CN101323579A - Method for preparing m-phenylenediamine - Google Patents
Method for preparing m-phenylenediamine Download PDFInfo
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- CN101323579A CN101323579A CNA2007100117299A CN200710011729A CN101323579A CN 101323579 A CN101323579 A CN 101323579A CN A2007100117299 A CNA2007100117299 A CN A2007100117299A CN 200710011729 A CN200710011729 A CN 200710011729A CN 101323579 A CN101323579 A CN 101323579A
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Abstract
The invention discloses a method for preparing metaphenylene diamine by catalytic hydrogenation of m-dinitrobenzene, comprising the following steps of: taking m-dinitrobenzene as a raw material, and carrying out hydrogenation reduction in the solvent of alcohol or benzene under the existence of a palladium-ruthenium loaded catalyst. The reaction conditions are temperature of 20 DEG C to150 DEG C, pressure of 0.1MPa to 6.0MPa and input amount of catalyst of 0.1g to 1.0g/100g nitryl materials. The method for preparing the metaphenylene diamine provided by the invention has advantages of simple production technology, moderate operation conditions and easy control. The catalyst used for the reaction has high activity, good selectivity, low cost and long service life.
Description
Technical field
The invention belongs to Chemicals and make the field, particularly, relate to a kind of method for preparing mphenylenediamine.
Background technology
Mphenylenediamine is the important intermediate of dyestuff, agricultural chemicals, medicine, functional materials, also is the raw material that is widely used in producing Resorcinol at present.The method of in the past producing mphenylenediamine adopts iron powder reducing or sodium sulfide reducing technology substantially, and also there is poor product quality in this technology, the shortcoming that yield is low except that producing a large amount of three wastes.The technology with skeletal nickel catalyst shortening production mphenylenediamine of exploitation has in recent years solved the big problem of quantity of three wastes, sees CN1439456A, CN1462740A.But nickel is inflammable, safety in utilization is poor, and consumption is also bigger; Skeleton nickel is highly brittle, easy broken inactivation; Nickel proportion is bigger, needs high-speed stirring could guarantee to react and carries out fully.Single-activity component catalyst shortening system mphenylenediamines such as human 5%, 10% palladium charcoal such as pretty river or 3% platinum charcoal [Journal of Qin gram daoUniversity of Science and Technolo gram y Vol.24 (9) rises in Qingdao University of Science and Technology, 2003], the Meta-dinitrobenzene transformation efficiency is lower than 60%.Method with palladium ruthenium binary composite catalyst catalysis Meta-dinitrobenzene hydrogenation system mphenylenediamine is not reported so far.
Summary of the invention
The object of the present invention is to provide a kind of new Meta-dinitrobenzene shortening to prepare the method for mphenylenediamine, this method reaction conditions gentleness, be easy to control, purpose product yield height.
In order to realize purpose of the present invention, the present invention adopts palladium and the ruthenium binary catalyst with concerted catalysis effect, and this catalyzer cost is low, the life-span long, activity is high, selectivity is good, has better effect and economy than single-activity component catalyst.
Technical scheme of the present invention is as follows: be raw material with the Meta-dinitrobenzene, in the presence of palladium ruthenium supported catalyst, in alcohols or benzene kind solvent, carry out hydrogenating reduction, reaction conditions is: temperature 20-150 ℃, pressure 0.1-6.0Mpa, catalyzer add-on 0.1-1.0 gram/100 gram nitro things.
Suitable reaction conditions is: temperature 80-130 ℃, and pressure 0.5-2.5Mpa, catalyzer add-on 0.1-0.8 gram/100 gram nitro things; Preferred reaction conditions is: temperature 100-120 ℃, pressure is 1.0-2.0Mpa, catalyzer add-on 0.15-0.25 gram/100 gram nitro things.
React used alcoholic solvent and be selected from the Fatty Alcohol(C12-C14 and C12-C18) that contains 1-4 carbon, benzene kind solvent is selected from and is benzene, toluene or dimethylbenzene.Preferred solvent is methyl alcohol, ethanol or benzene.
Technical scheme of the present invention also comprises provides a kind of catalyzer that the Meta-dinitrobenzene shortening prepares mphenylenediamine that is exclusively used in: this catalyzer with gac or aluminum oxide as carrier, two kinds of active ingredients of supported palladium and ruthenium on carrier.Described palladium and ruthenium both can be that metal also can be its salt, and charge capacity (in the weight of palladium and ruthenium, down together) is respectively 1-10%.Suitable charge capacity is palladium 2-8%, ruthenium 1-8%.Catalyzer can be recycled repeatedly.Generally after recycling 5 times, for guaranteeing certain reaction speed, should add the part raw catalyst, additional amount is the 5-20% of initial add-on usually, for example adds the raw catalyst about 10%.
The method for preparing mphenylenediamine provided by the invention has that production technique is simple, operational condition is gentle, be easy to advantages such as control.Reaction catalyst system therefor activity is high, selectivity is good, cost is low, the life-span is long.The Meta-dinitrobenzene transformation efficiency is greater than 99%, and the mphenylenediamine selectivity is greater than 98%, and the gas chromatographic analysis product purity is more than 98.5%.
Embodiment
Following specific embodiment is used to further specify the present invention.But the present invention only limits to these examples absolutely not, can carry out various conversion according to claim institute restricted portion.
Example 1: Preparation of Catalyst
Palladous chloride 1 gram is dissolved in 2 milliliters of concentrated hydrochloric acids, dilutes with 20 ml waters again; Ruthenium chloride 0.78 gram is dissolved in 10 ml waters, and two solution mix standby.Add in 250 milliliters of four-hole bottles (having agitator, thermometer, condenser and dropping funnel) with 120 ml waters with through gac 9 grams that nitric acid treatment is crossed, drip ready made Palladous chloride and ruthenium chloride mixing solutions down in 70-85 ℃ of stirring, drip off and continue to stir 10 minutes.Add 2 milliliter of 85% hydrazine hydrate again and be incubated 30 minutes.Afterwards, be cooled to 25 ℃, filter, repeatedly with deionized water wash.The catalyzer that obtains (Pd 6%, Ru 4%) store in sealing the bottle in standby.
Use same quadrat method, the add-on of adjusting palladium and ruthenium can obtain the catalyzer (for example Pd1-10%, Ru1-8%) of desired content.
Example 2:
Palladous chloride 1 gram is dissolved in 2 milliliters of concentrated hydrochloric acids, dilutes with 20 ml waters again; Ruthenium chloride 0.78 gram is dissolved in 10 ml waters, and two solution mix standby.With 120 ml waters and 9 gram Al
2O
3Add in 250 milliliters of four-hole bottles (having agitator, thermometer, condenser and dropping funnel), drip ready made Palladous chloride and ruthenium chloride mixing solutions down, drip off and continue to stir 180 minutes in 70-85 ℃ of stirring.Add 2 milliliter of 85% hydrazine hydrate again and be incubated 30 minutes.Be cooled to 25 ℃ afterwards, filter, repeatedly with deionized water wash.The catalyzer that obtains (Pd 6%, Ru 4%) store in sealing the bottle in standby.
Use same quadrat method, the add-on of adjusting palladium and ruthenium can obtain the catalyzer (for example Pd 1-10%, Ru1-8%) of desired content.
Example 3
Meta-dinitrobenzene 20 grams, Pd-Ru/C catalyzer (Pd 5%, Ru 3%) 0.042 gram, methyl alcohol add for 100 milliliters to be with in the autoclave that stirs, use nitrogen and hydrogen exchange gas reactor air respectively each 3 times, then hydrogen pressure in the still is added to 1.5Mpa, start stirring, heat temperature raising, and 100 ℃ of control reaction temperature, carry out hydrogenation reaction.Obtain the mphenylenediamine methanol solution after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams methyl alcohol, and underpressure distillation obtains mphenylenediamine 12.65 grams then, and yield 98.5% is through gas chromatographic analysis (area normalization method, together following) purity 99%.
Above-mentioned catalyst recirculation is used 5 times, product purity that obtains and yield basically identical.
Case of comparative examples 3
Operation and reaction conditions all are same as example 3, add above-mentioned catalyzer and the additional example 3 used raw catalysts 0.004 that recycled 5 times and restrain.Obtain mphenylenediamine 12.6 grams, yield 98%, purity 99%.
Example 4
At Meta-dinitrobenzene 20 grams, Pd-Ru/Al
2O
3(Pd 6%, Ru 3%) catalyzer 0.042 gram, ethanol add for 100 milliliters to be with in the autoclave that stirs, use nitrogen and hydrogen exchange gas reactor respectively each 3 times, then hydrogen pressure in the still is added to 1.5Mpa, start stirring, heat temperature raising, and 100 ℃ of control reaction temperature carry out hydrogenation reaction, obtain the mphenylenediamine ethanolic soln after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams solvent, and underpressure distillation obtains mphenylenediamine 12.6 grams, yield 98%, purity 99.2%.
Example 5
Meta-dinitrobenzene 35 grams, Pd-Ru/C (Pd 6%, Ru 2%) catalyzer 0.07 gram, benzene add for 100 milliliters to be with in the autoclave that stirs, after the conventional displacement, hydrogen pressure 1.0Mpa in the still, 100 ℃ of control reaction temperature, carry out hydrogenation reaction, obtain mphenylenediamine solution after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams benzene, and underpressure distillation obtains mphenylenediamine 22.2 grams, yield 98.5%, purity 99%.
Example 6
Meta-dinitrobenzene 35 grams, Pd-Ru/Al
2O
3In catalyzer (Pd 6%, Ru 2%) 0.07 gram, 100 milliliters of adding autoclaves of methyl alcohol, after the conventional displacement, hydrogen pressure 2.0Mpa, 120 ℃ of temperature of reaction, carry out hydrogenation reaction, obtain the mphenylenediamine methanol solution after hydrogenation is complete, filter and tell the catalyst recirculation use.Normal pressure steams methyl alcohol, and underpressure distillation obtains mphenylenediamine 22.1 grams, yield 98%, purity 99%.
Example 7
In Meta-dinitrobenzene 50 grams, Pd-Ru/C catalyzer (Pd 7%, Ru 2%) 0.1 gram, 100 milliliters of adding autoclaves of ethanol, after the conventional displacement, hydrogen pressure is added to 1.0Mpa, 100 ℃ of control reaction temperature, carry out hydrogenation reaction, reaction obtains the mphenylenediamine ethanolic soln after finishing, and filters and tells the catalyst recirculation use.Normal pressure steams ethanol, and underpressure distillation obtains mphenylenediamine 31.7 grams, yield 98.5%, purity 99.3% then.
Example 8
Meta-dinitrobenzene 50 grams, Pd-Ru/Al
2O
3Catalyzer (Pd 8%, Ru 2%) 0.1 gram, benzene add for 100 milliliters to be with in the autoclave that stirs, and after the conventional displacement, hydrogen pressure is added to 2.0Mpa in the still, 120 ℃ of temperature, carry out hydrogenation reaction, obtain mphenylenediamine solution after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams solvent, and underpressure distillation obtains mphenylenediamine 31.6 grams, yield 98.5%, purity 99% then.
Example 9
In Meta-dinitrobenzene 50 grams, Pd-Ru/C catalyzer (Pd 7%, Ru 2%) 0.075 gram, 100 milliliters of adding autoclaves of ethanol, after the conventional displacement, hydrogen pressure is added to 1.5Mpa, 100 ℃ of control reaction temperature, carry out hydrogenation reaction, reaction obtains the mphenylenediamine ethanolic soln after finishing, and filters and tells the catalyst recirculation use.Normal pressure steams ethanol, and underpressure distillation obtains mphenylenediamine 31.5 grams, yield 98%, purity 98.7% then.
Example 10
In Meta-dinitrobenzene 50 grams, Pd-Ru/C catalyzer (Pd 7%, Ru 2%) 0.125 gram, 100 milliliters of adding autoclaves of ethanol, after the conventional displacement, hydrogen pressure is added to 1.5Mpa, 100 ℃ of control reaction temperature, carry out hydrogenation reaction, reaction obtains the mphenylenediamine ethanolic soln after finishing, and filters and tells the catalyst recirculation use.Normal pressure steams ethanol, and underpressure distillation obtains mphenylenediamine 31.5 grams, yield 98%, purity 99.3% then.
Example 11
Meta-dinitrobenzene 50 grams, Pd-Ru/Al
2O
3Catalyzer (Pd 8%, Ru 2%) 0.075 gram, benzene add for 100 milliliters to be with in the autoclave that stirs, and after the conventional displacement, hydrogen pressure is added to 1.5Mpa in the still, 120 ℃ of temperature, carry out hydrogenation reaction, obtain mphenylenediamine solution after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams solvent, and underpressure distillation obtains mphenylenediamine 31.5 grams, yield 98%, purity 98.5% then.
Example 12
Meta-dinitrobenzene 50 grams, Pd-Ru/Al
2O
3Catalyzer (Pd 8%, Ru 2%) 0.125 gram, benzene add for 100 milliliters to be with in the autoclave that stirs, and after the conventional displacement, hydrogen pressure is added to 1.5Mpa in the still, 120 ℃ of temperature, carry out hydrogenation reaction, obtain mphenylenediamine solution after hydrogenation reaction is complete, filter and tell the catalyst recirculation use.Normal pressure steams solvent, and underpressure distillation obtains mphenylenediamine 31.8 grams, yield 98.8%, purity 99.1% then.
Claims (4)
1, a kind of method for preparing mphenylenediamine, it is characterized in that: be raw material with the Meta-dinitrobenzene, in the presence of palladium ruthenium supported catalyst, hydrogenating reduction in alcohols or benzene kind solvent, reaction conditions is: temperature 20-150 ℃, pressure 0.1-6.0Mpa, catalyzer add-on 0.1-1.0 gram/100 gram nitro things.
2, in accordance with the method for claim 1, it is characterized in that: the palladium ruthenium supported catalyst in the hydrogenation reduction with gac or aluminum oxide as carrier; The palladium consumption is 2-8% in the load active component, and the ruthenium consumption is 1-8%.
3, according to claim 1 or 2 described methods, it is characterized in that: described alcoholic solvent is selected from the Fatty Alcohol(C12-C14 and C12-C18) that contains 1-4 carbon, and described benzene kind solvent is selected from benzene, toluene or dimethylbenzene; Temperature of reaction 80-130 ℃, reaction pressure 0.5-2.5Mpa, catalyzer add-on 0.1-0.8 gram/100 gram nitro things.
4, in accordance with the method for claim 3, it is characterized in that: described solvent is selected from methyl alcohol, ethanol or benzene; Temperature of reaction 100-120 ℃, reaction pressure is 1.0-2.0Mpa, catalyzer add-on 0.15-0.25 gram/100 gram nitro things.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211970A (en) * | 2011-04-06 | 2011-10-12 | 常州介孔催化材料有限公司 | Production method of diamido-arene |
| CN102350343A (en) * | 2011-08-17 | 2012-02-15 | 武汉工程大学 | Pd-Pt alloy structural catalyst, and preparation method and application thereof |
| CN102731377A (en) * | 2011-04-08 | 2012-10-17 | 中国中化股份有限公司 | Method for preparing 2, 3, 5, 6-tetraaminopyrimidine hydrochloride |
| CN103242116A (en) * | 2012-02-10 | 2013-08-14 | 淮海工学院 | Novel method for preparing arylamine through reducing aromatic nitro compound |
| CN103977818A (en) * | 2014-05-15 | 2014-08-13 | 太原理工大学 | Raney nickel catalyst used for low-pressure hydrogenation of dinitrotoluenem, preparation method and application thereof |
| CN113429299A (en) * | 2021-07-27 | 2021-09-24 | 深圳市濯欣科技有限公司 | Method for purifying phenylenediamine |
-
2007
- 2007-06-15 CN CN2007100117299A patent/CN101323579B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211970A (en) * | 2011-04-06 | 2011-10-12 | 常州介孔催化材料有限公司 | Production method of diamido-arene |
| CN102211970B (en) * | 2011-04-06 | 2015-04-22 | 常州介孔催化材料有限公司 | Production method of diamido-arene |
| CN102731377A (en) * | 2011-04-08 | 2012-10-17 | 中国中化股份有限公司 | Method for preparing 2, 3, 5, 6-tetraaminopyrimidine hydrochloride |
| CN102350343A (en) * | 2011-08-17 | 2012-02-15 | 武汉工程大学 | Pd-Pt alloy structural catalyst, and preparation method and application thereof |
| CN102350343B (en) * | 2011-08-17 | 2013-07-10 | 武汉工程大学 | Pd-Pt alloy structural catalyst, and preparation method and application thereof |
| CN103242116A (en) * | 2012-02-10 | 2013-08-14 | 淮海工学院 | Novel method for preparing arylamine through reducing aromatic nitro compound |
| CN103977818A (en) * | 2014-05-15 | 2014-08-13 | 太原理工大学 | Raney nickel catalyst used for low-pressure hydrogenation of dinitrotoluenem, preparation method and application thereof |
| CN113429299A (en) * | 2021-07-27 | 2021-09-24 | 深圳市濯欣科技有限公司 | Method for purifying phenylenediamine |
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