CN109851582A - The purification process of propylene oxide - Google Patents
The purification process of propylene oxide Download PDFInfo
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- CN109851582A CN109851582A CN201810153546.9A CN201810153546A CN109851582A CN 109851582 A CN109851582 A CN 109851582A CN 201810153546 A CN201810153546 A CN 201810153546A CN 109851582 A CN109851582 A CN 109851582A
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- propylene oxide
- logistics
- purification process
- entrainer
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000746 purification Methods 0.000 title claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 79
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 35
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 32
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 239000013589 supplement Substances 0.000 claims description 18
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 16
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 16
- 238000005191 phase separation Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 42
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 20
- 238000000926 separation method Methods 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- 238000004064 recycling Methods 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002373 hemiacetals Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 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 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IOECHPRJJXZKDO-UHFFFAOYSA-N butane;formaldehyde Chemical compound O=C.CCCC IOECHPRJJXZKDO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The present invention relates to a kind of purification process of propylene oxide, are included in the presence of entrainer, and the feed stream containing propylene oxide and aqueous and oxygen-containing organic compound impurity is the knockout tower rectifying the step of；The entrainer is selected from C4 alkane.The method can be used in the industrial production of propylene oxide.
Description
Technical field
The present invention relates to a kind of purification process of propylene oxide.
Background technique
Propylene oxide (PO) is mainly used for the production of polyether polyol, propylene glycol and propylene glycol, in acryloyl derivative
Yield be only second to polypropylene, be the second largest acryloyl derivative.According to statistics, 2011, the whole world was for polyether polyols alcohol production
Propylene oxide accounts for about the 66% of aggregate consumption, accounts for about 17% for propylene glycol production, the epoxy third for propylene glycol production
Alkane accounts for about 6%.2011, global propylene oxide production capacity was 882.2 ten thousand tons, had broken through 10,000,000 tons within 2016.Expect 2020
Year, production of propylene oxide ability is up to 12,000,000 tons/year, and demand reaches 10,000,000 tons/year.On long terms, world wide
Interior propylene oxide market prospects are still optimistic.
It is expected that the year demand growth amount of coming years propylene oxide is 4~8%, wherein Asian market demand may speedup
Comparatively fast, China and India Market are more swift and violent compared with other countries' increase for propylene oxide consumption figure especially in recent years.It is expected that not
The annual requirement for carrying out 5 years propylene oxide is up to 1300~14,000,000 tons or so.
Propylene oxide main production area in the world's is in West Europe, North America and Asia.External propylene oxide industrial concentration is very high,
U.S.'s Dow chemistry and Lyondell company are maximum manufacturers in the world, control most of market of world's propylene oxide.
Dow Chemical Company has process units on the U.S., Germany, Brazil and other places respectively, is all made of chloropharin law technology.Lyondell company
Process units is had on the U.S., France, Holland, China and other places respectively, using conjugated oxidation technology.Currently, the world uses chloropharin
The propylene oxide production capacity of method route accounts for the 40~45% of aggregated capacity, and conjugated oxidation production capacity accounts for 55~60%.With environmental requirement
It improves, chlorohydrination will be gradually substituted.
Method as production propylene oxide, it is known to the method that cumyl hydroperoxide (or ethylbenzene) is reacted with propylene.
There is purpose reaction product propylene oxide in the reaction solution that the reaction obtains, also contains C5~C6 hydro carbons, water, aldehyde (formaldehyde, second
Aldehyde, propionic aldehyde) and the oxygen-containing organic compounds impurity such as methanol, acetone, methyl formate.Therefore, it is necessary to separate, return from reaction solution
Receive the multiple refining step of high-purity propylene oxide.
Product propylene has strict demand to water, aldehyde, alcohol, ketone, and water will affect the hydroxyl value and foam performance of polymer, aldehyde
Content be environmental requirement, C5~C6 hydro carbons will affect the coloration of product, and therefore, national standard has strict demand to product purity.
National standard oxypropylene high-class product quality purity requirement are as follows: propylene oxide >=99.95%, water≤0.02%, acetaldehyde+
Propionic aldehyde≤0.005%, acid≤0.003%.
In propylene ring oxidation reaction product, contain the impurity such as water, methanol, formaldehyde, acetaldehyde, acetone, propionic aldehyde, methyl formate.
Wherein, the impurity such as water, methanol, acetaldehyde, propionic aldehyde, methyl formate and propylene oxide form azeotropic mixture or relative volatility close to 1,
Conventional distillation is difficult to reach product propylene standard.Meet the high-purity propylene oxide that polymerization requires in order to obtain, it is necessary to will
The impurity contained in propylene oxide is separated off.Crude propene oxide can remove formaldehyde and major part by de- light (conventional distillation)
Acetaldehyde, de- weight (conventional distillation) can remove acetone and the propionic aldehyde more than 98%, and about 50% or so water.
The purifying of propylene oxide generally uses C7~C20 straight chain and branch hydro carbons and (or) glycols as extractant.From
Economy considers that the purification process of propylene oxide is using the mixture of C8 straight chain and branched paraffin as extractant.Extractant
Addition makes acetaldehyde, water, methanol, methyl formate become larger propylene oxide relative volatility, and acetaldehyde, water, methanol, methyl formate are from tower
Top removes.
Document CN100537553C discloses a kind of purification process of propylene oxide, and this method is to contain methyl formate conduct
The purification process of the propylene oxide of impurity, using the hydrocarbon of carbon atom number 7~10 as extractant, using the method for extractive distillation, extraction
Water is added in the distillate for taking the tower top of destilling tower to obtain, and carries out water-oil separating operation, isolated oil reservoir is reused in extraction
In destilling tower, on the other hand, isolated water layer is removed to outside system, the tower bottom liquid as extraction distillation column obtains methyl formate
The propylene oxide that concentration decreases.The technology is only available for light group that can be lower than propylene oxide with the boiling point of extractant azeotropic
Point impurity, and when split-phase impurity water allocation proportion be much larger than and impurity the impurity of extractant allocation proportion removing.
Document CN1307168C discloses a kind of refining methd of propylene oxide, and this method uses C in extraction distillation column7-20
Hydrocarbon extractant, to it is being reacted by isopropyl benzene hydroperoxide with propylene, containing propylene oxide and contain water, hydrocarbon and oxygen-containing
The reaction solution of the impurity such as organic compound carries out extractive distillation.And it is described in detail about the PG concentration reduced in extractant
Method, distillation separation, absorption, washing, settle and separate, the separation methods such as extraction, preferably washing method separation can be enumerated.
From the prior art, current status be still required it is a kind of investment it is small, propylene oxide high income, low energy consumption
Propylene oxide purification process.
Summary of the invention
The present inventor in the presence of entrainer on the basis of existing technology by diligent the study found that by carrying out essence
The impurity in method removing propylene oxide reaction solution evaporated, so that it may solve the problems, such as that at least one is aforementioned, and thus complete
The present invention.
Specifically, the present invention relates to a kind of epoxyalkane purification process.The method includes in the presence of entrainer,
Feed stream containing propylene oxide and aqueous and oxygen-containing organic compound impurity is the knockout tower rectifying the step of；It is described total
It boils agent and is selected from C4 alkane.
According to an aspect of the present invention, by weight percentage, the entrainer and feed stream oxypropylene
Ratio is (2~15): 1, preferably (3~10): 1, more preferable (4~8): 1.
According to an aspect of the present invention, production of the raw material source from organic hydroperoxide and propylene ring oxidation reaction
Object.
According to an aspect of the present invention, by weight percentage, in the feed stream impurity content be 0.001~
5.0%, preferably 0.001~2.5%, more preferable 0.001~2.0%.
According to an aspect of the present invention, the oxygen-containing organic compound include selected from by methanol, formaldehyde, acetaldehyde, propionic aldehyde,
At least one of the group of acetone and methyl formate composition.
According to an aspect of the present invention, the knockout tower is being enough that entrainer and at least one impurity is made to form azeotropic mixture
Under conditions of operate.
According to an aspect of the present invention, the condition includes: 0.25~1.20MPaG of tower top pressure, preferably 0.35~
1.00MPaG；15~100 DEG C of tower top temperature, preferably 42~90 DEG C；70~130 DEG C of bottom temperature, preferably 80~120 DEG C.
According to an aspect of the present invention, the knockout tower number of theoretical plate be 15~80, preferably 20~65, more preferable 20~
50。
According to an aspect of the present invention, after rectifying, product propylene is obtained in the knockout tower tower reactor, tower top obtains
First logistics；The first logistics Phase separation is to recycle entrainer.
According to an aspect of the present invention, first logistics enters phase-splitter, and light phase logistics and heavy phase are obtained after split-phase
Logistics；The light phase logistics is back to knockout tower, and system is discharged in the heavy phase logistics.
According to an aspect of the present invention, phase-splitter is entered after first logistics is cooling.
According to an aspect of the present invention, supplement water logistics are added when Phase separation.
According to an aspect of the present invention, by weight percentage, the flow of the supplement water logistics is feed stream institute
(0.01~10) of impure flow: 1, preferably (0.1~8): 1, more preferable (1~4): 1.
Beneficial effects of the present invention: the method for the present invention using entrainer C4 alkane can at least part in impurity,
Such as water, methanol, formaldehyde, acetaldehyde, propionic aldehyde, methyl formate form azeotropic, and can be improved cannot formed azeotropic mixture
Impurity, such as acetone, to the relative volatility of propylene oxide, so that water and oxygen-containing organic compound impurity be arranged from system
Out, the purity and yield of propylene oxide are improved.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
Description of symbols:
1 feed stream
2 product propylene logistics
3 first logistics: top gaseous phase logistics (mainly entrainer and impurity)
4 first logistics after cooling
The 5 light phase logistics (organic phase) containing a large amount of entrainers
The 6 heavy phase logistics (water phase) containing a large amount of impurity
A knockout tower
B cooler
C phase-splitter
The present invention is described in detail with reference to the accompanying drawing, it should be noted however that protection scope of the present invention is simultaneously
It is not limited, it but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all are incorporated by reference into
Herein.Unless otherwise defined, all technical and scientific terms used herein all there are those skilled in the art routinely to manage
The meaning of solution.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made
Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal
It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with
It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards
For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the case where not clearly indicating, the number of theoretical plate being previously mentioned in this specification is all to calculate from top to bottom, i.e.,
Overhead condenser is first piece of theoretical plate, and tower reactor reboiler is last block theoretical plate.
In the case where not clearly indicating, the pressure being previously mentioned in this specification refers to relative pressure.
Raw material used in purification process of the invention is the logistics containing crude propene oxide.It is anti-that the logistics is originated from epoxidation of propylene
It answers product to take off light equal treated raw propylene oxide stream again by de-, mainly contains propylene oxide, mass fraction is more than or equal to
98wt%, it is less than or equal to 99.95wt%, impurity is water and exists including methanol, formaldehyde, acetaldehyde, propionic aldehyde, acetone, methyl formate
Interior oxygen-containing organic compound.By weight percentage, in raw material impurity content be 0.001~5.0%, preferably 0.001~
2.5%, more preferable 0.001~2.0%.
Oxide purification carries out extracting rectifying using extractant and is known.Generally use C7~C20 straight chain and branch
As extractant, extracting rectifying refines propylene oxide for catenanes and (or) glycols.And the present invention creatively uses entrainer
Azeotropic distillation refines propylene oxide.The principle of selection entrainer is can completely or partially to form low-boiling azeotrope with impurity,
Without forming azeotropic mixture with propylene oxide；Meanwhile for not with azeotropic dosage form, at the impurity of azeotropic mixture, extractant can be played
Effect increases its relative volatility to propylene oxide, is greater than 1, to separate from tower top.The present inventor sends out after study
It is existing, C4 alkane can form azeotropic, and acetone can be improved with water impurity, methanol, formaldehyde, acetaldehyde, propionic aldehyde, methyl formate etc.
Impurity to the relative volatility of propylene oxide, thus by the impurity such as water, methanol, formaldehyde, acetaldehyde, propionic aldehyde, methyl formate, acetone from
It is discharged in system.Entrainer is selected from C4 alkane, such as normal butane and iso-butane, preferably normal butane.
According to the present invention, in Fig. 1, enter knockout tower A containing the feed stream 1 of propylene oxide and impurity, tower reactor obtains epoxy
Bromopropane product logistics 2, tower top obtain the-the first logistics of top gaseous phase logistics 3.Water in feed stream and oxygen-containing organic as a result,
System is discharged in the impurity such as compound.
According to the present invention, knockout tower operates under conditions of being enough makes entrainer and at least one impurity formation azeotropic mixture.
The present inventor controls knockout tower operating condition the study found that passing through, when azeotropic mixture pressure is lower than 551kPaA (in terms of absolute pressure),
Entrainer C4 alkane and water impurity, methanol, formaldehyde, acetaldehyde, propionic aldehyde, methyl formate form low temperature azeotropic mixture, utilize this azeotropic
Object and azeotropic type, low temperature azeotropic mixture from separation overhead extraction；Meanwhile the impurity of azeotropic mixture is not formed with C4 alkane, for example,
Acetone increases the relative volatility of propylene oxide, is greater than 1, is extracted into tower top.When pressure is more than or equal to 551kPaA (with exhausted
Pressure meter) when, entrainer C4 alkane and water impurity, methanol, formaldehyde, acetaldehyde, propionic aldehyde, methyl formate, acetone form low temperature azeotropic
Object, using this azeotropic mixture and azeotropic type, low temperature azeotropic mixture is from separation overhead extraction.
The present inventor's research also found, for entrainer C4 alkane and water impurity, methanol, formaldehyde, acetaldehyde, propionic aldehyde, formic acid
The low temperature azeotropic mixture that methyl esters, acetone are formed, with the raising of pressure, except the content of entrainer in normal butane-formaldehyde azeotropic composition
Micro- to have outside raising, the content of entrainer gradually decreases in most of azeotropic compositions, and the content of impurity increases.So improving pressure
It is beneficial to whole separating effect, the dosage of entrainer can be reduced；But then, improving pressure will increase equipment wall thickness,
Equipment material grade is improved, to increase investment.
The present inventor's research also found that small part formaldehyde, acetaldehyde can react with methanol generates hemiacetal, acetal, and
Hemiacetal, acetal boiling point are higher than propylene oxide, crude propene oxide product stream can be followed to enter in knockout tower separation subsequent
Product propylene tower, in product propylene tower, hemiacetal, acetal decompose again generates formaldehyde, acetaldehyde and methanol, follows
Propylene oxide enters tower top, influences the purity of product propylene.And high-temperature operation, it is possible to reduce formaldehyde, acetaldehyde and methanol are sent out
Raw reaction forms hemiacetal and acetal.
In summary factor considers, knockout tower rectifying condition includes: 0.25~1.20MPaG of tower top pressure, preferably 0.35~
1.00MPaG；15~100 DEG C of tower top temperature, preferably 42~90 DEG C；70~130 DEG C of bottom temperature, preferably 80~120 DEG C.
According to the present invention, by weight percentage, the ratio of entrainer and feed stream oxypropylene is (2~15):
1, preferably (3~10): 1, more preferable (4~8): 1.Because entrainer is to be recycled, entrainer and feed stream middle ring
The ratio of Ethylene Oxide refers to the ratio of entrainer and feed stream oxypropylene in knockout tower overhead reflux liquid (i.e. logistics 5).
According to the present invention, knockout tower number of theoretical plate is 15~80, preferably 20~65, more preferable 20~50.
According to the present invention, logistics 3 recycles entrainer by Phase separation, and this method is convenient, simple, cheap.As this
One preferred embodiment of invention, such as Fig. 1, the first logistics 3 enter phase-splitter C, preferably enter split-phase after cooler B is cooling
Device C.The light phase logistics 5 (organic phase) containing a large amount of entrainers and the heavy phase logistics 6 (water phase) containing a large amount of impurity are obtained after split-phase.Gently
Phase logistics 5 cycles back to knockout tower A, and system is discharged in heavy phase logistics 6.As a result, by the impurity such as water and oxygen-containing organic compound from
It is discharged in entrainer circulating system, has purified circulation entrainer, improve entrainer purity, reduce the loss of entrainer.And
And with it is traditional, using extractant carry out extracting rectifying purified propene oxide need extractant recovery tower recycle cycling extraction agent
It compares, the method for the present invention is not required to entrainer recovery tower, it is only necessary to which phase-splitter simplifies process, saves equipment investment, reduces
Energy consumption.
As a preferred embodiment of the present invention, to contain methanol, formaldehyde, acetaldehyde, propionic aldehyde, acetone, formic acid esters etc.
Oxygen organic compound impurities are preferably separated with entrainer C4 hydrocarbon, and supplement water logistics are added when phase-splitter Phase separation (in figure not
It shows).Supplement water logistics can be liquid water, be also possible to middle pressure steam.Because of methanol, formaldehyde, acetaldehyde, propionic aldehyde, acetone, first
The oxygenatedchemicals impurity such as sour methyl esters is all dissolved in water, carries out being sufficiently mixed washing split-phase by the water for being added a small amount of, can be obviously strong
Change phase process, reduces by 20% or more entrainer loss, entrainer purity improves 1~5%.Supplementing water logistics can be in knockout tower
Top gas is mutually adopted any position before being exported to phase-splitter and is added.But supplement water logistics are added excessively, will increase equipment investment expense
With, while will increase wastewater flow rate, it is therefore desirable to supplement water logistics are added in a certain range in control, by weight percentage, mend
The flow of water-filling logistics is feed stream impurities flow (0.01~10): 1, preferably (0.1~8): 1, more preferably (1~
4):1。
In the method for the present invention, impurity removal effect is indicated with impurity removal percentage.Impurity removal percentage is defined as: with weight percent
The ratio of impurity level in the impurity level and feed stream contained than meter, in heavy phase logistics (water phase).
Below by specific embodiment, the invention will be further elaborated.
Specific embodiment
[embodiment 1]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 6.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.25MPaG, 37 DEG C of operation temperature, 75 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.30%, separation column entrainer loss late 0.26%, impurity removal percentage 86.50%.
[embodiment 2]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 6.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.35MPaG, 46 DEG C of operation temperature, 84 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.40%, separation column entrainer loss late 0.22%, impurity removal percentage 88.50%.
[embodiment 3]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 6.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.60%, separation column entrainer loss late 0.18%, impurity removal percentage 90.50%.
[embodiment 4]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 6.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 1.00MPaG, 83 DEG C of operation temperature, 120 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.62%, separation column entrainer loss late 0.17%, impurity removal percentage 90.55%.
[embodiment 5]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 4.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.50%, separation column entrainer loss late 0.20%, impurity removal percentage 89.50%.
[embodiment 6]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 8.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.70%, separation column entrainer loss late 0.16%, impurity removal percentage 91.50%.
[embodiment 7]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 10.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.72%, separation column entrainer loss late 0.15%, impurity removal percentage 91.70%.
[embodiment 8]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 4.0:1, knockout tower number of theoretical plate 30；By weight percentage, impurity content in feed stream
It is 1.5%, supplement water logistics flow is the ratio 4:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.55%, separation column entrainer loss late 0.22%, impurity removal percentage 89.70%.
[embodiment 9]
According to process flow shown in Fig. 1, entrainer is normal butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 4.0:1, knockout tower number of theoretical plate 20；By weight percentage, impurity content in feed stream
It is 1.0%, supplement water logistics flow is the ratio 6:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.60%, separation column entrainer loss late 0.24%, impurity removal percentage 89.90%.
[embodiment 10]
According to process flow shown in Fig. 1, entrainer is iso-butane, by weight percentage, in entrainer and feed stream
The ratio of 1,2- propylene oxide is 5.0:1, knockout tower number of theoretical plate 45；By weight percentage, impurity content in feed stream
It is 2.0%, supplement water logistics flow is the ratio 2:1 of feed stream impurities flow.
Knockout tower operating pressure 0.90MPaG, 79 DEG C of operation temperature, 118 DEG C of tower reactor crude propene oxide product temperature.
According to process flow shown in Fig. 1, separating tower bottom and obtaining 1,2- product propylene purity is 99.95%, recycling
Rate 99.35%, separation column entrainer loss late 0.25%, impurity removal percentage 86.48%.
Claims (13)
1. a kind of purification process of propylene oxide, is included in the presence of entrainer, containing propylene oxide and aqueous and oxygen-containing have
The feed stream of the impurity of machine compound is the knockout tower rectifying the step of；The entrainer is selected from C4 alkane.
2. the purification process of propylene oxide according to claim 1, which is characterized in that by weight percentage, the azeotropic
The ratio of agent and feed stream oxypropylene is (2~15): 1, preferably (3~10): 1, more preferable (4~8): 1.
3. the purification process of propylene oxide according to claim 1, which is characterized in that the raw material source is from organic hydroperoxide
The product of object and propylene ring oxidation reaction.
4. the purification process of propylene oxide according to claim 1, which is characterized in that by weight percentage, the raw material
Impurity content is 0.001~5.0%, preferably 0.001~2.5%, more preferable 0.001~2.0% in logistics.
5. the purification process of propylene oxide according to claim 1, which is characterized in that the oxygen-containing organic compound includes choosing
At least one of free methanol, formaldehyde, acetaldehyde, propionic aldehyde, acetone and group of methyl formate composition.
6. the purification process of propylene oxide according to claim 1, which is characterized in that the knockout tower is being enough to make entrainer
It is formed under conditions of azeotropic mixture and is operated at least one impurity.
7. the purification process of propylene oxide according to claim 7, which is characterized in that the condition includes: tower top pressure
0.25~1.20MPaG, preferably 0.35~1.00MPaG；15~100 DEG C of tower top temperature, preferably 42~90 DEG C；Bottom temperature 70~
130 DEG C, preferably 80~120 DEG C.
8. the purification process of propylene oxide according to claim 1, which is characterized in that the knockout tower number of theoretical plate be 15~
80, preferably 20~65, more preferable 20~50.
9. the purification process of propylene oxide according to claim 1, which is characterized in that after rectifying, in the knockout tower tower reactor
Product propylene is obtained, tower top obtains the first logistics；The first logistics Phase separation is to recycle entrainer.
10. the purification process of propylene oxide according to claim 9, which is characterized in that first logistics enters phase-splitter,
Light phase logistics and heavy phase logistics are obtained after split-phase；The light phase logistics is back to knockout tower, and system is discharged in the heavy phase logistics.
11. the purification process of propylene oxide according to claim 10, which is characterized in that enter after first logistics is cooling
Phase-splitter.
12. the purification process of propylene oxide according to claim 11, which is characterized in that supplement water object is added when Phase separation
Stream.
13. the purification process of Ethylene Oxide according to claim 12, which is characterized in that by weight percentage, the supplement
The flow of water logistics is feed stream impurities flow (0.01~10): 1, preferably (0.1~8): 1, more preferable (1~4):
1。
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| CN112694457A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for treating material flow obtained after reaction of propylene and organic peroxide |
| CN113651777A (en) * | 2020-05-12 | 2021-11-16 | 中国石油化工股份有限公司 | Reaction rectification dealdehyding process |
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