CN103420948B - A kind of separation method of epoxychloropropane - Google Patents
A kind of separation method of epoxychloropropane Download PDFInfo
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- CN103420948B CN103420948B CN201210156886.XA CN201210156886A CN103420948B CN 103420948 B CN103420948 B CN 103420948B CN 201210156886 A CN201210156886 A CN 201210156886A CN 103420948 B CN103420948 B CN 103420948B
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Abstract
A kind of separation method of epoxychloropropane, comprise: after the solution that contains epoxychloropropane, methyl alcohol, chlorallylene and water is mixed with extractant, be separated, the liquid phase that obtains being rich in the liquid phase of epoxychloropropane and be rich in methyl alcohol, the liquid phase that is rich in epoxychloropropane that distillation obtains, obtains epoxychloropropane; Wherein, described extractant comprises water and contains oxygen atom and the organic solvent of halogen atom-containing not with water is immiscible, the ability of organic solvent extraction methyl alcohol lower than water and extraction epoxychloropropane ability higher than water, and organic solvent is different from the boiling point of epoxychloropropane, the density ratio water of organic solvent is large. Method of the present invention is very easy to realize good being separated, and can obtain epoxychloropropane product from distillation tower top by simple distillation, at the bottom of destilling tower, reclaim organic solvent, organic solvent does not need just can reclaim through pervaporation, with adopt than compared with the method for the low-boiling extractant of epoxychloropropane, low-energy-consumption can fall effectively.
Description
Technical field
The present invention relates to a kind of separation method of epoxychloropropane.
Background technology
Epoxychloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in synthesizingThe multiple products such as epoxy resin, glycerine, chlorohydrin rubber, medicine, agricultural chemicals, surfactant, plasticizer.
It is catalyst that epoxychloropropane can adopt HTS, and hydrogen peroxide and chlorallylene are occurredEpoxidation reaction preparation. Because chlorallylene and hydrogen peroxide do not dissolve each other, cause reaction speed slow, because ofThis, need to add a large amount of solvents as methyl alcohol, makes chlorallylene and hydrogen peroxide, in this solvent, epoxy occurChange reaction. In the epoxidation reaction product obtaining after HTS Separation of Solid and Liquid, it is excessive conventionally to containReactant chlorallylene, solvent methanol, object product epoxychloropropane, hydrogen peroxide charging bring intoWith the water of reaction generation, and a small amount of accessory substance such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine. Therefore needIsolate product epoxychloropropane, and reclaim solvent methanol and excessive reactant chlorallylene.
The method of existing separation epoxychloropropane is generally the method for direct distillation or is undertaken by extractantThe method of extraction. For example, CN1534030A discloses a kind of direct distillating method of epoxychloropropane,The method by by the epoxidation reaction product obtaining according to the height of component boiling point directly in destilling towerDistill to separate epoxychloropropane. In the time of separated methyl alcohol and epoxychloropropane, find, need to adoptWith thering is the destilling tower of very high theoretical cam curve and very high reflux ratio, could be by epoxychloropropane and firstAlcohol separated. Owing to containing a large amount of solvent methanols in epoxidation reaction product, cause separatedEquipment investment is high, energy consumption is large. And, in the time that first alcohol and water exists, epoxy chlorine in still-processPropane also can with first alcohol and water generation side reaction, generate the by-products such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorineThing, the yield of reduction epoxychloropropane.
US6350888B1 discloses a kind of method of carrying out extract and separate epoxychloropropane by extractant,The method, by adding a kind of organic extractant extraction epoxychloropropane, then distills out the ring that contains obtainingExtractant in the liquid phase of oxygen chloropropane, separates and obtains epoxychloropropane. Although the method can reach pointFrom the object of epoxychloropropane, still, extract epoxychloropropane from epoxidation reaction product time, not only needUse a large amount of extractants, and part methyl alcohol also can be extracted together with epoxychloropropane, stillNeed direct separated methyl alcohol and epoxychloropropane, cause separated epoxychloropropane and reclaim extractionSolvent need to consume a large amount of energy; In addition, in the direct process of separated methyl alcohol and epoxychloropropaneIn, epoxychloropropane also can with methyl alcohol generation side reaction, generate the accessory substances such as propylene glycol of chlorine monomethyl ether, fallThe yield of low epoxychloropropane.
CN101293882A discloses one and has adopted two kinds of immiscible extractant A and extractant B simultaneouslyThe method of extract and separate epoxychloropropane, the extractant A that the method adopts is liquid halogenated hydrocarbon or monobasicEther, extractant B is water or liquid polyol. When extractant A is chlorallylene, extractant B isWater, separated extraction heavy phase and extraction gently obtain respectively mutually epoxychloropropane product and reclaim reaction dissolventWhen methyl alcohol, energy consumes minimum. But there is the density ratio extractant of extractant chlorallylene in the methodLittle and the difficult problem that causes being easily separated in extraction process of the density of water, and due to extractionThe boiling point of agent chlorallylene, lower than epoxychloropropane, needs first by distilling whole 3-chlorine third after extractionAlkene, from distillation recovered overhead, and then distills the materials at bottom of tower of isolating after chlorallylene, then fromDistillation tower top obtains epoxychloropropane product, and whole chlorallylene extractants all needs through pervaporation abilityReclaim, the energy consumption that causes separating epoxychloropropane is still higher.
In sum, there is in extraction process, be separated difficulty and steaming in the separation method of existing epoxychloropropaneHeat up in a steamer the higher problem of energy consumption rate in process.
Summary of the invention
The object of the invention is the energy existing in the separation method in order to overcome existing epoxychloropropaneThe problem that consumption rate is higher, provides a kind of separation method of epoxychloropropane of low energy consumption, so that on large ruleIn mould continuous flow procedure, apply.
In order to realize object of the present invention, the invention provides a kind of separation method of epoxychloropropane, shouldMethod comprises: after the solution that contains epoxychloropropane, methyl alcohol, chlorallylene and water is mixed with extractantBe separated, the liquid phase that obtains being rich in the liquid phase of epoxychloropropane and be rich in methyl alcohol, distillation obtainsThe liquid phase that is rich in epoxychloropropane, obtains epoxychloropropane; Wherein, described extractant comprises water and and waterImmisciblely contain oxygen atom and the organic solvent of halogen atom-containing not, the ability of organic solvent extraction methyl alcoholLower than the ability of water and extraction epoxychloropropane, higher than water, and the boiling point of organic solvent and epoxychloropropane is notWith, the density ratio water of organic solvent is large.
Because organic solvent and water in extractant of the present invention are immiscible, the energy of organic solvent extraction methyl alcoholPower lower than water and extraction epoxychloropropane ability higher than water, make organic solvent will contain epoxy chlorineMost epoxychloropropane in the solution of propane, methyl alcohol, chlorallylene and water are extracted into organic solventPhase (being the liquid phase that is rich in epoxychloropropane), and contain epoxychloropropane, methyl alcohol, chlorallylene andMost of methyl alcohol in the solution of water is extracted to water (being the liquid phase that is rich in methyl alcohol). And excellentUnder selection condition, make the adding of organic solvent and water most epoxy chloropropionates that comprise that extract and separate obtainsThe organic solvent phase of alkane has density more than 60 kilograms per cubic meter with the water that comprises most of methyl alcoholPoor, make in extraction process, to be very easy to realize good being separated. And, in preferred enforcement sideIn formula, because the boiling point of organic solvent under 1 atmospheric pressure is higher more than 20 DEG C than the boiling point of epoxychloropropane,Thereby can obtain epoxychloropropane product from distillation tower top by simple distillation, at the bottom of destilling tower, reclaimOrganic solvent, organic solvent does not need just can reclaim through pervaporation, with employing than the boiling point of epoxychloropropaneThe method of low extractant is compared, and can effectively fall low-energy-consumption.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 separates the organic solvent phase that obtains (in figure referred to as A phase) according to separation method of the present inventionThe flow chart distilling with water;
Fig. 2 separates according to the method for prior art the stream that the chlorallylene phase that obtains and water distillCheng Tu.
Description of reference numerals
1: the first destilling tower 2: after-fractionating tower;
4: the four destilling towers of 3: the three destilling towers.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The separation method that the invention provides a kind of epoxychloropropane, the method comprises: will contain epoxy chlorineThe solution of propane, methyl alcohol, chlorallylene and water is separated after mixing with extractant, obtains being rich in ringThe liquid phase of oxygen chloropropane and the liquid phase that is rich in methyl alcohol, the liquid phase that is rich in epoxychloropropane that distillation obtains,Obtain epoxychloropropane; Wherein, described extractant comprises water and contains oxygen atom and not with water is immiscibleThe organic solvent of halogen atom-containing, the ability of organic solvent extraction methyl alcohol is lower than water and extraction epoxychloropropaneAbility higher than water, and organic solvent is different from the boiling point of epoxychloropropane, the density ratio water of organic solventGreatly.
The method according to this invention, for easy realization in extraction process is separated fast, preferably instituteState the large 10-2000 kilograms per cubic meter of density of the density ratio water of organic solvent, more preferably large 50-1000 thousandGram/cubic metre.
In the present invention, can realize the present invention as long as the boiling point of described organic solvent and epoxychloropropane is differentObject, for the present invention, (for example reduce follow-up steaming in order to realize more fully object of the present inventionHeat up in a steamer energy consumption), the boiling point of preferred described organic solvent is higher than the boiling point of epoxychloropropane, has described in more preferablyThe boiling point of machine solvent under 1 atmospheric pressure is than the high 20-300 DEG C of the boiling point of epoxychloropropane, further preferably high30-200℃。
In the present invention, if described organic solvent is mixed solvent, the boiling point of described organic solvent refers toThe boiling point of various organic solvents in mixed solvent, if or described mixed solvent can form azeotropic mixture,The boiling point of described organic solvent refers to the azeotropic point of azeotropic mixture, and need to further illustrate, if instituteWhat state mixed organic solvents formation is minimum azeotropic mixture, and described azeotropic point refers to minimum boiling point, ifWhat described mixed organic solvents formed is maximum azeotrope thing, and described azeotropic point refers to mixed solventHigh azeotropic point.
In the present invention, unless stated otherwise, density all refers to 20 DEG C, 1 density that normal atmosphere is depressed.
The method according to this invention, can realize object of the present invention according to aforementioned techniques scheme, for thisInvention, under preferable case, described organic solvent is the ester type compound of halogen atom-containing not, described ester classCompound generally refers to oxyacid and reacts with alcohol or phenols the product obtaining, and wherein acid can be organic acidAnd/or inorganic acid. Further under preferable case, liquid carboxylic acid's ester that described organic solvent is C6-C14,One or more in the phosphate of C10-C25, the phosphite ester of C10-C25.
The method according to this invention, the described organic solvent that meets aforementioned requirement includes but not limited to: formic acidBenzyl ester, phenylacetate, benzyl acetate, diethyl oxalate, dimethyl malenate, diethyl malonate,Dimethyl succinate, dimethyl maleate, diethyl maleate, ethyl pyruvate, benzene firstAcid methyl esters, ethyl benzoate, Ergol, gaultherolin, salethyl, phosphoric acid hexichol-2-One or more in Octyl Nitrite and triphenyl phosphite, be preferably benzyl acetate, dimethyl malenate,One or more in methyl benzoate, salethyl and triphenyl phosphite.
The method according to this invention, further, under preferable case, what described separation obtained is rich in epoxy chloropropionateThe liquid phase (if not otherwise specified, being designated hereinafter simply as organic solvent phase) of alkane and be rich in methyl alcohol liquid phase (asNot specified, be designated hereinafter simply as water) density contrast be 60-2000 kilograms per cubic meter, be preferably100-1000 kilograms per cubic meter, thus two liquid phases are separated better.
The method according to this invention, as the optional scope of the organic solvent of extractant and the consumption of waterWide, for the present invention, preferably contain epoxychloropropane, methyl alcohol, chlorallylene with respect to 100 mass partsWith the solution of water, the consumption of described organic solvent is 10-1000 mass parts, is preferably 30-300 mass parts;The consumption of described water is 10-1000 mass parts, is preferably 20-200 mass parts.
The method according to this invention, describedly will contain the molten of epoxychloropropane, methyl alcohol, chlorallylene and waterOptional wider range of the condition that liquid mixes with extractant, for the present invention, under preferable case, described generalTemperature (the i.e. extraction that the solution that contains epoxychloropropane, methyl alcohol, chlorallylene and water mixes with extractantThe temperature separating) be 1-80 DEG C, be preferably 5-40 DEG C. Under aforementioned preferred extract and separate condition, bothThe solution that contains epoxychloropropane, methyl alcohol, chlorallylene and water described in can making fully mixes with extractant,Reach the object of extraction, described in can reducing again, contain epoxychloropropane, methyl alcohol, chlorallylene and waterThe side reaction of the epoxychloropropane in solution and first alcohol and water.
The method according to this invention, contains epoxychloropropane, methyl alcohol, chlorallylene and water described in preferablyIn solution, the content of epoxychloropropane is that the content of 5-25 quality %, methyl alcohol is 35-65 quality %, 3-chlorineThe content of propylene is that the content of 4-35 quality % and water is 5-25 quality %.
The method according to this invention, contains epoxychloropropane, methyl alcohol, chlorallylene described in further preferablyBe the product of chlorallylene and hydrogen dioxide epoxidation reaction with the solution of water, concrete, described in contain ringThe solution of oxygen chloropropane, methyl alcohol, chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, withMethyl alcohol is solvent, the product after chlorallylene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution.
For method of the present invention is more suitable in suitability for industrialized production, under further preferable case, thisBright method also comprises: the liquid phase that is rich in methyl alcohol that distillation obtains obtains containing or do not contain the first of chlorallyleneAlcohol logistics and water logistics, contain or partly or entirely do not return to replacement containing the methanol stream of chlorallylene describedThe solvent that methyl alcohol contacts with hydrogen peroxide or aqueous hydrogen peroxide solution as described chlorallylene, by described waterStream portions or all return to that (general only water stream portions need be returned replaces extractant for extractionWater is for extraction).
As previously mentioned, further, under preferable case, method of the present invention is also included in the richness that distillation obtainsWhen obtaining epoxychloropropane containing the liquid phase of epoxychloropropane, obtain chlorallylene logistics and organic solventLogistics, using described chlorallylene stream portions or all return as water-soluble with hydrogen peroxide or hydrogen peroxideThe raw material of liquid contact, by described organic solvent stream portions or all return for extraction.
In the present invention, described extractant comprises water and contains oxygen atom and not halogen-containing former with water is immiscibleThe organic solvent of son refers to that water and described organic solvent are as extractant. In the present invention, as extractantOrganic solvent and water contained epoxychloropropane, methyl alcohol, chlorallylene and water described in both can having joined simultaneouslySolution in, also can be first by a kind of extractant (organic solvent or water) with described in contain epoxychloropropane,The solution of methyl alcohol, chlorallylene and water mixes, and then adds another kind of extractant (organic solvent or water).
In the present invention, in the ban by a kind of extractant (organic solvent or water) with described in contain epoxychloropropane,When the solution of methyl alcohol, chlorallylene and water mixes, described for the equipment mixing can be the pipeline known,The liquid contact mixing apparatus such as pipe-line mixer, stirred tank, mixing column.
In the present invention, when the organic solvent as extractant and water add simultaneously fashionable, extractant and described containingThere is being blended in extraction equipment of solution of epoxychloropropane, methyl alcohol, chlorallylene and water to carry out.
Described can be conventional extraction equipment well-known to those skilled in the art for the equipment extracting, asTank diameter, sieve-plate tower, packed tower, rotating disc column, valve tower, spray tower etc., both can take intermittently behaviourThe mode of doing, also can adopt the mode of continued operation, preferably adopts continued operation mode to facilitate realizationLarge-scale industrial production. While adopting continued operation mode, preferably adopt continuous countercurrent extraction tower as extractionTaking equipment.
In the present invention, the organic solvent liquid phase (referred to as heavy phase) of attaching most importance to mutually, water is that light liquid phase (is called for shortFor light phase). Separating of described organic solvent phase and water, both can be in extractions such as continuous countercurrent extraction towersIn taking equipment, automatically complete and obtain respectively water and organic solvent phase at the bottom of tower top and tower, also can be at listIn only device for phase saparation, carry out. Described device for phase saparation can be that subsider, settling tank, spinning liquid divideFrom the conventional device for phase saparation such as device and centrifuge.
According to the present invention, described HTS is that in titanium atom replacement zeolite lattice framework, a part of silicon is formerThe general name of one class zeolite of son. Described HTS is well known in the prior art, for example, and Ke YishiHave be similar to ZSM-5 aluminosilicate zeolite MFI topological structure titanium-containing zeolite TS-1, have and be similar toThe titanium-containing zeolite TS-2 of ZSM-11 aluminosilicate zeolite MEL topological structure, and have with modenite,The titaniferous of the skeleton structure of ZSM-12, MCM-22, MCM-41, MCM-48 and the beta-zeolite isomorphous dividesSon sieves etc., wherein, are preferably TS-1 and TS-2, are particularly preferably TS-1. The catalysis that the present invention is usedAgent can be that the former powder of these zeolites directly uses, and also can after overmolding, be made by the former powder of these zeolitesWith, specifically can select according to response situation.
According to the present invention, when described titanium-silicon molecular sieve catalyst add with slurry form fashionable, with described contactThe liquid phase of reaction is benchmark, and the content of described HTS is generally 0.5-30 quality %, is preferably 1-15Quality %, more preferably 1.5-10 quality %; In the time that catalyst is fixed in reactor, peroxidatingThe charging quality space-time speed of hydrogen (in the present invention, quality space-time speed generally also can be described as liquid hourly space velocity (LHSV),The ratio of the quality of the catalyst in charging quality and the reactor of finger unit interval hydrogen peroxide) generalFor 0.01-100h-1, be preferably 0.02-10h-1, more preferably 0.02-1h-1。
According to the present invention, the temperature that described chlorallylene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution(being the temperature of chlorallylene epoxidation reaction) is generally 10-120 DEG C, is preferably 40-80 DEG C; ContactTime be generally 0.01-100 hour, be preferably 0.1-10 hour; Described chlorallylene and hydrogen peroxideRaw materials components mole ratio be generally 1/1-10/1, be preferably 1.2/1-6/1; Entering of described methyl alcohol and chlorallyleneMaterial mass ratio is generally 0.5/1-15/1, is preferably 0.5/1-5/1.
According to the present invention, described chlorallylene can be AR and/or chemically pure reagent, but fromEconomic angle is considered preferably to use industrial products, and in industrial products, the content of chlorallylene is generally95-100 quality %, is preferably 97-99.9 quality %.
According to the present invention, can use hydrogen peroxide directly as oxidant, but for security consideration, oneAs preferably adopt aqueous hydrogen peroxide solution as oxidant, the concentration of hydrogen peroxide in aqueous hydrogen peroxide solutionCan be generally 5-90 quality %, be preferably 20-60 quality %.
The method according to this invention, described organic solvent has comprised in described epoxidation reaction product in mutuallyOverwhelming majority epoxychloropropane, most of chlorallylene, a small amount of methyl alcohol and minor amount of water. Due to chlorallyleneThe boiling point of depressing at 1 normal atmosphere is 45.0 DEG C, and epoxychloropropane boiling point is under the same conditions116.1 DEG C, the two differs 71.1 DEG C, is easy to realize separation by distillation; Equally, due to organic solventThan the high 20-300 DEG C of the boiling point of epoxychloropropane, also easily realize separation by simple distillation, and organicSolvent can be directly need through pervaporation from reclaiming at the bottom of destilling tower. A small amount of methyl alcohol wherein, becauseMethyl alcohol and chlorallylene form azeotropic mixtures (in azeotropic mixture containing 10.0 quality % methyl alcohol) and very at 40.0 DEG CEasily separate with epoxychloropropane with chlorallylene; As for minor amount of water wherein, canBy water and chlorallylene 43.0 DEG C form azeotropic mixtures (in azeotropic mixture containing 2.2 quality % water) andWater and epoxychloropropane remove at 88.0 DEG C of formation azeotropic mixtures (containing the water of 25 quality % in azeotropic mixture).
The most of methyl alcohol in described epoxidation reaction product, most of water and few in described water, are comprisedThe chlorallylene of amount. Because the boiling point of chlorallylene is lower than the boiling point of methyl alcohol (64.5 DEG C), and and methyl alcoholCan form than the low-boiling azeotropic mixture of chlorallylene with water, be easy in the time of separated methyl alcohol and waterSeparate. The boiling point of methyl alcohol does not form altogether than the boiling point of water (100 DEG C) low 35.5 DEG C and methyl alcohol and waterThe thing that boils, easily separates methyl alcohol by simple distillation with water, reclaim methanol loop for described epoxidationReaction, extractant water does not need to reclaim by evaporating yet.
Known by above description, utilize simple distillation can realize epoxychloropropane from organic moltenIn agent mutually, separate and methyl alcohol and chlorallylene can be reclaimed, and do not need to extract by evaporationExtractant organic solvent and water are reclaimed in agent, and the energy that can effectively reduce epoxychloropropane separation disappearsConsumption.
The method according to this invention, described distillation can adopt normal pressure well known to those skilled in the art, subtractThe Distallation systm of pressure or the two combination.
The present invention to distillation condition there is no concrete requirement, the distillation condition of organic solvent phase and water withThe composition of organic solvent is different and different, can select according to actual conditions.
Describe in more detail the present invention below by embodiment, but the present invention is not limited to this.
Preparation Example
The solution (being epoxidation reaction product) that contains epoxychloropropane, methyl alcohol, chlorallylene and waterPreparation:
Extract epoxidation reaction product used according to the disclosed method of embodiment in CN101747296A 1In fixed bed jacketed pipe type reactor, carry out the epoxidation reaction of chlorallylene and aqueous hydrogen peroxide solutionPrepare. Jacket oil bath temperature be 50 DEG C, adopt concentration be the aqueous hydrogen peroxide solution of 30 quality %With the reaction condition of 0.40MPa pressure, the raw materials components mole ratio by changing chlorallylene and hydrogen peroxide withThe charging mass ratio of methyl alcohol and chlorallylene, obtains respectively the epoxidation reaction that the difference shown in table 1 formsProduct S 1-S3(is following also referred to as the solution S 1-S3 that contains epoxychloropropane, methyl alcohol, chlorallylene and water).
Embodiment 1
The present embodiment is for illustrating the separation method of epoxychloropropane provided by the invention.
At 12 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 60 mass parts with the solution S 1 of waterPoint is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then use the benzene of 120 mass parts(ladder is uncommon likes that (Shanghai) changes into industrial development Co., Ltd to methyl formate, and the density 20 DEG C time is 1093 kilograms/ cubic meter, boiling point is 199.5 DEG C) five parts of point five light phases in extraction upper strata of quality, merging institute such as be divided intoSome heavy phases obtain methyl benzoate phase, and methyl benzoate is middle epoxychloropropane, methyl alcohol, chlorallylene mutuallyBe respectively 5.96 quality %, 1.21 quality %, 20.60 quality % and 0.23 quality % with the content of water,What finally obtain is gently water, the content of epoxychloropropane, methyl alcohol, chlorallylene and water in water mutuallyBe respectively 0.09 quality %, 36.18 quality %, 0.00 quality % and 63.00 quality %, methyl benzoatePhase and the density contrast of water in the time of 20 DEG C are 144.1 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtaining is introduced in the first destilling tower 1 and carried out separated,Organic solvent phase (be also methyl benzoate phase, in figure referred to as A phase) is introduced to after-fractionating tower 2In carry out separated.
Water, under normal pressure, obtains methanol stream circulation via the tower top (65 DEG C) of the first destilling tower 1 and returnsWinding oxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics; The water logistics part circulation of gained is returnedExtraction, another part is as discharge of wastewater.
Methyl benzoate, under normal pressure, obtains containing methyl alcohol via the tower top (41 DEG C) of after-fractionating tower 2Return to epoxidation reaction with the chlorallylene logistics circulation of minor amount of water, at the bottom of tower, (189 DEG C) obtain containing epoxyThe methyl benzoate logistics of chloropropane and minor amount of water; Gained is containing the benzoic acid first of epoxychloropropane and minor amount of waterEster logistics further separates and to obtain the epoxychloropropane of tower top (88 DEG C) and water in the 3rd destilling tower 3Azeotropic mixture (containing the water of 25 quality %) is separated into containing 97.44 quality % rings in return tank (50 DEG C)The circulation of oxygen chloropropane return the 3rd destilling tower 3 proceed separate logistics (turn back to the 3rd distillationThe logistics that heavy phase part in tower 3 separates) and return to extraction tower containing the circulation of 92.58 quality % waterIn light phase logistics, at the bottom of tower, (189 DEG C) obtain the thing of water-free epoxychloropropane and methyl benzoateStream; The logistics of the water-free epoxychloropropane of gained and methyl benzoate is further in the 4th destilling tower 4Separation obtains the methyl benzoate at the bottom of epoxychloropropane product stream and the tower of tower top (13 kPas, 60 DEG C)Extraction is returned in logistics circulation.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, distillation energy consumption is steamed for separation obtains the water that epoxychloropropane product per ton consumesGas, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Comparative example 1
At 14 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 60 mass parts with the solution S 1 of water100 DEG C of points) fully mix, after stratification, collect lower floor's heavy phase, then use the 3-chlorine of 80 mass parts(content of chlorallylene is 98 matter to propylene for industrial chloropropene, Ba Ling petrochemical industry Co., LtdAmount %, the density 20 DEG C time is 939.2 kilograms per cubic meter, boiling point is 45 DEG C) five parts of quality such as be divided intoDivide the light phases in extraction upper strata five times, merge all heavy phases and obtain chlorallylene phase, chlorallylene is middle epoxy mutuallyThe content of chloropropane, methyl alcohol, chlorallylene and water is respectively 8.04 quality %, 1.80 quality %, 89.60Quality % and 0.36 quality %, what finally obtain is gently water mutually, epoxychloropropane in water, methyl alcohol,The content of chlorallylene and water is respectively 0.10 quality %, 34.99 quality %, 3.33 quality % and 61.20Quality %, chlorallylene phase and the water density contrast in the time of 20 DEG C is 38.7 kilograms per cubic meter.
According to flow process shown in Fig. 2, the water obtaining is introduced in the first destilling tower 1 and carried out separated,Chlorallylene is introduced mutually and in after-fractionating tower 2, carried out separated.
Water under normal pressure, obtained containing a small amount of chlorallylene by the tower top (64 DEG C) of the first destilling tower 1 andEpoxidation reaction is returned in the methanol stream circulation of minor amount of water, and at the bottom of tower, (104 DEG C) obtain moisture logistics,Wherein extraction is returned in part circulation, and another part is as discharge of wastewater.
Chlorallylene, under normal pressure, obtains containing a small amount of first via the tower top (43 DEG C) of after-fractionating tower 2The chlorallylene logistics of alcohol and minor amount of water, epoxidation reaction is returned in part circulation, and another part circulation is returnedReturn extraction, at the bottom of tower, (121 DEG C) obtain the logistics of water-free epoxychloropropane; The water-free ring of gainedThe logistics of oxygen chloropropane further separates the ring that obtains tower top (13 kPas, 60 DEG C) in the 3rd destilling tower 3Heavy constituent logistics at the bottom of oxygen chloropropane product stream and tower.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, distillation energy consumption is steamed for separation obtains the water that epoxychloropropane product per ton consumesGas, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Embodiment 2
The present embodiment is for illustrating the separation method of epoxychloropropane provided by the invention.
At 24 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 50 mass parts with the solution S 2 of waterPoint is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then use the second of 150 mass partsAcid benzyl ester (ladder is uncommon likes that (Shanghai) changes into industrial development Co., Ltd, the density 20 DEG C time be 1060 kilograms/Cubic meter, boiling point is 214 DEG C) five parts of point five light phases in extraction upper strata of quality such as be divided into, merge and ownHeavy phase obtain benzyl acetate phase, benzyl acetate mutually in epoxychloropropane, methyl alcohol, chlorallylene and waterContent is respectively 6.94 quality %, 1.19 quality %, 11.37 quality % and 0.21 quality %, finally obtainsBe gently mutually water, in water, the content of epoxychloropropane, methyl alcohol, chlorallylene and water is respectively 0.21Quality %, 41.26 quality %, 0.00 quality % and 57.47 quality %, benzyl acetate phase and water are at 20 DEG CTime density contrast be 145.6 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtaining is introduced in the first destilling tower 1 and carried out separated,Organic solvent phase (be also benzyl acetate phase, in figure referred to as A phase) is introduced in after-fractionating tower 2Row separated.
Water, under normal pressure, obtains methanol stream circulation via the tower top (65 DEG C) of the first destilling tower 1 and returnsWinding oxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics; The water logistics part circulation of gained is returnedExtraction, another part is as discharge of wastewater.
Benzyl acetate under normal pressure, obtain containing methyl alcohol via the tower top (41 DEG C) of after-fractionating tower 2 andEpoxidation reaction is returned in the chlorallylene logistics circulation of minor amount of water, and at the bottom of tower, (183 DEG C) obtain containing epoxy chlorineThe benzyl acetate logistics of propane and minor amount of water; Gained is containing the benzyl acetate logistics of epoxychloropropane and minor amount of waterFurther in the 3rd destilling tower 3, separate and obtain the epoxychloropropane of tower top (88 DEG C) and the azeotropic mixture of water(containing the water of 25 quality %) is separated into containing 97.44 quality % epoxy chloropropionates in return tank (50 DEG C)The logistics of proceeding to separate that the 3rd destilling tower 3 is returned in the circulation of alkane (turns back to the 3rd destilling tower 3In the logistics that separates of heavy phase part) and return in extraction tower containing the circulation of 92.58 quality % waterLight phase logistics, at the bottom of tower, (185 DEG C) obtain the logistics of water-free epoxychloropropane and benzyl acetate; InstituteThe logistics that obtains water-free epoxychloropropane and benzyl acetate further separates and obtains in the 4th destilling tower 4Benzyl acetate logistics circulation at the bottom of epoxychloropropane product stream and the tower of tower top (13 kPas, 60 DEG C) is returnedReturn extraction.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, the water that the epoxychloropropane product per ton that distillation energy consumption obtains for separation consumesSteam, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Comparative example 2
At 22 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 50 mass parts with the solution S 2 of water100 DEG C of points) fully mix, after stratification, collect lower floor's heavy phase, then use the 3-chlorine of 70 mass parts(content of chlorallylene is 98 matter to propylene for industrial chloropropene, Ba Ling petrochemical industry Co., LtdAmount %, the density 20 DEG C time is 939.2 kilograms per cubic meter, boiling point is 45 DEG C) five parts of quality such as be divided intoDivide the light phases in extraction upper strata five times, merge all heavy phases and obtain chlorallylene phase, chlorallylene is middle epoxy mutuallyThe content of chloropropane, methyl alcohol, chlorallylene and water is respectively 12.37 quality %, 2.61 quality %, 84.24Quality % and 0.44 quality %, what finally obtain is gently water mutually, epoxychloropropane in water, methyl alcohol,The content of chlorallylene and water is respectively 0.28 quality %, 39.90 quality %, 3.22 quality % and 56.11Quality %, chlorallylene phase and the water density contrast in the time of 20 DEG C is 56.3 kilograms per cubic meter.
According to the method identical with comparative example 1, the water obtaining is introduced to the first destilling tower 1, by 3-chlorinePropylene is introduced after-fractionating tower 2 mutually, distills according to the flow process shown in Fig. 2, obtains epoxychloropropaneProduct.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, distillation energy consumption is steamed for separation obtains the water that epoxychloropropane product per ton consumesGas, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Embodiment 3
The present embodiment is for illustrating the separation method of epoxychloropropane provided by the invention.
At 13 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 60 mass parts with the solution S 3 of waterPoint is 100 DEG C) contact mixing, after stratification, collect lower floor's heavy phase, then use third of 100 mass partsTwo dimethyl phthalates (Shanghai Experimental Reagent Co., Ltd., the density 20 DEG C time is 1152.8 kilograms per cubic meter,Boiling point is 180-181 DEG C) five parts of points of five light phases in extraction upper strata of quality such as be divided into, merge all weightsObtain mutually dimethyl malenate phase (be the phase of organic solvent described in the present invention, below also like this), the third twoDimethyl phthalate mutually in the content of epoxychloropropane, methyl alcohol, chlorallylene and water be respectively 7.89 quality %,1.53 quality %, 19.97 quality % and 0.32 quality %, what finally obtain is gently water mutually, in waterThe content of epoxychloropropane, methyl alcohol, chlorallylene and water be respectively 0.24 quality %, 36.90 quality %,0.00 quality % and 61.99 quality %, dimethyl malenate phase and the water density contrast in the time of 20 DEG C is185.0 kilograms per cubic meter.
According to flow process shown in Fig. 1, the water obtaining is introduced in the first destilling tower 1 and carried out separated,Organic solvent phase (be also dimethyl malenate phase, in figure referred to as A phase) is introduced to after-fractionating tower 2In carry out separated.
Water, under normal pressure, obtains methanol stream circulation via the tower top (65 DEG C) of the first destilling tower 1 and returnsWinding oxidation reaction, at the bottom of tower, (104 DEG C) obtain water logistics; The water logistics part circulation of gained is returnedExtraction, another part is as discharge of wastewater.
Dimethyl malenate, under normal pressure, obtains containing first via the tower top (41 DEG C) of after-fractionating tower 2Epoxidation reaction is returned in the chlorallylene logistics circulation of alcohol and minor amount of water, and at the bottom of tower, (170 DEG C) obtain containing ringThe dimethyl malenate logistics of oxygen chloropropane and minor amount of water; Gained is containing the third two of epoxychloropropane and minor amount of waterDimethyl phthalate logistics further separates the epoxychloropropane that obtains tower top (88 DEG C) in the 3rd destilling tower 3Azeotropic mixture (containing the water of 25 quality %) with water is separated into containing 97.44 matter in return tank (50 DEG C)The circulation of amount % epoxychloropropane is returned to the logistics that the 3rd destilling tower 3 proceeds to separate and (is turned back to theThe logistics that heavy phase part in three destilling towers 3 separates) and return containing the circulation of 92.58 quality % waterLight phase logistics in extraction tower, at the bottom of tower, (171 DEG C) obtain water-free epoxychloropropane and malonic acid twoThe logistics of methyl esters; The logistics of the water-free epoxychloropropane of gained and dimethyl malenate is further the 4thIn destilling tower 4, separate and obtain at the bottom of the epoxychloropropane product stream of tower top (13 kPas, 60 DEG C) and towerExtraction is returned in dimethyl malenate logistics circulation.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, the water that the epoxychloropropane product per ton that distillation energy consumption obtains for separation consumesSteam, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Comparative example 3
At 14 DEG C, by known 100 mass parts compositions epoxychloropropane, methyl alcohol, the chlorallylene of containingFirst (density 20 DEG C time is 998.2 kilograms per cubic meter, boils with the water of 50 mass parts with the solution S 3 of water100 DEG C of points) fully mix, after stratification, collect lower floor's heavy phase, then use the 3-chlorine of 70 mass parts(content of chlorallylene is 98 matter to propylene for industrial chloropropene, Ba Ling petrochemical industry Co., LtdAmount %, the density 20 DEG C time is 939.2 kilograms per cubic meter, boiling point is 45 DEG C) five parts of quality such as be divided intoDivide the light phases in extraction upper strata five times, merge all heavy phases and obtain chlorallylene phase, chlorallylene is middle epoxy mutuallyThe content of chloropropane, methyl alcohol, chlorallylene and water is respectively 10.41 quality %, 2.30 quality %, 86.66Quality % and 0.38 quality %, what finally obtain is gently water mutually, epoxychloropropane in water, methyl alcohol,The content of chlorallylene and water is respectively 0.24 quality %, 38.52 quality %, 4.48 quality % and 56.30Quality %, the density contrast in the time of 20 DEG C of chlorallylene phase and water is 50.6 kilograms per cubic meter.
According to the method identical with comparative example 1, the water obtaining is introduced to the first destilling tower 1, by 3-chlorinePropylene is introduced after-fractionating tower 2 mutually, distills according to the flow process shown in Fig. 2, obtains epoxychloropropaneProduct.
Solvent quantity (with respect to the epoxidation reaction product of 100 mass parts) and epoxychloropropane yieldAnd the energy consumption of separated, distillation energy consumption is steamed for separation obtains the water that epoxychloropropane product per ton consumesGas, unit is ton/ton, as shown in table 2.
Contained ring in the epoxychloropropane/initial solution of the yield (%) of epoxychloropropane=finally obtainOxygen chloropropane.
Table 1
Table 2
Known by embodiments of the invention, the separation method of epoxychloropropane provided by the invention and contrastExample is compared, and in the time that epoxychloropropane separation yield is basic identical, the energy consumption of separated significantly reduces.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned realityExecute the detail in mode, within the scope of technical conceive of the present invention, can be to technical side of the present inventionCase is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (8)
1. a separation method for epoxychloropropane, the method comprises: will contain epoxychloropropane, firstThe solution of alcohol, chlorallylene and water is separated after mixing with extractant, obtains being rich in epoxychloropropaneLiquid phase and be rich in the liquid phase of methyl alcohol, the liquid phase that is rich in epoxychloropropane that distillation obtains, obtains epoxyChloropropane; It is characterized in that, described extractant comprise water and with the immiscible halogen atom that do not contain of waterEster type compound organic solvent, the ability of organic solvent extraction methyl alcohol is lower than water and extraction epoxychloropropaneAbility is higher than water, and organic solvent is different from the boiling point of epoxychloropropane, and the density ratio water of organic solvent is large,Wherein, described organic solvent is benzyl formate, phenylacetate, benzyl acetate, diethyl oxalate, thirdTwo dimethyl phthalates, diethyl malonate, dimethyl succinate, dimethyl maleate, maleic twoDiethyl phthalate, ethyl pyruvate, methyl benzoate, ethyl benzoate, Ergol, salicylic acid firstOne or more in ester, salethyl, phosphoric acid hexichol-2-Octyl Nitrite and triphenyl phosphite.
2. method according to claim 1, wherein, what described separation obtained is rich in epoxy chloropropionateThe liquid phase of alkane and the liquid phase that the is rich in methyl alcohol density contrast at 20 DEG C is 60-2000 kilograms per cubic meter.
3. method according to claim 1 wherein, contains ring described in 100 mass partsThe solution of oxygen chloropropane, methyl alcohol, chlorallylene and water, the consumption of described water is 10-1000 mass parts,The consumption of described organic solvent is 10-1000 mass parts.
4. method according to claim 1, wherein, described will contain epoxychloropropane, methyl alcohol,The temperature that the solution of chlorallylene and water mixes with extractant is 1-80 DEG C.
5. method according to claim 1, wherein, described in contain epoxychloropropane, methyl alcohol,In the solution of chlorallylene and water, the content of epoxychloropropane is that the content of 5-25 quality %, methyl alcohol is 35-65The content of quality %, chlorallylene is that the content of 4-35 quality % and water is 5-25 quality %.
6. method according to claim 5, wherein, described in contain epoxychloropropane, methyl alcohol,The solution of chlorallylene and water is: under titanium-silicon molecular sieve catalyst exists, and taking methyl alcohol as solvent, 3-chlorineProduct after propylene contacts with hydrogen peroxide or aqueous hydrogen peroxide solution.
7. method according to claim 6, wherein, the method also comprises: distillation obtainsThe liquid phase that is rich in methyl alcohol obtain containing or not containing methanol stream and the water logistics of chlorallylene, will describedly contain or notPartly or entirely return and replace methyl alcohol as described chlorallylene and peroxide containing the methanol stream of chlorallyleneThe solvent of changing hydrogen or aqueous hydrogen peroxide solution contact, returns to described water stream portions for extraction.
8. method according to claim 6, wherein, the method is also included in that distillation obtainsThe liquid phase that is rich in epoxychloropropane obtains chlorallylene logistics and organic molten when obtaining epoxychloropropaneAgent logistics, using described chlorallylene stream portions or all return as with hydrogen peroxide or aquae hydrogenii dioxidiThe raw material of solution contact, by described organic solvent stream portions or all return for extraction.
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| WO2012056005A1 (en) * | 2010-10-29 | 2012-05-03 | Solvay Sa | Process for manufacturing epichlorohydrin |
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| CN1224010A (en) * | 1997-11-27 | 1999-07-28 | 索尔维公司 | Epichlorohydrin-based product and process for manufacturing this product |
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