CN101121634B - Recovery method for styrene from pyrolysis gasoline - Google Patents
Recovery method for styrene from pyrolysis gasoline Download PDFInfo
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- CN101121634B CN101121634B CN2006100299748A CN200610029974A CN101121634B CN 101121634 B CN101121634 B CN 101121634B CN 2006100299748 A CN2006100299748 A CN 2006100299748A CN 200610029974 A CN200610029974 A CN 200610029974A CN 101121634 B CN101121634 B CN 101121634B
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Abstract
The present invention discloses a method for reclaiming cinnamene from a residue gasoline; the method is to solve the technical problem in the prior technical scheme that: when reclaiming cinnamene from the residue gasoline C8 fraction including cinnamene, the sulfur content is not high; the chroma is lower and the reclaim ratio if the product reaches high purity is lower. The steps in the presentinvention include: a) the residue gasoline including cinnamene is under the function of adding hydrogenation catalyzer, the material wipes off alkene and alkyne to produce the material flow I; b) thematerial flow I is taken with liquid phase oxidation by H2O2 to wipe off the sulfuration in the residue gasoline; the total content of the sulfuration in the residue gasoline is less than 5ppm to obtain the material flow II; c) the material flow II is separated by the common separated method to obtain cinnamene; the method can solve the problem greatly, which can be uses in the industrial production of cinnamene from residue gasoline.
Description
Technical field
The present invention relates to cinnamic recovery method in a kind of pyrolysis gasoline.
Background technology
Adopting naphthas is in the ethylene cracker of raw material, and the content of its dimethylbenzene is 0.06～0.07 ton of/ton ethene, and pyrolysis gasoline C
8Dimethylbenzene in the cut: vinylbenzene: the ratio of ethylbenzene is generally 4: 3: 1.Calculate in view of the above, the ethylene unit that a cover is 600,000 tons/year, recyclable vinylbenzene is about 2.9 ten thousand tons/year, if ethylbenzene dehydrogenation is wherein reclaimed, vinylbenzene output also can improve, and has certain recovery value.From pyrolysis gasoline, reclaim vinylbenzene and can eliminate the hydrogen gas consumption of vinylbenzene hydrogenation in traditional pyrolysis gasoline device, thereby alleviate the load of hydrogenation unit; The ethyl-benzene level that reclaims in the Mixed XYLENE significantly reduces, and can be used as the raw material that xylene isomerization is produced p-Xylol; Recyclable a considerable amount of vinylbenzene.
Contain and contain many component such as dimethylbenzene, the ethylbenzene etc. close in the cinnamic pyrolysis gasoline, adopt conventional distillating method to be difficult to separate, but because vinylbenzene is alkylating unsaturated aromatic compound with the vinylbenzene boiling point.Therefore can utilize polar extraction solvent that the character that unsaturated compound has bigger avidity is separated this class hydrocarbon compound.Therefore, extractive distillation is to reclaim the most effective cinnamic way from pyrolysis gasoline.Because of o-Xylol and cinnamic boiling point difference minimum, so o-Xylol is light key ingredient, vinylbenzene is heavy key.By reclaiming vinylbenzene, can improve the composition that reclaims dimethylbenzene, make it to become the suitable feedstock of xylene isomerization system p-Xylol.
DSM N. V. in 1980 has bought from pyrolysis gasoline from Toray company and has directly made cinnamic patented technology.Through the further exploitation of research department of DSM N. V., set up one with Badger company at Dutch Beek in 1996 and overlapped 2.7 ten thousand tons/year full scale plant.The pyrolysis gasoline that its raw material is used is provided by corresponding ethylene plant.The DSM method can obtain purity greater than 99.7% vinylbenzene, can produce p-Xylol simultaneously, and product carries out extracting and separating by the special-purpose extraction agent of they exploitations.
120～160 ℃ component in the proposition employing steam cracking among the patent US3763015 of Toray company, obtain crude styrene through extractive distillation, obtain colourless high-purity benzene ethene through the distillation purification, extraction solvent adopts the N,N-DIMETHYLACETAMIDE that contains the nitrite stopper.The vinylbenzene decoloring method that it adopts is the nitric acid treatment with 60%, and alkali cleaning is underpressure distillation again.
US5849982 and US5877385 use tetramethylene sulfone and water as solvent to improve dimethylbenzene to cinnamic relative volatility.Process comprises prefractionation, it is dense to carry, extraction, solvent recuperation, operation such as refining.The purity of styrene product can reach 99.9%, and phenylacetylene content is less than 50ppm.The recyclable high-quality dimethylbenzene of the overhead fraction of extraction distillation column.
(petrochemical complex important news 1998 is thought by Krupp Uhde company; (12): 13), the N-formyl morpholine is very suitable to reclaim cinnamic solvent.Simultaneously for preventing that cinnamic polymerization from needing to add stopper DNBP (the 2-tertiary butyl-4,6-dinitrophenol(DNP)) in raw pyrolysis gasoline.Because phenylacetylene can not be removed in extractive distillation, thus hydrogenation must before extraction, be selected, and adopt a kind of precious metals palladium catalyst.Propose a kind of technology of the vinylbenzene decolouring that will from pyrolysis gasoline, obtain in the patent of the said firm, adopted at least a close diolefine body (as: cis-butenedioic anhydride) and resistance aggressiveness (as: the 2-tertiary butyl-4,6-dinitrophenol).This mixture is heated between 50～140 ℃, isolate colourless vinylbenzene then.
JP56-145230 employing two, triglycol are extraction solvent, extract vinylbenzene from steam cracking device, and the consumption of extraction solvent is 5～20 times of amounts, and vacuum tightness is 100 mmhg, keep tower still temperature to be lower than 100 ℃.Raw material weight is formed: 47.5% o-Xylol, 52.5% vinylbenzene; Cat head is taken out excess weight and is formed: 71.9% o-Xylol, 29.1% vinylbenzene; The purity of crude styrene: 4.2% o-Xylol, 95.8% vinylbenzene.
US3953300 adopts the N-N-formyl morpholine N-that contains 1～30% water as extraction solvent, adopts reextraction distillation method separating phenylethylene.C
8C in the raw material inlet amount
8Alkane and alkene 3.5%, o-Xylol 17.0 weight %,, p-Xylol 43.1 weight %, ethylbenzene 8.6 weight %, vinylbenzene 27.8 weight %.Extraction solvent adopts the N-N-formyl morpholine N-that contains 5% water, and solvent ratio is 15.Extraction distillation column operational condition: top vacuum degree 140 mmhg; 80 of stage number; Reflux ratio 5.Cat head is taken out excess weight and is consisted of C
8Alkane and alkene 4.8%, o-Xylol 23.3%,, p-Xylol 59.6%, ethylbenzene 11.9%, vinylbenzene 0.41%.Weight is formed at the bottom of the tower: vinylbenzene 84.9%, o-Xylol 15.1%.Extraction distillation column 2 operational conditions are: the top vacuum degree: 160 mmhg; 60 of stage number; 100 ℃ of column bottom temperatures; Reflux ratio 2.5.Cat head is taken out excess weight and is formed: vinylbenzene 62.0%, o-Xylol 38.0%; Form at the bottom of the tower: vinylbenzene 99.8%, o-Xylol 0.2%.
US4714793 adopts N-aminoalkyl piperazine as extraction solvent and styrene polymerization inhibitor, from C
8Benzene extraction ethene in the cut, technological process are 1, extraction distillation column compound such as the o-Xylol that vinylbenzene and boiling point is approaching with it separates with ethylbenzene; 2, the separated from solvent tower is separated vinylbenzene and high boiling material (as: phenylacetylene) from ammonia solvent; 3, extraction distillation column is separated vinylbenzene from high boiling material; 4, the separated from solvent tower is separated high boiling material from ammonia solvent; 5 solvent purification towers are removed heavy component (as: polymkeric substance) from ammonia solvent.The colourity APHA of styrene product is less than 5.
It is extraction solvent that US4031153 adopts the succinonitrile that contains 0.5～3% water, from containing ethylbenzene, dimethylbenzene, vinylbenzene and a small amount of C
8～C
9The C of non-aromatics
8Separating phenylethylene in the cut.O-Xylol, cinnamic heavy constituent and p-Xylol and m-xylene and ethylbenzene are separated earlier, through another distillation tower o-Xylol, vinylbenzene are separated from heavy constituent again by distillation tower.Isolate through extractive distillation again and contain the vinylbenzene rich solvent.Isolate vinylbenzene through the separated from solvent tower again.US412605 also proposes to adopt alkyl benzene sulphonate (ABS) copper (as: Witco 1298 Soft Acid) as alkene complexing agent, separation of C
8Vinylbenzene in the cut, this technological process is: will contain cinnamic C earlier
8The cut selective hydrogenation is to remove diolefin and the alkynes in the raw material, carry out complexing with alkyl benzene sulphonate (ABS) copper again, the complexing product is separated, and the vinylbenzene that will contain alkene with CO cements out again, and the vinylbenzene that will contain non-aromatic alkene is at last isolated vinylbenzene by the water distilling apparatus of routine.
Summary of the invention
Technical problem to be solved by this invention be exist in the prior art from containing vinylbenzene pyrolysis gasoline C
8When reclaiming vinylbenzene in the fraction, product sulphur content height, the low technical problem of the rate of recovery provided cinnamic recovery method in a kind of new pyrolysis gasoline when the low and product of colourity reached higher degree.The styrene product sulphur content that this method has recovery is low, and colourity is good, and the high characteristics of the rate of recovery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: cinnamic recovery method in a kind of pyrolysis gasoline may further comprise the steps:
A) containing cinnamic pyrolysis gasoline raw material isolates boiling point and compares C
8Light component and boiling point that aromatic hydrocarbons is low compare C
8Behind the high heavy component of aromatic hydrocarbons, under the effect of selective hydrogenation catalyst, carry out selective hydrogenation, remove diolefin and alkynes in the pyrolysis gasoline raw material, produce feed stream I;
B) feed stream I carries out liquid-phase oxidation with hydrogen peroxide solution, contain by weight percentage at least a organic acid in 60～95% the compound that is selected from formic acid, acetate or diacetyl oxide during liquid-phase oxidation in the hydrogen peroxide solution as catalyzer, remove the sulphur compound in the pyrolysis gasoline, make total sulfur in the pyrolysis gasoline less than 5ppm, feed stream II;
C) feed stream II gets styrene product after routine is separated.
In the technique scheme, during liquid-phase oxidation in the hydrogen peroxide solution organic acid weight percentage preferable range be 75～95%.Routine separate before the styrene product, to be feed stream decolour as sorbent material with being selected from least a in gac, atlapulgite or the molecular sieve preferred version, the colourity that makes the pyrolysis gasoline raw material is less than 10.The selective hydrogenation catalyst preferred version is the aluminium oxide catalyst of supported palladium, nickel, and wherein the consumption of palladium is 0.01～1% of a vehicle weight, and the consumption of nickel is 1～25% of a vehicle weight.The temperature of selective hydrogenation is 10 ℃～80 ℃, and preferred temperature range is 20 ℃～55 ℃; Reaction pressure in gauge pressure is 0～300 * 10
5Pa, the preferred pressure scope is 1～10 * 10
5Pa; The reaction liquid the time volume space velocity be 0.1～300 hour
-1, volume space velocity is 0.5～15 hour during preferred liquid
-1Preferred version is among the feed stream I after the light component of cat head of styrene product tower and tower still heavy component all turn back to hydrogenation, to improve the cinnamic rate of recovery in the conventional sepn process.
Among the present invention, because in the sepn process of pyrolysis gasoline raw material, adopting with the hydrogen peroxide is the oxidation desulfuration process of the organic acid as catalyst of oxygenant, has removed sulphur compound in the raw material effectively.Employing is decoloured as sorbent material to be selected from least a in activated carbon, atlapulgite or the molecular sieve, has improved the colourity of styrene product.Because the cat head and the logistics of tower still of styrene product tower are all looped back in the stream I, further reclaim vinylbenzene wherein, under the condition that guarantees styrene product purity, improved the rate of recovery effectively.The present invention is by evidence, adopt the inventive method, the cinnamic colourity of its product can be low to moderate below 10, sulphur content can be low to moderate 20ppm, guaranteeing that product vinylbenzene purity by weight percentage is not less than under 99.7% the condition, the vinylbenzene rate of recovery can reach 95%, has obtained better technical effect.
Description of drawings
Accompanying drawing 1 is for adopting liquid phase catalytic oxidation desulfurization eddy flow branch and be separated and the flow example of two sections adsorption beds
Logistics 1 expression contains cinnamic pyrolysis gasoline raw material in the accompanying drawing 1, and the carbonatoms of contained compound is 5～9; C in the 2 expression logistics 1
5～7Light component; C is removed in 3 expressions
5～7Light component after pyrolysis gasoline; C is removed in 4 expressions
9The pyrolysis gasoline of above heavy component is mainly and contains cinnamic C
8Aromatic hydrocarbons; C in the 5 expression pyrolysis gasolines
9Above heavy component; 6 expression hydrogenation take off the cinnamic C that contains behind the phenylacetylene
8Aromatic hydrocarbons; 7 expression extraction distillation solvents; 8 expression C
8Saturated aromatic hydrocarbons and non-aromatics; 9 expressions contain the extraction distillation solvent of vinylbenzene and a small amount of heavy component, claim rich solvent again; The extraction distillation solvent that 10 expressions are reclaimed; 11 crude styrenes of representing extracting rectifying to obtain; The oxidation liquid after the 12 expression employing liquid-phase oxidation desulfurization and the mixture of crude styrene; 13 for oxidation liquid after crude styrene separates; 14 are the crude styrene after the desulfurization; 15 is one section crude styrene after the decolouring; 16 is two sections crude styrenes after the decolouring; Heavy component in the 17 expression crude styrenes; Contained light component in the 18 expression crude styrenes; 19 expression styrene product, 20 represent the mixture of logistics 6,18 and 19.B1 in the accompanying drawing 1 represents first knockout tower; B2 represents second knockout tower; B3 represents phenylacetylene selective hydrogenation device; B4 represents the 3rd knockout tower, i.e. extractive distillation column; B5 represents the 4th knockout tower, i.e. the solvent recovery tower; B6 represents liquid liquid catalytic oxidation desulfurization reactor; B7 represents the liquid Liquid Separation Hydrocyclone; B8 represents first section decolouring adsorption bed; B9 represents second section adsorption bleaching bed; B10 represents the 5th knockout tower, i.e. the vinylbenzene treating tower.
Below in conjunction with accompanying drawing the present invention is elaborated.
In accompanying drawing 1, contain the C such as styrene8The raw material 1 of aromatic hydrocarbons separates through the first knockout tower B1, remove light component 2 from cat head, tower reactor logistics 3 enters the second knockout tower B2, removes the component 5 heavier than styrene by tower reactor, enrichment cinnamic logistics 4 come out by tower B1 top, enter selective catalytic hydrogenation reactor B 3. First knockout tower operates under normal pressure, and second knockout tower operates under negative pressure, and preferred operating pressure scope is 1～100KPa, more preferably 5～30KPa. The preferred reactor types of hydrogenation reactor is fixed bed reactors, and preferred operating pressure scope is 100～1000KPa, and preferred pressure limit is 100～500KPa. Preferred reaction temperature is 20～200 ℃, more preferably 35～100 ℃. Catalyst system therefor Al preferably in the reactor B 32O
3The palladium of load (Pd) or nickel (Ni) catalyst. Logistics 6 behind the hydrogenation enters the 3rd knockout tower B4 middle part, and high boiling solvent 7 enters B4 by the position of the cat head of the 3rd knockout tower, and its cat head is isolated saturated aromatic hydrocarbons and the lower boiling compound of part, and tower reactor mainly is extraction distillation solvent and styrene 9. The preferred operating pressure scope of the 3rd knockout tower B4 is 1～20KPa, more preferably 5～15KPa; Greater than the rectifying section height, preferably the operating temperature of this Tata still is less than 120 ℃ greater than extracting rectifying section height for the stripping section height of preferred this tower; Preferred extraction distillation solvent comprises following component by weight percentage: a) 15%～55% sulfone compound; B) surplus contains nitrogen compound. Separate on the top that B4 tower reactor logistics 9 enters the 4th knockout tower B5, and cat head gets crude styrene logistics 11, and tower reactor gets extraction distillation solvent 10 and loops back the 3rd knockout tower B4 top and recycle. Crude styrene logistics 11 enters perfectly mixed reactor B6 and carries out oxidation sweetening, and preferred desulfurization oxidant is H2O
2The aqueous solution, and at least a as catalyst with in formic acid, acetic acid, acetic anhydride or the cis-butenedioic anhydride. Preferred reaction time is 3～60 minutes, more preferably 3～20 minutes. Reacted logistics 12 enters cyclone B7 to be carried out liquid liquid and separates, and wherein catalyst recovery and wastewater treatment are gone in water logistics 13, and oil phase logistics 14 enters two sections decolorization adsorption tower B8 or B9, and it is one standby that two sections adsorbent beds one are opened, handover operation. The crude styrene logistics 16 of process adsorption bleaching enters the 5th knockout tower B1 middle part crude styrene is made with extra care, cat head is isolated than the low-boiling light component 18 of styrene, tell the heavy component higher than styrene boiling point at the bottom of the tower, styrene product is from the position side line extraction near cat head. The operating pressure scope of preferred the 5th knockout tower is 1～30KPa, and preferred pressure limit is 5～20KPa. Preferred decolorizing adsorbent is activated carbon, Al in the decolorization adsorption tower2O
3, at least a in the molecular sieve, atlapulgite.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Adopt the flow process shown in the accompanying drawing 1, the pyrolysis gasoline raw material consists of C5～C9, separates C through two knockout towers
7-Component and C
9+Behind the component, its weight percent consists of: dicyclopentadiene 3.02%, benzene 0.95%, toluene 1.27%, ethylbenzene 13.16%, p-Xylol 9.62%, m-xylene 24.39%, o-Xylol 13.07%, vinylbenzene 32.43%, phenylacetylene 0.96%, all the other are non-aromatics.
Main C after two towers separate
8Cut enters the fixed-bed catalytic hydrogenator, and catalyzer is loading type Al
2O
3Catalyzer is at Al
2O
3On the carrier load be 0.3% palladium by weight percentage.Weight percent consists of behind the hydrogenation: dicyclopentadiene 3.02%, and benzene 0.95%, toluene 1.27%, ethylbenzene 13.32%, p-Xylol 9.62%, m-xylene 24.39%, o-Xylol 13.07%, vinylbenzene 33.23%, all the other are non-aromatics.
Logistics behind the hydrogenation separates through extractive distillation column, the extractive distillation column theoretical plate number is 60, the solvent feed position is the 8th theoretical stage, the logistics feed entrance point is the 32nd theoretical stage behind the hydrogenation, and the solvent quality ratio is 7, and reflux ratio is 0.6, the quality recovery ratio is 36.25%, obtaining tower still discharging logistics weight percent consists of: vinylbenzene 4.52%, dicyclopentadiene 0.41%, solvent 95.07%.
The logistics of extracting rectifying Tata still gets the crude styrene quality group after the crude styrene tower separates become: vinylbenzene 91.68%, dicyclopentadiene 8.32%.
Crude styrene enters the liquid-phase mixing reactor and carries out desulfurization, and the desulfurization oxygenant is H
2O
2The aqueous solution, catalyzer is a formic acid, the crude styrene sulphur content is reduced to 25ppm by 200ppm, crude styrene after the desulfurization enters two sections decolouring adsorption towers, and sorbent material is an atlapulgite, and crude styrene colourity (platinum-cobalt reference liquid comparison) is reduced to 10# by 800#, crude styrene after the decolouring obtains commercial benzene ethene through the separation of vinylbenzene treating tower, vinylbenzene purity is 99.95%, sulphur content≤25ppm by weight percentage, colourity≤10.
[embodiment 2]
Keep other operations of embodiment [1] constant, the weight ratio of solvent and raw material in the extractive distillation column is brought up to 10: 1 with this value, and the solvent feed position is moved to the 15th theoretical stage in the change technology, and catalyzer is the aluminum oxide of load 15% weight nickel.The hydrogenation logistics separates through extractive distillation column, and other conditions are constant to be obtained the percentage composition of tower still discharging weight of material and be: vinylbenzene 3.22%, dicyclopentadiene 0.29%, solvent 96.5%.Getting the crude styrene weight percent after the crude styrene tower separates consists of: vinylbenzene 91.84%, dicyclopentadiene 8.16%.Obtain commercial benzene ethene purity 99.96% through the vinylbenzene treating tower again.
[embodiment 3]
Keep other operations of embodiment [1] constant, extractive distillation column operational condition in the change technology becomes 0.8 with the weight reflux ratio of this tower.Obtain the tower still discharging same embodiment of weight of material percentage composition [1].
Claims (6)
1. cinnamic recovery method in the pyrolysis gasoline may further comprise the steps:
A) containing cinnamic pyrolysis gasoline raw material isolates boiling point and compares C
8Light component and boiling point that aromatic hydrocarbons is low compare C
8Behind the high heavy component of aromatic hydrocarbons, under the effect of selective hydrogenation catalyst, carry out selective hydrogenation, remove diolefin and alkynes in the pyrolysis gasoline raw material, produce feed stream I;
B) feed stream I carries out liquid-phase oxidation with hydrogen peroxide solution, contain by weight percentage at least a organic acid in 60～95% the compound that is selected from formic acid, acetate or diacetyl oxide during liquid-phase oxidation in the hydrogen peroxide solution as catalyzer, remove the sulphur compound in the pyrolysis gasoline, make total sulfur in the pyrolysis gasoline less than 5ppm, feed stream II;
C) feed stream II gets styrene product after routine is separated.
2. cinnamic recovery method in the pyrolysis gasoline according to claim 1, it is characterized in that routine separate before the styrene product, feed stream decolours as sorbent material with being selected from least a in gac, atlapulgite or the molecular sieve, and the colourity that makes the pyrolysis gasoline raw material is less than 10.
3. cinnamic recovery method in the pyrolysis gasoline according to claim 1, it is characterized in that selective hydrogenation catalyst is the aluminium oxide catalyst of supported palladium, nickel, the consumption of palladium is that the weight percent of carrier is 0.01～0.3%, and the consumption of nickel is that the weight percent of carrier is 1～25%.
4. cinnamic recovery method in the pyrolysis gasoline according to claim 1, the temperature that it is characterized in that selective hydrogenation are 10 ℃～80 ℃; Reaction pressure in gauge pressure is 0～300 * 10
5Volume space velocity is 0.1～300 hour when Pa, the liquid of reaction
-1
5. according to cinnamic recovery method in the described pyrolysis gasoline of claim 4, it is characterized in that selecting the temperature of hydrogenation is 20～55 ℃, is 1～10 * 10 in the reaction pressure of gauge pressure
5Volume space velocity is 0.5～15 hour when pa, the liquid of reaction
-1
6. cinnamic recovery method in the pyrolysis gasoline according to claim 1 is characterized in that among the feed stream I after the light component of cat head of styrene product tower in the conventional sepn process and tower still heavy component all turn back to hydrogenation.
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| CN104109555B (en) * | 2013-04-16 | 2017-02-15 | 中国石油化工股份有限公司 | Alkylation product treatment method |
| CN112574783B (en) * | 2019-09-29 | 2022-06-28 | 中国石油化工股份有限公司 | Method for comprehensively utilizing styrene tar |
| CN114133954B (en) * | 2020-09-03 | 2024-08-09 | 中国石油化工股份有限公司 | Method and device for preparing low-sulfur petroleum coke by processing residual oil |
| CN115772061B (en) * | 2023-02-13 | 2023-04-25 | 天津科技大学 | A method for catalytically removing thiophene sulfur-containing compounds in styrene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115208A (en) * | 1975-08-25 | 1978-09-19 | Stamicarbon, B.V. | Recovery of styrene from cracked hydrocarbon fractions |
| US4714793A (en) * | 1983-08-17 | 1987-12-22 | The Dow Chemical Company | Process for separating an ethylenically unsaturated hydrocarbon from a hydrocarbon mixture |
| US5849982A (en) * | 1996-05-21 | 1998-12-15 | Hfm International, Inc. | Recovery of styrene from pyrolysis gasoline by extractive distillation |
| US5877385A (en) * | 1996-05-21 | 1999-03-02 | Hfm International, Inc. | Process including extractive distillation and/or dehydrogenation to produce styrene from petroleum feedstock including ethyl-benzene/xylene mixtures |
-
2006
- 2006-08-11 CN CN2006100299748A patent/CN101121634B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115208A (en) * | 1975-08-25 | 1978-09-19 | Stamicarbon, B.V. | Recovery of styrene from cracked hydrocarbon fractions |
| US4714793A (en) * | 1983-08-17 | 1987-12-22 | The Dow Chemical Company | Process for separating an ethylenically unsaturated hydrocarbon from a hydrocarbon mixture |
| US5849982A (en) * | 1996-05-21 | 1998-12-15 | Hfm International, Inc. | Recovery of styrene from pyrolysis gasoline by extractive distillation |
| US5877385A (en) * | 1996-05-21 | 1999-03-02 | Hfm International, Inc. | Process including extractive distillation and/or dehydrogenation to produce styrene from petroleum feedstock including ethyl-benzene/xylene mixtures |
Non-Patent Citations (1)
| Title |
|---|
| US4031153` 1977.06.21 |
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