CN108997138A - A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline - Google Patents
A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline Download PDFInfo
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- CN108997138A CN108997138A CN201810941845.9A CN201810941845A CN108997138A CN 108997138 A CN108997138 A CN 108997138A CN 201810941845 A CN201810941845 A CN 201810941845A CN 108997138 A CN108997138 A CN 108997138A
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- fluoroaniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides a kind of methods of solvent-free catalytic hydrogenation production para-fluoroaniline, using p-fluoronitrobenzene as raw material, under condition of no solvent, catalytic hydrogenation prepares para-fluoroaniline in autoclave under the conditions of adding catalyst and phosphate, the present invention is using solvent-free plus hydrogen method, solvent compared to the past adds hydrogen, greatly increase the efficiency of reaction, utilization rate of equipment and installations significantly improves, recycling design bring energy consumption and cost of equipment can be effectively avoided simultaneously, the environmentally friendly technique for belonging to green non-pollution effectively avoids generating a large amount of waste water, waste residue.The present invention uses this noble metal catalyst of Pt/C, has preparation simple, catalyst itself can be recycled in the reaction, and metal can recycle, to further decrease production cost, dehydrogenation inhibitor is acted not only as using phosphate, and reaction conversion ratio can be improved.
Description
Technical field
The invention belongs to technical field of catalytic hydrogenation, and in particular to a kind of solvent-free catalytic hydrogenation production para-fluoroaniline
Method.
Background technique
Para-fluoroaniline is a kind of important fine-chemical intermediate, is mainly used for medicine, dyestuff and pesticide etc., external
More early to the product development, the country starts from the beginning of the nineties in last century.
In the prior art about there are two types of the production methods of para-fluoroaniline: one is by triazobenzene (United States Patent (USP)
) or N- phenyl aqua ammonia (United States Patent (USP) US4291991) or parachloronitrobenzene (United States Patent (USP) US3900519) US4145364
Para-fluoroaniline is directly synthesized through single step reaction Deng for raw material.This method is limited by raw material sources or need to be using deep-etching hydrofluoric acid etc.
Reason, industrialization are difficult.Another method is to produce para-fluoroaniline through reduction using p-fluoronitrobenzene as raw material, p-fluoronitrobenzene
Reduction mainly has iron powder reducing method, sodium sulfide reducing method and catalytic hydrogenating reduction method, and iron powder reducing method equipment is simple, operation side
Just, but a large amount of waste water and waste residue can be generated, the problem of sodium sulfide reducing method equally exists waste water, and catalytic hydrogenating reduction
Method, high income and generates the seldom three wastes, belongs to environmentally friendly friendly process.It would therefore be highly desirable to propose a kind of catalytic hydrogenation
The method for producing para-fluoroaniline.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline, should
Method and process is simple, high income, at low cost, environmentally protective.
The present invention is achieved by the following technical solutions:
A kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline, using p-fluoronitrobenzene as raw material, under condition of no solvent,
Catalytic hydrogenation prepares para-fluoroaniline in autoclave under the conditions of addition catalyst and phosphate.
Preferably, the catalyst is Pt/C catalyst, and the Pt load capacity of catalyst is 1% or 3%, and dosage is to fluorine nitro
The 0.5%-1% of benzene quality.
Preferably, the phosphate in sodium hypophosphite, hydrogen phosphite sodium, disodium hydrogen phosphate, sodium phosphate one
Kind, dosage is the 1%-3% of p-fluoronitrobenzene quality.
Preferably, the condition of catalytic hydrogenation are as follows: pressure 0.5-2.0Mpa, reaction temperature are 60-150 DEG C.
The step of catalytic hydrogenation reaction described above are as follows:
(1) by the p-fluoronitrobenzene, catalyst, phosphate is added in autoclave, and nitrogen, hydrogen are respectively replaced three times；
(2) stirring is opened, 60-150 DEG C is warming up to, is passed through hydrogen 0.5-2.0Mpa, start to react, control reaction temperature is 60-
150℃；
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, is dropped with the interior Hydrogen Vapor Pressure reacted per minute to indicate, instead
Answer speed are as follows: 0.10-0.3Mpa/min；
(4) the reaction used time is 1-4 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero；
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, obtains most after vacuum distillation
Finished product para-fluoroaniline.
The conversion ratio of the reaction of product obtained by the above method is 100%, product purity>99.5%, defluorinate<0.2%, product
Yield > 98%.
Beneficial effect
(1) for the present invention using solvent-free plus hydrogen method, the solvent compared to the past adds hydrogen, greatly increases the efficiency of reaction,
Utilization rate of equipment and installations significantly improves, while can effectively avoid recycling design bring energy consumption and cost of equipment.
(2) method that the present invention uses catalytic hydrogenation, belongs to the environmentally friendly technique of green non-pollution, effectively avoids producing
Raw a large amount of waste water, waste residue.
(3) present invention uses this noble metal catalyst of Pt/C, has preparation simple, and catalyst itself in the reaction can be with
It is recycled, and metal can recycle, to further decrease production cost.
(4) present invention use lower reaction temperature and reaction pressure, para-fluoroaniline is prepared, have simple process,
The advantages of high income.
(5) present invention acts not only as dehydrogenation inhibitor using phosphate, and reaction conversion ratio can be improved, and reacts
Time is shorter, 1-4 hour can fully reacting, and yield is higher, and defluorinate rate is lower.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
(1) by 200g p-fluoronitrobenzene, 1g 1%Pt/C catalyst, 1g sodium hypophosphite is added in autoclave, nitrogen, hydrogen
Each displacement is three times.
(2) stirring is opened, 60 DEG C is warming up to, is passed through hydrogen 0.9Mpa, start to react, control reaction temperature is 85 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.12Mpa/min.
(4) the reaction used time is 3 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products para-fluoroaniline, the conversion ratio of reaction is 100%, product purity 99.6%, defluorinate 0.15%, product yield 98%.
Embodiment 2
Under the premise of embodiment 1, carry out catalyst applies experiment (i.e. catalyst circulation use):
(1) by 200g p-fluoronitrobenzene, 0.2g 1%Pt/C catalyst is added, 1g sodium hypophosphite is added in autoclave, nitrogen
Gas, hydrogen are respectively replaced three times.
(2) stirring is opened, 60 DEG C is warming up to, is passed through hydrogen 0.9Mpa, start to react, control reaction temperature is 85 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.13Mpa/min.
(4) the reaction used time is 45 minutes 2 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed
Degree is zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products para-fluoroaniline, the conversion ratio of reaction is 100%, product purity 99.75%, defluorinate 0.10%, product yield 98.5%.
Embodiment 3:
Continuing to apply 10 batches under the premise of embodiment 1, embodiment 2, to obtain result as follows:
Wherein serial number 8 is that the sodium hypophosphite in embodiment 1 is changed to sodium phosphate, and other conditions are constant；
Serial number 9 is that the sodium hypophosphite in embodiment 1 is changed to disodium hydrogen phosphate, and other conditions are constant；
Serial number 10 is that the sodium hypophosphite in embodiment 1 is changed to hydrogen phosphite sodium, and other conditions are constant；
It is 30 DEG C that serial number 11, which is by the control reaction temperature in embodiment 1, and other conditions are constant；
It is 150 DEG C that serial number 12, which is by the control reaction temperature in embodiment 1, and other conditions are constant.
Embodiment 4:
(1) by 200g p-fluoronitrobenzene, 1g 3%Pt/C catalyst, 2g sodium hypophosphite is added in autoclave, nitrogen, hydrogen
Each displacement is three times.
(2) stirring is opened, 60 DEG C is warming up to, is passed through hydrogen 1.0Mpa, start to react, control reaction temperature is 95 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.22Mpa/min.
(4) the reaction used time is 1 hour 50min, and at the end of reaction, reaction pressure is increased, and reaction temperature reduces, reaction speed
It is zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products para-fluoroaniline, the conversion ratio of reaction is 100%, product purity 99.5%, defluorinate 0.20%, product yield 98.12%.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (5)
1. a kind of method of solvent-free catalytic hydrogenation production para-fluoroaniline, it is characterised in that: using p-fluoronitrobenzene as raw material, nothing
Under solvent condition, catalytic hydrogenation prepares para-fluoroaniline in autoclave under the conditions of adding catalyst and phosphate.
2. the method according to claim 1, wherein the catalyst is Pt/C catalyst, the Pt of catalyst
Load capacity is 1% or 3%, the 0.5%-1% of dosage p-fluoronitrobenzene quality.
3. the method according to claim 1, wherein the phosphate is selected from sodium hypophosphite, hydrogen phosphite
One of sodium, disodium hydrogen phosphate, sodium phosphate, dosage are the 1%-3% of p-fluoronitrobenzene quality.
4. according to the method described in claim 2, it is characterized in that, the condition of catalytic hydrogenation are as follows: pressure 0.5-2.0Mpa, instead
Answering temperature is 60-150 DEG C.
5. method described in one of -4 according to claim 1, which is characterized in that the step of catalytic hydrogenation reaction are as follows:
(1) by the p-fluoronitrobenzene, catalyst, phosphate is added in autoclave, and nitrogen, hydrogen are respectively replaced three times；
(2) stirring is opened, 60-150 DEG C is warming up to, is passed through hydrogen 0.5-2.0Mpa, start to react, control reaction temperature is 60-
150℃；
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, is dropped with the interior Hydrogen Vapor Pressure reacted per minute to indicate, instead
Answer speed are as follows: 0.10-0.3Mpa/min；
(4) the reaction used time is 1-4 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero；
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, obtains most after vacuum distillation
Finished product para-fluoroaniline.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023271A (en) * | 2023-01-13 | 2023-04-28 | 山东国邦药业有限公司 | Synthesis method of p-fluoroaniline |
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| CN116023271B (en) * | 2023-01-13 | 2023-06-20 | 山东国邦药业有限公司 | Synthesis method of p-fluoroaniline |
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