CN1557553A - Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method - Google Patents
Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method Download PDFInfo
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- CN1557553A CN1557553A CNA2004100021998A CN200410002199A CN1557553A CN 1557553 A CN1557553 A CN 1557553A CN A2004100021998 A CNA2004100021998 A CN A2004100021998A CN 200410002199 A CN200410002199 A CN 200410002199A CN 1557553 A CN1557553 A CN 1557553A
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Abstract
The catalyst is VIII metal oxide or VIII metal oxide loaded on silica carrier, and has the composition of MOx or nMOx/SiO2, where SiO2 is mesoporous silica of pore size 1.5-30 nm, MOx is the oxide of VIII metal Fe or Co, and n=0.5 %-8 % is the weight percentage of metal oxide in the catalyst. The catalyst is prepared through ion exchange process or soaking process. Under proper reaction condition, the styrene converting rate within 4 hr may reach 40 %, epoxide selectivity may reach 60 %, and the side product is benzaldehyde mainly except small amount of phenylacetaldehyde and benzoic acid. The catalyst has no obviously lowered styrene converting rate and epoxide selectivity after repeated use.
Description
Technical field
The present invention relates to a kind of is the solid catalyst of the epoxidation of styrene system Styryl oxide of oxygen source with oxygen.
Background technology
Styryl oxide can be used as thinner, UV-absorption agent, the sweetener of Resins, epoxy, it also is the important intermediate of organic synthesis, pharmacy and perfume industry, for example the bata-phenethyl alcohol that makes of Styryl oxide hydrogenation is rose oil, Syzygium aromaticum stem oil, flores aurantii main body of oil, and is widely used in synthetic food, tobacco, soap and cosmetic essence.Both at home and abroad to the demand sharp increase of bata-phenethyl alcohol and medical LEVAMISOLE HCL, supply falls short of demand for Styryl oxide in recent years, brought vast potential for future development for the research of preparation Styryl oxide.
Industrial, Styryl oxide is by halogenohydrin method or the preparation of hydrogen peroxide catalyzed epoxidation vinyl benzene synthesis method.The halogenohydrin method is a simple and direct synthetic method, but this method material consumption and energy consumption are very high, and seriously polluted.Hydrogen peroxide catalyzed epoxidation vinyl benzene has advantages such as safety, economy, non-environmental-pollution, but needs corresponding catalyzer.That research is more at present is HTS/H
2O
2Epoxidation process.Human TS-1/H such as Taramasso and Perego G.
2O
2System epoxidation vinyl benzene, the transformation efficiency that obtains are 97% (H
2O
2), the selectivity of Styryl oxide is 96%.But H
2O
2Cost an arm and a leg, and the production cost of HTS is higher, and the technology that needs exploitation and reacting phase to mate.With oxygen and air is that oxygen source system Styryl oxide is most economical, can reduce production costs greatly.People such as Spadle Marian use PhCMe
2OOH makes radical initiator, in high-pressure reactor, with MeCHClCH
2Cl is a solvent, and under the 100 ℃/3atm, air velocity is 3L, obtains Styryl oxide (selectivity 44.3%) and phenyl aldehyde by molecular oxygen oxidation vinylbenzene.People such as Hiroyoshi Kanai have reported with μ-oxo-three caryogram metal acetate compounds (as [Fe
2 IIIZn
IIO (OAc)
6(H
2O)
3], [Cr
2 IIIFe
IIO (OAc)
6(H
2O)
3] etc.) make catalyzer, use O
2Styrene oxide 98min., the primary product that obtains are Styryl oxide and phenyl aldehyde.Learn by experimental result, under moderate temperature (80～95 ℃), reduce oxygen partial pressure, the selectivity of epoxide raises, but cinnamic transformation efficiency is reduced, and the epoxy product selectivity is up to 50%, 1/20 when speed of reaction but has only 1atm when being 4kPa as pressing at oxygen.People such as M.M.Taqui Khan have reported with Ru
III-EDTA compound as catalyst is with molecular oxygen oxidation epoxidation alkene.It is catalyzer that Japanese Patent JP9325149 discloses with methyl ethyl diketone Fe (III) complex compound, at solvent C H
2ClCH
2Under Cl, low aldehyde (MeCHO) condition, oxygen and vinylbenzene liquid-phase oxidation prepare Styryl oxide.People (Pol.P162668) such as Rusczynski Jerzy feed reaction system with oxygen or air, with trialkyl or triaryl orthophosphoric acid salt is catalyzer, catalyzed oxidation vinylbenzene prepares Styryl oxide and phenyl aldehyde, temperature of reaction is controlled at 80～120 ℃, the productive rate that obtains Styryl oxide is 22%, and the productive rate of phenyl aldehyde is 21%.In addition, but Co salen title complex also catalytic molecular oxygen Styrene oxide 98min. prepare Styryl oxide, make co-conducer but need to add isobutyric aldehyde.Oxygen also can carry out catalytic epoxidation with vinylbenzene and prepares Styryl oxide under gas phase condition, for example people such as Murakami Yuichi is in continuous flow reactor, with vinylbenzene in the enterprising promoting the circulation of qi phase oxidation of Ag catalyzer, the selectivity of epoxide is almost 100%, but cinnamic transformation efficiency is very low.In sum, though oxygen and air are ideal as oxygen source Styrene oxide 98min. system Styryl oxide, but this method is in present stage and immature, and use composition catalyst mostly, operate in the homogeneous reaction mode, catalyzer is difficult to reclaim, and is seriously polluted, thereby be necessary to seek be easy to separate with product, repeatedly used new solid-phase catalyst and reaction system, and guarantee the high styrene conversion rate and the selectivity of Styryl oxide.
Summary of the invention
The object of the present invention is to provide a kind of is oxygen source is prepared Styryl oxide by epoxidation of styrene solid catalyst efficiently with oxygen or air.
The said catalyzer of the present invention is the oxide compound of group VIII metal or the oxide compound that is carried on the group VIII metal on the silica supports, and its chemical constitution is:
MO
xOr nMO
x/ SiO
2
SiO wherein
2Finger-hole directly is the mesoporous silicon oxide of 1.5～30nm, as: MCM-41, MCM-48, SBA-1 or SBA-15 etc.; MO
xBe the oxide compound of group VIII metal, said group VIII metal is iron or cobalt; N is the weight percentage of metal oxide in catalyzer, n=0.5%～8%.
The said catalyzer of the present invention adopts ion exchange method or immersion process for preparing, and its concrete steps are as follows:
Method for preparing catalyst (one) (template ion exchange method)
1) the synthetic not precursor of the mesopore molecular sieve of removed template method for preparing of hydro-thermal;
2) press catalyzer and form proportioning weighing cobalt salt or molysite, compound concentration is the iron of 0.1～1mol/L or the aqueous solution or the alcoholic solution of cobalt;
3) with the solution of the precursor of mesopore molecular sieve and iron or cobalt at 60～80 ℃ of following ion-exchange 3～24h;
4) said mixture is filtered, solid is with a large amount of deionized water thorough washing, behind the ion that removal is not exchanged, at 20～100 ℃ of following vacuum-drying 20～24h;
5) with dried solid at 400～650 ℃ of following roasting 6～12h, temperature rise rate is controlled within the 1 ℃/min;
6) catalyzer will be used as behind the solid grinding powder after the roasting.
Method for preparing catalyst (two) (pickling process)
1) the synthetic preparation of hydro-thermal mesopore molecular sieve;
2) press catalyzer and form proportioning weighing cobalt salt or molysite, with deionized water or anhydrous alcohol solution;
3) press catalyzer and form proportioning weighing mesopore molecular sieve, join in the aqueous solution or alcoholic solution of above-mentioned iron or cobalt, stir 2～4h under the room temperature after, place 20～24h, then boil off water or ethanol at 60～80 ℃;
4) with the solid behind the evaporate to dryness at 40 ℃ of vacuum-drying 20～24h, dried solid after grinding at 550 ℃ of roasting 6h as catalyzer.
Evaluating catalyst is bathed in the formula reactor at normal pressure and is carried out.Take by weighing a certain amount of catalyzer and add and be equipped with in the glass flask of vinylbenzene and dimethyl formamide (DMF) solvent, temperature of reaction is controlled by oil bath, and temperature fluctuation is controlled at ± and 1 ℃.During the reaction beginning, with O
2Feed in the reaction solution by bubbling.After reaction finishes, catalyzer is filtered, product liquid is analyzed by Tianjin, island GC 14B type gas chromatograph capillary column, FID.Catalyzer of the present invention cinnamic transformation efficiency under proper reaction conditions can reach more than 40% within the 4h, the selectivity of epoxide is more than 60%, and except that a spot of phenylacetic aldehyde and phenylformic acid, other by product is phenyl aldehyde, and catalyzer does not have obvious decline in the selectivity that is repeatedly used cinnamic transformation efficiency in back and epoxide.
Embodiment
Embodiment 1: take by weighing Co (NO
3)
26H
2O 0.34g adds the 160g deionized water dissolving, then adds the not MCM-41 8.0g of removed template method, at room temperature stir 1h after, in 80 ℃ of water-baths, place 20h.Above-mentioned mixed solution is filtered, with a large amount of deionized water wash, the cobalt ion that flush away is not exchanged; With filter cake 40 ℃ of vacuum-dryings 1 day; At 550 ℃ of roasting 6h, temperature rise rate is controlled at 1 ℃/min with dried solid; Solid abrasive powdered after the roasting is promptly obtained 0.78wt%CoO
x/ MCM-41 catalyzer.The MCM-41 molecular sieve of removed template method does not adopt the hydrothermal synthesis method preparation, and concrete steps are as follows: take by weighing Na
2SiO
39H
2O 33.8g, hexadecyl trimethyl ammonium bromide 22.3g are respectively with mixing behind the deionized water dissolving, the PH that the hydrochloric acid that is about 4N with concentration is regulated above-mentioned mixed solution is about 11, the limit edged stirs, then under agitation keep 1h, at last above mixture is moved in the stainless steel autoclave that has poly-tetrafluoro lining, synthesized 4 days 120 ℃ of hydro-thermals.Mixture after synthetic is filtered, with behind a large amount of deionized water wash 40 ℃ of vacuum-dryings 1 day, obtain the not MCM-41 molecular sieve of removed template method.
Catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask 0.78wt%CoO into
x/ MCM-41 catalyzer 0.2g drops in the above mixed solution.During the reaction beginning, with O
2Feed below the reaction solution liquid level control O by airway
2Flow (about 3～6ml/min), make O
2Enter reaction solution by bubbling, temperature of reaction is controlled by oil bath, and temperature is controlled at 100 ± 1 ℃.Behind the reaction 4h, catalyzer is filtered, product liquid is analyzed by Tianjin, island GC 14B type gas chromatograph capillary column, FID.Catalyzed reaction the results are shown in table 1.
Table 1 0.78wt%CoO
xThe reactivity worth of/MCM-41 catalyzer
| Styrene conversion rate (%) | ????44.7 |
| Styryl oxide selectivity (%) | ????62.3 |
| Turn over number | ????169 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????43.4 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????58.6 |
| Turn over number after three circulations of catalyzer | ????164 |
Embodiment 2: take by weighing Co (NO
3)
26H
2O 2.4g adds the 160g deionized water dissolving, then adds the not MCM-41 8.0g of removed template method, at room temperature stir 1h after, in 80 ℃ of water-baths, place 20h.Above-mentioned mixed solution is filtered, with a large amount of deionized water wash, the cobalt ion that flush away is not exchanged; With filter cake 40 ℃ of vacuum-dryings 1 day; At 550 ℃ of roasting 6h, temperature rise rate is controlled at 1 ℃/min with dried solid; Solid grind into powder after the roasting is promptly obtained 6.1wt%CoO
x/ MCM-41 catalyzer.The MCM-41 molecular sieve of removed template method does not adopt the hydrothermal synthesis method preparation with embodiment 1.
Catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask 6.1wt%CoO into
x/ MCM-41 catalyzer 0.2g drops in the above mixed solution.Reaction conditions and product analysis are with embodiment 1.Catalyzed reaction the results are shown in table 2.
Table 2 6.1wt%CoO
xThe reactivity worth of/MCM-41 catalyzer
| Styrene conversion rate (%) | ????45.2 |
| Styryl oxide selectivity (%) | ????60.0 |
| Turn over number | ????21.9 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????42.8 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????62.0 |
| Turn over number after three circulations of catalyzer | ????20.7 |
Embodiment 3: take by weighing Co (NO
3)
26H
2O 1.2g adds the 160g deionized water dissolving, then adds the not MCM-41 8.0g of removed template method, at room temperature stir 1h after, in 80 ℃ of water-baths, place 20h.Above-mentioned mixed solution is filtered, with a large amount of deionized water wash, the cobalt ion that flush away is not exchanged; With filter cake 40 ℃ of vacuum-dryings 1 day; At 550 ℃ of roasting 6h, temperature rise rate is controlled at 1 ℃/min with dried solid; Solid grind into powder after the roasting is promptly obtained 2.1wt%CoO
x/ MCM-41 catalyzer.The MCM-41 molecular sieve of removed template method does not adopt the hydrothermal synthesis method preparation with embodiment 1.
Catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask 2.1wt%CoO into
x/ MCM-41 catalyzer 0.2g drops in the above mixed solution.Reaction conditions and product analysis are with embodiment 1.Catalyzed reaction the results are shown in table 3.
Table 3 2.1wt%CoO
xThe reactivity worth of/MCM-41 catalyzer
| Styrene conversion rate (%) | ????42.6 |
| Styryl oxide selectivity (%) | ????56.6 |
| Turn over number | ????59.8 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????43.1 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????61.5 |
| Turn over number after three circulations of catalyzer | ????60.5 |
Embodiment 4: with Fe
3O
4Be catalyzer, catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask, take by weighing commodity Fe
3O
4(Shanghai chemical reagent purchasing and supply station chemical reagent work) 0.0027g drops in the above mixed solution.During the reaction beginning, with O
2Feed below the reaction solution liquid level control O by airway
2Flow (about 3～6ml/min), make O
2Enter reaction solution by bubbling, temperature of reaction is controlled by oil bath, and temperature is controlled at 100 ± 1 ℃.Behind the reaction 4h, catalyzer is filtered, product liquid is analyzed by Tianjin, island GC 14B type gas chromatograph capillary column, FID.Catalyzed reaction the results are shown in table 4.
Table 4 Fe
3O
4The reactivity worth of catalyzer
| Styrene conversion rate (%) | ????41.6 |
| Styryl oxide selectivity (%) | ????62.3 |
| Turn over number | ????122 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????40.5 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????62.8 |
| Turn over number after three circulations of catalyzer | ????118 |
Embodiment 5: take by weighing Fe (NO
3)
26H
2O 0.28g adds 160g and removes anhydrous alcohol solution, then adds the not MCM-41 8.0g of removed template method, at room temperature stir 1h after, in 60 ℃ of water-baths, place 20h.Above-mentioned mixed solution is filtered, with a large amount of deionized water wash, the cobalt ion that flush away is not exchanged; With filter cake 40 ℃ of vacuum-dryings 1 day; At 550 ℃ of roasting 6h, temperature rise rate is controlled at 1 ℃/min with dried solid; Solid grind into powder after the roasting is promptly obtained 1.1wt%FeO
x/ MCM-41 catalyzer.The MCM-41 molecular sieve of removed template method does not adopt the hydrothermal synthesis method preparation with embodiment 1.
Catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask 1.1wt%FeO into
x/ MCM-41 catalyzer 0.2g drops in the above mixed solution.Reaction conditions and product analysis are with embodiment 1.Catalyzed reaction the results are shown in table 5.
Table 5 1.1wt%FeO
xThe reactivity worth of/MCM-41 catalyzer
| Styrene conversion rate (%) | ????20.6 |
| Styryl oxide selectivity (%) | ????57.2 |
| Turn over number | ????28.6 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????21.3 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????60.3 |
| Turn over number after three circulations of catalyzer | ????29.6 |
Embodiment 6: take by weighing Co (NO
3)
26H
2O 1.48g adds the 40ml deionized water dissolving, takes by weighing SBA-15 4.0g again, adds in the above-mentioned solution, at room temperature stir 4h after, place 20h, then with mixture at 80 ℃ of water bath methods; Above solid 40 ℃ of vacuum-dryings 1 day, after fully grinding, at 550 ℃ of roasting 6h, is obtained 7.5wt%CoO with the temperature rise rate of 1 ℃/min
x/ SBA-15 catalyzer.Mesoporous molecular sieve SBA-15 adopts the hydrothermal synthesis method preparation, concrete steps are as follows: take by weighing P123 (triblock copolymer of polyoxyethylene glycol and polypropylene glycol) 9.6g, the HCl solution 300g that adds 2M, after being stirred to dissolving fully, add 40 ℃ of reactions of 20.4gTEOS (tetraethyl orthosilicate) 20h, then above mixture is moved in the stainless steel autoclave that has poly-tetrafluoro lining, at 100 ℃ of hydro-thermal Synthetic 2 4h.Mixture after synthetic is filtered, with behind a large amount of deionized water wash 40 ℃ of vacuum-dryings 1 day, the temperature rise rate with 1 ℃/min after fully grinding obtains the SBA-15 molecular sieve at 550 ℃ of roasting 6h.
Catalyzed reaction is bathed in the formula reactor at normal pressure and is carried out.Pipette vinylbenzene 1.146ml and 20ml DMF solvent and pack in the 100ml glass flask 7.5wt%CoO into
x/ SBA-15 catalyzer 0.2g drops in the above mixed solution.Reaction conditions and product analysis are with embodiment 1.Catalyzed reaction the results are shown in table 6.
Table 6 7.5wt%CoO
xThe reactivity worth of/SBA-15 catalyzer
| Styrene conversion rate (%) | ????33.0 |
| Styryl oxide selectivity (%) | ????63.3 |
| Turn over number | ????13.0 |
| Three circulation backs of catalyzer cinnamic transformation efficiency (%) | ????33.1 |
| Three circulation backs of catalyzer Styryl oxide selectivity (%) | ????62.6 |
| Turn over number after three circulations of catalyzer | ????13.0 |
Claims (6)
1. the solid catalyst of epoxidation of styrene system Styryl oxide is characterized in that said catalyzer is the group VIII metal oxide or is carried on group VIII metal oxide on the silica supports, and its chemical constitution is: MO
xOr nMO
x/ SiO
2, SiO wherein
2Be mesoporous silicon oxide, MO
xBe the group VIII metal oxide, n is the weight percentage of metal oxide in catalyzer, n=0.5%～8%.
2. the solid catalyst of epoxidation of styrene system Styryl oxide as claimed in claim 1 is characterized in that said mesoporous silicon oxide is MCM-41, MCM-48, SBA-1 or SBA-15.
3. the solid catalyst of epoxidation of styrene system Styryl oxide as claimed in claim 1, the aperture that it is characterized in that said mesoporous silicon oxide is 1.5～30nm.
4. the solid catalyst of epoxidation of styrene system Styryl oxide as claimed in claim 1 is characterized in that said group VIII metal oxide is the oxide compound of iron or cobalt.
5. the preparation method of the solid catalyst of epoxidation of styrene system Styryl oxide is characterized in that catalyzer adopts ion exchange method or immersion process for preparing, and its concrete steps are as follows:
The template ion exchange method:
1) the synthetic not precursor of the mesopore molecular sieve of removed template method for preparing of hydro-thermal;
2) press catalyzer and form proportioning weighing metal oxide, compound concentration becomes the aqueous solution or the alcoholic solution of 0.1～1mol/L;
3) with the solution of the precursor of mesopore molecular sieve and metal oxide at 60～80 ℃ of following ion-exchange 3～24h;
4) said mixture is filtered, the washing back is at 20～100 ℃ of following vacuum-drying 20～24h;
5) with dried solid at 400～650 ℃ of following roasting 6～12h;
6) catalyzer will be used as behind the solid grinding powder after the roasting;
Pickling process:
1) the synthetic preparation of hydro-thermal mesopore molecular sieve;
2) press catalyzer and form proportioning weighing metal oxide, with deionized water or anhydrous alcohol solution;
3) press catalyzer and form proportioning weighing mesopore molecular sieve, join in the aqueous solution or alcoholic solution of above-mentioned metal oxide, stir 2～4h under the room temperature after, place 20～24h, then boil off solvent at 60～80 ℃;
4) with the solid behind the evaporate to dryness at 40 ℃ of vacuum-drying 20～24h, dried solid after grinding at 550 ℃ of roasting 6h as catalyzer;
The composition proportioning of said catalyzer is the group VIII metal oxide or is carried on group VIII metal oxide on the silica supports that its chemical constitution is: MO
xOr nMO
x/ SiO
2, SiO wherein
2Be mesoporous silicon oxide, MO
xBe the group VIII metal oxide, n is the weight percentage of metal oxide in catalyzer, n=0.5%～8%.
6. the preparation method of the solid catalyst of epoxidation of styrene system Styryl oxide as claimed in claim 5 is characterized in that the temperature rise rate of roasting in the template ion exchange method step 5 is controlled within the 1 ℃/min.
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| CN112569934A (en) * | 2020-12-10 | 2021-03-30 | 万华化学集团股份有限公司 | Oxidation catalyst, preparation method and method for co-production of styrene oxide and benzaldehyde by air oxidation of styrene |
| CN114950536A (en) * | 2022-05-19 | 2022-08-30 | 许昌学院 | Preparation method of high-dispersion Co-MCM-41 mesoporous molecular sieve |
| CN114950536B (en) * | 2022-05-19 | 2024-04-30 | 许昌学院 | Preparation method of high-dispersion Co-MCM-41 mesoporous molecular sieve |
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