | 2014-12-24 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound |
| CN102861573B (en) * | 2012-10-12 | 2014-11-05 | 康纳新型材料(杭州)有限公司 | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound |
| 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 |
| CN103977833A (en) * | 2014-05-20 | 2014-08-13 | 中国科学院福建物质结构研究所 | Preparation method and application of coordination polymer platinum-loaded nano-catalyst |
| CN110590570B (en) * | 2019-10-10 | 2023-05-05 | 西安凯立新材料股份有限公司 | Method for preparing halogenated p-aminophenol by catalytic hydrogenation of non-para-halogenated nitrobenzene |
| CN113200876A (en) * | 2021-05-20 | 2021-08-03 | 安徽东至广信农化有限公司 | Synthesis process of p-aminophenol |
| CN115197074A (en) * | 2022-06-28 | 2022-10-18 | 辽宁世星药化有限公司 | Production method of p-aminophenol |
-
1985
- 1985-05-22 CN CN85103667A patent/CN85103667B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85103667A (en) | 1986-09-03 |
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