CN1075489C - Process for synthesizing p-aminophenol - Google Patents
Process for synthesizing p-aminophenol Download PDFInfo
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- CN1075489C CN1075489C CN98121078A CN98121078A CN1075489C CN 1075489 C CN1075489 C CN 1075489C CN 98121078 A CN98121078 A CN 98121078A CN 98121078 A CN98121078 A CN 98121078A CN 1075489 C CN1075489 C CN 1075489C
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- aminophenol
- synthetic method
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- nylon
- mirbane
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Abstract
The present invention discloses a synthesis method for p-aminophenol. In the method, a Pt/nylon catalyst is adopted for the hydrogenation reaction of nitrobenzene and gaseous hydrogen, and the p-aminophenol is generated by rearrangement in an acidic medium. The present invention effectively solves the problem of serious environmental pollution of the prior art, and has higher application value for industrialization.
Description
The present invention relates to a kind of synthetic method of p-aminophenol, especially the oil of mirbane shortening prepares the method for p-aminophenol.
P-aminophenol is a sharp important organic intermediate, is widely used in dyestuff, rubber, and medicine, in the industry such as sensitive materials, p-aminophenol personated old man production art causes market comparatively nervous because serious environmental is polluted numerous and confused the stopping production in recent years.
The synthetic method of p-aminophenol mainly contains: 1. the iron powder reducing method of p-NP, the 2. electrochemical reducing of oil of mirbane, 3. the catalytic hydrogenation method of p-NP, 4. the catalytic hydrogenation method of oil of mirbane.The industrialized preparing process of traditional p-aminophenol is the iron powder reducing method of p-NP normally, since the cost height of p-NP, the iron mud serious environment pollution after the reduction.And the electrochemical reducing of oil of mirbane, energy consumption is big, and sewage is serious.P-NP catalytic hydrogenation method exists the high shortcoming of raw materials cost too.
So people's number of research projects concentrates on the synthetic p-aminophenol of catalytic hydrogenation method of oil of mirbane in recent years, this method is owing to use hydrogen and the catalyzer p-nitrophenyl that can recycle to carry out hydrogenation reaction, reduced pollution to environment, use therein catalyzer is generally platinum/C catalyst, the synthetic method of the disclosed p-aminophenol of Chinese patent CN85103667A for example, employed is the Pt/ C catalyst, selectivity is good, but it is owing to the metal of this kind catalyzer runs off easily, so very big to the life of catalyst influence.Will reach described highly selective, speed of response will reduce greatly in addition, and the reaction times is extremely long, lack practicality.U.S. Pat 4,885, the synthetic method of 389 disclosed p-aminophenol, Pt/C catalyzer or Pt/ aluminium oxide catalyst have been used, wherein the Pt/C catalyzer also exists the shortcoming that metal runs off easily, and Pt/ aluminium oxide catalyst carrier in the presence of acidic medium dissolves easily, and inactivation is very fast.
The objective of the invention is to propose a kind of synthetic method of practicable p-aminophenol, solve problem of environmental pollution of the prior art, and reactive metal is difficult for running off on the catalyzer, catalyst life obtains prolonging.
The technical scheme that solves the object of the invention is as follows:
Under the condition that hydrogen, tensio-active agent and acidic medium exist, oil of mirbane is contacted with the Pt/ nylon catalyst, react separating obtained then p-aminophenol.
Above-mentioned tensio-active agent can be cats product, anion surfactant or nonionogenic tenside.Acidic medium can be sulfuric acid, hydrochloric acid or etc. protonic acid or the like.Oil of mirbane can be taken from industrial raw material oil of mirbane.
The consumption of tensio-active agent is a benchmark with the weight percent of oil of mirbane, is 0.2%～0.7%.
Consumption in the above-mentioned acidic medium with sulfuric acid be example can for: sulfuric acid concentration is 12%～20%, with the volume ratio of oil of mirbane be 3～5: 1.
The processing condition of hydrogenation reaction are: temperature of reaction is 10～200 ℃, is preferably 50～100 ℃; The pressure of reactive system is 0.01～5.0MPa, is preferably 0.1～1.0MPa; Weight percent with oil of mirbane is a benchmark, and catalyst consumption is 0.5%～50%, is preferably 5%～15%.
The carrier of Pt/ nylon catalyst can be one or more in the polyamide-based materials such as nylon-6, nylon-66, nylon-10 11, nylon-1010, nylon-10 12.Weight percent with catalyzer is a benchmark, and the content of Pt is 0.01%～10%, is preferably 1%～3%.
Can include auxiliary agent in the Pt/ nylon catalyst, auxiliary agent can be one or more among transition metal such as Rh, Ru and the Sn.The mol ratio of auxiliary agent and Pt is 0.00: 1～1: 1, is preferably 0.05: 1～0.2: 1.
The concise and to the point process of Pt/ nylon catalyst preparation can for:
Nylon is made powder, then as required, take by weighing an amount of nylon powder; put into there-necked flask; add water, stir, according to the platinum containing amount of preparing the preparation catalyzer or the amount of other auxiliary agent; add an amount of platinum acid chloride solution chloride soln of other metallic elements (or add simultaneously); nitrogen protection is reduced to catalyzer, filters; at air drying, obtain the Pt/ nylon catalyst.
The reduction mode of catalyzer can be the organic solvent reduction, also can be that hydrogen directly reduces.
Above-mentioned organic solvent can be to be easy to oxidized material, for example, can be in methyl alcohol or the formaldehyde one or both.
Compared with prior art, the present invention has following advantage and effect:
The present invention successfully is applied to the Pt/ nylon catalyst reaction of hydrogenation of chloronitrobenzene one-step synthesis p-aminophenol, has reduced the environmental pollution of traditional technology, has reduced problem such as metal loss on the catalyzer, has prolonged the work-ing life of catalyzer.And the hydrogenation technique condition comparatively relaxes, and is easy and simple to handle, and turndown ratio is bigger, and raw materials cost is lower, for the industrial production p-aminophenol provides a kind of reality feasible method.
Details is seen the following examples:
The test catalyst system therefor sees Table 1, the hydrogenation process of oil of mirbane is: with the Pt/ nylon catalyst, tensio-active agent (following examples adopt be cetyl trimethylammonium bromide) and acidic medium (following examples adopt be aqueous sulfuric acid 10ml), oil of mirbane 3.4ml puts into 250ml there-necked flask reactor, the bottleneck sealing, air in the system is replaced into hydrogen, and makes in the hydrogen metering pipe that links to each other with the water surge tank and be full of hydrogen, the consumption of hydrogen in the record reaction process.Thereby mensuration activity of such catalysts, product obtain generating in the product selectivity of p-aminophenol through liquid-phase chromatographic analysis.Reaction conditions and the results are shown in Table 2.
Table 1 test catalyst system therefor is formed
| The catalyzer numbering | 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?9 | ?10 |
| Pt content % | 1.2 | ?2.0 | ?3.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.0 |
| Used carrier | N66 | ?N66 | ?N66 | ?N6 | ?N1012 | ?N1010 | ?N66 | ?N66 | ?N66 | ?N66 |
| Adjuvant used | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | ?Sn | ?Rh | Do not have | Do not have |
| Auxiliary agent content % | ?0.13 | ?0.13 | ||||||||
| The method of reducing of catalyzer | H 2 | ?H 2 | ?H 2 | ?H 2 | ?H 2 | ?H 2 | ?H 2 | ?H 2 | Methyl alcohol | Formaldehyde |
Annotate: Pt content in this table, auxiliary agent content etc. all are that the weight percent with catalyzer is a benchmark.
Table 2 reaction conditions and reaction result
| Embodiment | 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?9 |
| Catalyzer | 1 | ?2 | ?2 | ?2 | ?2 | ?3 | ?4 | ?5 | ?6 |
| Temperature of reaction ℃ | 70 | ?70 | ?70 | ?70 | ?80 | ?70 | ?50 | ?70 | ?70 |
| Reaction pressure Mpa | 0.1 | ?0.1 | ?0.1 | ?0.2 | ?0.1 | ?0.1 | ?0.1 | ?0.1 | ?0.1 |
| Catalyst levels % | 5 | ?5 | ?10 | ?15 | ?10 | ?10 | ?10 | ?10 | ?5 |
| Sulfuric acid concentration % | 20 | ?15 | ?15 | ?15 | ?15 | ?10 | ?15 | ?15 | ?15 |
| Dosage of surfactant % | 0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.4 |
| Active | 0.0208 | ?0.0285 | ?0.0180 | ?0.0115 | ?0.0186 | ?0.0101 | ?0.0085 | ?0.0191 | ?0.0196 |
| Selectivity | 4.9 | ?2.8 | ?3.1 | ?2.9 | ?3.0 | ?1.6 | ?2.1 | ?3.0 | ?3.2 |
Continuous table 2
| Embodiment | 10 | ?11 | ?12 | ?13 | ?14 | ?15 | ?16 | ?17 | ?18 |
| Catalyzer | 2 | ?7 | ?8 | ?9 | ?10 | ?2 | ?2 | ?2 | ?2 |
| Temperature of reaction ℃ | 70 | ?80 | ?70 | ?70 | ?80 | ?100 | ?70 | ?70 | ?70 |
| Reaction pressure Mpa | 0.5 | ?0.1 | ?0.1 | ?0.2 | ?0.1 | ?0.1 | ?0.1 | ?0.1 | ?0.8 |
| Catalyst levels % | 10 | ?10 | ?5 | ?10 | ?10 | ?5 | ?20 | ?10 | ?10 |
| Sulfuric acid concentration % | 15 | ?15 | ?15 | ?15 | ?10 | ?15 | ?15 | ?15 | ?15 |
| Dosage of surfactant % | 0.4 | ?0.4 | ?0.4 | ?0.4 | ?0.6 | ?0.4 | ?0.2 | ?0.4 | ?0.4 |
| Active | 0.0210 | ?0.0010 | ?0.0015 | ?0.0151 | ?0.0184 | ?0.0236 | ?0.0106 | ?0.0276 | ?0.0291 |
| Selectivity | 1.8 | ?2.8 | ?5.9 | ?1.6 | ?2.4 | ?2.2 | ?2.9 | ?2.9 | ?2.5 |
Annotate: catalyst levels, dosage of surfactant are to be benchmark with used oil of mirbane weight percent in this table; Activity is meant that 1mmol catalyst oil of mirbane/hydrogen system per minute consumes the mole number of hydrogen; Selectivity is meant the ratio of the p-aminophenol that generated and the weight of aniline.Catalyzer among the embodiment 17 is the catalyzer 2 that recycles after 50 times, and the catalyzer among the embodiment 18 is the catalyzer 2 that recycles after 85 times.
Claims (18)
1. the synthetic method of a p-aminophenol, oil of mirbane reacts under the condition that hydrogen, tensio-active agent, catalyzer and acidic medium exist, and isolates p-aminophenol then, it is characterized in that the catalyzer that reacts used is the Pt/ nylon catalyst.
2. according to the synthetic method of the described p-aminophenol of claim 1, it is characterized in that described reaction conditions is:
10～200 ℃ of temperature of reaction;
The pressure of reactive system is 0.01～5.0MPa;
Weight percent with oil of mirbane is a benchmark, and catalyst consumption is 0.5%～50%.
3. according to the synthetic method of the described p-aminophenol of claim 1, the carrier that it is characterized in that described Pt/ nylon catalyst is one or more in nylon-6, nylon-66, nylon 1011, nylon 1010, the nylon 1012.
4. according to the synthetic method of the described p-aminophenol of claim 1, it is characterized in that described dosage of surfactant is a benchmark with the oil of mirbane weight percent, is 0.2%～0.7%.
5. according to the synthetic method of the described p-aminophenol of claim 1, it is characterized in that described acidic medium is a sulfuric acid, vitriolic concentration is 12～20%, with the volume ratio of oil of mirbane be 3～5: 1.
6. according to the synthetic method of claim 1 or 2 described p-aminophenol, it is characterized in that temperature of reaction is 50～100 ℃.
7. according to the synthetic method of claim 1 or 2 described p-aminophenol, it is characterized in that reaction pressure is 0.1～1.0MPa.
8. according to the synthetic method of claim 1 or 2 described p-aminophenol, it is characterized in that described catalyst levels is a benchmark in the weight percent of oil of mirbane, is 5%～15%.
9. according to the synthetic method of claim 1 or 3 described p-aminophenol, it is characterized in that described nylon is nylon-66.
10. according to the synthetic method of the described p-aminophenol of claim 1, it is characterized in that containing auxiliary agent in the described catalyzer.
11. according to the synthetic method of the described p-aminophenol of claim 1, the content that it is characterized in that Pt in the described catalyzer is benchmark in the weight percent of catalyzer, is 0.01%～10%.
12., it is characterized in that described auxiliary agent is one or more among Rh, Ru, the Sn according to the synthetic method of the described p-aminophenol of claim 10.
13. according to the synthetic method of the described p-aminophenol of claim 1, the content that it is characterized in that Pt in the described catalyzer is benchmark in the weight percent of catalyzer, is 1%～3%.
14. according to the synthetic method of claim 10 or 12 described p-aminophenol, the mol ratio that it is characterized in that described auxiliary agent and Pt is 0.001: 1～1: 1.
15. according to the synthetic method of claim 10 or 12 described p-aminophenol, the mol ratio that it is characterized in that described auxiliary agent and Pt is 0.005: 1～0.2: 1.
16., it is characterized in that described catalyzer is to reduce with hydrogen according to the synthetic method of the described p-aminophenol of claim 1.
17., it is characterized in that described catalyzer is to reduce with organic solvent according to the synthetic method of the described p-aminophenol of claim 1.
18., it is characterized in that described organic solvent is one or both in methyl alcohol and the formaldehyde according to the synthetic method of the described p-aminophenol of claim 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121078A CN1075489C (en) | 1998-12-16 | 1998-12-16 | Process for synthesizing p-aminophenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121078A CN1075489C (en) | 1998-12-16 | 1998-12-16 | Process for synthesizing p-aminophenol |
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| CN1257065A CN1257065A (en) | 2000-06-21 |
| CN1075489C true CN1075489C (en) | 2001-11-28 |
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| CN98121078A Expired - Fee Related CN1075489C (en) | 1998-12-16 | 1998-12-16 | Process for synthesizing p-aminophenol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325159C (en) * | 2004-03-22 | 2007-07-11 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328244C (en) * | 2002-03-15 | 2007-07-25 | 南京工业大学 | Process for producing para-amino-phenol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085511A2 (en) * | 1982-01-29 | 1983-08-10 | MALLINCKRODT, INC.(a Missouri corporation) | Process for preparing p-aminophenol and alkyl substituted p-aminophenol |
| US4885389A (en) * | 1987-06-08 | 1989-12-05 | Industrial Technology Research Institute | Process for manufacturing p-aminophenol |
-
1998
- 1998-12-16 CN CN98121078A patent/CN1075489C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0085511A2 (en) * | 1982-01-29 | 1983-08-10 | MALLINCKRODT, INC.(a Missouri corporation) | Process for preparing p-aminophenol and alkyl substituted p-aminophenol |
| US4885389A (en) * | 1987-06-08 | 1989-12-05 | Industrial Technology Research Institute | Process for manufacturing p-aminophenol |
Non-Patent Citations (1)
| Title |
|---|
| 《辽宁化工》，VOT.26，NO.3，1997年5月 1997.5.1 张超等人，"硝基苯催化氢化法合成对氨基苯酚的进展" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325159C (en) * | 2004-03-22 | 2007-07-11 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
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| CN1257065A (en) | 2000-06-21 |
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