US3681202A - Method of purifying unsaturated hydrocarbons by extractive distillation with side stream removal and solvent mix - Google Patents
Method of purifying unsaturated hydrocarbons by extractive distillation with side stream removal and solvent mix Download PDFInfo
- Publication number
- US3681202A US3681202A US41945A US3681202DA US3681202A US 3681202 A US3681202 A US 3681202A US 41945 A US41945 A US 41945A US 3681202D A US3681202D A US 3681202DA US 3681202 A US3681202 A US 3681202A
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- United States
- Prior art keywords
- solvent
- tower
- extractive distillation
- reflux
- hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S203/00—Distillation: processes, separatory
- Y10S203/20—Power plant
Definitions
- the external premixing also allows adjustment of the solvent feed temperature to compensate for the variations in endothermic heat of solubility from'variat'ions, in-the hydrocarbon composition in the tower.
- Thisinvention relates to an improvement in the separation of hydrocarbons of 4 to 5 carbon atoms, including. unsaturated hydrocarbons, using extractive distillation.
- Unsaturated hydrocarbons of 4 to 5 carbon atoms have been prepared commercially by the dehydrogenation of more saturated hydrocarbons such as alkanes, or alkenes. These processes provide a mixture of hydrocarbons containing varying degrees of unsaturation, for example, butene or butane or mixtures thereof may be dehydrogenatedto produce a mixture of hydrocarbons containing butane,-butene, butadiene and the minor amount of alkynes such as vinylacetylene and methylacetylene. Similar mixtures of hydrocarbon products may be obtained from other reactions such. as the catalytic or non catalytic cracking of hydrocarbons.
- the fractionating capabilities of the tower are related directly to the internal reflux or dissolved hydrocarbon flowing down through the tower with the solvent.
- the amount of dissolved hydrocarbon should be as close as possible to the solubility limit.
- the solubility limit is exceeded the towers frequently go into uncontrollable stacks or flooded conditions. These upsets can result in considerable loss of specification product and costly reruns.
- the prior practice has been to control the amount of internal reflux by controlling the solvent feed temperatures as well as controlling the amount of external reflux. In practice the solvent is normally'fed into the tower a few trays from the top in order to provide for removal of solvent vapors from the overhead product.
- the drawing is a schematic representation of one method of obtaining the objects of the present invention.
- An organic feed comprising a hydrocarbon mixture containing C or C alkadiene, alkene, and alkane is fed to an extractive distillation tower A where it is contacted with a solvent.
- the solvent is added to the extractive distillation tower A by being premixed with a draw stream 20 from the upper portion of A.
- the solvent is preferential for the most unsaturated compound.
- a rich solvent is fed to solvent stripper B where the contained C and C are removed as overhead.
- the lean solvent from B then recycles to A.
- the objects of the present invention can be obtained by mixing a portion of the external hydrocarbon reflux which has been withdrawn from the extractive distillation tower with the solvent prior to adding the solvent to the extractive distillation tower.
- premixing in this fashion it is possible to obtain essentially complete solution of that portion of the external hydrocarbon reflux in the solvent. It may be 'desirable undersome operations to premix all or substantially all of the external hydrocarbon reflux with the incoming solvent.
- the solution within the tower of the external hydrocarbon reflux can be controlled at any level desired.
- the vaporized feed 15 to the extractive distillation tower A comprises unsaturated hydrocarbons of 4 to 5 carbon atoms such as alkadienes contaminated with minor amounts of alkyne of the same number of carbon atoms; a mixture of alkenes and al'kadienes, alkenes, alkenes and alkadienes; or alkenes, alkadienes and alkynes.
- the alkadiene may be butadiene-1,3, contaminated with vinyl acetylene or may be isoprene contaminated with isopropyl or isopropenyl acetylene and possibly l-pentyne, or 2-pentyne.
- the feed may be butene-lcontaminated with aminor amount of butadiene-l,3.
- the feed stream will be a hydrocarbon stream as described and may contain in addition thereto other hydrocarbons such as those having 2 to 8 carbon atoms.
- the extractive distillation column A may be any conventional equipment suchas a plate or packed type column.
- the bottoms 11 contain solvent and unsaturated hydrocarbon.
- solvent stripper B the unsaturated hydrocarbon is overhead 4.
- the overhead 4 is condensed at 6 and accumulated at 2.
- a portion of the condensed overhead is recycle 8. The remainder is taken off as unsaturated product which can be further purified if desired by a repetition of similar extractive distillations, straight fractionation, or any other known purification method.
- the bottoms 12 in the solvent stripper B will contain principally solvent, although there may be some retained unsaturated material.
- the lean solvent 12 is recycled for use in the extractive distillation tower A, and is injected into stream which is a portion of the external recycle hydrocarbon which was withdrawn from tower A.
- Stream 20 will be a more saturated hydrocarbon than found in recycle stream 8 for example.
- Stream 20 is withdrawn at a point above the solvent feed, generally from the tray above the solvent feed tray, although it may be a combination of several of the upper trays.
- the two streams, 12 and 20 pass through an inline mixer 16 and then through a cooler 18. Combined streams 12 and 20 are then fed to the tower A on the solvent feed tray.
- the overhead 3 from tower A goes through a condenser 5 and accumulator 14 from whence a portion 7 is recycled to the tower and stream 9 is withdrawn.
- water may be present as a part of the solvent system.
- water in the overheads of both towers A and B is knocked out respectively as streams 17 and 13.
- These combined streams can be added to lean solvent 12 as makeup or water from other sources (not shown) can be used entirely.
- Solvent makeup is made through stream 19 as needed.
- the solvents employed in the extractive distillation tower may include any of the polar solvents known to separate relatively more unsaturated hydrocarbons from less unsaturated hydrocarbons such as acetone, acetonitrile, dimethyl formamide, dimethyl sulphoxide, furfural, n-methyl pyrrolidone, methylethyl ketone, dimethyl acetamide, 3-methoxypropionitrile, mixtures of these solvents froma catalytic dehydrogenation andcontains-OA.
- polar solvents known to separate relatively more unsaturated hydrocarbons from less unsaturated hydrocarbons
- acetone acetonitrile
- dimethyl formamide dimethyl sulphoxide
- furfural n-methyl pyrrolidone
- methylethyl ketone dimethyl acetamide
- 3-methoxypropionitrile mixtures of these solvents froma catalytic dehydrogenation andcontains-OA.
- Hydrocarbonfeed, 15 is fed to the extractive distillation tower A at a rate of about 239 barrels per hoiii'rThe bottoms 11 consists of 88.0 vol. percent furfural, 7.6 vol. percent water, 4.4 vol.
- Aproduct stream 10 is taken off the condensedhydrocarbon overhead. at the rate of about barrels per hour. Stream-10;
- the lean solvent 12 can have makeup solvent and/or water added as necessary. Since the lean solvent 12 is coming out of the stripper B at about 320 F. it is usually cooled (not shown) by indirect heat exchange in reboilers on tower A and in feed Vaporizers in which the incoming feed is vaporized and fed to tower A at about 150 F. Additional cooling may be used to bring the'temperature of the lean solvent 12 down to about 140 F. at thej point it enters stream 20. The lean solvent 12 is being recycled to tower A at the rate "of about 1990 barrels per hour. Stream 20 is the external recycle of the condensed hydro carbon overhead 3 of tower A.
- Stream 20 is taken off of the tray above the solvent feed'tray at the rate of about 166 barrels per hour and is composed of 0.7 vol. percent propane, propylene, 0.5 vol. percent isobutane, 88.8 vol. percent n-butane, 7.8 vol. percent butene-l, 0.5 vol. percent isobutene, 1.1 volpercent butene-Z' and 0.6 vol. percent pentanes.
- This is actually over 100% of the condensed hydrocarbon refiux 7 which is returned to tower A at the rate of 160 barrels per hour, and is the result of the condensation of vaporous material in the tower, (i.e., 118 F.) condensed hydrocarbon reflux.
- a portion is actually over 100% of the condensed hydrocarbon refiux 7 which is returned to tower A at the rate of 160 barrels per hour, and is the result of the condensation of vaporous material in the tower, (i.e., 118 F.) condensed hydrocarbon reflux.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4194570A | 1970-06-01 | 1970-06-01 |
Publications (1)
Publication Number | Publication Date |
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US3681202A true US3681202A (en) | 1972-08-01 |
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US41945A Expired - Lifetime US3681202A (en) | 1970-06-01 | 1970-06-01 | Method of purifying unsaturated hydrocarbons by extractive distillation with side stream removal and solvent mix |
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898135A (en) * | 1971-07-23 | 1975-08-05 | Petro Tex Chem Corp | Extractive distillation of C{HD 4 {B hydrocarbons using a three component solvent system |
US3951754A (en) * | 1974-02-19 | 1976-04-20 | Liakumovich Alexandr Grigoriev | Method of inhibiting the thermopolymerization of isoprene and butadiene |
US4081332A (en) * | 1976-08-27 | 1978-03-28 | The B. F. Goodrich Company | Extractive distillation of C5 hydrocarbons using acetonitrile and additives |
US4113575A (en) * | 1976-03-23 | 1978-09-12 | Phillips Petroleum Company | Separation of acetone from n-butane by distillation |
US4268361A (en) * | 1980-05-19 | 1981-05-19 | The B. F. Goodrich Company | Inhibiting polymerization in extractive distillation of C-4 hydrocarbons using alkoxynitrile-containing solvent |
US4269668A (en) * | 1980-05-19 | 1981-05-26 | The B. F. Goodrich Company | Extractive distillation of C-4 hydrocarbons using modified alkoxynitrile solvent |
US4277315A (en) * | 1979-03-23 | 1981-07-07 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
US4278504A (en) * | 1979-03-23 | 1981-07-14 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
FR2474024A1 (en) * | 1980-01-23 | 1981-07-24 | Inst Francais Du Petrole | PROCESS FOR PRODUCING BUTENE-1 FROM A C4 CUTTING OF HYDROCARBONS |
FR2474512A1 (en) * | 1980-01-28 | 1981-07-31 | Int Synthetic Rubber | PROCESS AND PLANT FOR PURIFYING MONOMERS AND SOLVENTS IN A POLYMERIZATION PLANT |
US4310388A (en) * | 1979-03-23 | 1982-01-12 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 hydrocarbon |
US5399244A (en) * | 1993-12-06 | 1995-03-21 | Glitsch, Inc. | Process to recover benzene from mixed hydrocarbons by extractive distillation |
US6375802B1 (en) | 1997-09-03 | 2002-04-23 | Hfm International, Inc. | Method of retrofitting existing equipment for an improved aromatics separation process |
US6616831B1 (en) | 1997-09-03 | 2003-09-09 | Gtc Technology Inc. | Aromatics separation process and method of retrofitting existing equipment for same |
US20040000474A1 (en) * | 2002-02-22 | 2004-01-01 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US20100025220A1 (en) * | 2008-08-04 | 2010-02-04 | Baojun Dong | Process for extractive distillation |
-
1970
- 1970-06-01 US US41945A patent/US3681202A/en not_active Expired - Lifetime
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898135A (en) * | 1971-07-23 | 1975-08-05 | Petro Tex Chem Corp | Extractive distillation of C{HD 4 {B hydrocarbons using a three component solvent system |
US3951754A (en) * | 1974-02-19 | 1976-04-20 | Liakumovich Alexandr Grigoriev | Method of inhibiting the thermopolymerization of isoprene and butadiene |
US4113575A (en) * | 1976-03-23 | 1978-09-12 | Phillips Petroleum Company | Separation of acetone from n-butane by distillation |
US4081332A (en) * | 1976-08-27 | 1978-03-28 | The B. F. Goodrich Company | Extractive distillation of C5 hydrocarbons using acetonitrile and additives |
US4277315A (en) * | 1979-03-23 | 1981-07-07 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
US4278504A (en) * | 1979-03-23 | 1981-07-14 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 -hydrocarbon mixture |
US4310388A (en) * | 1979-03-23 | 1982-01-12 | Basf Aktiengesellschaft | Isolation of a conjugated diolefin from a C4 - or C5 hydrocarbon |
FR2474024A1 (en) * | 1980-01-23 | 1981-07-24 | Inst Francais Du Petrole | PROCESS FOR PRODUCING BUTENE-1 FROM A C4 CUTTING OF HYDROCARBONS |
FR2474512A1 (en) * | 1980-01-28 | 1981-07-31 | Int Synthetic Rubber | PROCESS AND PLANT FOR PURIFYING MONOMERS AND SOLVENTS IN A POLYMERIZATION PLANT |
US4339623A (en) * | 1980-01-28 | 1982-07-13 | The International Synthetic Rubber Company, Limited | Monomer/solvent purification |
US4268361A (en) * | 1980-05-19 | 1981-05-19 | The B. F. Goodrich Company | Inhibiting polymerization in extractive distillation of C-4 hydrocarbons using alkoxynitrile-containing solvent |
US4269668A (en) * | 1980-05-19 | 1981-05-26 | The B. F. Goodrich Company | Extractive distillation of C-4 hydrocarbons using modified alkoxynitrile solvent |
US5399244A (en) * | 1993-12-06 | 1995-03-21 | Glitsch, Inc. | Process to recover benzene from mixed hydrocarbons by extractive distillation |
US6375802B1 (en) | 1997-09-03 | 2002-04-23 | Hfm International, Inc. | Method of retrofitting existing equipment for an improved aromatics separation process |
US6565742B1 (en) | 1997-09-03 | 2003-05-20 | Gtc Technology Inc. | Aromatics separation process and method of retrofitting existing equipment for same |
US6616831B1 (en) | 1997-09-03 | 2003-09-09 | Gtc Technology Inc. | Aromatics separation process and method of retrofitting existing equipment for same |
US20040000474A1 (en) * | 2002-02-22 | 2004-01-01 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US20050119356A1 (en) * | 2002-02-22 | 2005-06-02 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US7091252B2 (en) | 2002-02-22 | 2006-08-15 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US20060235092A1 (en) * | 2002-02-22 | 2006-10-19 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US20060290016A1 (en) * | 2002-02-22 | 2006-12-28 | Catalytic Distillation Technologies. | Liquid-continuous column distillation |
US7287745B2 (en) | 2002-02-22 | 2007-10-30 | Catalytic Distillation Technologies | Liquid-continuous column distillation |
US20100025220A1 (en) * | 2008-08-04 | 2010-02-04 | Baojun Dong | Process for extractive distillation |
US8551297B2 (en) * | 2008-08-04 | 2013-10-08 | Baojun Dong | Process for extractive distillation |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PETRO-TEX CHEMICAL CORPORATION, C/O TENNECO OIL CO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TEXAS PETROCHEMICAL CORPORATION;REEL/FRAME:004634/0711 |
|
AS | Assignment |
Owner name: TEXAS PETROCHEMICALS CORPORATION, A CORP. OF TX Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PETRO-TEX CHEMICAL CORPORATION, A CORP. OF DE;REEL/FRAME:004748/0270 Effective date: 19870518 |
|
AS | Assignment |
Owner name: TEXAS PETROCHEMICALS CORPORATION, 8707 KATY FREEWA Free format text: TERMINATION OF SECURITY AGREEMENT RECORDED JULY 25, 1986. REEL 4634 FRAME 711-723, DEBT HAS BEEN PAID;ASSIGNOR:PETRO-TEK CHEMICAL CORPORATION;REEL/FRAME:005060/0478 Effective date: 19860725 |