CN105315236B - The method for producing 3,4- epoxy-1-butylene - Google Patents
The method for producing 3,4- epoxy-1-butylene Download PDFInfo
- Publication number
- CN105315236B CN105315236B CN201410314378.9A CN201410314378A CN105315236B CN 105315236 B CN105315236 B CN 105315236B CN 201410314378 A CN201410314378 A CN 201410314378A CN 105315236 B CN105315236 B CN 105315236B
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- Prior art keywords
- alpha
- epoxy
- butylene
- cumyl hydroperoxide
- reaction
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- 230000003647 oxidation Effects 0.000 claims abstract description 90
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims abstract description 89
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
The present invention relates to a kind of methods for producing 3,4- epoxy-1-butylene, and mainly solving the prior art, that there are feed stock conversions is low, the problem that waste is serious and product yield is low.The present invention is by using comprising steps of a) isopropylbenzene and air reaction obtain hydrogen peroxide cumene oxidation liquid；B) weight percentage for controlling organic acid in cumyl hydroperoxide oxidation solution is not more than 0.3%, and the weight percentage of alkali or alkaline earth metal ion is not more than 0.1%, and the weight percentage of water is not more than 0.5%；C) cumyl hydroperoxide oxidation solution is reacted with 1,3- butadiene generates 3,4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol；D) α, alpha-alpha-dimethyl benzylalcohol is reacted with hydrogen generates isopropylbenzene, the isopropylbenzene of generation is recycled to step a) as the technical solution for the raw material for preparing cumyl hydroperoxide and preferably solves the problems, such as this, in the industrial production that can be used for preparing 3,4- epoxy-1-butylene.
Description
Technical field
The present invention relates to a kind of methods for producing 3,4- epoxy-1-butylene.
Background technique
3,4- epoxy-1-butylenes (EPB) are a kind of novel fine-chemical intermediates, by 1,3-butadiene epoxy compound
At having a vast market potentiality, due to the compound not only aerobic ring, but also have double bond, be a kind of rare important containing two kinds
The intermediate of functional group, few organic intermediates have so wide purposes.But for a long time since production cost is excessively high,
Market attention is not obtained always.
Hundreds of important subsequent product can be prepared by being set out by 3,4- epoxy-1-butylene, be related to bulk chemical, fining
The multiple fields such as product and special chemical article are various pharmaceutical intermediates, chipal compounds, new flame retardant, functional polymer
The best synthesis material of material is fine chemicals in short supply both at home and abroad.For example, 4- epoxy-1-butylene sets out from 3, can derive
Out dihydrofuran, tetrahydrofuran, 1,4- butanediol, cyclopropylamine, butylene acetate/carbonic ester, halogenated epoxy butane etc. hundreds of
Chemicals.The development and production of pharmaceutical intermediate have become the new industry and hot spot industry of domestic chemical circles, cyclopropylamine in recent years
As important medicinal fine-chemical intermediate, the situation that supply falls short of demand, the increase of cyclopropylamine production capacity is presented in domestic market
It will be greatly facilitated the development of broad-spectrum antibiotic Ciprofloxacin of new generation again, and makes cyclopropylamine in medicine, pesticide and organic conjunction
Application rapid proliferation in, this also requires the production of 3,4- epoxy-1-butylene that must get caught up in.
In addition, 3,4- epoxy-1-butylenes are through halogenation, vulcanization and acetic acid and CO2The reaction such as addition, produces series of halogenating
(substitution) vinyl epoxy compound, carbonic ester, acetate monomers prepare various block polyethers, gather through oligomerisation or copolyreaction
The functional polymer materials such as ester, fire proofing, novel lubricating material, photoactive coating or adhesive.They have the prominent advantages that,
These polymerizates still retain C=C double bond or epoxy group, can further modification.
The technique of 1,3- butadiene catalysis epoxidation production 3,4- epoxy-1-butylene can be divided into two classes: first is that using molecule
Oxygen carry out gas phase selective epoxidation, this be also in alkene in addition to ethylene epoxidizing unique industrialization technology.It is studied
Active period is 1996~2007 years, which is that 14~18%, 3,4- epoxy-1-butylenes are selectively
87~90%.US5081096 uses the Ag catalyst similar with ethylene epoxidizing, using K, Rb and Cs as auxiliary agent.US5138077 is adopted
Use Ag-Tl/Al2O3Catalyst, 1,3-butadiene conversion ratio are 14.5%, and 3,4- epoxy-1-butylenes are selectively 90.0%.
US6011163 uses low-carbon alkanes and hydrofluorocarbons for diluent, with Ag-Cs/ α-Al2O3For catalyst, 1,3-butadiene conversion ratio
It is 17.5%, 3,4- epoxy-1-butylenes are selectively 87.6%.The Lanzhou Chemistry and Physics Institute, the Chinese Academy of Sciences has carried out 1,3- butadiene epoxidation
The research for making 3,4- epoxy-1-butylene, to catalyst studies have shown that the Ag/ α-Al promoted in Ba, Cs, Cl2O3On catalyst
It can get higher 1,3-butadiene conversion ratio and 3,4- epoxy-1-butylene selectivity, the interaction of Cs-Ag can promote oxygen object
Kind insertion butadiene in formed epoxides (Journal of Molecular Catalysis, 20 (04), 2006；Journal of Molecular Catalysis, 21 (01), 2007).In molecule
Oxygen selective oxidation 1,3-butadiene system 3,4- epoxy-1-butylene reaction in, due to 1,3-butadiene conversion ratio and 3,4- epoxy -1-
Butylene is selectively low, and 1,3-butadiene waste is serious, and as 1,3-butadiene resource is increasingly in short supply, price is constantly soaring, in the recent period
Research steering using peroxide as oxidant, using homogeneous catalyst by butadiene highly selective (99%), high conversion
(80%~90%) be converted into the pilot study of 3,4- epoxy-1-butylene.Although homogeneous catalyst activity is high, product selection
Property it is good, but catalyst is easy to remain in the product, and the separation of catalyst also can make technique more complicated, increase production cost.
Summary of the invention
The technical problem to be solved by the present invention is to the prior art, that there are feed stock conversions is low, and waste is serious and product yield
Low problem provides a kind of new production 3,4- epoxy-1-butylene method.This method has catalyst activity height, nothing in product
Residual, feed stock conversion are high, and stability is good, and 3,4- epoxy-1-butylenes selectivity is high, environmentally protective and the characteristics of without joint product.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of production 3,4- epoxy-1-butylene
Method, comprising the following steps:
A) peroxidization occurs for isopropylbenzene and air, obtains hydrogen peroxide cumene oxidation liquid；
B) organic acid in cumyl hydroperoxide oxidation solution, alkali or alkaline earth metal ion are removed, Yi Jishui makes it
In organic acid weight percentage be not more than 0.3%, the weight percentage of alkali or alkaline earth metal ion is not more than
0.1%, the weight percentage of water is not more than 0.5%；
C) through step b) handle cumyl hydroperoxide oxidation solution and 1,3-butadiene under the effect of the catalyst, in liquid
Selective oxidation reduction reaction occurs under the conditions of phase, wherein 1,3-butadiene is oxidized to 3,4- epoxy-1-butylene, hydrogen peroxide
Isopropylbenzene is reduced into alpha, alpha-dimethyl benzyl alcohol；
D) hydrogenolysis generation isopropylbenzene occurs for alpha, alpha-dimethyl benzyl alcohol and hydrogen；The isopropylbenzene of generation is recycled to step a)
As the raw material for preparing cumyl hydroperoxide oxidation solution.
In above-mentioned technical proposal, it is preferable that the reaction condition of step a) are as follows: 0~200 DEG C of reaction temperature, reaction pressure 0.1
~5.0MPa.It is highly preferred that 50~150 DEG C of reaction temperature, 0.1~2.0MPa of reaction pressure.
In above-mentioned technical proposal, it is preferable that the weight percentage of organic acid in control cumyl hydroperoxide oxidation solution
No more than 0.1%, the weight percentage of alkali or alkaline earth metal ion is not more than 500ppm, and the weight percentage of water is not
Greater than 0.2%.It is highly preferred that the weight percentage of organic acid is not more than in control cumyl hydroperoxide oxidation solution
The weight percentage of 600ppm, alkali or alkaline earth metal ion are not more than 200ppm, and the weight percentage of water is not more than
0.1%.
In above-mentioned technical proposal, it is preferable that the organic acid is selected from formic acid, acetic acid, propionic acid, ethanedioic acid, malonic acid, lactic acid
Or at least one of phenol.
In above-mentioned technical proposal, it is preferable that step c) reaction condition are as follows: 25~160 DEG C of reaction temperature, reaction pressure 0.1
The molar ratio 1~20 of~10.0MPa, 1,3-butadiene and cumyl hydroperoxide, the weight space velocity of cumyl hydroperoxide
0.05~20.0 hour-1, catalyst used be titanium-containing meso-porous or macroporous silica catalysis material Ti-HMS, Ti-MCM-41,
Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2.It is highly preferred that reaction temperature is 40~130 DEG C, reaction pressure is
The molar ratio of 0.5~8.0MPa, 1,3-butadiene and cumyl hydroperoxide is 2~15, and the weight of cumyl hydroperoxide is empty
Speed is 0.1~15.0 hour-1。
In above-mentioned technical proposal, it is preferable that the reaction condition of step d) are as follows: 80~400 DEG C of reaction temperature, reaction pressure
0.1~6.0MPa.
In above-mentioned technical proposal, it is preferable that the weight of cumyl hydroperoxide in the cumyl hydroperoxide oxidation solution
Percentage concentration is 1~90%.It is highly preferred that 10~80%.
In the method for the present invention, step a) is oxidation step, using molecular oxygen by cumene oxidation at cumyl hydroperoxide,
This is a classical radical reaction.Molecular oxygen used is either air can also use oxygen-enriched air.The reaction both may be used
To be carried out in the presence of catalyst or additive, can also efficiently be carried out without any catalyst or additive in the case where.
Used catalyst or additive are generally the hydroxide or carbonate of alkali metal, alkaline-earth metal, ammonia, but from oxidation solution it is rear from
Angle is managed to consider, it is preferential using the air-oxidation system for being free of any additive.Under normal conditions, oxidation step is anti-
Temperature and pressure is answered to be respectively preferably 50~150 DEG C and 0.1~2.0MPa.Temperature is too low, and reaction efficiency is low, or can not be into
Row；And excessively high temperature is then easy to cause cumyl hydroperoxide to decompose or generate other by-products.
In the method for the present invention, step b) is depickling, dealkalize metal or alkaline-earth metal ions and decompression concentrate step.Wherein take off
Acid is the organic acid removed in oxidation step in generated cumyl hydroperoxide oxidation solution.In oxidation step, with anti-
The progress answered, can generate the organic acid of some small molecules, such as formic acid, acetic acid, propionic acid, ethanedioic acid, malonic acid, lactic acid or phenol
Deng.Organic acid can both be removed using organic solvent abstraction technique, can also use the hydrogen of alkali metal, alkaline-earth metal or ammonia
The aqueous solution of oxide or carbonate carries out washing removing (generally NaCO3Or the aqueous solution of NaOH), or use small molecule
Organic amine, such as methylamine, ethamine, propylamine, ethylenediamine removed, or is directlyed adopt water and washed.Thus can not
Introduce alkali or alkaline earth metal ion and water again in oxidation solution with avoiding.Alkali or alkaline earth metal ion is (generally
Na+) removing can use water-washing method, then remove water therein by being dried.Pass through depickling, de- Na+And decompression mentions
Dense processing is supplied in the cumyl hydroperoxide oxidation solution of epoxidation step, the weight content of organic acid preferably≤
0.1%, more preferably≤600ppm；Na+Weight content preferably≤500ppm, more preferably≤200ppm；The weight of water
Content is preferably≤0.2%, more preferably≤0.1%.
The measurement of organic acid content can be using the chromatography of ions or acid base titration in cumyl hydroperoxide oxidation solution
The measurement of mode, alkali or alkaline earth metal ion concentration can use the chromatography of ions, and water content can use gas-chromatography
Method is measured.
In step c), it is alternatively that the 1,3-butadiene of property redox reaction raw material, to its purity without particular/special requirement, one
As in the case of 1,3- butadiene purity be greater than 80 volume %.Cumyl hydroperoxide alternatively property redox reaction
The carrier of oxygen is generally formed by form of mixtures with isopropylbenzene with it and uses, and being typically chosen its concentration is 1~90 weight %, preferably
10~80 weight %.Concentration is too low, redox reaction inefficiency, less economical；Excessive concentration, then reaction heat effect is bright
Aobvious, reaction heat removes difficulties, and excessively high concentration leads to the too high levels of benzylalcohol and other by-products in product, also to oxidation
The performance of raw catalyst is unfavorable, is easy to cause catalyst inactivation.Selective redox reaction under liquid-phase condition in solvent into
Row, used solvent are liquid under reaction temperature and pressure, and it is inertia to reactants and products.It is used molten
Agent include the alkanes such as hexane, hexamethylene, heptane, octane, nonane, decane, hendecane, dodecane and benzene,toluene,xylene,
The benzene such as trimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene and substituted benzene, preferably isopropylbenzene, in this way can be to avoid introducing additional object
Matter increases separating energy consumption.Selective oxidation reduction reaction temperature is preferably 40~130 DEG C.Temperature crosses low reaction and is difficult to carry out, temperature
Spending height is then easy to cause cumyl hydroperoxide to decompose, and by-product increases.Reaction pressure is to maintain reaction raw materials to be in a liquid state i.e.
Can, preferably 0.5~8.0MPa.Hypotony is easy to cause material to vaporize, and not can guarantee and carries out under liquid-phase condition, pressure mistake
It is high then reaction heat is caused to increase, and power consumption increases, and influences economy.Selective oxidation reduction reaction both can be in slurry bed
It carries out, can also be carried out in fixed bed reactors in reactor.But from the angle of large-scale industrial production, it is preferred to use
Fixed bed reactors.Catalyst used is titanium-containing meso-porous or macroporous silica catalysis material Ti-HMS, Ti-MCM-41, Ti-
TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2。
In above-mentioned technical proposal, Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO are urged
Agent is prepared using post-synthesis, first synthesis pure silicon HMS, MCM-41, TUD-1, SBA-15, KIT-1 mesoporous material or choosing
Select suitable macro-pore SiO2Powder.
Pure silicon HMS original powder the preparation method is as follows: being RNH with general formula2Organic amine be template agent, wherein R be containing 5~40
The chain alkylene of a carbon atom, using esters of silicon acis or amorphous silica as silicon source, using alcohol and water as solvent, using hydrothermal synthesis method
Preparation.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, tetraethyl orthosilicate, four n-propyl of positive silicic acid, four isopropyl of positive silicic acid
Ester or positive tetrabutyl silicate；The RNH2Middle R is preferably the linear paraffin base for containing 10~20 carbon atoms；The alcohol is selected from first
Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, vinyl alcohol, allyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, cyclohexanol, second two
At least one of alcohol or propylene glycol.With molar ratio computing, silicon source: template: water: alcohol=1:(0.05~0.5): (10~60):
(3~15).
Silica MCM-41 original powder the preparation method is as follows: using cetyl trimethylammonium bromide as template, with esters of silicon acis
Or amorphous silica is silicon source, is taken water as a solvent, and is prepared in alkaline environment using hydrothermal synthesis method.Wherein, the silicon
Acid esters is selected from positive quanmethyl silicate, tetraethyl orthosilicate, four fourth of four n-propyl of positive silicic acid, positive silicic acid tetra-isopropyl or positive silicic acid
Ester.With molar ratio computing, silicon source: template: water: alkali=1:(0.05~0.35): (15~40): (0.1~0.4).
Pure silicon TUD-1 original powder the preparation method is as follows: using triethanolamine as template, using esters of silicon acis as silicon source, with pure and mild
Water is solvent, is prepared in alkaline environment using hydrothermal synthesis method.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, positive silicon
Sour tetra-ethyl ester, four n-propyl of positive silicic acid, positive silicic acid tetra-isopropyl or positive tetrabutyl silicate；The alcohol is selected from methanol, ethyl alcohol, positive third
Alcohol or isopropanol, the alkali are selected from tetraethyl ammonium hydroxide.With molar ratio computing, silicon source: template: water: alcohol: alkali=1:(0.3~
3.0): (5~30): (0.5~5.0): (0.1~0.5).
Pure silicon SBA-15 original powder the preparation method is as follows: using triblock copolymer (PEO-PPO-PEO), be with esters of silicon acis
Silicon source is in strong acidic environment, hydrothermal synthesis method preparation.Wherein, the esters of silicon acis is selected from positive quanmethyl silicate, positive silicic acid tetrem
Ester, four n-propyl of positive silicic acid, positive silicic acid tetra-isopropyl or positive tetrabutyl silicate, the acid preferably molar concentration are rubbed for 0.5~3.5
You/liter hydrochloric acid solution.With molar ratio computing, silicon source: PEO-PPO-PEO:H2O:HCl=1:(0.005~0.04): (20~
100): (3~10).
Pure silicon KIT-1 original powder the preparation method is as follows: using cetyl trimethylammonium bromide as template agent, be with esters of silicon acis
Silicon source, in the presence of EDTA (sodium ethylene diamine tetracetate) and water, hydrothermal synthesis method preparation.Wherein, the esters of silicon acis is selected from positive silicon
Sour four methyl esters, tetraethyl orthosilicate, four n-propyl of positive silicic acid, positive silicic acid tetra-isopropyl or positive tetrabutyl silicate.With molar ratio computing,
Silicon source: template: EDTA: water=1:(0.1~0.4): (0.5~1.5): (20~100).
It will be in pure silicon mesoporous silicon oxide or macroporous silica selected from HMS, MCM-41, TUD-1, SBA-15, KIT-1
At least one original powder and binder be shaped to carrier；The dosage of original powder is 50~99 weight %；
Using halogenated titanium or titanate esters as titanium source, use organic solvent in the form of liquid-phase grafting, or with dry gas be carry
Gas uses gas phase graft form, and the active titanium species with four-coordination are implanted in resulting carrier framework, it is more to obtain titaniferous
Hole SiO 2 catalyst.It is preferred that using organosilicon reagent to carry titanium after the further surface grafting silanization treatment of catalyst,
Make it have the hydrophobic property of height.The organosilicon is selected from least one of halosilanes, silazane or silylamine.It urges
The way of contact of agent and organosilicon can impregnate the catalyst Precursors organic silicon solution being dissolved in organic solvent,
It can be handled with the organosilicon steam grafting being scattered in dry gas.It is porous in the titaniferous with very hydrophobic characteristic
The weight percentage of titanium is 0.05~30% in SiO 2 catalyst.Wherein, Ti content is 0.1~20% in catalyst,
It is preferred that 0.2~10%.
In order to guarantee that α, alpha-alpha-dimethyl benzylalcohol hydrogenolysis can be gone on smoothly, the utilization of cumyl hydroperoxide is improved
Rate reduces the loss of isopropylbenzene, to improve the conversion ratio of cumyl hydroperoxide as far as possible, reduces its containing in the reaction product
Amount.In general, 1,3-butadiene and 3 are isolated by rectifying, after 4- epoxy-1-butylene, in the benzyl for being supplied to hydrogenolysis step
The weight content of cumyl hydroperoxide should control below 3% in the cumene solution of alcohol.This can be by improving catalyst
Activity realize, can also be completed by the methods of rectifying, absorption, extraction.It pays the utmost attention to using the work for improving catalyst
Property, the methods of rectifying and absorption reduce the content of cumyl hydroperoxide.
Hydrogenolysis step is in the presence of a catalyst by alpha, alpha-dimethyl benzyl alcohol caused by selective oxidation reduction step
Hydrogenolysis generates isopropylbenzene, which carries out in solvent under the conditions of gas-solid-liquid three-phase, and solvent is inert to reactants and products
It and is at reaction conditions in liquid condition.Selected solvent include hexane, hexamethylene, heptane, octane, nonane, decane, hendecane,
The benzene such as the alkanes such as dodecane and benzene,toluene,xylene, trimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene and substituted benzene, preferably
Isopropylbenzene can increase separating energy consumption in this way to avoid additional substance is introduced.Used catalyst includes being carried on active oxidation
Ni-based, copper-based, palladium base on the carriers such as aluminium, silica, zeolite molecular sieve and active carbon etc. has the catalysis of catalytic hydrogenolysis function
Material.The temperature and pressure of hydrogenolysis is respectively preferably 80~400 DEG C and 0.1~6.0MPa.Hydrogenolysis can both become silted up
It carries out, can also be carried out in fixed bed reactors in slurry bed reactor.But from the angle of large-scale industrial production, preferably
Using fixed bed reactors.
The inventors discovered that Organic Acid and Base metal or alkaline-earth metal ions and water in cumyl hydroperoxide oxidation solution
Excessive concentration can seriously affect the selectivity of selective oxidation reduction reaction and the service life of catalyst.Only control peroxide
The weight percentage for changing organic acid in hydrogen cumene oxidation liquid is not more than 0.1%, the weight of alkali or alkaline earth metal ion
Percent concentration is not more than 500ppm, and the weight percent concentration of water is not more than 0.2%, just can guarantee redox reaction Gao Xuan
The progress of selecting property；Simultaneously it is also ensured that catalyst possesses longer service life, catalyst can be improved using the time
100%；In addition, the method for the present invention in addition to purpose product 3, outside 4- epoxy-1-butylene, generates, as most without other joint product
The isopropylbenzene of first raw material can be recycled in system, and Technical Economy is good, achieves preferable technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
In 105 DEG C, 0.4MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air aoxidize instead
It answers, obtains cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
NaOH weight content is used to wash hydrogen peroxide cumene oxidation liquid for 2% aqueous solution, wherein oxidation solution and alkali
The volume ratio of liquid is 3:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 3:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
75 DEG C of dense temperature obtains the oxidation solution that cumyl hydroperoxide concentration is 50 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 90ppm,
H2The weight content of O is 200ppm, Na+Weight content be 55ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 50 weight %) in the Ti-HMS catalyst (weight of Ti
Percentage composition be 1.6%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate 3,
4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.Wherein 1,3-butadiene/CHP=5:1 (mole), weight space velocity=4 of CHP
Hour-1, 100 DEG C of reaction temperature, reaction pressure 3.0MPa.
Reaction mixture is passed through butadiene recovery column and recycles excessive 1,3-butadiene recycling, wherein butadiene returns
It receives tower to operate under normal pressure, -4.5 DEG C of tower top temperature, 150 DEG C of bottom temperature, normal pressure.Tower reactor epoxy-1-butylene containing 3,4-, α, α-
The material of the pure and mild isopropylbenzene of dimethylbenzyl etc. enters 3,4- epoxy-1-butylene knockout tower, which operates under normal pressure, tower top temperature
66 DEG C, 160 DEG C of bottom temperature.
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol is in 0.5%Pd/Al2O3Hydrogenolysis generates isopropylbenzene in the presence of catalyst.Reaction temperature is 160
DEG C, reaction pressure 2.0MPa, H2The molar ratio of/α, alpha-alpha-dimethyl benzylalcohol are 3:1, and the weight space velocity of α, alpha-alpha-dimethyl benzylalcohol are
1.0 hour-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result such as table 1
It is shown.
[embodiment 2]
In 100 DEG C, 0.3MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air aoxidize instead
It answers, obtains cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
Using Na2CO3The aqueous solution that weight content is 5% washs hydrogen peroxide cumene oxidation liquid, wherein oxidation solution and alkali
The volume ratio of liquid is 4:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
Dense temperature 70 C obtains the oxidation solution that cumyl hydroperoxide concentration is 40 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 100ppm,
H2The weight content of O is 250ppm, Na+Weight content be 40ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 40 weight %) in the Ti-MCM-41 catalyst (weight of Ti
Measure percentage composition be 2.0%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate
3,4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.The weight space velocity of wherein 1,3-butadiene/CHP=5:1 (mole), CHP=
4.5 hour-1, 98 DEG C of reaction temperature, reaction pressure 2.8MPa.
Butadiene recycling and product separation process are the same as [embodiment 1].
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis in the presence of 0.2%Pd/C catalyst generates isopropylbenzene.Reaction temperature is 150 DEG C, instead
Answering pressure is 2.0MPa, H2/ α, the molar ratio of alpha-alpha-dimethyl benzylalcohol are 3:1, and α, the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 small
When-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result is as shown in table 1.
[embodiment 3]
In 98 DEG C, 0.3MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air carry out oxidation reaction,
Obtain cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
NaOH weight content is used to wash hydrogen peroxide cumene oxidation liquid for 2% aqueous solution, wherein oxidation solution and alkali
The volume ratio of liquid is 3:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
80 DEG C of dense temperature obtains the oxidation solution that cumyl hydroperoxide concentration is 60 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 70ppm,
H2The weight content of O is 100ppm, Na+Weight content be 30ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 60 weight %) in the Ti-TUD-1 catalyst (weight of Ti
Measure percentage composition be 1.5%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate
3,4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.The weight space velocity of wherein 1,3-butadiene/CHP=6:1 (mole), CHP=
4 hours-1, 100 DEG C of reaction temperature, reaction pressure 3.5MPa.
Butadiene recycling and product separation process are the same as [embodiment 1].
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis in the presence of 0.2%Pd/C catalyst generates isopropylbenzene.Reaction temperature is 165 DEG C, instead
Answering pressure is 2.4MPa, H2/ α, the molar ratio of alpha-alpha-dimethyl benzylalcohol are 2:1, and α, the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 small
When-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result is as shown in table 1.
[embodiment 4]
In 100 DEG C, 0.3MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air aoxidize instead
It answers, obtains cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
NaOH weight content is used to wash hydrogen peroxide cumene oxidation liquid for 2% aqueous solution, wherein oxidation solution and alkali
The volume ratio of liquid is 4:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
80 DEG C of dense temperature obtains the oxidation solution that cumyl hydroperoxide concentration is 55 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 75ppm,
H2The weight content of O is 110ppm, Na+Weight content be 40ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 55 weight %) in the Ti-SBA-15 catalyst (weight of Ti
Measure percentage composition be 3.0%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate
3,4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.The weight space velocity of wherein 1,3-butadiene/CHP=7:1 (mole), CHP=
4.5 hour-1, reaction temperature is 100 DEG C, reaction pressure 3.5MPa.
Butadiene recycling and product separation process are the same as [embodiment 1].
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol is in 0.2%Pd/Al2O3Hydrogenolysis generates isopropylbenzene in the presence of catalyst.Reaction temperature is 165
DEG C, reaction pressure 2.3MPa, H2The molar ratio of/α, alpha-alpha-dimethyl benzylalcohol are 3:1, and the weight space velocity of α, alpha-alpha-dimethyl benzylalcohol are
1.0 hour-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result such as table 1
It is shown.
[embodiment 5]
In 102 DEG C, 0.3MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air aoxidize instead
It answers, obtains cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
Using Na2CO3The aqueous solution that weight content is 5% washs hydrogen peroxide cumene oxidation liquid, wherein oxidation solution and alkali
The volume ratio of liquid is 4:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 3:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
80 DEG C of dense temperature obtains the oxidation solution that cumyl hydroperoxide concentration is 55 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 80ppm,
H2The weight content of O is 120ppm, Na+Weight content be 45ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 55 weight %) in the Ti-KIT-1 catalyst (weight of Ti
Measure percentage composition be 2.6%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate
3,4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.The weight space velocity of wherein 1,3-butadiene/CHP=6:1 (mole), CHP=
4 hours-1, reaction temperature is 100 DEG C, reaction pressure 3.5MPa.
Butadiene recycling and product separation process are the same as [embodiment 1].
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis in the presence of 0.2%Pd/C catalyst generates isopropylbenzene.Reaction temperature is 155 DEG C, instead
Answering pressure is 2.2MPa, H2/ α, the molar ratio of alpha-alpha-dimethyl benzylalcohol are 3:1, and α, the weight space velocity of alpha-alpha-dimethyl benzylalcohol is 1.0 small
When-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result is as shown in table 1.
[embodiment 6]
In 95 DEG C, 0.2MPa, under the conditions of controlling tail oxygen volume content lower than 5%, isopropylbenzene and air carry out oxidation reaction,
Obtain cumyl hydroperoxide (CHP) oxidation solution that weight concentration is 20~24%.
Using Na2CO3The aqueous solution that weight content is 5% washs hydrogen peroxide cumene oxidation liquid, wherein oxidation solution and alkali
The volume ratio of liquid is 4:1, removes organic acid therein.Then oxidation solution is washed with deionized, removes remaining because of alkali cleaning
Na+, wherein the volume ratio of oxidation solution and deionized water is 4:1.According to epoxidation reaction needs, vacuum concentrate is carried out to it, is mentioned
80 DEG C of dense temperature obtains the oxidation solution that cumyl hydroperoxide concentration is 50 weight %, because washing institute is remaining while concentrate
Water is also removed to a certain extent.After processing, the organic acid weight content in cumyl hydroperoxide oxidation solution is 80ppm,
H2The weight content of O is 120ppm, Na+Weight content be 40ppm.
By above-mentioned cumyl hydroperoxide oxidation solution (CHP concentration is 50 weight %) in Ti-SiO2Catalyst (the weight of Ti
Percentage composition be 1.0%) in the presence of, in fixed bed reactors and 1,3-butadiene carry out selective redox reaction generate 3,
4- epoxy-1-butylene and alpha, alpha-dimethyl benzyl alcohol.Wherein 1- butylene/CHP=8:1 (mole), weight space velocity=4 of CHP are small
When-1, 100 DEG C of reaction temperature, reaction pressure 3.2MPa.
Butadiene recycling and product separation process are the same as [embodiment 1].
3,4- epoxy-1-butylene knockout tower tower reactor enters benzylalcohol hydrogenolysis containing the material of alpha, alpha-dimethyl benzyl alcohol and isopropylbenzene etc.
Reactor.Alpha, alpha-dimethyl benzyl alcohol is in 0.5%Pd/Al2O3Hydrogenolysis generates isopropylbenzene in the presence of catalyst.Reaction temperature is 160
DEG C, reaction pressure 2.0MPa, H2The molar ratio of/α, alpha-alpha-dimethyl benzylalcohol are 3:1, and the weight space velocity of α, alpha-alpha-dimethyl benzylalcohol are
1.0 hour-1.The isopropylbenzene of generation is recycled to oxidation step as the raw material for preparing cumyl hydroperoxide.Reaction result such as table 1
It is shown.
[comparative example 1]
With [embodiment 1], only alkali cleaning is not carried out to oxidation solution, including the weight content of the organic acid including phenol
For 800ppm, H2The weight content of O is 300ppm, Na+Weight content reach 55ppm, reaction result is shown in Table 2.
[comparative example 2]
With [embodiment 1], the oxidation solution after alkali cleaning is not washed only, including the organic acid including phenol
Weight content be 100ppm, H2The weight content of O is 200ppm, Na+Weight content reach 400ppm, reaction result is shown in
Table 2.
[comparative example 3]
With [embodiment 1], only decompression concentrate is not carried out to the oxidation solution after alkali cleaning, washing, existed including phenol
The weight content of interior organic acid is 100ppm, H2The weight content 0.2% of O, Na+Weight content be 80ppm.Hydrogen peroxide
The concentration of cumene oxidation liquid is 22.0 weight %.Its reaction result is shown in Table 2.
[comparative example 4]
With [embodiment 1], only alkali cleaning, washing are not carried out to oxidation solution, including the weight of the organic acid including phenol
Amount content is 750ppm, H2The weight content of O is 100ppm, Na+Weight content reach 90ppm, reaction result is shown in Table 2.
Table 1
Note: CHP- cumyl hydroperoxide, EPB-3,4- epoxy-1-butylene.
Table 2
Note: CHP- cumyl hydroperoxide, EPB-3,4- epoxy-1-butylene.
It can be seen that, through depickling, take off Na from the above+And the cumyl hydroperoxide oxidation solution of decompression concentrate processing,
The weight percentage for controlling organic acid is not more than 0.3%, and the weight percentage of alkali or alkaline earth metal ion is not more than
0.1%, the weight percentage of water is not more than 0.5%.The weight percentage for especially controlling organic acid is not more than 600ppm,
The weight percentage of alkali or alkaline earth metal ion is not more than 200ppm, and the weight percentage of water is not more than 0.1%.It can
With high yield, with high selectivity by 1,3-butadiene catalysis epoxidation at 3,4- epoxy-1-butylene, and catalyst is with good
Stability.
Claims (6)
1. a kind of method for producing 3,4- epoxy-1-butylene, comprises the steps of:
A) peroxidization occurs for isopropylbenzene and air, obtains hydrogen peroxide cumene oxidation liquid；
B) organic acid, sodium ion and the water in cumyl hydroperoxide oxidation solution are removed, the weight hundred of organic acid therein is made
Dividing content is 70-100ppm, and the weight percentage of sodium ion is 30-55ppm, and the weight percentage of water is 100-
250ppm, the organic acid are selected from least one of formic acid, acetic acid, propionic acid, ethanedioic acid, malonic acid, lactic acid or phenol；
C) through step b) handle cumyl hydroperoxide oxidation solution and 1,3-butadiene under the effect of the catalyst, in liquid phase item
Selective oxidation reduction reaction occurs under part, wherein 1,3-butadiene is oxidized to 3,4- epoxy-1-butylene, hydrogen peroxide isopropyl
Benzene is reduced into α, alpha-alpha-dimethyl benzylalcohol, catalyst used be titanium-containing meso-porous or macroporous silica catalysis material Ti-HMS,
Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2, the reaction condition of step c) are as follows: reaction temperature 25
~160 DEG C, 0.1~10.0MPa of reaction pressure, the molar ratio 1~20 of 1,3-butadiene and cumyl hydroperoxide, hydrogen peroxide
The weight space velocity of isopropylbenzene 0.05~20.0 hour-1；
D) hydrogenolysis generation isopropylbenzene occurs for alpha, alpha-dimethyl benzyl alcohol and hydrogen；The isopropylbenzene of generation is recycled to step a) conduct
Prepare the raw material of cumyl hydroperoxide oxidation solution.
2. producing 3 according to claim 1, the method for 4- epoxy-1-butylene, it is characterised in that the reaction condition of step a)
Are as follows: 0~200 DEG C of reaction temperature, 0.1~5.0MPa of reaction pressure.
3. producing 3 according to claim 2, the method for 4- epoxy-1-butylene, it is characterised in that the reaction condition of step a)
Are as follows: 50~150 DEG C of reaction temperature, 0.1~2.0MPa of reaction pressure.
4. producing 3 according to claim 1, the method for 4- epoxy-1-butylene, it is characterised in that the reaction condition of step c)
Are as follows: reaction temperature is 40~130 DEG C, and reaction pressure is 0.5~8.0MPa, mole of 1,3-butadiene and cumyl hydroperoxide
Than being 2~15, the weight space velocity of cumyl hydroperoxide is 0.1~15.0 hour-1。
5. producing 3 according to claim 1, the method for 4- epoxy-1-butylene, it is characterised in that the reaction condition of step d)
Are as follows: 80~400 DEG C of reaction temperature, 0.1~6.0MPa of reaction pressure.
6. producing 3 according to claim 1, the method for 4- epoxy-1-butylene, it is characterised in that the cumyl hydroperoxide
The concentration expressed in percentage by weight of cumyl hydroperoxide is 1~90% in oxidation solution.
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| CN1432005A (en) * | 2000-03-24 | 2003-07-23 | 住友化学工业株式会社 | Process for producing propylene oxide |
| CN101348472A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing epoxide |
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| CN101348472A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing epoxide |
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| Catalytic monoepoxidation of butadiene over titanium silicate molecular sieves TS-1;Xiaoming Zhang et al.;《 Catalysis Letters》;20001231;第66卷;第176页 左栏 2.3，第177页表2，第175页 右栏 2.1，第176页 3.1及表1 |
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