CN104974047B - Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene - Google Patents
Method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene Download PDFInfo
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Abstract
The invention relates to a method for preparing aminostyrene through catalytic hydrogenation of nitrostyrene. According to the method, in environment-friendly solvents H2O, ethanol, n-heptane, H2O-ethanol or H2O-n-heptane, nitrostyrene is catalyzed by Pt/SnO2-Sb2O3 serving as a catalyst to have hydrogenation reaction at 35-120 DEG C to prepare aminostyrene. Pt/SnO2-Sb2O3 has high selectivity in generation of aminostyrene; in H2O, ethanol and n-heptane, the selectivity for aminostyrene is respectively greater than 97%, greater than 95% and greater than 96%; the reaction rate in H2O is highest and the yield of aminostyrene is greater than 97%; no accumulation of harmful intermediates such as phenyl hydroxylamine is generated in the reaction process; since Pt/SnO2-Sb2O3 almost has no catalytic activity for hydrogenation of aminostyrene, the yield of aminostyrene does not decrease when time goes by after the reactants are completely converted.
Description
Technical field
The present invention relates to the method that nitrostyrolene catalytic hydrogenation prepares aminostyryl.Specifically related to Pt/SnO2-
Sb2O3For catalyst, in green solvent H2O, ethanol, normal heptane, H2O- ethanol or H2In O- n-heptane system, it is catalyzed Nitrobenzol second
The method that aminostyryl is prepared in alkene selective hydrogenation.
Background technology
Aminostyryl is one kind of aromatic amine compounds, is to produce medicine, stabilizer, antibacterial, Insecticides (tech) ＆ Herbicides (tech)
Intermediate etc. important chemical products.
Nitrostyrolene catalytic hydrogenation is the effective ways preparing aminostyryl.In nitrostyrolene molecule, nitro and
Vinyl group is all easily hydrogenated reduction, and research and development have greater activity and have relatively low work to vinyl group hydrogenation to nitro hydrogenation
Property catalyst, be improve aminostyryl yield key.In addition, hydrogenation process should manage to avoid generation phenylhydroxyamine etc. harmful
The accumulation of intermediate.The catalyst being presently used for this reaction has：CoS3、Co3O4、Fe2O3Deng gold such as compound and Au, Ag, Pt
Metal catalyst.In methyl alcohol, with CoS3Catalysis 50g nitrostyrolene hydrogenation 5h, obtains 37g aminostyryl, molar yield is
92.6%（US4051177）.The weak point that this catalyst exists is, in hydrogenation process, produces sulfur byproduct species, fall
Low product quality, and limit the recycling of solvent.In addition, producing the sulfur-bearing of the high volatilities such as hydrogen sulfide in course of reaction
Compound, this is likely to result in serious safety problem in the case that large-scale industry is combined to.CN1149287A disclose with
The modified supporting Pt of Pb is catalyst, iron salt is promoter, quaternary amine alkali is common promoter, and preparation is containing unsaturated carbon-to-carbon
The method of the aromatic amine compound of key substituent group.The noble metal catalysts such as Pt are modified through phosphorus compound, also can catalyzing aromatic hydrocarbon nitre
Based compound is hydrogenated with, and prepares multiple aromatic amine compound such as aminostyryl, adds the compound of vanadium or ferrum, energy in reaction system
Effectively suppress the accumulation of harmful intermediate phenylhydroxyamine（US6258982, WO9813331）.Two kinds of sides of above-mentioned use Pt catalyst
Method, needs to add the additional materials such as the compound of iron salt, vanadium and phosphorus in reaction system, and this will increase complexity and the product of operation
The separating difficulty of thing.Au/TiO is adopted in toluene2、Au/Fe2O3, or adopt Ag/Al in oxolane2O3Catalysis Nitrobenzol
Ethylene hydrogenation, is not required to any additive, and course of reaction does not have the accumulation of phenylhydroxyamine, and the yield of aminostyryl is up to 94%～96%
（WO2007116111,（Corma, Serna, Science, 2006）, JP2011036748,（Shimizu, Miyamoto et
Al., J. Catal., 2010））.With TiO2、Fe2O3With the metallic catalysts such as activated carbon supported 5%Ni, 0.2%Pt, 1%Ru, warp
After 450 DEG C of reduction, catalysis nitrostyrolene hydrogenation in toluene, the yield of aminostyryl is 70%～94%.Improve metal to bear
Carrying capacity, will lead to catalyst choice to reduce, for example, with 0.2%Pt/TiO2For catalyst, the yield of aminostyryl is 92%；
According to 2%Pt/TiO2, yield is down to 55%（WO2009071727,（Corma, Serna et al., J. Am. Chem.
Soc., 2008））.The Co being prepared by high temperature thermal decomposition method3O4And Fe2O3Catalyst, in oxolane or oxolane-water
In solvent, 110～120 DEG C of multiple aromatic amine compounds that can catalyze and synthesize including aminostyryl（DE102012209634,
（Westerhaus, Jagadeesh et al., Nat. Chem., 2013）,（Jagadeesh, Surkus et al.,
Science,2013））.
At present, there is following subject matter for aminostyryl in Hydrogenation：（1）Reaction is many to be had in toluene, oxolane etc.
Poison is harmful, carry out in volatile organic solvent.（2）Above-mentioned CoS3、Co3O4、Fe2O3And the catalyst such as Au, Ag, activity is relatively
Low, reaction needs higher temperature（110～160 DEG C）And longer time.（3）Method disclosed in WO2009071727, i.e. profit
The method at the strong interaction modified metal center between the metal being produced with high temperature reduction and carrier, has following deficiency：High temperature is also
After former, catalyst activity is remarkably decreased；In addition, content of metal is relatively low, if improving content of metal, catalyst choice will be led to
Property is decreased obviously.（4）The catalyst such as above-mentioned Au, Ag, p-aminophenyl ethylene C=C key hydrogenation is active, therefore, complete in reactant
After conversion, continue to extend the response time, the aminostyryl of generation, by further hydro-conversion, leads to its yield to reduce, this increasing
Add the difficulty controlling reaction in producing（（Shimizu, Miyamoto et al., J. Catal., 2010）,（Shimizu,
Miyamoto et al., J. Phys. Chem. C, 2009））.
Content of the invention
The present invention relates in green solvent H2O, environment acceptable solvent ethanol, normal heptane, H2O- ethanol or H2O- normal heptane
In, with Pt/SnO2-Sb2O3For catalyst, it is catalyzed the method that aminostyryl is prepared in nitrostyrolene selective hydrogenation.
The technical solution used in the present invention is：By solvent（Water, ethanol, normal heptane, water-ethanol or water-normal heptane）, nitro
Styrene, Pt/SnO2-Sb2O3Catalyst adds in reactor, and solvent with the mass ratio of nitrostyrolene is（0.5～50）:1,
Nitrostyrolene with the mass ratio of catalyst is（1～100）:1, in catalyst, the mass content of Pt is 0.1～3%, tightens reaction
Device, purges 5min, the air in exclusion reactor with high pure nitrogen under room temperature, then reactor is heated to 35～120 DEG C, excellent
Select 50～90 DEG C, be filled with 0.1～8MPa H2, preferably 0.5～4MPa H2, open stirring, react 5～240min, obtain aminobenzene
Ethylene.
Described nitrostyrolene is 3- nitrostyrolene and 4- nitrostyrolene.
Described Pt/SnO2-Sb2O3Catalyst is adopted and is prepared with the following method：SnCl by certain proportioning4、SbCl3Hydrochloric acid
Mixed liquor, is simultaneously added dropwise to polyvinyl alcohol water solution with ammonia, and adjusting pH value is 3.5, prepared SnO2-Sb2O3Presoma sink
Shallow lake compound, by this compound after 80～150 DEG C of dryings, is ground into powder, 500～800 DEG C of calcining 3～6h in Muffle furnace,
Obtain carrier S nO2-Sb2O3, the mol ratio of wherein Sb and Sn is（0～0.2）：1；Using equi-volume impregnating or excessive dipping-
Ultrasonic method is by H2PtCl6Or Pt (NH3)4Cl2It is loaded to SnO2-Sb2O3On, in catalyst, the mass content of Pt is 0.1%～3%；Adopt
During with excessive dipping-ultrasonic method, by SnO2-Sb2O3Powder pours the excessive H of volume into2PtCl6Or Pt (NH3)4Cl2In solution, will
The ultrasonic 30min of this serosity, then in 50 DEG C of stirred in water bath, until thick taking-up；Through 80～120 DEG C of dryings, 350～500
DEG C calcining 3～6h after, use H2Or H2-N2Gaseous mixture in 200～250 DEG C of reductase 12 h, for reacting.
The invention has the advantages that：（1）H2O is green solvent, and ethanol and normal heptane are environment acceptable solvents, adopts
H2O, ethanol, normal heptane are reaction medium, reduce the hazardous solvent pollution on the environment such as toluene, oxolane.Using
H2O- ethanol or H2O- normal heptane is solvent, can reduce the consumption of ethanol and normal heptane further.
（2）Pt/SnO2-Sb2O3To nitro hydrogenation, there is greater activity, and vinyl double bond is hydrogenated with catalytically inactive, because
This can be catalyzed nitrostyrolene high-selective and hydrogenating and generate aminostyryl, aminostyryl highest selectivity>97%；In reaction
After thing converts completely, even if continuing to extend the response time, the yield of aminostyryl hardly declines, and it reduces scale metaplasia
Control the difficulty of reaction in product.
（3）In catalyst, the load capacity of Pt can change in relative broad range, increase the load capacity of Pt, will not make aminostyryl
Selectivity reduce.
（4）Catalyst need not be modified it is not required that adding any additive in reaction system.
（5）Course of reaction does not have the accumulation of harmful intermediate such as phenylhydroxyamine, nitroso compound, azo-compound.
In sum, using Pt/SnO2-Sb2O3Catalyst, in H2O, ethanol, normal heptane, H2O- ethanol or H2O- normal heptane
Middle catalysis nitrostyrolene Hydrogenation, for aminostyryl, is the technical process of a kind of efficient, safety and environmental protection.
Specific embodiment
Embodiment 1 3- nitrostyrolene is hydrogenated with
5mL H is added in 50mL autoclave2The catalyst Pt that O, 0.25g 3- nitrostyrolene, 0.15g reduce/
SnO2-Sb2O3, the mass content of Pt is the mol ratio of 0.5%, Sb and Sn is 0.1：1, using equi-volume impregnating supporting Pt, instead
Answer procatalyst in H2In 250 DEG C of reductase 12 h.Tighten and use high-purity N under reactor, room temperature2Purging 5min, the sky in exclusion reactor
Gas.Reactor preheats 15min in 50 DEG C of waters bath with thermostatic control, is filled with 4MPa H2, open stirring, react 3h.Reactor is cooled down fall
Temperature, product extracts through toluene, uses gas chromatographic analysiss.Nitrostyrolene conversion ratio is 96.7%, aminostyryl selectivity
For 98.1%.
Embodiment 2 3- nitrostyrolene is hydrogenated with
The mass content of Pt is 1.0%, and the response time is 2h, and other conditions are with embodiment 1.Nitrostyrolene conversion ratio is
98.2%, aminostyryl selectivity is 98.4%.
Embodiment 3
Response time is 4h, and catalyst and other conditions are with embodiment 2.Nitrostyrolene conversion ratio is 100%, aminobenzene
Ethylene selectivity is 97.3%.
From embodiment 2 and embodiment 3, extend the response time, aminostyryl selectivity is almost unchanged, shows Pt/
SnO2-Sb2O3Almost there is no catalysis activity to target product aminostyryl hydrogenation.
Embodiment 4 3- nitrostyrolene is hydrogenated with
The mass content of Pt is 2.0%, and the response time is 1h, and other conditions are with embodiment 1.Nitrostyrolene conversion ratio is
91.7%, aminostyryl selectivity is 98.1%.
Embodiment 5 3- nitrostyrolene is hydrogenated with
Catalyst Pt/SnO2-Sb2O3Using excessive dipping-ultrasonic method preparation, the mass content of Pt is 0.5%, other conditions
With embodiment 1.Nitrostyrolene conversion ratio is 100%, and aminostyryl selectivity is 97.6%.
Embodiment 6 3- nitrostyrolene is hydrogenated with
Solvent is 5mL normal heptane, and, with embodiment 1, product uses gas phase after ethanol dilution for catalyst and other conditions
Chromatography.Nitrostyrolene conversion ratio is 82.4%, and aminostyryl selectivity is 96.3%.
Embodiment 7 4- nitrostyrolene is hydrogenated with
The catalyst Pt that addition 5mL ethanol, 0.25g 4- nitrostyrolene, 0.15g reduce in 50mL autoclave/
SnO2-Sb2O3, with embodiment 1, product uses gas chromatographic analysiss after ethanol dilution for catalyst and other condition.Nitrobenzol
Conversion of ethylene is 97.6%, and aminostyryl selectivity is 95.6%.
Embodiment 8 3- nitrostyrolene is hydrogenated with
Solvent is 5mL H2O- normal heptane, H2O is 1 with the volume ratio of normal heptane:1, catalyst Pt/SnO2-Sb2O3Using
Amount dipping-ultrasonic method preparation, the mass content of Pt is the mol ratio of 0.5%, Sb and Sn is 0.025：1, the response time is 2h, its
Its condition is with embodiment 1.Nitrostyrolene conversion ratio is 90.4%, and aminostyryl selectivity is 97.4%.
Embodiment 9 3- nitrostyrolene is hydrogenated with
Reaction temperature is 120 DEG C, H2Press as 1 MPa, the response time is 50min, catalyst and other same embodiment of condition
1.Nitrostyrolene conversion ratio is 100%, and aminostyryl selectivity is 94.7%.
Claims (6)
1. nitrostyrolene catalytic hydrogenation prepares the method for aminostyryl it is characterised in that by solvent, nitrostyrolene, urging
Agent Pt/SnO2-Sb2O3Add in reactor, solvent with the mass ratio of nitrostyrolene is（0.5～50）:1, nitrostyrolene
Mass ratio with catalyst is（1～100）:1, tighten reactor, purge 5min with high pure nitrogen under room temperature, in exclusion reactor
Air, then reactor is heated to 35～120 DEG C, is filled with 0.1～8MPa H2, open stirring, react 5～240min；
Described nitrostyrolene is 3- nitrostyrolene and 4- nitrostyrolene；
Described solvent is one of the following：H2O, ethanol, normal heptane, the H of arbitrary proportion2O- alcohol mixture, arbitrary proportion
H2O- normal heptane mixture；
Described catalyst is Pt/SnO2-Sb2O3, the mass content of Pt is that the mol ratio of 0.1～3%, Sb and Sn is（0～
0.2）：1.
2. prepare the method for aminostyryl it is characterised in that institute according to the nitrostyrolene catalytic hydrogenation described in claim 1
The carrier of the catalyst stated is the SnO being prepared by coprecipitation method2-Sb2O3, the mol ratio of Sb and Sn is（0～0.2）：1.
3. prepare the method for aminostyryl it is characterised in that institute according to the nitrostyrolene hydrogenation catalyst described in claim 1
Catalyst Pt/the SnO stating2-Sb2O3, the mass content of Pt is 0.1%～3%.
4. prepare the method for aminostyryl it is characterised in that institute according to the nitrostyrolene catalytic hydrogenation described in claim 1
Catalyst Pt/the SnO stating2-Sb2O3Calcine 3～6h at 350～500 DEG C.
5. prepare the method for aminostyryl it is characterised in that institute according to the nitrostyrolene catalytic hydrogenation described in claim 1
Catalyst Pt/the SnO stating2-Sb2O3Use H2Or H2-N2Gaseous mixture is in 200～250 DEG C of reductase 12 h.
6. prepare the method for aminostyryl it is characterised in that institute according to the nitrostyrolene catalytic hydrogenation described in claim 1
The reactor heating-up temperature stated is 35～120 DEG C.
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| CN105753738B (en) * | 2016-04-05 | 2018-10-12 | 长春工业大学 | A kind of method of nitrobenzoyl catalytic hydrogenation of nitriles synthesizing amino benzonitrile |
| CN106810628A (en) * | 2016-11-28 | 2017-06-09 | 佛山市尚好门窗有限责任公司 | A kind of preparation method of polynitrobenzene ethene |
| CN107216255B (en) * | 2017-05-26 | 2021-06-15 | 长春工业大学 | Method for preparing aminophenylacetylene by hydrogenation of nitrophenylacetylene |
| CN112403460B (en) * | 2019-08-23 | 2022-05-06 | 中国科学院大连化学物理研究所 | Platinum catalyst based on metal-carrier strong interaction and preparation and application thereof |
| CN113135824B (en) * | 2021-03-05 | 2023-11-17 | 内蒙古大学 | Process for preparing aminostyrene catalyst by high-selectivity hydrogenation of nitrostyrene |
| CN115869955A (en) * | 2022-11-28 | 2023-03-31 | 东南大学 | Co-based multi-phase magnetic catalyst and preparation and application thereof |
| CN116078371A (en) * | 2022-12-30 | 2023-05-09 | 南通立洋化学有限公司 | Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof |
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| WO2007116111A1 (en) * | 2006-04-10 | 2007-10-18 | Consejo Superior De Investigaciones Científicas | Method for preparing amino compounds using gold catalysts |
| CN101260044A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院长春应用化学研究所 | Method for preparing arylamines compounds by arene nitro compound catalysis hydrogenation in H2O-CO2 system |
| RU2485094C1 (en) * | 2012-06-07 | 2013-06-20 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Method of producing 4-aminostyrene |
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