CN110467534A - A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene - Google Patents
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene Download PDFInfo
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- CN110467534A CN110467534A CN201910874147.6A CN201910874147A CN110467534A CN 110467534 A CN110467534 A CN 110467534A CN 201910874147 A CN201910874147 A CN 201910874147A CN 110467534 A CN110467534 A CN 110467534A
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- phenylenediamine
- dinitrobenzene
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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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Abstract
The present invention provides a kind of techniques of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, the following steps are included: putting into phenylenediamine aqueous solution into reaction kettle, the weight ratio of phenylenediamine and water controls between 0.7~1.5, catalyst is put into again, inventory is controlled the 5% or less of phenylenediamine aqueous solution weight, finally put into dinitrobenzene, inventory is controlled the 7%~10% of phenylenediamine aqueous solution weight, temperature is controlled at 100~200 DEG C, pressure is in 1.0~5.0MPa or more, it is reacted, reaction product phenylenediamine yield is 99% or more.Dinitrobenzene of the present invention catalytic hydrogenation synthesis phenylenediamine under organic solvent-free is a friendly process route, and safety and environmental protection, energy-saving and emission-reduction are of great significance to the green chemical industry development of chemical production process.
Description
Technical field
The invention belongs to phenylenediamine production technical fields, specifically, being related to a kind of solvent-free catalytic hydrogenation of dinitrobenzene
The technique for synthesizing phenylenediamine.
Background technique
Currently, dinitrobenzene hydrogenation synthesis phenylenediamine is all made of organic solvent catalytic hydrogenation method, it is to be existed using dinitrobenzene
In the presence of organic solvent and catalyst (nickel-loaded or palladium) under the conditions ofs certain temperature, pressure etc. hydrogenation synthesis phenylenediamine.It is added
The effect of organic solvent is first is that the concentration of reduction dinitrobenzene in the reaction system, avoids reacting because of dinitrobenzene excessive concentration
Acutely, second is that the partial heat that absorbing reaction generates, avoid it is out of control because react overtemperature, third is that elimination dinitrobenzene and catalyst
Between mass transfer and limit.
It needs to have using volatility however, dinitrobenzene is synthesized in phenylenediamine reaction process by organic solvent catalytic hydrogenation
Solvent, organic solvent is not only expensive, and the use of organic solvent, so that separating technology is complicated, separation process energy consumption is high,
Environmental pollution is serious, system production capacity reduces；Meanwhile there is easy loss, easy intoxicating, inflammable easy in effumability in use
Quick-fried problem.
Summary of the invention
For deficiency above-mentioned in the prior art, the purpose of the present invention is to provide a kind of solvent-free catalysis of dinitrobenzene to add
The technique of hydrogen synthesis phenylenediamine synthesize dinitrobenzene can by catalytic hydrogenation under the conditions of organic solvent-free using this method
Phenylenediamine, can safety and environmental protection, energy-saving and emission-reduction while guaranteeing that reaction is able to achieve high conversion.
In order to achieve the above object, the solution that the present invention uses is:
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
(1) substance of following weight ratio is separately added into reaction kettle:
100 parts by weight of phenylenediamine aqueous solution, 7~10 parts by weight of dinitrobenzene, 1~5 parts by weight of catalyst；
(2) 100~200 DEG C of reactor temperature, 1.0~5.0Mpa of pressure are controlled, hydrogen is filled with and carries out hydrogenation reaction；
(3) reactant through step (2) is transported in filter, is separated by filtration catalyst, obtain phenylenediamine aqueous solution；
(4) phenylenediamine aqueous solution will be obtained through step (3) to be dehydrated, distilled, obtain phenylenediamine finished product；
(5) phenylenediamine finished product will be obtained in step (4) and carry out film-making packaging under the conditions of inert atmosphere protection, obtain height
Purity phenylenediamine finished product.
Further, the substance of following weight ratio is separately added into reaction kettle in step (1): phenylenediamine aqueous solution 100
Parts by weight, 8~10 parts by weight of dinitrobenzene, 2~04 parts by weight of catalyst.
Further, the control of the weight ratio of the phenylenediamine of phenylenediamine aqueous solution described in step (1) and water is 0.7~1.5
Between.
Further, after being used nitrogen displaced air at least 3 times in the reaction kettle of step (1), then extremely with hydrogen displacement nitrogen
It is 3 times few.
Further, catalyst described in step (1) is Raney nickel, palladium catalyst or platinum catalyst.
Further, the Raney nickel is one of skeleton nickel, carrier nickel, reduced nickel or nickel borides.
Further, the palladium catalyst is one of palladium carbon, palladium oxide, palladium black or carrier palladium.
Further, the platinum catalyst is one of platinum oxide, platinum black and carrier platinum.
Further, inert atmosphere described in step (5) is the one or more of high-purity nitrogen, helium or argon gas.
The beneficial effects of the present invention are:
1. dinitrobenzene of the present invention catalytic hydrogenation synthesis phenylenediamine under organic solvent-free is a friendly process route, peace
Loopful guarantor, energy-saving and emission-reduction are of great significance to the green chemical industry development of chemical production process.
2. the present invention carries out the technique of catalytic hydrogenation using organic solvent compared with the existing technology, present invention process is guaranteeing
Reaction not only reduces supplies consumption and production cost, equipment investment and distillation separation circular flow while being able to achieve high yield
Expense, and have simple process, low energy consumption, pollution-free, production safety advantage.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to it is provided in an embodiment of the present invention it is a kind of prepare high-purity polymer grade m-phenylene diamine (MPD) method carry out specifically
It is bright.
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
(1) substance of following weight ratio is separately added into reaction kettle:
100 parts by weight of phenylenediamine aqueous solution, 7~10 parts by weight of dinitrobenzene, 1~5 parts by weight of catalyst；
For the present invention using being solid under phenylenediamine room temperature, being heated to fusing point (63~65 DEG C) or more becomes the property of liquid,
When reacting progress, reaction product phenylenediamine can have both the effect of the alcohol organic solvent in prior art production technology, point
Dissipate raw material dinitrobenzene；By reducing the concentration of dinitrobenzene in the reaction system, eliminate between dinitrobenzene and catalyst
Mass transfer and limit makes dinitrobenzene that can synthesize phenylenediamine under hydroconversion condition by catalyst under conditions of organic solvent-free；This
In order to enable phenylenediamine aqueous solution can all dissolve dinitrobenzene in invention system, in investment dinitrobenzene raw material for the first time,
The inventory for controlling dinitrobenzene is the 7%~10% of phenylenediamine aqueous solution weight；This reaction produces benzene two by catalytic hydrogenation
Amine aqueous solution, therefore phenylenediamine aqueous solution can serve as always the effect of solvent in the reaction system, in subsequent successive reaction
In the process, without putting into phenylenediamine aqueous solution again.
(2) 100~200 DEG C of reactor temperature, 1.0~5.0Mpa of pressure are controlled, hydrogenation reaction is carried out；Existed by control
Under temperature of the invention, pressure condition, phenylenediamine on the one hand can be made to reach fusing point as phenylenediamine aqueous solution in the reaction system
The effect of solvent is played, is on the other hand conducive to the progress of catalytic hydrogenation reaction under temperature of the present invention, pressure condition.
(3) reactant of step (2) is transported in filter, is separated by filtration catalyst, obtain phenylenediamine aqueous solution；For
Keep the purity of reaction product higher, catalyst need to be filtered out when collecting phenylenediamine aqueous solution.
(4) step (3) is obtained phenylenediamine aqueous solution to be dehydrated, distill, obtains phenylenediamine finished product；The present invention uses benzene
Solvent of two amine aqueous solutions as reaction system, it is not necessary that the organic solvents such as methanol are added, therefore without carrying out in present treatment technique
The problem of dealcoholation treatment consumes energy low so that this technique separating technology is simpler, avoids environmental pollution, the reduction of system production capacity.
(5) phenylenediamine finished product will be obtained in step (4) and carry out film-making packaging under the conditions of inert atmosphere protection, obtain high-purity
Spend phenylenediamine finished product.
Further, the substance of following weight ratio is separately added into reaction kettle in step (1): phenylenediamine aqueous solution 100
Parts by weight, 8~10 parts by weight of dinitrobenzene, 2~4 parts by weight of catalyst.
Further, the control of the weight ratio of the phenylenediamine of phenylenediamine aqueous solution described in step (1) and water is 0.7~1.5
Between.For substituting alcoholic solvent in the prior art, such as methanol, ethyl alcohol equal solvent, an organic solvent-free is built for this reaction
Reaction system.
Further, after being used nitrogen displaced air at least 3 times in the reaction kettle of step (1), then extremely with hydrogen displacement nitrogen
It is 3 times few.In order to replace away the air in reaction kettle completely, guarantee that the safety of reaction system carries out.
Further, catalyst described in step (1) is Raney nickel, palladium catalyst or platinum catalyst.The present embodiment is excellent
Choosing uses palladium catalyst.
Further, the Raney nickel is one of skeleton nickel, carrier nickel, reduced nickel or nickel borides.
Further, the palladium catalyst is one of palladium carbon, palladium oxide, palladium black or carrier palladium.The present embodiment is preferred
Use palladium carbon.
Further, the platinum catalyst is one of platinum oxide, platinum black and carrier platinum.
Further, inert atmosphere described in step (5) is the one or more of high-purity nitrogen, helium or argon gas.This
Embodiment preferably uses nitrogen.
Embodiment 1
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 200g distilled water, 300g phenylenediamine, 35g dinitrobenzene, 25g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 3 times after closed, then with hydrogen displacement nitrogen 3 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 1.0Mpa, slow heating is warming up to 100 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product, phenylenediamine after reaction
Product yield is 99.2%.
Embodiment 2
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 294g distilled water, 206g phenylenediamine, 45g dinitrobenzene, 5g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 5 times after closed, then with hydrogen displacement nitrogen 5 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 5.0Mpa, slow heating is warming up to 200 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product.Phenylenediamine after reaction
Product yield is 99.8%.
Embodiment 3
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 245g distilled water, 255g phenylenediamine, 38g dinitrobenzene, 15g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 4 times after closed, then with hydrogen displacement nitrogen 4 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 1.5Mpa, slow heating is warming up to 120 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product.Phenylenediamine after reaction
Product yield is 99.3%.
Embodiment 4
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 214g distilled water, 286g phenylenediamine, 50g dinitrobenzene, 10g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 3 times after closed, then with hydrogen displacement nitrogen 3 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 2.0Mpa, slow heating is warming up to 140 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product.Phenylenediamine after reaction
Product yield is 99.5%.
Embodiment 5
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 261g distilled water, 239g phenylenediamine, 43g dinitrobenzene, 20g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 4 times after closed, then with hydrogen displacement nitrogen 4 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 3.0Mpa, slow heating is warming up to 160 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product.Phenylenediamine after reaction
Product yield is 99.6%.
Embodiment 6
A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, comprising the following steps:
By 282g distilled water, 218g phenylenediamine, 48g dinitrobenzene, 13g palladium-carbon catalyst is separately added into 2L autoclave
In, it is first used nitrogen displaced air 3 times after closed, then with hydrogen displacement nitrogen 3 times, be then charged with hydrogen, adjusts hydrogen valve, made anti-
System pressure is answered to reach pressure 4.0Mpa, slow heating is warming up to 180 DEG C of progress catalytic hydrogenation reactions；If reaction need continue into
Row, then continuing the addition dinitrobenzene into reaction kettle can successive reaction production phenylenediamine aqueous solution；If desired phenylenediamine is collected
Reactant is then transported in filter by finished product, is separated by filtration catalyst, then is dehydrated, is distilled, and phenylenediamine finished product is obtained；
Phenylenediamine finished product is carried out to film-making packaging under the conditions of nitrogen protection again, obtains high-purity benzene diamines finished product.Phenylenediamine after reaction
Product yield is 99.5%.
Comparative example 1
This comparative example provides a kind of technique of dinitrobenzene catalytic hydrogenation synthesis phenylenediamine, comprising the following steps:
Using dinitrobenzene as raw material, in the presence of palladium-carbon catalyst, the hydrogenating reduction in alcohols or other organic solvents, instead
Answer condition are as follows: 100~200 DEG C of temperature, 1.0~5.0Mpa of pressure, 1-5 grams of catalyst charge/100 gram nitro compounds, reactant
After being separated by filtration catalyst, benzene need to be just obtained by the separating technology of a series of complexity such as dealcoholysis, dehydration, decoking, distillation
Two amine products.
Alcohols need to be added while raw material dinitrobenzene is added in process of production for comparative example 1 or other are organic molten
Agent, and then need the subsequent technique for carrying out dealcoholysis, dealcoholysis complex process increases supplies consumption, and production cost increases, energy consumption compared with
Height, and there are problems that polluting environment.
In conclusion dinitrobenzene organic solvent-free catalytic hydrogenation synthesis phenylenediamine of the present invention is a friendly process road
Line, relative to the technique of existing catalytic hydrogenation under the conditions of organic solvent, present invention process is able to achieve high receipts in guarantee reaction
Supplies consumption and production cost and equipment investment and distillation separation circular flow expense are not only reduced while rate, and are had
Have that simple process, low energy consumption, pollution-free, production safety advantage.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene, which comprises the following steps:
(1) substance of following weight ratio is separately added into reaction kettle:
100 parts by weight of phenylenediamine aqueous solution, 7~10 parts by weight of dinitrobenzene, 1~5 parts by weight of catalyst；
(2) 100~200 DEG C of reactor temperature, 1.0~5.0Mpa of pressure are controlled, hydrogen is filled with and carries out hydrogenation reaction；
(3) reactant through step (2) is transported in filter, is separated by filtration catalyst, obtain phenylenediamine aqueous solution；
(4) the phenylenediamine aqueous solution obtained through step (3) is dehydrated, distilled, obtain phenylenediamine finished product；
(5) film-making packaging will be carried out under the conditions of inert atmosphere protection through the phenylenediamine finished product that step (4) obtain, obtain high-purity
Phenylenediamine finished product.
2. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 1, which is characterized in that step
Suddenly the substance of following weight ratio is separately added into reaction kettle in (1): 100 parts by weight of phenylenediamine aqueous solution, dinitrobenzene 8~10
Parts by weight, 2~4 parts by weight of catalyst.
3. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 1, which is characterized in that step
Suddenly the control of the weight ratio of the phenylenediamine in phenylenediamine aqueous solution described in (1) and water is between 0.7~1.5.
4. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 1, which is characterized in that step
With after nitrogen displaced air at least 3 times in the reaction kettle of (1) suddenly, then replaced at least 3 times with hydrogen.
5. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 1, which is characterized in that step
Suddenly catalyst described in (1) is Raney nickel, palladium catalyst or platinum catalyst.
6. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 5, which is characterized in that institute
Stating Raney nickel is one of skeleton nickel, carrier nickel, reduced nickel or nickel borides.
7. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 5, which is characterized in that institute
Stating palladium catalyst is one of palladium carbon, palladium oxide, palladium black or carrier palladium.
8. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 5, which is characterized in that institute
Stating platinum catalyst is one of platinum oxide, platinum black and carrier platinum.
9. the technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene according to claim 1, which is characterized in that step
Suddenly in (5), the inert atmosphere is the one or more of high-purity nitrogen, helium or argon gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111217712A (en) * | 2020-01-21 | 2020-06-02 | 江苏扬农化工集团有限公司 | Method for preparing o-phenylenediamine from aniline |
| CN111662182A (en) * | 2020-07-17 | 2020-09-15 | 四川北方红光特种化工有限公司 | Method for producing phenylenediamine by dinitrobenzene solvent-free hydrogenation continuous reaction |
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| CN102827008A (en) * | 2012-10-16 | 2012-12-19 | 江苏科圣化工机械有限公司 | Method and device for producing phenylenediamine by taking water as solvent through liquid phase continuous hydrogenation method |
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| CN101434548A (en) * | 2008-11-07 | 2009-05-20 | 甘肃中科药源生物工程有限公司 | Method for preparing diaminobenzene from dinitro benzene |
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| CN111217712B (en) * | 2020-01-21 | 2023-01-10 | 江苏扬农化工集团有限公司 | Method for preparing o-phenylenediamine from aniline |
| CN111662182A (en) * | 2020-07-17 | 2020-09-15 | 四川北方红光特种化工有限公司 | Method for producing phenylenediamine by dinitrobenzene solvent-free hydrogenation continuous reaction |
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Application publication date: 20191119 |
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| RJ01 | Rejection of invention patent application after publication |