CN105085438B - A kind of preparation method of propylene oxide - Google Patents
A kind of preparation method of propylene oxide Download PDFInfo
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- CN105085438B CN105085438B CN201510469135.7A CN201510469135A CN105085438B CN 105085438 B CN105085438 B CN 105085438B CN 201510469135 A CN201510469135 A CN 201510469135A CN 105085438 B CN105085438 B CN 105085438B
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Abstract
The invention discloses a kind of preparation methods of propylene oxide.This method is using propylene as raw material, and using oxygen as oxidant, organic solvent and auxiliary agent is added, and using metal porphyrins as catalyst, control is 30 ~ 140 in reaction temperatureoC, reaction pressure carry out catalysis under conditions of being 0.3 ~ 3.0MPa and propylene oxide are obtained by the reaction.The present invention has many advantages, such as reaction condition mild, excellent catalytic effect, propylene oxide high selectivity, simple for process.
Description
Technical field
The present invention relates to a kind of preparation methods of propylene oxide, specifically, being to be related to a kind of bionic catalysis propylene epoxy
The method that change prepares propylene oxide.
Background technology
Propylene oxide (PO) is the third-largest organic chemical industry production that yield is only second to polypropylene and acrylonitrile in acryloyl derivative
Product.Propylene oxide purposes is very extensive, at present other than being used to produce polyether polyol and glycerine, it can also be used to produce the third two
Alcohol, nonionic surfactant, oil field demulsifier, farm chemical emulgent and wetting agent etc..With propylene oxide purposes expansion and
The continuous growth of downstream product dosage, market increase the demand of propylene oxide year by year.
Currently, the main method for industrially producing propylene oxide is chlorohydrination, conjugated oxidation (also referred to as indirect oxidation method, or
It is Halcon methods) and hydrogen peroxide oxidation method (also referred to as HPPO methods).Chlorohydrination because generating a large amount of brine waste in process of production
It is seriously gradually eliminated with organic chloride, equipment corrosion and blowdown.The long flow path of conjugated oxidation, investment are big, coproduction product
It is more, it is restricted by the market factor serious.Disadvantage in hydrogen peroxide oxidation method is the of high cost of hydrogen peroxide, and safety is not high.Therefore, it opens
Hair has important foreground with the technique that oxygen or air direct oxidation propylene prepare propylene oxide.
In recent years, domestic and international researcher has been devoted to that flow is simple, by-product is few and the green of free of contamination production PO
The research of Catalytic processes.Molecular oxygen is cheap and easy to get and pollution-free, is optimal oxygen source, therefore propylene-oxygen Direct Epoxidation
It is the hot spot of people's research.But the gas-solid phase reaction being catalyzed with modified Ag series catalysts is mostly concentrated at present, required is anti-
It answers condition harsh, needs higher temperature and pressure, and also it is still necessary to further increase for the selectivity of propylene oxide.
Metalloporphyrins are effective analogies of cytochrome P 450 monooxygenases, have very high activation to oxygen
Ability can realize the high-selectivity oxidation of hydrocarbon compound under mild conditions.Chinese patent ZL201010239648.6 is public
A kind of method with catalysis of metalloporphyrin preparing epoxypropane by epoxidation of propene is opened, this method is with methacrylaldehyde and its derivative
Co-conducer, but the oleic series compound generated is easy to polymerize in system so that and reaction system control difficulty is big, catalysis
Agent easy in inactivation.
Therefore, for exploitation one kind using propylene as raw material, oxygen is oxidant, and mild condition, simple for process, high selectivity
Propylene oxide preparation process will have highly important application prospect.
Invention content
The purpose of the present invention is to provide a kind of methods that propylene liquid phase oxidation prepares propylene oxide.
To achieve the purpose of the present invention, used technical solution is：It is oxidation with oxygen using gaseous propylene as raw material
Organic liquid solvent is added in agent, auxiliary agent isoprene is added, with mononuclear porphyrin or general formula with logical formula (I) structure
(II) μ-oxygen-dinuclear metalloporphyrin of structure is the oxygen-dinuclear metalloporphyrin of catalyst or logical formula (III) structure, control in reaction temperature
Degree is 30~150 DEG C, and reaction pressure carries out catalysis under conditions of being 0.3~3.0MPa and is obtained by the reaction propylene oxide, propylene with help
The molar ratio of agent is 1:0.1~1:5,
M in logical formula (I)1Transition metal atoms Mg, Al, Cr, Mn, Fe, Co, Ni, Cu or Zn, R be hydrogen or carboxyl or
Sulfonic group；M in logical formula (II)2It is metallic atom Cr, Ni, Cu, Zn, Rh or Sn, X is halogen or hydrogen, R1、R2、R3、R4And R5
Selected from hydrogen, halogen, nitro, alkyl, alkoxy, hydroxyl, carboxyl, sulfydryl or sulfonic group, dentate X1It is chlorine or imidazoles or pyridine；
M in logical formula (III)3It is metallic atom Mo, Fe, Mn, V, Ti, Ru or Rh, R1、R2、R3、R4And R5It is selected from hydrogen, halogen, nitre
Base, alkyl, alkoxy, hydroxyl, carboxyl, sulfydryl or sulfonic group；M in logical formula (IV)4Be metallic atom Al, Co, Zn, Ru or
Rh, R1、R2、R3、R4And R5It is selected from hydrogen, halogen, nitro, alkyl, alkoxy, hydroxyl, carboxyl, sulfydryl or sulfonic group.
In above-mentioned propylene oxide process, the molar ratio of the propylene and auxiliary agent is 1:1~1:3.
In above-mentioned propylene oxide process, the organic liquid solvent be selected from methanol, ethyl alcohol, ethyl acetate,
At least one of acetonitrile, toluene, dichloromethane or N,N-dimethylformamide.
The preferred reaction temperature of the method for the present invention is 60~100 DEG C, and preferred reaction pressure is 1.0~2.0MPa, preferably
Catalyst concn be 1~100ppm.
The present invention has synthesized the quasi-enzyme catalytics agent such as metal phthalocyanine, metalloporphyrin first, and catalyst is solved homogeneously in solvent
In, auxiliary agent is added, so that propylene and oxygen is carried out catalysis reaction under the effect of the catalyst and propylene oxide is made.The auxiliary agent of addition is different
Pentadiene is large industrial chemicals of industry, the purpose is to promote the activation of oxygen during bionic catalysis, so as to add
The epoxidation rate of fast propylene and the selectivity for improving propylene oxide.
Compared with prior art, the present invention has the advantages that：
1, the present invention prepares propylene oxide using the method for propylene and oxygen Direct Epoxidation, avoids using chlorine
Environment that alcohol method or conjugated oxidation are brought, the shortcomings of product is complicated.
2, the high selectivity of propylene oxide of the present invention, operation is simple, easy, and product can be easily separated.
3, reaction condition of the present invention is mild, reduces the energy consumption of production process, while safety is also improved.
Specific implementation mode
With reference to embodiment and comparative example, the present invention is described further, but protection scope of the present invention not office
It is limited to the range of embodiment expression.
Embodiment 1
Contain 0.1mmol cobalts phthalocyanine in 25mL and (leads to R=H, M in formula (I)1=Co) acetonitrile solution in, be added 0.01mol
Isoprene, be filled with the propylene of 0.8MPa and the oxygen of 1.2MPa respectively, temperature be 30 DEG C at be stirred reaction, through color
The conversion ratio of spectrum analysis, propylene is 26%, and the selectivity of propylene oxide is 94%.
Embodiment 2
Contain 1.0 × 10 in 25mL-3Mmol tetracarboxylics copper phthalocyanine (leads to R=COOH, M in formula (I)1=Cu) acetonitrile solution
In, 5.0mmol isoprene is added, is filled with the propylene of 0.1MPa and the oxygen of 0.2MPa respectively, is carried out at being 50 DEG C in temperature
It is stirred to react, through chromatography, the conversion ratio of propylene is 38%, and the selectivity of propylene oxide is 95%.
Embodiment 3
Contain 1.5 × 10 in 25mL-3Mmol chlorinations (lead to R in formula (II) to nitro tetraphenyl Ru porphines3=NO2,R1=R2
=R4=R5=H, M3=Ru, X=H, X1=Cl) acetonitrile solution in, the isoprene of 0.2mol is added, is filled with respectively
The propylene of 0.4MPa and the oxygen of 0.6MPa are stirred reaction, through chromatography, the conversion ratio of propylene at being 60 DEG C in temperature
It is 56%, the selectivity of propylene oxide is 96%.
Embodiment 4
Contain 0.8 × 10 in 25mL-3Mmol chlorination neighbour's hydroxyl tetraphenyls manganoporphyrin (leads to R in formula (II)1=OH, R2=R3=
R4=R5=H, M3=Mn, X=H, X1=Cl) ethanol solution in, the isoprene of 0.3mol is added, is filled with 0.4MPa respectively
Propylene and 2.6MPa oxygen, temperature be 90 DEG C at be stirred reaction, through chromatography, the conversion ratio of propylene is
45%, the selectivity of propylene oxide is 93%.
Embodiment 5
Contain 1.8 × 10 in 25mL-3Mmol 3,4- disulfonic acid base tetraphenylarsonium chloride bases ferriporphyrin (leads to R in formula (II)2=R4
=SO3H,R1=R3=R5=H, M3=Fe, X=H, X1=Cl) methanol solution in, the isoprene of 6.0mmol is added, respectively
It is filled with the propylene of 0.6MPa and the air of 0.8MPa, reaction is stirred at being 60 DEG C in temperature, through chromatography, propylene turns
Rate is 54%, and the selectivity of propylene oxide is 95%.
Embodiment 6
Contain 0.5 × 10 in 25mL-3Mmol chlorination neighbour's chlorine tetraphenyls manganoporphyrin (leads to R in formula (II)1=Cl, R2=R3=R4
=R5=H, M3=Mn, X=H, X1=Cl) dichloromethane solution in, the isoprene of 0.3mol is added, is filled with respectively
The propylene of 0.5MPa and the oxygen of 1.0MPa are stirred reaction at being 80 DEG C in temperature, and through gas chromatographic analysis, propylene turns
Rate is 42%, and the selectivity of propylene oxide is 96%.
Embodiment 7
Contain 1.5 × 10 in 50mL-3Methyl tetraphenyl ferriporphyrin (leads to R in formula (II) between mmol chlorinations2=CH3,R1=R3
=R4=R5=H, M3=Fe, X=H, X1=Cl) ethyl acetate solution in, the isoprene of 0.06mol is added, is filled with respectively
The propylene of 0.6MPa and the oxygen of 1.8MPa are stirred reaction, through chromatography, the conversion of propylene at being 150 DEG C in temperature
Rate is 59%, and the selectivity of propylene oxide is 90%.
Embodiment 8
Contain 0.6 × 10 in 25mL-3Eight bromine chlorination adjacent nitro tetraphenyl manganoporphyrins of mmol (lead to R in formula (II)1=NO2,R2
=R3=R4=R5=H, M3=Mn, X=Br, X1=Cl) toluene solution in, the isoprene of 0.5mol is added, is filled with respectively
The propylene of 0.8MPa and the oxygen of 1.6MPa are stirred reaction, through chromatography, the conversion ratio of propylene at being 80 DEG C in temperature
It is 62%, the selectivity of propylene oxide is 97%.
Embodiment 9
Contain 0.6 × 10 in 25mL-3Mmol (leads to R in formula (III) to bromine oxo tetraphenyl molybdenum porphyrin1、R2、R4、R5=H,
R3=NO2,M3=Mo) acetonitrile solution in, the isoprene of 0.2mol is added, is filled with the propylene and 1.6MPa of 0.4MPa respectively
Oxygen, be stirred reaction at being 60 DEG C in temperature, through chromatography, the conversion ratio of propylene is 42%, the choosing of propylene oxide
Selecting property is 94%.
Embodiment 10
Contain 0.6 × 10 in 25mL-3Methyl oxo tetraphenyl vanadium porphyrin (leads to R in formula (III) between mmol1、R2、R3、R4、R5
=CH3,M3=V) ethyl acetate solution in, the isoprene of 0.6mol is added, is filled with the propylene and 1.8MPa of 0.9MPa respectively
Oxygen, be stirred reaction at being 90 DEG C in temperature, through chromatography, the conversion ratio of propylene is 52%, the choosing of propylene oxide
Selecting property is 97%.
Embodiment 11
Contain 0.6 × 10 in 25mL-3Carboxyl oxygen (leads to R in formula (III) for tetraphenyl Ru porphines between mmol1、R2、R3、R4、R5
=COOH, M3=Ru) acetonitrile solution in, the isoprene of 1.0mol is added, is filled with the propylene and 1.5MPa of 0.5MPa respectively
Oxygen, be stirred reaction at being 60 DEG C in temperature, through chromatography, the conversion ratio of propylene is 32%, the choosing of propylene oxide
Selecting property is 97%.
Embodiment 12
Contain 0.8 × 10 in 25mL-4Mmol μ-oxygen-double-core tetraphenyls manganoporphyrin (leads to R in formula (IV)1=R2=R3=R4=
R5=H, M4=Mn) ethanol solution in, the isoprene of 0.1mol is added, is respectively filled with the propylene and 1.2MPa of 0.4MPa
Oxygen is stirred reaction at being 60 DEG C in temperature, and through chromatography, the conversion ratio of propylene is 47%, the selection of propylene oxide
Property is 95%.
Embodiment 13
Contain 1.5 × 10 in 25mL-4Mmol μ-oxygen-double-core neighbour's chlorine tetraphenyls ferriporphyrin (leads to R in formula (IV)1=Cl, R2=
R3=R4=R5=H, M4=Fe) n,N-Dimethylformamide solution in, the isoprene of 0.4mol is added, is filled with respectively
The propylene of 0.8MPa and the oxygen of 1.2MPa are stirred reaction, through chromatography, the conversion ratio of propylene at being 80 DEG C in temperature
It is 51%, the selectivity of propylene oxide is 93%.
Claims (6)
1. a kind of preparation method of propylene oxide, it is characterised in that using gaseous propylene as raw material, using oxygen as oxidant, addition has
Auxiliary agent isoprene is added, with the μ-of mononuclear porphyrin or logical formula (II) structure with logical formula (I) structure in machine liquid flux
Oxygen-dinuclear metalloporphyrin is that the oxygen-dinuclear metalloporphyrin of catalyst or logical formula (III) structure or logical formula (IV) structure, control are being reacted
Temperature is 30~150 DEG C, and reaction pressure carries out catalysis under conditions of being 0.3~3.0MPa and is obtained by the reaction propylene oxide, propylene with
The molar ratio of auxiliary agent is 1:0.1~1:5,
M in logical formula (I)1It is transition metal atoms Fe, Co, Ni or Cu, R is hydrogen；
R in logical formula (II)3=NO2,R1=R2=R4=R5=H, M2=Ru, X=H, X1=Cl；R in logical formula (II)1=OH, R2=
R3=R4=R5=H, M2=Mn, X=H, X1=Cl；Or R2=R4=SO3H,R1=R3=R5=H, M2=Fe, X=H, X1=Cl；
Or R1=Cl, R2=R3=R4=R5=H, M2=Mn, X=H, X1=Cl；Or R2=CH3,R1=R3=R4=R5=H, M2=Fe, X
=H, X1=Cl；Or R1=NO2,R2=R3=R4=R5=H, M2=Mn, X=Br, X1=Cl；
M in logical formula (III)3It is metallic atom Mo, V or Ru, R1、R2、R3、R4And R5It is selected from hydrogen, nitro or carboxyl；
R in logical formula (IV)1=R2=R3=R4=R5=H, M4=Mn；Or R1=Cl, R2=R3=R4=R5=H, M4=Fe.
2. according to the method described in claim 1, it is characterized in that the molar ratio of propylene and auxiliary agent is 1:1~1:3.
3. according to the method described in claim 1, it is characterized in that the organic liquid solvent is selected from methanol, ethyl alcohol, acetic acid second
At least one of ester, acetonitrile, toluene, dichloromethane or N,N-dimethylformamide.
4. according to the method described in claim 1, it is characterized in that the temperature of catalysis reaction is 60~100 DEG C.
5. according to the method described in claim 1, it is characterized in that reaction pressure is 1.0~2.0MPa.
6. according to the method described in claim 1, it is characterized in that catalyst concn is 1~100ppm.
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| CN107903164A (en) * | 2017-10-24 | 2018-04-13 | 山东联创互联网传媒股份有限公司 | The method for preparing organic acid and epoxy butane at the same time |
| CN110950822A (en) * | 2019-10-25 | 2020-04-03 | 中山大学惠州研究院 | Method for catalyzing olefin epoxidation |
| CN110746380A (en) * | 2019-10-25 | 2020-02-04 | 中山大学 | Preparation method of epichlorohydrin |
| CN110759875B (en) * | 2019-11-11 | 2022-01-11 | 中国科学技术大学 | Preparation method of propylene oxide |
| CN111217771B (en) * | 2020-02-15 | 2023-06-06 | 中山大学惠州研究院 | Method for directly epoxidation of propylene and molecular oxygen |
| CN113385230B (en) * | 2021-05-13 | 2022-07-22 | 中山大学 | Coordination molybdenum oxygen heterocyclic catalyst and preparation method and application thereof |
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