CN106397363A - Purifying method for 1,2-epoxybutane - Google Patents
Purifying method for 1,2-epoxybutane Download PDFInfo
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- CN106397363A CN106397363A CN201510467821.0A CN201510467821A CN106397363A CN 106397363 A CN106397363 A CN 106397363A CN 201510467821 A CN201510467821 A CN 201510467821A CN 106397363 A CN106397363 A CN 106397363A
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- extractant
- epoxy butane
- distillation column
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- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 238000000605 extraction Methods 0.000 claims abstract description 53
- 238000004821 distillation Methods 0.000 claims abstract description 47
- 238000000746 purification Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000000926 separation method Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 21
- 239000008346 aqueous phase Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 18
- 208000035126 Facies Diseases 0.000 claims description 11
- 238000000895 extractive distillation Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000012805 post-processing Methods 0.000 claims description 7
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 5
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 238000004581 coalescence Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000001299 aldehydes Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 229940083957 1,2-butanediol Drugs 0.000 description 4
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000622 liquid--liquid extraction Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 235000013844 butane Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a purifying method for 1,2-epoxybutane. The purifying method mainly overcomes the problems of low yield of 1,2-epoxybutane, great loss of extractant and high waste water treatment cost since waste water of an extraction distillation column carries 1,2-epoxybutane and the extractant in the prior art. According to the invention, a liquid-liquid separator is additionally arranged and the extractant is used for treating and recovering 1,2-epoxybutane in waste water, so the above problems are overcome; and the purifying method provided by the invention can be applied to industrial production of purification of 1,2-epoxybutane.
Description
Technical field
The present invention relates to a kind of 1,2- epoxy butane purification process.
Background technology
1,2- epoxy butane (1,2-Butene oxide, BO), also known as butylene oxide, in manufacturing
Mesosome and polymer, for example, be used for producing 1,2- butanediol, be also used for replacing acetone as nitrate paint
Diluent.1,2- epoxy butane also can be also used for foam processed as the standard substance of chromatography
Plastics, synthetic rubber, nonionic surfactant etc..Industrial, there is the 1- of cleaning procedure
Butylene catalysis epoxidation method (as CHP method) produces 1,2- epoxy butane and is just progressively replacing traditional chlorine
Alcohol method technique.1-butylene catalysis epoxidation produce 1,2- epoxy butane during produce water, aldehyde,
The impurity such as alcohol, ester, such as methanol, water are all and 1,2- epoxy butane forms azeotropic mixture, propionic aldehyde and formic acid first
Close to 1, this results in the method using conventional distillation to the relative volatility of ester and 1,2- epoxy butane
Very difficult separating-purifying 1,2- epoxy butane.But only there is the 1,2- epoxy butane ability of higher degree
Enough polymerizations, therefore will carry out separating-purifying to 1, the 2- epoxy butane crude product of synthesis.And 1,2- epoxy
Butane occurs polymerization not require nothing more than 1,2- epoxy butane purity and reach 99.9wt%, to water impurity, aldehyde,
The content of the impurity such as alcohol and esters has strict demand.
Separate remove above impurity method generally have distillation (include extractive distillation and azeotropic distillation),
Exchange Resin by Adsorption, liquid-liquid extraction and chemical reaction handling.Chemical reaction handling mainly has
The hydrolysis of esters and the neutralization reaction (using alkali metal hydroxide) of acid, follow-up employing is distilled
Mode.The general use of chemical reaction handling is less, because some can be occurred undesirable anti-
The product loss of correlation should be caused.
Document US4402794 adopts C7-C9Hydro carbons, preferably normal octane as extractant single extract
Rectification is taken to separate the water containing in thick 1,2- epoxy butane solution, methanol, acetone, methyl formate etc. miscellaneous
Matter, is not involved with the separation of impurity aldehydes.Organic after the layering of extractive distillation column overhead phase separator
Layer removes rectifying column separated methanol, acetone etc., and tower reactor reclaims extractant, increased equipment investment
And operating cost, water layer is directly outer to be arranged, and the extractant containing in water layer and 1,2- epoxy butane lose.
Document JPS5646874 utilizes 1,2- epoxy butane to form azeotropic mixture with water, should from side take-off
Azeotropic mixture, after cooling split-phase, the organic faciess mainly containing 1,2- epoxy butane return tower, primary aqueous
Aqueous phase goes post processing.1,2- epoxy butane dissolubility in water is larger, and in aqueous phase, 1,2- epoxy butane damages
Lose larger, and increased wastewater treatment expense.
When containing aldehydes and water-solubility impurity such as alcohols (as methanol, ethanol), soluble ester (such as
Methyl formate, ethyl acetate) and during organic acid (as formic acid, acetic acid), it is also dissolved in aqueous phase
In.But a part of 1,2- epoxy butane is also dissolved in aqueous phase simultaneously.1,2- epoxy butane when 20 DEG C
Dissolve 5.91% in water, water dissolves 2.65% in 1,2- epoxy butane.Temperature is higher, dissolubility
Bigger.
During extracting rectifying, aldehyde, water, alcohol, ester impurities remove from extractive distillation column overhead
System, can carry a certain amount of 1,2- epoxy butane and extractant secretly, and direct discharge can cause 1,2- epoxy
Butane and the loss of extractant.
Content of the invention
The technical problem to be solved is folder in extractive distillation column overhead stream in prior art
With 1,2- epoxy butane and extractant, lead to that 1,2- epoxy butane yield is low, extractant loss is big
Problem, provides a kind of new 1,2- epoxy butane purification process.The method has 1,2- epoxy butane and receives
The feature that rate is high, extractant loss is low.
For solving above-mentioned technical problem, the technical scheme that the present invention takes is as follows：A kind of 1,2- epoxy fourth
Alkane purification process, comprises the following steps：
A) impure thick 1,2- epoxy butane logistics enters extraction distillation column, exists in extractant A
Lower extracting rectifying；
B) extraction distillation column tower reactor liquid phase stream enters solvent recovery tower, and tower top obtains product 1,2- ring
Oxygen butane, the extractant A that tower reactor is recycled；
C) enter phase separator after extraction distillation column top gaseous phase logistics condensation, be separated into oil reservoir and water layer；
D) optionally, described oil reservoir is recycled to extractive distillation column overhead；
E) described water layer and extractant B enter blender, enter Liquid liquid Separation device after being sufficiently mixed,
After separating, organic faciess are back to described phase separator, and aqueous phase delivers to post processing.
In technique scheme it is preferable that described thick 1,2- epoxy butane logistics be 1-butylene with organic
Obtain after peroxide reactions；Described impurity is water, C4Hydro carbons, C1～6Aldehyde, C1～6Ketone,
C1～6Alcohol, C1～6Acid or C1～6Ester at least one.
It is preferable that being calculated in mass percent in technique scheme, described thick 1,2- epoxy butane thing
In stream, the content of 1,2- epoxy butane is 92～96%, and the content of water is 2～5%, and remaining is C4Hydrocarbon
Class, C1～6Aldehyde, C1～6Ketone, C1～6Alcohol, C1～6Acid or C1～6Ester at least one.
It is preferable that described extractant A and extractant B is C in technique scheme7～C12Aliphatic series
At least one in hydrocarbon.It is highly preferred that described extractant A and extractant B is C8In aliphatic hydrocarbon
At least one.
It is preferable that the theoretical cam curve of described extraction distillation column is 30～60 in technique scheme
Block, operating pressure is 100～200kPa, and operation temperature is 60～85 DEG C, and solvent ratio is for 2～8.
It is preferable that the theoretical cam curve of described solvent recovery tower is 20～40 in technique scheme
Block, operating pressure is 100～200kPa, and operation temperature is 60～90 DEG C.
It is preferable that described Liquid liquid Separation device operating pressure is 100～300kPa in technique scheme,
Operation temperature is 30～60 DEG C.
It is preferable that the extractant A that the recovery of solvent recovery tower tower reactor obtains follows in technique scheme
Loopback extraction distillation column.
It is preferable that having one or more taper inside described Liquid liquid Separation device in technique scheme
Coalescence filter core structure.
An embodiment of the invention is：A kind of 1,2- epoxy butane purification process, walks including following
Suddenly：
A) impure thick 1,2- epoxy butane logistics enters extraction distillation column, in the presence of extractant
Extracting rectifying；
B) extraction distillation column tower reactor liquid phase stream enters solvent recovery tower, and tower top obtains product 1,2- ring
Oxygen butane, the extractant stream that tower reactor is recycled；Described extractant stream is divided into first burst of extraction
Agent logistics and second burst of extractant stream；
C) enter phase separator after extraction distillation column top gaseous phase logistics condensation, be separated into oil reservoir and water layer；
D) described first burst of extractant stream and described oil reservoir are recycled to extractive distillation column overhead；
E) described water layer and described second burst of extractant stream enter blender, enter after being sufficiently mixed
Liquid liquid Separation device, after separating, organic faciess are back to described phase separator, and aqueous phase delivers to post processing.
It is preferable that first burst of extractant stream and second burst of extractant stream in technique scheme
Weight than be (200:1)～(800:1).
In technique scheme it is preferable that described extraction distillation column top gaseous phase logistics by with
Pressure steam or deionized water contact and condense.
By, in the presence of well-known catalyst, organic peroxide and 1-butylene react
Reaction mixture to after 1,2- epoxy butane is particularly suitable, and it at least contains aldehydes as miscellaneous
Matter.In addition to containing aldehydes, also contain hydro carbons such as butylene, butane；Water；Alcohols such as methanol and
Ethanol；Organic acid；Ketone such as acetone；With esters such as methyl formate and ethyl acetate.Using with
The liquid being obtained with distillation distillation column rough segmentation before washing, then the aldehyde with separation of extractive distillation remnants,
Acid, ketone, hydro carbons, water, alcohol, ester impurities, then reclaim 1,2- epoxy butane and extraction with liquid-liquid extraction
Take agent, the loss of active component such as 1,2- epoxy butane, extractant and butylene can be reduced.
The present invention uses hydro carbons extractant first by aldehyde, acid, ketone, hydro carbons, water, alcohol, ester impurities
From thick 1,2- epoxy butane solution separation of extractive distillation out, to containing these impurity and a small amount of 1,2-
Spray into middle pressure steam or deionized water in the tower overhead gas of epoxy butane and extractant, be fully contacted and
Mixing, is separated into oil reservoir and water layer in phase separator after condensation, makes impurity enter aqueous phase as far as possible, oil
Layer and recovery extractant are recycled to extraction distillation column as extractant, also serve as flowing back simultaneously.
Water layer and the extractant reclaiming enter after blender is sufficiently mixed and enter Liquid liquid Separation device, for increasing
Plus the time of staying, improve separation efficiency in Liquid liquid Separation device for the water-oil phase, in Liquid liquid Separation device
There is one or more taper Coalescence filter core structure in portion, so that water-oil phase is repeatedly separated step by step.
With hydro carbons extractant, in Liquid liquid Separation device, the 1,2- epoxy containing in aqueous phase is reclaimed in liquid-liquid extraction
Butane is effective.After Oil-water separation in Liquid liquid Separation device, most of 1,2- epoxy butanes and extraction
Take agent to be transferred in organic faciess, and aldehyde, acid, ketone, hydro carbons, water, alcohol, ester impurities are transferred to
In aqueous phase.In addition to aldehyde, acid, ketone, hydro carbons, water, alcohol, ester impurities, a small amount of 1,2- epoxy
Butane is dissolved in the aqueous phase obtaining, in the present invention, it is preferred to pass through aqueous phase and extracting rectifying mistake
Journey identical extractant contacts, and 1, the 2- epoxy butane in aqueous phase is selectively transferred to extractant one
Side, i.e. organic faciess, thus aldehyde in 1,2- epoxy butane, acid, ketone, hydro carbons, water, alcohol,
Ester impurities are separated.By Liquid liquid Separation device, 1,2- epoxy butane is reclaimed from this organic facies, then
The loss of 1,2- epoxy butane can be reduced.Additionally, it is preferred that being steamed in extraction by recycling organic faciess
Evaporate in tower, then can reduce the loss of 1,2- epoxy butane.
Liquid liquid Separation device separation efficiency is high, equipment investment is low, do not need consumption energy consumption, can reach back
Receive the purpose of extractant and 1,2- epoxy butane.
Meanwhile, using hydro carbons as extractant during, 1 under the concurrent conditionses of water and epoxy fourth a heatable brick bed,
2- butanediol easily generates, thus 1,2- epoxy butane production or refined when inevitably generate
1,2- butanediol.1,2- butanediol exist under conditions of, extractant recycle during, meeting
Part reduces extractant effect of extracting even makes effect of extracting lose, and increases separation process energy consumption and fall
Low yield quality.Partial extraction agent is adopted to enter Liquid liquid Separation device in the present invention, 1,2- butanediol is easily
Enter aqueous phase and reach detached purpose, produce or subtractive process in 1, the 2- butanediol that produces would not be
Accumulate in system, extractant extraction efficiency can be improved.
It should be noted that the extractant disclosed in the present invention can be using one pack system it is also possible to make
Mixture with these compounds.From the viewpoint of industrial implementation, preferably industrially easily obtain
Normal heptane, normal octane.
Below by embodiment, the invention will be further elaborated.
Brief description
Fig. 1 is the process flow diagram of one embodiment of the inventive method.
In Fig. 1, T101 extraction distillation column, T102 solvent recovery tower, M101- blender,
S101 Liquid liquid Separation device, D101 phase separator.1 is thick BO charging, and 2 is extraction distillation column
T101 tower overhead gas, 3 is middle pressure steam or deionized water, and 4 is extraction distillation column T101 overhead condensation
Liquid, 5 is extraction distillation column T101 water layer, and 6 is extraction distillation column T101 organic layer, and 7 is extraction
Distillation column T101 backflow, 8 is Liquid liquid Separation device S101 extractant, and 9 is that Liquid liquid Separation device is organic
Phase, 10 is waste water (Liquid liquid Separation device aqueous phase), and 11 is extraction distillation column T101 kettle liquid, and 12 are
Solvent recovery tower T102 kettle liquid, that is, reclaim extractant, and 13 is BO product.
Using extraction distillation column T101, by thick 1, the 2- epoxy butane solution 1 containing impurity for giving
C7～C12Hydro carbons is as in the extraction distillation column of extractant；Tower overhead gas 2 in extraction distillation column T101
In spray into middle pressure steam or deionized water 3, condensed fluid 4 is separated into oil reservoir in phase separator D101
6 and water layer 5, oil reservoir 6 and reclaim extractant 12 and be recycled to extraction distillation column T101 as extractant,
Also serve as flowing back 7 simultaneously；Extraction distillation column T101 kettle liquid 11 enters solvent recovery tower T102, point
From rear, tower top obtains 1,2- epoxy butane product 13, and solvent recovery tower bottoms 12 is divided into two strands, its
In one I is recycled to extraction distillation column as extractant, in addition one II delivers to blender M101
Liquid liquid Separation device S101 is entered, after separating, organic faciess 9 are back to split-phase after being sufficiently mixed with logistics 5
Device, aqueous phase 10 delivers to post processing.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Thick 1,2- epoxy butane solution is calculated in mass percent, 1,2- epoxy butane 93.5%, water 5%,
Remaining is propionic aldehyde, methanol and methyl formate impurity.
Using extraction distillation column T101, by thick 1, the 2- epoxy butane solution 1 containing impurity for giving
C7～C12Hydro carbons is as in the extractive distillation of extractant；In the tower overhead gas 2 of extraction distillation column T101
Spray into middle pressure steam or deionized water 3, condensed fluid 4 is separated into oil reservoir 6 in phase separator D101
With water layer 5, oil reservoir 6 and reclaim extractant 12 and be recycled to extraction distillation column T101 as extractant,
Also serve as flowing back 7 simultaneously；Extraction distillation column T101 kettle liquid 11 enters solvent recovery tower T102, point
From rear, tower top obtains 1,2- epoxy butane product 13, and solvent recovery tower bottoms 12 is divided into two strands, its
In one I is recycled to extraction distillation column as extractant, in addition one II delivers to blender M101
Liquid liquid Separation device S101 is entered, after separating, organic faciess 9 are back to split-phase after being sufficiently mixed with logistics 5
Device, aqueous phase 10 delivers to post processing.
Wherein, the theoretical cam curve of extraction distillation column is 35 pieces, and operating pressure is 120kPa, operation
Temperature is 67 DEG C.
The solvent of extraction distillation column is than for 6.
The theoretical cam curve of solvent recovery tower is 25 pieces, and operating pressure is 120kPa, and operation temperature is
69℃.
Liquid liquid Separation device operating pressure is 110kPa, and operation temperature is 45 DEG C.
Extractant A is normal octane.
The weight of logistics I and logistics II is than for 500：1.
It is calculated in mass percent, in logistics 13,1,2- epoxy butane product purity reaches 99.95%, third
Aldehyde 15ppm, normal octane 15ppm., more than 99%, extractant loss is little for 1, the 2- epoxy butane response rate
In 0.02%.
【Embodiment 2】
Thick 1,2- epoxy butane solution is calculated in mass percent, 1,2- epoxy butane 94.5%, water 4%,
Remaining is propionic aldehyde, methanol and methyl formate impurity.
Embodiment with【Embodiment 1】Identical, except for the difference that：
The theoretical cam curve of extraction distillation column is 45 pieces, and operating pressure is 160kPa, and operation temperature is
78℃.
The solvent of extraction distillation column is than for 5.
The theoretical cam curve of solvent recovery tower is 35 pieces, and operating pressure is 160kPa, operation temperature
For 80 DEG C.
Liquid liquid Separation device operating pressure is 130kPa, and operation temperature is 40 DEG C.
Extractant A is isobutyltrimethylmethane..
The weight of logistics I and logistics II is than for 600：1.
It is calculated in mass percent, in logistics 13,1,2- epoxy butane product purity reaches 99.96%, third
Aldehyde 10ppm, normal octane 10ppm.More than 99.2%, extractant loses 1, the 2- epoxy butane response rate
Less than 0.025%.
【Embodiment 3】
Thick 1,2- epoxy butane solution is calculated in mass percent, 1,2- epoxy butane 96%, water 2%,
Remaining is propionic aldehyde, methanol and methyl formate impurity.
Embodiment with【Embodiment 1】Identical, except for the difference that：
The theoretical cam curve of extraction distillation column is 60 pieces, and operating pressure is 200kPa, and operation temperature is
85℃.
The solvent of extraction distillation column is than for 4.
The theoretical cam curve of solvent recovery tower is 40 pieces, and operating pressure is 200kPa, operation temperature
For 90 DEG C.
Liquid liquid Separation device operating pressure is 160kPa, and operation temperature is 45 DEG C.
Extractant A is 2- methylpentane.
The weight of logistics I and logistics II is than for 650：1.
It is calculated in mass percent, in logistics 13,1,2- epoxy butane product purity reaches 99.98%, third
Aldehyde 5ppm, normal octane 8ppm., more than 99.4%, extractant loss is little for 1, the 2- epoxy butane response rate
In 0.01%.
【Comparative example 1】
Embodiment with【Embodiment 1】Identical, except for the difference that cancel Liquid liquid Separation device.
It is calculated in mass percent, in logistics 13,1,2- epoxy butane product purity reaches 99.95%, third
Aldehyde 50ppm, normal octane 50ppm.1, the 2- epoxy butane response rate is 95%, and extractant loss is more than
1%.
【Comparative example 2】
Embodiment with【Embodiment 1】Identical, Liquid liquid Separation device washes tower (liquid-liquid extraction tower) with water.
It is calculated in mass percent, in logistics 13,1,2- epoxy butane product purity reaches 99.95%, third
Aldehyde 50ppm, normal octane 50ppm.1, the 2- epoxy butane response rate is 98%, and extractant loss is more than
0.05%.
Closed from the above it can be seen that implementing the present invention and being separated with economic and convenient method
1, the 2- epoxy butane product of lattice, improves product yield, reduces extractant loss.
Claims (10)
1. one kind 1,2- epoxy butane purification process, comprise the following steps：
A) impure thick 1,2- epoxy butane logistics enters extraction distillation column, exists in extractant A
Lower extracting rectifying；
B) extraction distillation column tower reactor liquid phase stream enters solvent recovery tower, and tower top obtains product 1,2- ring
Oxygen butane, the extractant A that tower reactor is recycled；
C) enter phase separator after extraction distillation column top gaseous phase logistics condensation, be separated into oil reservoir and water layer；
D) optionally, described oil reservoir is recycled to extractive distillation column overhead；
E) described water layer and extractant B enter blender, enter Liquid liquid Separation device after being sufficiently mixed,
After separating, organic faciess are back to described phase separator, and aqueous phase delivers to post processing.
2. according to claim 11,2- epoxy butane purification process it is characterised in that described
Thick 1,2- epoxy butane logistics is obtained after being reacted with organic peroxide for 1-butylene；Described impurity
For water, C4Hydro carbons, C1～6Aldehyde, C1～6Ketone, C1～6Alcohol, C1～6Acid or C1～6Ester in
At least one.
3. according to claim 21,2- epoxy butane purification process it is characterised in that with quality
Percent meter, in described thick 1,2- epoxy butane logistics, the content of 1,2- epoxy butane is 92～96%,
The content of water is 2～5%, and remaining is C4Hydro carbons, C1～6Aldehyde, C1～6Ketone, C1～6Alcohol, C1～6
Acid or C1～6Ester at least one.
4. according to claim 11,2- epoxy butane purification process it is characterised in that described extraction
Agent A and extractant B is taken to be C7～C12At least one in aliphatic hydrocarbon.
5. according to claim 41,2- epoxy butane purification process it is characterised in that described extraction
Agent A and extractant B is taken to be C8At least one in aliphatic hydrocarbon.
6. according to claim 11,2- epoxy butane purification process it is characterised in that described extraction
The theoretical cam curve taking distillation column is 30～60 pieces, and operating pressure is 100～200kPa, operation temperature
For 60～85 DEG C, solvent is than for 2～8；
The theoretical cam curve of described solvent recovery tower is 20～40 pieces, and operating pressure is 100～200kPa,
Operation temperature is 60～90 DEG C；
Described Liquid liquid Separation device operating pressure is 100～300kPa, and operation temperature is 30～60 DEG C.
7. according to claim 11,2- epoxy butane purification process it is characterised in that solvent returns
Receipts tower tower reactor reclaims the extractant A obtaining and loops back extraction distillation column.
8. according to claim 11,2- epoxy butane purification process it is characterised in that described liquid
There is one or more taper Coalescence filter core structure inside liquid/gas separator.
9. one kind 1,2- epoxy butane purification process, comprise the following steps：
A) impure thick 1,2- epoxy butane logistics enters extraction distillation column, in the presence of extractant
Extracting rectifying；
B) extraction distillation column tower reactor liquid phase stream enters solvent recovery tower, and tower top obtains product 1,2- ring
Oxygen butane, the extractant stream that tower reactor is recycled；Described extractant stream is divided into first burst of extraction
Agent logistics and second burst of extractant stream；
C) enter phase separator after extraction distillation column top gaseous phase logistics condensation, be separated into oil reservoir and water layer；
D) described first burst of extractant stream and described oil reservoir are recycled to extractive distillation column overhead；
E) described water layer and described second burst of extractant stream enter blender, enter after being sufficiently mixed
Liquid liquid Separation device, after separating, organic faciess are back to described phase separator, and aqueous phase delivers to post processing.
10. according to claim 91,2- epoxy butane purification process it is characterised in that first strand
The weight ratio of extractant stream and second burst of extractant stream is (200:1)～(800:1)；Described extraction is steamed
Evaporate column overhead gaseous stream by contacting and condensing with middle pressure steam or deionized water.
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| CN109851585A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process of epoxy butane |
| CN109851576A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | Epoxy butane purification process and purification devices |
| CN109851591A (en) * | 2018-02-22 | 2019-06-07 | 中国石油化工股份有限公司 | The purification process and device of epoxyalkane |
| CN109851579A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | Epoxyalkane production method |
| CN109851584A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | The refining methd and device of epoxyalkane |
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| CN112694456A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for pretreating and supplementing extracting agent in propylene oxide purification process |
| CN112851601A (en) * | 2019-11-27 | 2021-05-28 | 北京诺维新材科技有限公司 | Method for purifying alkylene oxide |
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| CN108017597B (en) * | 2016-11-04 | 2021-06-22 | 中国石油化工股份有限公司 | Epoxy butane composition |
| CN108017598B (en) * | 2016-11-04 | 2021-06-22 | 中国石油化工股份有限公司 | Epoxy butane composition and preparation method thereof |
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| CN110357838A (en) * | 2019-07-16 | 2019-10-22 | 湖南理工学院 | Fractional extraction separating-purifying 1,2- epoxy butane new method |
| CN110357838B (en) * | 2019-07-16 | 2024-05-24 | 湖南理工学院 | New method for separating and purifying 1, 2-epoxybutane by fractional extraction |
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| CN115845484A (en) * | 2023-02-21 | 2023-03-28 | 中国科学院过程工程研究所 | Separation and refining device and method for crude epoxybutane product |
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