CN101885672B - Method for preparing benzaldehyde through catalytic oxidation of styrene - Google Patents
Method for preparing benzaldehyde through catalytic oxidation of styrene Download PDFInfo
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- CN101885672B CN101885672B CN201010221553.1A CN201010221553A CN101885672B CN 101885672 B CN101885672 B CN 101885672B CN 201010221553 A CN201010221553 A CN 201010221553A CN 101885672 B CN101885672 B CN 101885672B
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Abstract
The invention relates to a method for preparing benzaldehyde through catalytic oxidation of styrene, in particular to a method for preparing the benzaldehyde through the catalytic oxidation of the styrene by using an iron-platinum (FePt) nano-wire as a catalyst. The method comprises the following steps of: using the iron-platinum nano-wire as the catalyst and one of toluene, dioxane, dimethyl formamide, dimethyl sulfoxide, acetonitrile or chloroform as a solvent; in an oxygen atmosphere and under normal pressure, reacting for 3 to 32 hours at the temperature of between 50 and 90 DEG C; cooling the mixture after the reaction, and separating the mixture to obtain the benzaldehyde. The preparation method has a mild reaction condition, has an improved yield compared with that of the prior art, and is more economical and environment-friendly.
Description
Technical field
The present invention relates to a kind of method of preparing benzaldehyde through catalytic oxidation of styrene, be specifically related to a kind ofly take iron platinum (FePt) nano wire and prepare the method for phenyl aldehyde as catalyst Styrene oxide 98min..
Background technology
Phenyl aldehyde is called again benzaldehyde, is the important source material of medicine, dyestuff, spices and Resin Industry, also can be used as solvent, softening agent and low-temperature grease etc.; In essence industry, be mainly used in allocating food flavour, on a small quantity for daily chemical essence and flavouring essence for tobacco.
The traditional technology method of preparing phenyl aldehyde is mainly to adopt Benzyl Side-Chain Chloride to become dichloro benzal, and then hydrolysis, oxidation obtain phenyl aldehyde.The method need just can make phenyl aldehyde and consume a large amount of chlorine and sour, alkali through four step organic reactions, atom utilization is low, seriously corroded, and productive rate is not high, complex process, environment is caused to very big pollution, and this technique is used a large amount of chlorine as raw material simultaneously, makes product contain toxic ingredient chlorine and can not be used as the raw material of medicine, foodstuff production, if remove micro-chlorine, need to expend a large amount of energy and carry out rectifying, application is restricted, and does not meet the requirement of Green Chemistry and cleaner production.
In order to develop phenyl aldehyde new process of production, all carried out a large amount of research work both at home and abroad, nano material catalyzed oxidation vinylbenzene has more caused that chemists pay close attention to greatly.
For example, be published in nature (Selective oxidation with dioxygen by gold nanoparticlecatalysts derived from 55-atom clusters (selective catalytic oxidation containing the golden nanometer particle of 55 clusters under oxygen atmosphere), Nature, 2008, 454 (7207), P981～984) document discloses a kind of method of utilizing golden catalyst system preparing benzaldehyde through catalytic oxidation of styrene, select the Au nanoparticle of loading type as catalyzer, at pressure 0.5bar, catalyzed oxidation vinylbenzene at 100 ℃ of temperature of reaction, in catalyzer gold consumption (by weight) with respect to every g vinylbenzene at 0.48～0.56mg, its final transformation efficiency can reach 25.8%, and in product, the selectivity of phenyl aldehyde can reach 82.1%, and the productive rate that generates phenyl aldehyde is about 21.18%.
Aforesaid method is having and is having some superiority aspect product purity, catalyzer low toxicity, yet also has following shortcoming: (1) transformation efficiency is lower, only has 25.8%, and the productive rate of final phenyl aldehyde only has 21.18% left and right, awaits further raising; (2) reaction conditions is harsher, and reaction is carried out under high pressure (surpassing normal atmosphere 0.5bar), does not meet the theme of Green Chemistry; (3) amount ratio of catalyzer is larger, and noble metal Au is to be carried on carrier with nano shape, and through converting, with respect to every 1g vinylbenzene, the consumption of Au is 0.48～0.56mg, thereby cost is higher.
Therefore, develop a kind of gentleer, green, highly selective, the applied widely method of preparing phenyl aldehyde, have important practical significance.
Summary of the invention
The object of the invention is to provide a kind of method of preparing benzaldehyde through catalytic oxidation of styrene.
For achieving the above object, the technical solution used in the present invention is: a kind of method of preparing benzaldehyde through catalytic oxidation of styrene, take nanometer Fe-Pt line as catalyzer, a kind of in toluene, dioxane, dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile or chloroform of take is solvent, in oxygen atmosphere, under normal pressure, under whipped state, in 50～90 ℃ of reaction 3～32h, reaction finishes rear cooling, separation and obtains phenyl aldehyde.
In technique scheme, described nanometer Fe-Pt linear diameter is less than or equal to 3nm, described iron platinum (FePt) nano wire can be with reference to being published in Angew.Chem.Int.Ed.2007, document A General Strategy for Synthesizing FePt Nanowires and Nanorods on 46,6333-6335 (universal method of synthetic Fe-Pt nano wire and nanometer rod).
In technique scheme, the usage ratio of ethene and catalyzer is: every 1ml vinylbenzene correspondence 0.4～1.0mg nanometer Fe-Pt line.
In technique scheme, the volume ratio of described vinylbenzene and solvent is 1: 4～7; In preferred technical scheme, described solvent is selected from: dimethyl sulfoxide (DMSO) or acetonitrile.
In above-mentioned reaction, temperature of reaction is preferably 70 ℃, and in preferably 24～32 hours reaction times, productive rate is the highest.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. method of the present invention has higher transformation efficiency, and the yield of phenyl aldehyde is also higher, experiment showed, that in atmospheric oxygen atmosphere the yield of phenyl aldehyde can reach 38.2% in 70 ℃ of reaction 24h, and the selectivity of phenyl aldehyde also has 77.1%.
2. the present invention be take nanometer Fe-Pt line as catalyzer, compares with loaded nano particle catalyst, has saved the complex process of preparing part, and catalyst levels is few, and atom utilization is high.
3. the present invention reacts in atmospheric oxygen atmosphere, and reaction conditions is gentleer, green.
4. method for preparing catalyst technique of the present invention is simple, easy handling, and cost is lower, is suitable for applying.
Accompanying drawing explanation
Fig. 1 is the TEM figure of nanometer Fe-Pt line in embodiment mono-;
Fig. 2 is the reaction schematic diagram that in embodiment, catalyst is prepared phenyl aldehyde.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment mono-:
Iron platinum catalyst synthetic: the methyl ethyl diketone platinum that reduces in the oleyl amine of 160 ℃ thermolysis simultaneously pentacarbonyl iron obtain diameter 2-3nm FePt nano wire (referring to Angew.Chem.Int.Ed.2007,46,6333-6335); Gained nano wire is carried out to electron-microscope scanning, and result is as Fig. 1, and as can be seen from Figure 1, the diameter of nanometer Fe-Pt line is 2～3nm.
For the ease of experimental implementation, nanometer Fe-Pt line is scattered in normal hexane, and because normal hexane boiling point is low, is convenient to remove, better to iron platinum dispersion effect, can prevent nano wire reunion.
Under ultrasound condition, above-mentioned nanometer Fe-Pt line is scattered in normal hexane, every 1m normal hexane correspondence 1.6～4mg nanometer Fe-Pt line, obtains the hexane solution of nanometer Fe-Pt line.
Embodiment bis-
The hexane solution 100 μ L (take normal hexane away with vacuum pump, leave catalyst solid) that pack successively nanometer Fe-Pt line in reaction flask into; Acetonitrile 2ml; Vinylbenzene 500 μ L; N-dodecane 50 μ L (mark in doing).This system is connected to oxygen bag and prolong, then cooling-vacuumize-put oxygen, circulate 3～4 times, put into oxygen, return to room temperature; This system, in the oil bath of 70 ℃, obtains product after heating while stirring 24h.
After reacting, mixed solution is centrifugal, get the upper strata stillness of night and carry out gas-matter coupling (GC-MS) and gas-chromatography (GC) analysis (contrast of directly taking standard raw materials to do in test process, proof has obtained required compound really), result is as follows: the absolute yield of phenyl aldehyde is 38.2%, phenyl aldehyde, phenylformic acid, the selectivity of benzo ring oxidative ethane is respectively 77.1: 4.1: 18.8, wherein have the methyl phenyl ketone of denier to generate, reaction process as shown in Figure 2.
Embodiment tri-
The nanometer Fe-Pt line solution 100 μ L (take normal hexane away with vacuum pump, leave catalyst solid) that pack successively respectively normal hexane in 8 reaction flasks into; Solvent (as following table 1) 2ml; Vinylbenzene 500 μ L; N-dodecane 50 μ L (mark in doing).This system is connected to oxygen bag and prolong, then cooling-vacuumize-put oxygen, circulate 3～4 times, put into oxygen, return to room temperature; Then 8 reaction systems are all placed in the oil bath of 60 ℃, obtain product after heating while stirring 24h.
After reacting, mixed solution is centrifugal, gets the upper strata stillness of night and carry out gas-matter coupling (GC-MS) and gas-chromatography (GC) analysis (contrast of directly doing by standard raw materials, proves and really obtained required compound) in test process, and result is as following table:
The impact of table 1 different solvents on reaction
From table, when adopting acetonitrile as solvent, the productive rate of phenyl aldehyde is the highest.
Embodiment tetra-
The nanometer Fe-Pt line solution 100 μ L (take normal hexane away with vacuum pump, leave catalyst solid) that pack successively respectively normal hexane in 5 reaction flasks into; Acetonitrile 2ml; Vinylbenzene 500 μ L; N-dodecane 50 μ L (mark in doing).This system is connected to oxygen bag and prolong, then cooling-vacuumize-put oxygen, circulate 3～4 times, put into oxygen, return to room temperature; Then by this 5 individual system respectively at 50 ℃, 60 ℃, 70 ℃, 80 ℃, in the oil bath of 90 ℃, obtain product after heating while stirring 24h.
After reacting, mixed solution is centrifugal, gets the upper strata stillness of night and carry out gas-matter coupling (GC-MS) and gas-chromatography (GC) analysis (contrast of directly doing by standard raw materials, proves and really obtained required compound) in test process, and result is as following table 2:
The impact of table 2 differential responses temperature on reaction
From table, when temperature is 70 ℃, the productive rate of phenyl aldehyde is the highest, along with the selectivity of temperature rising phenyl aldehyde declines to some extent.
Embodiment five
The nanometer Fe-Pt line solution 100 μ L (take normal hexane away with vacuum pump, leave catalyst solid) that pack successively normal hexane in reaction flask into; Acetonitrile 2ml; Vinylbenzene 500 μ L; N-dodecane 50 μ L (mark in doing).This system is connected to oxygen bag and prolong, then cooling-vacuumize-put oxygen, circulate 3～4 times, put into oxygen, return to room temperature; This system is heating while stirring in the oil bath of 70 ℃, and at differential responses time sampling, the test reaction time affects reaction result.
Each sample mixed solution is centrifugal, to get the upper strata stillness of night and carry out gas-matter coupling (GC-MS) and gas-chromatography (GC) analysis (contrast of directly taking standard raw materials to do, proves and really obtained required compound) in test process, result is as follows:
The impact of table 3 differential responses temperature on reaction
From table, when temperature is 70 ℃, the productive rate along with the prolongation phenyl aldehyde in reaction times can increase within a certain period of time, and selectivity can decline gradually.
Claims (5)
1. the method for a preparing benzaldehyde through catalytic oxidation of styrene, it is characterized in that: take nanometer Fe-Pt line as catalyzer, a kind of in toluene, dioxane, dimethyl formamide, dimethyl sulfoxide (DMSO), acetonitrile or chloroform of take is solvent, in oxygen atmosphere, under normal pressure whipped state, in 50～90 ℃ of reaction 3～32h, reaction finishes rear cooling, separation and obtains phenyl aldehyde; Described nanometer Fe-Pt line for reducing the nanometer Fe-Pt line of methyl ethyl diketone platinum diameter 2～3nm that simultaneously thermolysis pentacarbonyl iron obtains in the oleyl amine of 160 ℃.
2. preparation method according to claim 1, is characterized in that: the usage ratio of vinylbenzene and catalyzer is: every 1ml vinylbenzene correspondence 0.4～1.0mg nanometer Fe-Pt line.
3. preparation method according to claim 1, is characterized in that: the volume ratio of described vinylbenzene and solvent is 1: 4～7.
4. preparation method according to claim 1, is characterized in that: described solvent is selected from: dimethyl sulfoxide (DMSO) or acetonitrile.
5. preparation method according to claim 1, is characterized in that: temperature of reaction is 70 ℃, and the reaction times is 24～32 hours.
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| CN111170838B (en) * | 2020-01-14 | 2023-04-14 | 中北大学 | Method and reaction device for preparing benzaldehyde by supergravity ozone oxidation of styrene |
| CN111718248B (en) * | 2020-07-30 | 2023-05-23 | 太原工业学院 | Catalyst for preparing benzaldehyde by catalytic oxidation of styrene, preparation method thereof and method for preparing benzaldehyde |
| CN112108147A (en) * | 2020-09-13 | 2020-12-22 | 北京工业大学 | Platinum-manganese-based bimetallic catalyst for catalyzing ethylene oxide at low temperature |
Citations (4)
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| CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
| CN101100419A (en) * | 2006-07-05 | 2008-01-09 | 中国科学院大连化学物理研究所 | Method for preparing ketone and aldehyde by using oxygen to directly oxidize olefin |
| US7491852B1 (en) * | 2007-12-07 | 2009-02-17 | National Tsing Hua University | Process for preparing aldehyde or ketone by oxidation of alcohol with a catalyst having a core-porous shell structure |
| CN101531576A (en) * | 2009-04-03 | 2009-09-16 | 苏州大学 | Method for preparing benzaldehyde through styrene catalytic oxidation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
| CN101100419A (en) * | 2006-07-05 | 2008-01-09 | 中国科学院大连化学物理研究所 | Method for preparing ketone and aldehyde by using oxygen to directly oxidize olefin |
| US7491852B1 (en) * | 2007-12-07 | 2009-02-17 | National Tsing Hua University | Process for preparing aldehyde or ketone by oxidation of alcohol with a catalyst having a core-porous shell structure |
| CN101531576A (en) * | 2009-04-03 | 2009-09-16 | 苏州大学 | Method for preparing benzaldehyde through styrene catalytic oxidation |
Non-Patent Citations (6)
| Title |
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| A General Strategy for Synthesizing FePt Nanowires and Nanorods;Chao Wang et al.;《Angew. Chem. Int. Ed.》;20071231;第46卷;第6333 –6335页 * |
| Chao Wang et al..A General Strategy for Synthesizing FePt Nanowires and Nanorods.《Angew. Chem. Int. Ed.》.2007,第46卷第6333 –6335页. * |
| Feng Shi et al..Tuning Catalytic Activity between Homogeneous and Heterogeneous Catalysis: Improved Activity and Selectivity of Free Nano-Fe2O3 in Selective Oxidations.《Angew. Chem. Int. Ed.》.2007,第46卷第8866－8868页. * |
| Tuning Catalytic Activity between Homogeneous and Heterogeneous Catalysis: Improved Activity and Selectivity of Free Nano-Fe2O3 in Selective Oxidations;Feng Shi et al.;《Angew. Chem. Int. Ed.》;20071231;第46卷;第8866－8868页 * |
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| 纳米催化剂研究进展;李敏等;《材料导报》;20060531;第20卷;第8－12，19页 * |
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Address after: 276800 shenganton Food Industrial Park, antonwei street, Lanshan, Rizhao City, Shandong Province Patentee after: Industry university research community (Shandong) scientific and technological achievements transformation Co., Ltd Address before: 276800 quanzimiao community, antonwei street, Lanshan, Rizhao City, Shandong Province (100m west of the second courtyard) Patentee before: Industry university research community (Shandong) scientific and technological achievements transformation Co., Ltd |