CN109134268A - The method of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine - Google Patents
The method of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine Download PDFInfo
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- CN109134268A CN109134268A CN201710509477.6A CN201710509477A CN109134268A CN 109134268 A CN109134268 A CN 109134268A CN 201710509477 A CN201710509477 A CN 201710509477A CN 109134268 A CN109134268 A CN 109134268A
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- paranitroanilinum
- phenylenediamine
- catalytic hydrogenation
- water
- hydrogenation synthesis
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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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to field of fine chemical, and in particular to a kind of method of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine.The method of the paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine, steps are as follows: (1) mixed liquor of paranitroanilinum, water and ethyl alcohol, tetrabutylammonium bromide, catalyst being added in autoclave, after sealing, with the air in nitrogen displacement kettle；(2) it is passed through hydrogen into kettle, stirs lower heating reaction；(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation obtains p-phenylenediamine product in bottom, solution crystallisation by cooling, filtering, filter cake vacuum drying.The present invention uses the mixed liquor of water and ethyl alcohol for solvent, and tetrabutylammonium bromide is added during the reaction, it solves the problems, such as individually to use alcoholic solvent high volatility, risk height, recycling loss big, simultaneously, it also overcomes and individually adopts water as the deficiency that Solvent Solubility is small, reaction speed is slow, oxidizable, be suitble to industrialized production.
Description
Technical field
The invention belongs to field of fine chemical, and in particular to a kind of side of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine
Method.
Background technique
P-phenylenediamine is a kind of important Organic Chemicals, is generally used for production dyestuff, rubber antioxidant etc..Traditional
The production method of p-phenylenediamine is to react preparation pair under high-temperature and high-pressure conditions with ammonium hydroxide (or ammonia) using paranitrochlorobenzene as raw material
Nitroaniline, paranitroanilinum passes through akali sulphide again or iron powder reducing generates p-phenylenediamine crude product, then passes through recrystallization purification
Prepare high-purity p-phenylenediamine.The maximum defect of the technique is that industrial wastewater is more, and iron powder reducing can also generate a large amount of iron cements, seriously
Environment is polluted, and the p-phenylenediamine purity of this technique production is lower, generally 95% or so, to obtain purity is 99% or more
Product also need to recrystallize purification, higher cost.
Wang Yanzhen of China University Of Petroleum Beijing etc. replaces iron powder also on the basis of traditional handicraft, with catalytic hydrogenating reduction technology generations
Original process prepare p-phenylenediamine, and hydrogenation catalyst is selected using molybdenum oxide, active carbon, silica gel, molecular sieve as carrier, palladium, platinum, rhodium,
One or more of ruthenium, nickel are the loaded noble metal catalyst of active component.Technique effective solution environmental pollution
Problem, but the technique is maximum the disadvantage is that the expensive noble metal catalyst used, cost are very high.In addition the technique pair
The purity of phenylenediamine is 99%, and yield 98%, purity and yield also can further improve.
Li Kuanyi etc. prepares P-aminoazobenzene using aniline as raw material, through reactions such as diazotising, coupling, indexings, then passes through
P-aminoazobenzene catalytic hydrogenating reduction is generated p-phenylenediamine by the noble metal catalysts such as palladium/carbon, platinum/carbon.The process route is multiple
Miscellaneous not easy to control, the p-phenylenediamine yield of generation is lower, and uses expensive noble metal catalyst, higher cost.
The nitrobenzene such as Joo and urea react at room temperature~200 DEG C in the polar organic solvent containing alkali, synthesize
To the mixture of nitrosoaniline and paranitroanilinum, then mixture is dissolved in ethanol solution, hydrogenation catalyst is added,
(Pd/C or Pt/C), under the pressure of 50~500Pa, reaction generates p-phenylenediamine.The technique outstanding advantages are no three wastes, but
It is that technical difficulty is higher, production control is relatively difficult, and there is also other many disadvantages for the method, as noble metal catalyst price is high
Expensive, easy poisoning is not easily recycled, and polar solvent dimethyl sulfoxide (DMSO), expensive, dimethyl sulfoxide is easy to make hydrogenation catalyst
Poisoning, causes product cost height.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of synthesis of paranitroanilinum catalytic hydrogenation to benzene two
The method of amine overcomes the problems, such as individually to adopt water as that Solvent Solubility is small, reaction speed is slow, overcome individually using ethyl alcohol as solvent,
High volatility, risk are high, big problem is lost in recycling, are suitble to industrialized production.
The method of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine of the present invention, steps are as follows:
(1) mixed liquor of paranitroanilinum, water and ethyl alcohol, tetrabutylammonium bromide, catalyst are added to autoclave
In, after sealing, with the air in nitrogen displacement kettle；
(2) it is passed through hydrogen into kettle, stirs lower heating reaction；
(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation is in bottom, the cooling knot of solution
Crystalline substance, filtering, filter cake vacuum drying obtain p-phenylenediamine product.
The mass ratio of the mixed liquor of the paranitroanilinum and water and ethyl alcohol is 1:1.5.
In the mixed liquor of the water and ethyl alcohol, the volume ratio of water and ethyl alcohol is 5~10:1.
The quality of the tetrabutylammonium bromide is the 0.5~1% of paranitroanilinum quality.
The catalyst is one or more of Raney's nickel, palladium/charcoal or platinum/charcoal.
The quality of the catalyst is the 0.1~0.5% of paranitroanilinum quality.
The reaction temperature is 40~60 DEG C, and reaction pressure is 2.0~5.0MPa.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention uses the mixed liquor of water and ethyl alcohol for solvent, and tetrabutylammonium bromide is added during the reaction,
It solves the problems, such as individually to use alcoholic solvent high volatility, risk height, recycling loss big, meanwhile, also overcome independent use
Water is the deficiency that Solvent Solubility is small, reaction speed is slow, oxidizable.
2, safety and environmental protection of the present invention, suitable industrialized production, yield is 99% or more.
Specific embodiment
The invention will be further described with reference to embodiments.
Raw material used in the examples is commercially available unless otherwise specified.
Embodiment 1
The method of the paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine, steps are as follows:
(1) by 500g paranitroanilinum, the mixed liquor of 750g water and ethyl alcohol, 2.5g tetrabutylammonium bromide, 0.5g Raney's nickel
It is added in autoclave, after sealing, with the air in nitrogen displacement kettle；
(2) it is passed through hydrogen into kettle, 50 DEG C of reactions, reaction pressure 3.5MPa are heated under stirring；
(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation is in bottom, the cooling knot of solution
Crystalline substance, filtering, filter cake vacuum drying obtain p-phenylenediamine product, yield 99.2%.
The volume ratio of the mixed liquor of the water and ethyl alcohol, water and ethyl alcohol is 8:1.
Embodiment 2
The method of the paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine, steps are as follows:
(1) 500g paranitroanilinum, the mixed liquor of 750g water and ethyl alcohol, 4.0g tetrabutylammonium bromide, 1.5g palladium/charcoal are added
Enter into autoclave, after sealing, with the air in nitrogen displacement kettle；
(2) it is passed through hydrogen into kettle, 60 DEG C of reactions, reaction pressure 2.0MPa are heated under stirring；
(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation is in bottom, the cooling knot of solution
Crystalline substance, filtering, filter cake vacuum drying obtain p-phenylenediamine product, yield 99.5%.
The volume ratio of the mixed liquor of the water and ethyl alcohol, water and ethyl alcohol is 5:1.
Embodiment 3
The method of the paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine, steps are as follows:
(1) 500g paranitroanilinum, the mixed liquor of 750g water and ethyl alcohol, 5.0g tetrabutylammonium bromide, 2.5g platinum/charcoal are added
Enter into autoclave, after sealing, with the air in nitrogen displacement kettle；
(2) it is passed through hydrogen into kettle, 40 DEG C of reactions, reaction pressure 5.0MPa are heated under stirring；
(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation is in bottom, the cooling knot of solution
Crystalline substance, filtering, filter cake vacuum drying obtain p-phenylenediamine product, yield 99.6%.
The volume ratio of the mixed liquor of the water and ethyl alcohol, water and ethyl alcohol is 10:1.
Claims (7)
1. a kind of method of paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine, it is characterised in that: steps are as follows:
(1) mixed liquor of paranitroanilinum, water and ethyl alcohol, tetrabutylammonium bromide, catalyst are added in autoclave, it is close
It is honored as a queen, with the air in nitrogen displacement kettle；
(2) it is passed through hydrogen into kettle, stirs lower heating reaction；
(3) end of reaction discharges hydrogen in kettle, and release separates reactant, and catalyst sedimentation is in bottom, solution crystallisation by cooling, mistake
Filter, filter cake vacuum drying, obtains p-phenylenediamine product.
2. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Paranitroanilinum and the mass ratio of mixed liquor of water and ethyl alcohol be 1:1.5.
3. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Water and ethyl alcohol mixed liquor in, the volume ratio of water and ethyl alcohol is 5~10:1.
4. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Tetrabutylammonium bromide quality be paranitroanilinum quality 0.5~1%.
5. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Catalyst be one or more of Raney's nickel, palladium/charcoal or platinum/charcoal.
6. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Catalyst quality be paranitroanilinum quality 0.1~0.5%.
7. the method for paranitroanilinum catalytic hydrogenation synthesis p-phenylenediamine according to claim 1, it is characterised in that: described
Reaction temperature be 40~60 DEG C, reaction pressure be 2.0~5.0MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734602A (en) * | 2019-01-29 | 2019-05-10 | 安徽高盛化工股份有限公司 | A method of p-phenylenediamine is prepared by hydrogen reducing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734602A (en) * | 2019-01-29 | 2019-05-10 | 安徽高盛化工股份有限公司 | A method of p-phenylenediamine is prepared by hydrogen reducing |
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Application publication date: 20190104 |
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| WW01 | Invention patent application withdrawn after publication |