CN104557786B - A kind of with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde - Google Patents
A kind of with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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Abstract
A kind of with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde, belongs to fine chemical product preparing technical field. It is taking styrene as substrate, and DMF is reaction dissolvent, and 30wt% hydrogen peroxide is oxidant, at SiO2Under the effect of-CoO composite aerogel catalyst, carry out epoxidation reaction of olefines, reaction temperature is 40 ~ 80 DEG C, does is the reaction time 4 ~ 10? h, reaction finish after by reactant liquor rectification process, the cut of getting respectively 180 DEG C and 190 DEG C, obtains benzaldehyde and Styryl oxide successively. SiO of the present invention2The preparation of-CoO composite aerogel catalyst is simple, with low cost, this catalyst can be repeatedly used, easy to operate, environmental friendliness, economic benefit are high, and its reaction condition gentleness, energy consumption of reaction are low, to consersion unit require low, easy to operately, the selective sum of product Styryl oxide and benzaldehyde is greater than 99%.
Description
Technical field
The invention belongs to fine chemical product preparing technical field, be specifically related to the preparation of a kind of reaction condition gentleness, catalyst simple and easily separate with reactant liquor, product convenient post-treatment, low in the pollution of the environment with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde.
Background technology
Styryl oxide, is called again styrene oxide, is a kind of fine chemicals, can be used as epoxy resin diluent, UV-absorbent, fumet, is also the important intermediate of organic synthesis, pharmaceuticals industry, perfume industry, and it is mainly made by epoxidation of styrene.
The production of industrial Styryl oxide adopts traditional halogenohydrin method and peroxy acid direct oxidation method, and the former accessory substance is many, equipment corrosion is serious, the latter's raw material expensive process complexity, and the two all can produce a large amount of pollutants. Sinopec Group (publication number CN103012323A) is taking molybdenum Schiff alkali complex compound as catalyst, and TBHP is oxygen source, and epoxidation makes Styryl oxide. Although the method has solved the problems such as accessory substance is many, equipment corrosion is serious to a certain extent, oxygen source organic peroxide is expensive, product separation post processing complexity, and catalyst recovery difficulty, is unfavorable for large-scale industrial production.
The distinct disadvantage existing in the processes such as separation, recovery and recirculation in order to overcome homogeneous reaction system, in recent years, the heterogeneous catalytic system of preparing Styryl oxide with the oxygen source styrene oxide of economic environmental protection obtains broad research. For example Sinopec Group (publication number CN101434587A) is using the molecular oxygen of economic environmental protection as oxygen source, hydrogen as sacrifice agent, and a kind of titanium silicalite material is catalyst, and benzene feedstock ethylene oxy is changed into Styryl oxide. This preparation technology's advantage is to adopt the oxygen of environmental friendliness and cheapness as oxidant, but the shortcoming existing is to sacrifice co-conducer. In addition, although make oxygen source and can obtain the epoxidation product of high selectivity with the molecular oxygen of economic environmental protection, because molecular oxygen is difficult to be activated, reaction system complexity, makes cinnamic conversion per pass extremely low. For example patent CN1754866 is taking the hydrogen peroxide of economic environmental protection as oxygen source, and a kind of micropore titanium silicon molecular sieve is catalyst, and styrene oxidation is become to Styryl oxide. This reaction is used hydrogen peroxide-HTS reaction system alkene epoxidation to high catalytic performance. But because microporous silicon HTS is the micro-pore zeolite with MFI structure, its aperture only has 0.55 nanometer, at the large molecular olefine of catalysis (as styrene, cyclohexene etc.) time catalytic performance general, and because its granularity is little, difficult separation and recycling causes commercial Application to be subject to great restriction. Patent CN102910643 using synthesize mesoporous-micropore titanium silicon molecular sieve is as catalyst, taking the hydrogen peroxide of economic environmental protection as oxygen source, styrene oxidation become to Styryl oxide. Although the method has increased the specific area of micro porous molecular sieve, overcome the little limitation that can not be used for the large molecular olefine of catalysis in its aperture, except product Styryl oxide and benzaldehyde, can produce a large amount of accessory substance phenylacetaldehydes and other accessory substance. In addition, Ti-Si zeolite production cost is high, and separating technology complexity, is unfavorable for large-scale industrial application.
Benzaldehyde is a kind of important fine chemical product, is widely used in the industrial circles such as medicine, dyestuff, spices, agricultural chemicals and material. Openly preparing at present the main production method of benzaldehyde has: chlorination toluene Hydrolyze method, benzoic acid (ester) reducing process and toluene direct oxidation method.
In the benzaldehyde that tradition chlorination toluene Hydrolyze method makes, unavoidably contain trace organic chlorine, limited its application in the industry such as medicine and spices. Patent CN1876616 has made benzaldehyde with benzoic ether reducing process, although this method conversion per pass and benzaldehyde are selectively all very high, reaction temperature must be more than 300 DEG C, and energy consumption is large, and cost of material is high. Patent CN1068755 discloses a kind of method that gas phase oxidation of toluene is prepared benzaldehyde, although the economic environmental protection of this method and benzaldehyde selectively up to 99%, the conversion per pass of toluene is low only 26%. In addition, gas phase oxidation of toluene reaction is strong exothermal reaction, and reaction temperature is wayward, and when excess Temperature, the easy over oxidation of benzaldehyde generates a series of accessory substances such as benzoic acid, carbon dioxide, in order to control reaction temperature, needs to strengthen equipment investment.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide the preparation of a kind of reaction condition gentleness, catalyst simple and easily separate with reactant liquor, product convenient post-treatment, low in the pollution of the environment with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde. The method only has Styryl oxide and two kinds of products of benzaldehyde, produces without other accessory substance.
Described one is with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde, it is characterized in that taking styrene as substrate, and DMF is reaction dissolvent, and 30wt% hydrogen peroxide is oxidant, at SiO2Under the effect of-CoO composite aerogel catalyst, carry out epoxidation reaction of olefines, reaction temperature is 40 ~ 80 DEG C, and the reaction time is 4 ~ 10h, after reaction finishes, by reactant liquor rectification process, gets respectively the cut of 180 DEG C and 190 DEG C, obtains successively benzaldehyde and Styryl oxide.
Described one is with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde, it is characterized in that described SiO2The preparation method of-CoO composite aerogel catalyst is: with ethyl orthosilicate do silicon source, cobalt acetate is done cobalt source, adopt collosol and gel-atmosphere pressure desiccation make.
Described one is with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde, it is characterized in that SiO2Silicon cobalt mol ratio in-CoO composite aerogel catalyst is 50 ~ 250:1, is preferably 200:1.
A kind of described method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst, is characterized in that styrene and SiO2-CoO composite aerogel catalyst mass ratio is 2.9 ~ 20:1, is preferably 2.9 ~ 4:1.
A kind of described method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst, is characterized in that the molar ratio of styrene and hydrogen peroxide is 1:0.5 ~ 2, is preferably 0.5 ~ 1:1.
A kind of described method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst, is characterized in that the SiO that silicon cobalt mol ratio is 2002-TiO2The preparation method of composite aerogel catalyst is as follows:
Adopt the preparation of collosol and gel-atmosphere pressure desiccation: by 10mlEtOH, 8mlTEOS, 2mLH2O mixes under vigorous stirring, adds 1mol/L salt acid for adjusting pH value to 2, and hydrolysis 30min, obtains SiO2Colloidal sol. By SiO2Colloidal sol and 10mLEtOH, the mixed solution of 44.8mg tetra-hydration cobalt acetates mixes under vigorous stirring, adds 2.5mol/L ammoniacal liquor to regulate pH value to 6.5, leaves standstill about 15min and obtain SiO under room temperature2The compound alcogel of-CoO, under normal temperature condition after aging 24h, aging 24h in the absolute ethyl alcohol/ethyl orthosilicate that is 4:1 in 50mL volume ratio again, to strengthen the skeleton structure of gel, then gel is carried out to solvent exchange, twice solvent of replacing in 24h with 50mL n-hexane, remove the ethanol in gel, water, acetic acid, and other organic molecules. At last 120 DEG C, dry 2h, obtains the SiO that silicon cobalt mol ratio is 2002-CoO composite aerogel.
A kind of described method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst, is characterized in that SiO2The characteristic aperture of-CoO composite aerogel is 5 ~ 20nm, and porosity is 85 ~ 99%, and specific area is 600 ~ 1500m2/g。
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) SiO of the present invention2-CoO composite aerogel has typical meso pore characteristics aperture (5 ~ 20nm), high porosity (85 ~ 99%), high-specific surface area (600 ~ 1500m2/ unique physical the chemical property such as g). Used as with H2O2During for the epoxidation of styrene catalyst of oxidant, not only overcome the restriction that microporous silicon titanium molecular sieve is not suitable for large molecular olefine epoxidation reaction, its unique physicochemical properties are more conducive to intermolecular diffusion simultaneously. Reaction finally only has Styryl oxide and two kinds of products of benzaldehyde, without other accessory substance.
2) SiO of the present invention2-CoO composite aerogel catalyst is compared with HTS, and without using the high template of price, without using high-temperature roasting processing, preparation is simple, with low cost.
3) SiO of the present invention2-CoO composite aerogel catalyst is easily separated in reactant liquor, after separation, can be repeatedly used, and easy to operate, environmental friendliness, economic benefit are high.
4) the present invention is taking hydrogen peroxide as oxygen source, and its accessory substance is water, meets Green Chemistry requirement, and DMF is solvent, solvent successful, and easily separated between reactant and water byproduct.
5) the present invention reaction is carried out under normal pressure, reaction condition gentleness, energy consumption of reaction be low, to consersion unit require low, easy to operately, the product Styryl oxide obtaining and the selective sum of benzaldehyde are greater than 99%.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1-5: the SiO of different n (Si/Co)2-CoO composite aerogel catalysis epoxidation vinyl benzene is combined and is prepared Styryl oxide and benzaldehyde
Respectively in bis-mouthfuls of round-bottomed flasks of five 50mL, the n (Si/Co) that adds above-mentioned preparation is 50,100,150,200,250 catalyst 0.25g, styrene 1.04g(10mmol), N, dinethylformamide 10g, flask isothermal reaction in 60 DEG C of oil baths, backflow 6h, constantly stir simultaneously, micro-sampling pump at the uniform velocity adds 30% hydrogen peroxide 10ml (10mmol), and time for adding is 0.5h. After reaction finishes, filter to isolate catalyst, filtrate gas chromatographic analysis. Filtrate rectifying, gets respectively the cut of 180 DEG C and 190 DEG C, obtains successively Styryl oxide and benzaldehyde. Product is by GC-MS(CP-3800/Saturn2000 gas/matter combined instrument, capillary look post: CP-SIL8, and 30m*0.25mm*0.25 μ m) carries out qualitative analysis, confirms as Styryl oxide and benzaldehyde. The results are shown in Table 1 by gas-chromatography evaluate catalysts epoxidation performance.
The lower epoxidation of styrene result of the different n of table 1 (Si/Co)
As can be seen from Table 1, along with the increase of silicon cobalt mol ratio, styrene conversion takes the lead in improving rear reduction and reaches the highest with n (Si/Co)=200 o'clock, and the selective % of the selective % of Styryl oxide and benzaldehyde changes little. Preferably silicon cobalt mol ratio is 200:1.
Case study on implementation 6 ~ 9: the SiO of different catalysts consumption2-CoO composite aerogel catalysis epoxidation vinyl benzene is combined and is prepared Styryl oxide and benzaldehyde result
Select the SiO of n (Si/Co)=2002-CoO composite aerogel is catalyst, take respectively 0.05g, 0.15g, 0.25g and 0.35g (mass ratio of substrate styrene and catalyst is respectively 20:1,6.7:1,4:1,2.9:1) and put into bis-mouthfuls of flasks of 4 50mL, other operating conditions are with embodiment 1 ~ 5, and reaction result is in table 2.
The impact of table 2 different catalysts consumption on epoxidation reaction
As can be seen from Table 2, styrene conversion takes the lead in increasing sharply to be increased slowly, Styryl oxide is selective and benzaldehyde is selective changes not quite, and from cost-saving consideration, preferred catalyst consumption is that 0.25 ~ 0.35g is that styrene is 2.9 ~ 4:1 with catalyst quality ratio.
Case study on implementation 10 ~ 12: different n (H2O2/ styrene) descend epoxidation vinyl benzene to combine the result of preparing Styryl oxide and benzaldehyde
Select the SiO of n (Si/Co)=2002-CoO composite aerogel is catalyst, adopts respectively n (H2O2/ styrene) be 0.5,1 and 2 30% hydrogen peroxide. Other operating conditions, with embodiment 1 ~ 5, the results are shown in Table 3.
Different n (the H of table 32O2/ styrene) impact on epoxidation reaction
In table 3, can find out, along with the increase of hydrogen peroxide consumption, styrene conversion rate % improves, and the selective % of the selective % of Styryl oxide and benzaldehyde changes little, but as n (H2O2/ styrene) exceed at 1 o'clock, styrene conversion rate % increases not obvious. In order to control the selfdecomposition degree of hydrogen peroxide, reduce danger in production process, preferably n (H2O2/ styrene) be 0.5 ~ 1:1.
Case study on implementation 13 ~ 15: the epoxidation vinyl benzene of differential responses time is combined the result of preparing Styryl oxide and benzaldehyde
Select the SiO of n (Si/Co)=2002-CoO composite aerogel is catalyst, and the reaction time is elected respectively 4h, 6h and 10h as, and other operate with embodiment 1 ~ 5. The results are shown in Table 4.
The impact of table 4 differential responses time on epoxidation reaction
As can be seen from Table 4, the reaction time exceedes 6h, and conversion ratio increase is all not obvious, so from saving production cost angle, preferred reaction time 6 ~ 10h.
Case study on implementation 16 ~ 18: the epoxidation vinyl benzene of differential responses temperature is combined the result of preparing Styryl oxide and benzaldehyde
Select the SiO of n (Si/Co)=2002-CoO composite aerogel is catalyst, and reaction temperature is elected respectively 40 DEG C, 60 DEG C and 80 DEG C as, and other operate with embodiment 1 ~ 5. The results are shown in Table 5.
The impact of table 5 differential responses temperature on epoxidation reaction
As can be seen from Table 5, reaction temperature exceedes after 60 DEG C, and conversion ratio increase is all not obvious, so from saving production cost angle, 60 ~ 80 DEG C of preferable reaction temperature.
Claims (6)
1. one kind with SiO2-CoO composite aerogel is that catalyst is combined the method for preparing Styryl oxide and benzaldehyde, it is characterized in that taking styrene as substrate, and DMF is reaction dissolvent, and 30wt% hydrogen peroxide is oxidant, at SiO2Under the effect of-CoO composite aerogel catalyst, carry out epoxidation reaction of olefines, reaction temperature is 40 ~ 80 DEG C, and the reaction time is 4 ~ 10h, reaction finish after by reactant liquor rectification process, the cut of getting respectively 180 DEG C and 190 DEG C, obtains benzaldehyde and Styryl oxide, described SiO successively2Silicon cobalt mol ratio in-CoO composite aerogel catalyst is 200:1, the SiO that silicon cobalt mol ratio is 2002-TiO2The preparation method of composite aerogel catalyst is as follows: adopt the preparation of collosol and gel-atmosphere pressure desiccation: by 10mlEtOH, 8mlTEOS, 2mLH2O mixes under vigorous stirring, adds 1mol/L salt acid for adjusting pH value to 2, and hydrolysis 30min, obtains SiO2Colloidal sol; By SiO2Colloidal sol and 10mLEtOH, the mixed solution of 44.8mg tetra-hydration cobalt acetates mixes under vigorous stirring, adds 2.5mol/L ammoniacal liquor to regulate pH value to 6.5, leaves standstill about 15min and obtain SiO under room temperature2The compound alcogel of-CoO, under normal temperature condition after aging 24h, more aging 24h in the absolute ethyl alcohol/ethyl orthosilicate that is 4:1 in 50mL volume ratio, to strengthen the skeleton structure of gel, with 50mL n-hexane, gel is carried out to solvent exchange again, in 24h, change twice solvent, remove the ethanol in gel, water, acetic acid, and other organic molecules, dry 2h, obtains the SiO that silicon cobalt mol ratio is 200 at last 120 DEG C2-CoO composite aerogel.
2. a kind of method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst according to claim 1, is characterized in that styrene and SiO2-CoO composite aerogel catalyst mass ratio is 2.9 ~ 20:1.
3. a kind of method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst according to claim 1, is characterized in that styrene and SiO2-CoO composite aerogel catalyst mass ratio is 2.9 ~ 4:1.
4. a kind of method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst according to claim 1, the molar ratio that it is characterized in that styrene and hydrogen peroxide is 1:0.5 ~ 2.
5. a kind of method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst according to claim 1, the molar ratio that it is characterized in that styrene and hydrogen peroxide is 0.5 ~ 1:1.
6. a kind of method of preparing Styryl oxide and benzaldehyde of combining taking SiO2-CoO composite aerogel as catalyst according to claim 1, is characterized in that SiO2The characteristic aperture of-CoO composite aerogel is 5 ~ 20nm, and porosity is 85 ~ 99%, and specific area is 600 ~ 1500m2/g。
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| DE4319909C2 (en) * | 1993-06-16 | 1996-11-07 | Solvay Deutschland | Airgel supported catalyst comprising palladium, platinum, nickel, cobalt and / or copper, process for its production and use of a palladium airgel supported catalyst |
| US6251851B1 (en) * | 1998-05-07 | 2001-06-26 | E. I. Du Pont De Nemours And Company | Process for the selective oxidation of organic compounds |
| CN1297345C (en) * | 2004-01-13 | 2007-01-31 | 厦门大学 | Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method |
| CN101972665B (en) * | 2010-10-26 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Styrene epoxidizing catalyst as well as preparation method and application thereof |
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