CN105585542A - Separation method for chloromethyloxirane - Google Patents
Separation method for chloromethyloxirane Download PDFInfo
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Abstract
The invention provides a separation method for chloromethyloxirane. The method comprises the following steps: subjecting reaction materials for epoxidation preparation of chloromethyloxirane with chloropropene as a raw material and H2O2 as an oxidant to extraction separation so as to obtain a raffinate phase and an extract phase; delivering the raffinate phase into a first rectifying system so as to separate an organic solvent and water; and delivering the extract phase into a second rectifying system so as to separate chloromethyloxirane and an extractant, wherein the first rectifying system comprises a first rectifying tower and a second rectifying tower; the conditions of the first rectifying tower are controlled, so that 1 to 40 wt% of the organic solvent in the raffinate phase is separated from the tower top of the first rectifying tower; and the conditions of the second rectifying tower are controlled, so that steam obtained from the tower top of the second rectifying tower can be used as at least one part of heat resources of the second rectifying system. The method provided by the invention can fully utilize steam condensation heat in the rectifying process of methanol, and greatly reduces energy consumption of separation in the preparation process of chloromethyloxirane by using a direct epoxidation method.
Description
Technical field
The present invention relates to a kind of method that separates epoxychloropropane, more particularly, relate to a kind of from peroxideChange hydrogen and react with chloropropene the method that separates epoxychloropropane in the product of preparing epoxychloropropane.
Background technology
Epoxychloropropane (chloromethyloxirane is called for short ECH) is a kind of important organic chemical industryRaw material and fine chemical product, be widely used in synthetic epoxy resin, glycerine, chlorohydrin rubber, medicine, agricultureMedicine, surfactant, fiberglass, ion exchange resin, coating and plasticizer etc.
The industrial process of ECH has propylene high-temperature chloridising, allyl acetate method and glycerine chlorine at presentThree kinds of change methods, all need, through chlorohydrination and saponification two procedures, to have serious equipment corrosion, simultaneouslyProduce a large amount of chlorine-contained wastewaters. Wherein, propylene high-temperature chloridising is main production method, with regard to domestic andSpeech, the production capacity of propylene high-temperature chloridising accounts for the more than 80% of ECH aggregated capacity. Propylene high-temperature chloridising toolThere is production technology maturation, stable operation, the advantage such as product is flexible; But, have that accessory substance is many, material consumptionHigh, energy consumption is large, the especially problem such as large and a large amount of calcium chloride waste residue difficult treatment of wastewater discharge.
Direct oxidation method is produced epoxychloropropane, be HTS (be called for short HTS) catalysis chloropropene withHydrogen peroxide (being called for short HPO) epoxidation is prepared ECH, directly, by chloropropene one-step synthesis ECH, goesChlorohydrination and saponification two operations, equipment corrosion and discharge of wastewater in existing ECH production technology are fallenAmount can reduce significantly, does not substantially produce waste residue, belongs to the process for cleanly preparing of ECH. Meanwhile,This reaction has relatively gentle, the selective high of reaction condition, be research and development at present focus itOne.
In the Direct Epoxidation technique of chloropropene and hydrogen peroxide, generally adopt a large amount of methyl alcohol as solvent, willExcessive chloropropene is dissolved in methanol solution and reacts with hydrogen peroxide, thereby the higher hydrogen peroxide of guaranteeConversion ratio and epoxychloropropane selective. Although the reaction of the Direct Epoxidation of chloropropene and hydrogen peroxide hasVery high selective and conversion ratio, but in product, exist a large amount of circulating solvents to make Direct Epoxidation workThe separation of products energy consumption of skill is very high. Meanwhile, product purify in adopt extraction extraction process, extractant returnReceive and also account for the very most of of plant energy consumption, therefore, the energy consumption that reduces solvent recovery is direct oxidation method techniqueCommitted step that can large-scale application.
If solvent recovery and extractant reclaim and all adopt the method for conventional distillation complete during epoxychloropropane is refiningBecome, be only applicable to the little situation of epoxychloropropane production scale. When epoxychloropropane production scale expandsAfter, required refining alcohols solvent amount and extraction dosage sharply increase, and energy consumption is obviously too high.
Summary of the invention
The technical problem to be solved in the present invention is to provide one can significantly reduce Direct Epoxidation legal systemThe method of the separating energy consumption of standby epoxychloropropane technique.
For realizing aforementioned object, the invention provides a kind of method that separates epoxychloropropane, the method bagDraw together: will be taking chloropropene as raw material, H2O2For the epoxidation of oxidant is prepared the reaction mass of epoxychloropropaneCarry out extract and separate, obtain raffinate phase and extraction phase, wherein, described reaction mass contain epoxychloropropane,Organic solvent and water, the boiling point of described organic solvent is lower than the boiling point of water, and the boiling point of extractant is than epoxy chlorineThe boiling point of propane is low, and described extraction phase comprises epoxychloropropane and extractant, and described raffinate phase comprises organicSolvent and water;
Described raffinate phase is sent into Separation of Organic and water in the first distillation system;
Described extraction phase is sent into and in the second distillation system, separated epoxychloropropane and extractant; Wherein, instituteState the first distillation system and comprise the first rectifying column and Second distillation column, the condition of controlling the first rectifying column makesThe organic solvent of the 1-40 % by weight in described raffinate phase separates from the tower top of described the first rectifying column; ControlThe condition of Second distillation column makes the steam obtaining from the tower top of described Second distillation column can serve as secondAt least part of thermal source of distillation system.
Method provided by the invention can be utilized the steam condensing heat in methanol rectification process completely, significantly reducesDirect Epoxidation legal system is for the separating energy consumption of epoxychloropropane technique, and its beneficial effect is:
Compared with conventional rectification technology, method provided by the invention can carried out product separation, essenceTime processed, adopt the thermal source of methanol vapor as reboiler, and without adopting extra steam to carry out rectifying behaviourDo, significantly reduced the energy consumption of device, compared with only adopting the Direct Epoxidation technique of direct rectificating method,Energy consumption can reduce approximately more than 30%; Meanwhile, in the time carrying out methanol rectification separation, methanol rectification column overheadMethanol vapor without adopting a large amount of recirculated cooling waters to carry out coolingly, not only saved plant investment, also fallThe operating cost of low device, has further reduced the energy consumption of device.
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 is the flow process of the method for the separation epoxychloropropane of a preferred embodiment of the inventionSchematic diagram.
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.
As previously mentioned, the invention provides a kind of method that separates epoxychloropropane, the method comprises:
Will be taking chloropropene as raw material, H2O2For the epoxidation of oxidant is prepared the reaction mass of epoxychloropropaneCarry out extract and separate, obtain raffinate phase and extraction phase, wherein, described reaction mass contain epoxychloropropane,Organic solvent and water, the boiling point of described organic solvent is lower than the boiling point of water, and the boiling point of extractant is than epoxy chlorineThe boiling point of propane is low, and described extraction phase comprises epoxychloropropane and extractant, and described raffinate phase comprises organicSolvent and water; Described raffinate phase is sent into Separation of Organic and water in the first distillation system;
Described extraction phase is sent into and in the second distillation system, separated epoxychloropropane and extractant; Wherein, instituteState the first distillation system and comprise the first rectifying column and Second distillation column, the condition of controlling the first rectifying column makesThe organic solvent of the 1-40 % by weight in described raffinate phase separates from the tower top of described the first rectifying column; ControlThe condition of Second distillation column makes the steam obtaining from the tower top of described Second distillation column can serve as secondAt least part of thermal source of distillation system.
The method according to this invention, the condition of preferably controlling the first rectifying column makes in described raffinate phaseThe organic solvent of 10-20 % by weight separates from the tower top of described the first rectifying column.
The method according to this invention, makes in described raffinate phase by controlling the condition of the first rectifying column1-40 % by weight, preferably the organic solvent of 10-20 % by weight separates from the tower top of described the first rectifying column,Make it possible to that the condition of Second distillation column makes to obtain from the tower top of described Second distillation column by controllingSteam can be served as the part of heat energy of the second distillation system, or can serve as the second distillation system and instituteState the part or all of thermal source of the first rectifying column.
The method according to this invention, makes in described raffinate phase by controlling the condition of the first rectifying columnThe organic solvent of 10-20 % by weight separates from the tower top of described the first rectifying column, makes it possible to by controllingThe condition of Second distillation column makes the steam obtaining from the tower top of described Second distillation column can serve as secondWhole thermals source of distillation system and described the first rectifying column.
The method according to this invention, preferably described the second distillation system comprises: the 3rd rectifying column, first trueVoid tower.
The method according to this invention, preferably the operating condition of described the 3rd rectifying column comprises: tower top pressure isNormal pressure is to 0.5MPaG, and theoretical cam curve is 10-50, and tower reactor temperature is 40-80 DEG C, and reflux ratio is 0.5-5.
The method according to this invention, preferably the operating condition of the first vacuum column comprises: tower top pressure is vacuum,Theoretical cam curve is 5-30, and tower reactor temperature is 80-150 DEG C.
According to one of the present invention preferred embodiment, the condition of preferably controlling Second distillation column make fromThe steam that the tower top of described Second distillation column obtains can be served as described the 3rd rectifying column and described firstWhole thermals source of rectifying column.
The method according to this invention, the condition of preferably controlling Second distillation column makes from described Second distillation columnThe steam that obtains of tower top in organic solvent content more than 90 % by weight.
The method according to this invention, meets optional wider range of the operating condition of aforementioned Second distillation column,For the present invention, the operating condition in preferred described Second distillation column comprises: tower top pressure is0.3-4.0MPaG, theoretical cam curve is 5-60, and tower reactor temperature is 110-200 DEG C, and reflux ratio is 0.5-3.
The method according to this invention, more preferably the operating condition in described Second distillation column comprises: tower top is pressedPower is 0.5-2.0MPaG, and theoretical cam curve is 10-45, and tower reactor temperature is 145-180 DEG C, and reflux ratio is1-2。
The method according to this invention, meets aforementioned requirement by the rectifying condition that makes Second distillation column, makesAt the bottom of the tower top methanol vapor of Second distillation column can be used as the tower of the second distillation system and the first rectifying columnThe thermal source of reboiler uses.
The method according to this invention, meets optional wider range of the operating condition of aforementioned the first rectifying column,For the present invention, preferably the condition in described the first rectifying column comprises: tower top pressure be normal pressure extremely1.0MPaG, theoretical cam curve is 5-60, and tower reactor temperature is 40-120 DEG C, and reflux ratio is 0.5-3.
The method according to this invention, more preferably the condition in described the first rectifying column comprises: tower top pressure isNormal pressure is to 0.5MPaG, and theoretical cam curve is 10-45, and tower reactor temperature is 60-100 DEG C, and reflux ratio is 1-2.
According to the present invention, make the 1-40 in described raffinate phase heavy by controlling the condition of the first rectifying columnAmount %, preferably the organic solvent of 10-20 % by weight separates from the tower top of described the first rectifying column, can makeThe overhead vapours of Second distillation column is boiled at the bottom of just in time meeting the tower of the second distillation system and the first rectifying column againThe heat supply of device.
In the present invention, the organic solvent of the 1-40 % by weight of raffinate phase, preferred 10-20 % by weight is firstThe tower top of rectifying column is separated, and the aqueous solutions of organic solvent obtaining in the first rectifying tower reactor is as secondThe charging of rectifying column.
In the present invention, isolating remaining organic solvent at Second distillation column tower top, is organic molten at the bottom of towerThe waste water that agent content is extremely low. In the present invention, by the preferred operation bar of the first rectifying column and Second distillation columnPart, makes the circulation organic solvent purity obtaining conventionally be greater than 90 % by weight, is preferably greater than 95 % by weight,More preferably greater than 98 % by weight, make the content of organic solvent in Second distillation column tower reactor waste water little simultaneouslyIn 1 % by weight, be preferably less than 0.5 % by weight, be more preferably less than 0.1 % by weight.
The method according to this invention, the organic solvent content in preferred described raffinate phase is 20-70 % by weight,Be preferably 40-50 % by weight.
The method according to this invention, preferably carries out described epoxidation: urge at HTS as followsUnder agent exists, taking organic solvent as solvent, chloropropene and hydrogen peroxide or aqueous hydrogen peroxide solution are connectTouch, obtain described reaction mass.
Wherein, the condition of contact can be that the routine of this area is selected, and the present invention is not described in detail at this.
The method according to this invention, preferably the method also comprises: the steam as thermal source is carried out to heat exchangeAt least part of organic solvent that rear condensation obtains is for as described chloropropene and hydrogen peroxide or peroxidatingThe solvent of aqueous solution of hydrogen contact.
According to the present invention, optional wider range of the kind of described organic solvent, specifically can be according to epoxyChange the required decision of reaction, for the present invention, preferred described organic solvent is methyl alcohol.
According to the present invention, optional wider range of the kind of described extractant, for the present invention, preferably instituteStating extractant is chloropropene.
The method according to this invention, preferred described reaction mass contains epoxychloropropane 5-20 % by weight, hasMachine solvent 20-70 % by weight, water 5-20 % by weight, chloropropene 5-30 % by weight, accessory substance 1-10 is heavyAmount %.
According to one of the present invention preferred embodiment, preferably prepare as follows epoxychloropropane rightAfter separate according to method of the present invention, wherein, organic solvent is methyl alcohol, extractant is chloropropene:
(1) hydrogen peroxide and chloropropene mixed dissolution in organic solvent, in epoxidation reactor withEpoxidation reaction is carried out in titanium-silicon molecular sieve catalyst contact, obtains the product that contains epoxychloropropane,Described product mainly comprises epoxychloropropane, organic solvent and water, can also comprise that a small amount of height boilsPoint accessory substance and unreacted chloropropene completely;
(2) enter epoxychloropropane extraction cells from the product of epoxidation reactor, through extractionGet adding of agent, isolate described extraction phase (also can claim organic phase) and described raffinate phase and (also can claim waterPhase), the organic solvent in product is separated with epoxychloropropane;
(3) enter the first distillation system from the raffinate phase of extraction cells, described the first distillation system bagDraw together the first rectifying column and Second distillation column, and the condition of control the first rectifying column makes in described raffinate phaseThe organic solvent of 10-40 % by weight separates from the tower top of described the first rectifying column; Control Second distillation columnCondition makes the steam obtaining from the tower top of described Second distillation column can serve as the second distillation system extremelySmall part thermal source, isolates organic solvent first alcohol and water, and organic solvent recycles;
(4) from the extraction phase of extraction cells enter the second distillation system isolate extractant chloropropene,Epoxychloropropane and high-boiling-point impurity, extractant recycles.
Below in conjunction with Fig. 1, the present invention is described further. Below be only particularly preferred reality of the present inventionExecute example, can not limit the scope of the invention with this, be i.e. every change of being done with the present patent application the scope of the claimsChange and amendment, still belong to the scope that patent of the present invention contains.
In Fig. 1, organic solvent is methyl alcohol, and extractant is chloropropene, by raffinate phase 1 (also claiming water 1)Send into the first rectifying column A1 and carry out the separation of water, methyl alcohol, obtain methyl alcohol 3 (containing small part chloropropene)With methanol aqueous solution 6; The operating condition of the first rectifying column A1 comprises: tower top pressure be normal pressure extremely1.0MPaG, theoretical cam curve is 5-60, and tower reactor temperature is 40-120 DEG C, and reflux ratio is 0.5-3, excellentSelect tower top pressure be normal pressure to 0.5MPaG, theoretical cam curve is 10-45, tower reactor temperature is 60-100 DEG C,Reflux ratio is 1-2;
Methanol aqueous solution 6 enters Second distillation column A2 again and separates. Second distillation column A2 operates barPart comprises: tower top pressure is 0.3-4.0MPaG, and theoretical cam curve is 5-60, and tower reactor temperature is 110-200DEG C, reflux ratio is 0.5-3, and preferably tower top pressure is 0.5-2.0MPaG, and theoretical cam curve is 10-45,Tower reactor temperature is 145-180 DEG C, and reflux ratio is 1-2; Thereby can control Second distillation column tower top methanol vaporTemperature, make it can be used as at least part of thermal source of the second distillation system; Wherein, Second distillation columnOperating condition through decision design, preferably to adopt pressure be steam 12 more than 1.0MPaG to tower reactorAs the thermal source of tower bottom reboiler, be greater than 90% thereby can obtain purity from Second distillation column A2 tower top,Be preferably greater than 95%, the methanol vapor 5 more preferably greater than 98%, obtains from Second distillation column A2 tower reactorWater 2;
Extraction phase 8 (also claiming organic phase 8) is sent into the 3rd rectifying column A3 and carry out chloropropene, epoxy chloropropionateThe separation of alkane, is extracted agent chloropropene 9 and epoxychloropropane solution 11, wherein, and the 3rd rectifying columnThe operating condition of A3 comprises: tower top pressure be normal pressure to 0.5MPaG, theoretical cam curve is 10-50, towerStill temperature is 40-80 DEG C, and reflux ratio is 0.5-5;
Epoxychloropropane solution 11 continues to be fed into the first vacuum column A4, and (tower top pressure is vacuum, theoretical towerPlate number is 5-30, and tower reactor temperature is 80-150 DEG C) separate, obtain epoxychloropropane 14 and chlorine thirdAlkene 13.
According to the present invention, preferably control the operating condition of Second distillation column and the first rectifying column, thereby set upThe cold and hot stream temperature gradient of suitable reboiler makes methanol vapor 5 can supply with the first rectifying column simultaneouslyThe reboiler of A1 and the 3rd rectifying column A3 is as whole thermals source. Methanol vapor 5 is through the first rectifying columnAfter the reboiler condensation of A1 and the 3rd rectifying column A3, the logistics 7 and the logistics 10 that obtain are combined as and followRing methyl alcohol is back to the epoxidation reaction system that epoxidation reaction is prepared epoxy chloropropionate alkene.
Embodiment 1
Adopt the technique shown in Fig. 1, the raffinate phase that epoxychloropropane separation and purification unit is obtained (is firstAlcohol solution) (content of methyl alcohol is 45 quality % to 881kg/h, and the content of water is 49 quality %, chlorine thirdAlkene content is 4 quality %, and all the other are impurity) (theoretical cam curve is 20, tower top to send into the first rectifying columnPressure is normal pressure, and tower reactor temperature is 80 DEG C, and reflux ratio is 1, and described methanol aqueous solution is from the 10thThe charging of theoretical plate place) carry out rectifying separation, tower reactor discharging (methanol aqueous solution) amount 801kg/h (formsFor: methyl alcohol 45 quality %, water 54 quality %, chloropropene content is 0 quality %, all the other are impurity),Isolating temperature from tower top is that 40 DEG C, purity are the methyl alcohol chloropropene solution 80kg/h of 50 quality %, itsIn, the methyl alcohol of 10 % by weight in described raffinate phase separates from the tower top of described the first rectifying column;
The first tower bottom of rectifying tower discharging (methanol aqueous solution) 801kg/h sends into Second distillation column (theoretical towerPlate number is 30, and methanol aqueous solution is from the 15th theoretical plate charging, and tower top pressure is 0.5MPa, towerStill temperature is 152 DEG C, and reflux ratio is 1) separate, by Second distillation column top draw temperature be 112 DEG C,Purity is the methanol vapor of 98 quality %, enters tower reactor and the 3rd tower bottom of rectifying tower of the first rectifying columnReboiler as whole thermals source, after condensation, partial reflux, part be back to epoxy as recycle methanolChange reaction and prepare the epoxidation reaction system of epoxy chloropropionate alkene;
Enter the second distillation system from the extraction phase of extraction cells and separate, the second distillation system comprises(tower top pressure is normal pressure to the 3rd rectifying column, and tower reactor temperature is 72 DEG C, and theoretical cam curve is 30, refluxesThan being 1.5) and the first vacuum column, separate that to be extracted agent chloropropene, epoxychloropropane and higher boiling assortedMatter.
The first rectifying tower bottom reboiler heat exchange load 80kW, reboiler heat exchange load at the bottom of Second distillation column292kW, the 3rd rectifying tower bottom reboiler heat exchange load 160kW.
Outside this embodiment is required, be 292kW to energy consumption.
Comparative example 1
According to the method for embodiment 1, different is the process conditions difference of Second distillation column, and the second essenceThe overhead vapours of heating up in a steamer tower is directly used in the solvent returning as reaction member, particularly:
Raffinate phase (being methanol aqueous solution) 880kg/h (its that epoxychloropropane separation and purification unit is obtainedIn, the content of methyl alcohol is 45 quality %, and the content of water is 49 quality %, and chloropropene content is 4 quality%, all the other are for impurity etc.) send into the first rectifying column (theoretical cam curve is 20, and tower top pressure is normal pressure,Tower reactor temperature is 80 DEG C, and described methanol aqueous solution is from the 10th theoretical plate charging) carry out rectifying and divideFrom, (discharging consists of tower reactor discharging (methanol aqueous solution) amount 800kg/h: methyl alcohol 45 quality %, water54 quality %, chloropropene content is 0 quality %, all the other are impurity), from tower top draw temperature be 40 DEG C,Purity is the methyl alcohol chloropropene solution that the flow of 50 quality % is 80kg/h, wherein, and in described raffinate phaseThe methyl alcohol of 10 % by weight separate from the tower top of described the first rectifying column;
Wherein, the first tower bottom of rectifying tower discharging (methanol aqueous solution) 800kg/h sends into Second distillation column (reasonThe opinion number of plates is 30, and methanol aqueous solution is from the 15th theoretical plate charging, and tower top pressure is normal pressure0.1MPa, tower reactor temperature is 102 DEG C) separate, the methanol purity 99.5% of separation, as circulationMethyl alcohol is back to the epoxidation reaction system that epoxidation reaction is prepared epoxy chloropropionate alkene;
Enter the second distillation system from the extraction phase of extraction cells and separate, the second distillation system comprises(tower top pressure is normal pressure to the 3rd rectifying column, and tower reactor temperature is 72 DEG C, and theoretical cam curve is 30, refluxesThan being 1.5) and the first vacuum column, separate that to be extracted agent chloropropene, epoxychloropropane and higher boiling assortedMatter.
The first rectifying tower bottom reboiler heat exchange load 80kW, reboiler heat exchange load at the bottom of Second distillation column243kW, the 3rd rectifying tower bottom reboiler heat exchange load 160kW.
Outside required according to this comparative example, be 483kW to energy consumption.
As can be seen here, adopt method of the present invention, what can make to obtain from the tower top of Second distillation column hasThe heat of machine solvent vapour all effectively utilizes, thus the maximized heat of utilizing whole separative elementAmount, has effectively saved energy consumption. Compared with only adopting the Direct Epoxidation technique of direct rectificating method, energy consumptionCan reduce approximately more than 30%.
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 (14)
1. a method that separates epoxychloropropane, is characterized in that, the method comprises:
Will be taking chloropropene as raw material, H2O2For the epoxidation of oxidant is prepared the reaction mass of epoxychloropropaneCarry out extract and separate, obtain raffinate phase and extraction phase, wherein, described reaction mass contain epoxychloropropane,Organic solvent and water, the boiling point of described organic solvent is lower than the boiling point of water, and the boiling point of extractant is than epoxy chlorineThe boiling point of propane is low, and described extraction phase comprises epoxychloropropane and extractant, and described raffinate phase comprises organicSolvent and water;
Described raffinate phase is sent into Separation of Organic and water in the first distillation system;
Described extraction phase is sent into and in the second distillation system, separated epoxychloropropane and extractant;
Wherein, described the first distillation system comprises the first rectifying column and Second distillation column, controls the first rectifyingThe organic solvent that the condition of tower makes the 1-40 % by weight in described raffinate phase is from described the first rectifying columnTower top separates; The condition of controlling Second distillation column makes the steam obtaining from the tower top of described Second distillation columnCan serve as at least part of thermal source of the second distillation system.
2. method according to claim 1, wherein, the condition of controlling the first rectifying column makes instituteThe organic solvent of stating the 10-20 % by weight in raffinate phase separates from the tower top of described the first rectifying column.
3. method according to claim 1 and 2, wherein, the condition of controlling Second distillation column makesThe steam that must obtain from the tower top of described Second distillation column can be served as the second distillation system and describedWhole thermals source of one rectifying column.
4. method according to claim 1 and 2, wherein, described the second distillation system comprises:The 3rd rectifying column and the first vacuum column, the operating condition of the 3rd rectifying column comprises: tower top pressure be normal pressure extremely0.5MPaG, theoretical cam curve is 10-50, and tower reactor temperature is 40-80 DEG C, and reflux ratio is 0.5-5; TheThe operating condition of one vacuum column comprises: tower top pressure is vacuum, and theoretical cam curve is 5-30, tower reactor temperatureFor 80-150 DEG C; The condition of controlling Second distillation column makes the steaming obtaining from the tower top of described Second distillation columnGas can be served as whole thermals source of described the 3rd rectifying column and described the first rectifying column.
5. method according to claim 1 and 2, wherein, the condition of controlling Second distillation column makesThe steam that must obtain from the tower top of described Second distillation column, organic solvent content is more than 90 % by weight.
6. method according to claim 1 and 2, wherein, the operation in described Second distillation columnCondition comprises: tower top pressure is 0.3-4.0MPaG, and theoretical cam curve is 5-60, and tower reactor temperature is 110-200DEG C, reflux ratio is 0.5-3.
7. method according to claim 6, wherein, the operating condition in described Second distillation columnComprise: tower top pressure is 0.5-2.0MPaG, theoretical cam curve is 10-45, and tower reactor temperature is 145-180DEG C, reflux ratio is 1-2.
8. method according to claim 1 and 2, wherein, the operation in described the first rectifying columnCondition comprises: tower top pressure be normal pressure to 1.0MPaG, theoretical cam curve is 5-60, tower reactor temperature is40-120 DEG C, reflux ratio is 0.5-3.
9. method according to claim 8, wherein, the operating condition in described the first rectifying columnComprise: tower top pressure be normal pressure to 0.5MPaG, theoretical cam curve is 10-45, tower reactor temperature is 60-100DEG C, reflux ratio is 1-2.
10. method according to claim 1 and 2, wherein, the organic solvent in described raffinate phaseContent is 20-70 % by weight.
11. methods according to claim 1 and 2, wherein, carry out described epoxy as followsChange: under titanium-silicon molecular sieve catalyst exists, taking organic solvent as solvent, by chloropropene and hydrogen peroxideOr aqueous hydrogen peroxide solution contact, obtain described reaction mass.
12. methods according to claim 11, wherein, the method also comprises: will serve as thermal sourceSteam carry out condensation obtains after heat exchange at least part of organic solvent for as described chloropropene withThe solvent of hydrogen peroxide or aqueous hydrogen peroxide solution contact.
13. methods according to claim 1 and 2, wherein, described organic solvent is methyl alcohol, instituteStating extractant is chloropropene.
14. methods according to claim 1 and 2, wherein, described reaction mass contains epoxy chlorinePropane 5-20 % by weight, organic solvent 20-70 % by weight, water 5-20 % by weight, chloropropene 5-30 is heavyAmount %, accessory substance 1-10 % by weight.
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| CN108530396A (en) * | 2018-06-12 | 2018-09-14 | 山东凯泰科技股份有限公司 | A kind of chloro propylene epoxidation method prepares the product purification method of epoxychloropropane |
| CN109966775A (en) * | 2017-12-28 | 2019-07-05 | 中国石油化工股份有限公司 | The liquid-liquid interface control method of continuous countercurrent extraction tower and application |
| CN109970683A (en) * | 2017-12-28 | 2019-07-05 | 中国石油化工股份有限公司 | The separation method of epoxychloropropane |
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| CN111592506A (en) * | 2020-06-02 | 2020-08-28 | 中国科学院理化技术研究所 | Epichlorohydrin separation process |
| CN111960921A (en) * | 2020-09-09 | 2020-11-20 | 江苏扬农化工集团有限公司 | Method and device for recovering chloropropene and methanol from epoxy chloropropane process water layer by hydrogen peroxide method |
| CN112778080A (en) * | 2021-01-12 | 2021-05-11 | 江苏扬农化工集团有限公司 | Method for recovering 3-chloropropene from solution containing 3-chloropropene and methanol |
| CN112811976A (en) * | 2021-01-12 | 2021-05-18 | 江苏扬农化工集团有限公司 | Method for recovering solvent in aqueous phase of epoxy chloropropane prepared by hydrogen peroxide method |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224010A (en) * | 1997-11-27 | 1999-07-28 | 索尔维公司 | Epichlorohydrin-based product and process for manufacturing this product |
| CN1444575A (en) * | 2000-07-06 | 2003-09-24 | 巴斯福股份公司 | Method for production of propylene oxide |
| CN103772326A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing epichlorohydrin |
| CN103788026A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Method of purifying propylene epoxide |
-
2014
- 2014-10-23 CN CN201410573482.XA patent/CN105585542B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224010A (en) * | 1997-11-27 | 1999-07-28 | 索尔维公司 | Epichlorohydrin-based product and process for manufacturing this product |
| CN1444575A (en) * | 2000-07-06 | 2003-09-24 | 巴斯福股份公司 | Method for production of propylene oxide |
| CN103772326A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for producing epichlorohydrin |
| CN103788026A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Method of purifying propylene epoxide |
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| CN109966775B (en) * | 2017-12-28 | 2021-05-14 | 中国石油化工股份有限公司 | Liquid-liquid interface control method and application of continuous countercurrent extraction tower |
| CN109966775A (en) * | 2017-12-28 | 2019-07-05 | 中国石油化工股份有限公司 | The liquid-liquid interface control method of continuous countercurrent extraction tower and application |
| CN109970683A (en) * | 2017-12-28 | 2019-07-05 | 中国石油化工股份有限公司 | The separation method of epoxychloropropane |
| CN109970683B (en) * | 2017-12-28 | 2020-09-22 | 中国石油化工股份有限公司 | Separation method of epoxy chloropropane |
| CN108530396A (en) * | 2018-06-12 | 2018-09-14 | 山东凯泰科技股份有限公司 | A kind of chloro propylene epoxidation method prepares the product purification method of epoxychloropropane |
| CN110078590A (en) * | 2019-05-28 | 2019-08-02 | 山东凯泰科技股份有限公司 | A method of producing recycling 3- chlorine-1,2-propylene glycol in epoxychloropropane waste water |
| CN111592506A (en) * | 2020-06-02 | 2020-08-28 | 中国科学院理化技术研究所 | Epichlorohydrin separation process |
| CN111960921A (en) * | 2020-09-09 | 2020-11-20 | 江苏扬农化工集团有限公司 | Method and device for recovering chloropropene and methanol from epoxy chloropropane process water layer by hydrogen peroxide method |
| CN111960921B (en) * | 2020-09-09 | 2023-01-13 | 江苏扬农化工集团有限公司 | Method and device for recovering chloropropene and methanol from epoxy chloropropane process water layer by hydrogen peroxide method |
| CN112778080A (en) * | 2021-01-12 | 2021-05-11 | 江苏扬农化工集团有限公司 | Method for recovering 3-chloropropene from solution containing 3-chloropropene and methanol |
| CN112811976A (en) * | 2021-01-12 | 2021-05-18 | 江苏扬农化工集团有限公司 | Method for recovering solvent in aqueous phase of epoxy chloropropane prepared by hydrogen peroxide method |
| CN112778080B (en) * | 2021-01-12 | 2023-01-06 | 江苏扬农化工集团有限公司 | Method for recovering 3-chloropropene from solution containing 3-chloropropene and methanol |
| CN112811976B (en) * | 2021-01-12 | 2023-01-13 | 江苏扬农化工集团有限公司 | Method for recovering solvent in aqueous phase of epoxy chloropropane prepared by hydrogen peroxide method |
| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
| CN115745920B (en) * | 2022-12-08 | 2024-05-03 | 万华化学集团股份有限公司 | Method for recovering effective components of waste liquid in epichlorohydrin production |
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