WO2013104692A1 - Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent - Google Patents
Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent Download PDFInfo
- Publication number
- WO2013104692A1 WO2013104692A1 PCT/EP2013/050366 EP2013050366W WO2013104692A1 WO 2013104692 A1 WO2013104692 A1 WO 2013104692A1 EP 2013050366 W EP2013050366 W EP 2013050366W WO 2013104692 A1 WO2013104692 A1 WO 2013104692A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crude
- cut
- hydrocarbons
- stripping column
- purified
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
Definitions
- the invention relates to a method for providing a vaporized purified R0h- C4- Thomase.es as feed stream for an extractive distillation with a selective solvent.
- C 4 cut denotes mixtures of hydrocarbons having predominantly 4 carbon atoms per molecule.
- C 4 cuts are obtained, for example, in the production of ethylene and / or propylene by thermal cracking, usually in steam crackers, especially naphtha crackers or fluidized catalytic cracking (FCC) crackers of a petroleum fraction, such as liquefied petroleum gas, light gasoline or gas oil. Furthermore, C 4 cuts are obtained in the catalytic dehydrogenation of n-butane and / or n-butene.
- C 4 cuts generally contain butanes, butenes, 1,3-butadiene, small amounts of C 3 and C 4 acetylenes, 1,2-butadiene and C 5+ hydrocarbons.
- the separation of C 4 cuts is a complicated distillation problem because of the small differences in the relative volatilities of the components. Therefore, the separation is carried out by a so-called extractive distillation, ie a distillation with the addition of a selective solvent (also referred to as extractant), which has a higher boiling point than the mixture to be separated and which increases the differences in the relative volatilities of the components to be separated.
- Crude C 4 sections contain impurities which would lead to problems in the extractive distillation, in particular foaming of the solvent and apparatus fouling, so that they must be separated just before the supply of R0h- C4- section for extractive distillation to a ensure reliable operation of the extractive distillation.
- Impurities leading to the above problems are particularly high relative to 1,3-butadiene higher boiling components, especially C 5+ hydrocarbons (predominantly hydrocarbons having 5 or more carbon atoms per molecule, isoprene, C 4 oligomers and polymers, ie Oligomers and optionally polymers of butadiene of the formula (C 4 H 6 ) n, where n is greater than or equal to 2.
- the proportion of C 5+ hydrocarbons in C 4 cuts is dependent in particular on the operating conditions during thermal cracking and is up to to 1000 ppm by weight or even up to 5000 ppm by weight, in individual cases up to 1 wt .-%, based on the total weight of R0h-C4-Schnitt.es.
- the C 4 oligomers and polymers are formed in particular by storage and transport, their proportion is therefore largely dependent on the storage and transport conditions, in particular temperature, duration, inerting of the atmosphere under which the storage and / or transport takes place.
- C 3 hydrocarbons ie hydrocarbons having three carbon atoms per molecule
- the extractive distillation can cause problems; These are in particular methylacetylene, which has a similar affinity to the commonly used selective solvents such as 1, 3-butadiene.
- the proportion of C 3 hydrocarbons should therefore be limited in the feed stream for extractive distillation to a maximum of 50 ppm by weight, based on the total weight of the feed stream.
- the bottom stream is then fed to an evaporator vessel for the purpose of separating the high-boiling components from 1,3-butadiene, ie an apparatus with a single separation stage.
- the depleted with C 3 components crude C 4 stream is almost completely evaporated, and indeed flow controlled, so that compared to 1, 3-butadiene high-boiling components in the remaining liquid content not above 5 wt .-%, in particular not above 1 wt .-%, or even not more than 0.1 wt .-%, based on the total weight of the crude boiler supplied to the evaporator C 4 - Thomases lie.
- the liquid stream remaining in the evaporator vessel is discharged as purge stream.
- the disadvantage here however, that high levels of recyclables, C 4 hydrocarbons are discharged via the purge stream together with the high boilers.
- This object is achieved by a method of providing a vapor purified crude C 4 fraction as a feed stream for an extractive distillation using a selective solvent, starting from a crude liquid C 4 fraction as a feed stream containing, in addition butanes, butenes and 1, 3 Butadiene C 3 hydrocarbons, C 4 oligomers and polymers, and C 5+ hydrocarbons, wherein the purified crude vapor C 4 - cut less than two-thirds of the C 5+ hydrocarbons contained in the feed stream and less than 5 wt .-% of the feed stream contained in the C 4 oligomers and polymers containing the process steps
- a stripping column to the evaporator boiler, that is to provide evaporator boiler and stripping column as separate apparatuses.
- Evaporator boilers are known in the process engineering simple apparatus. They usually include a boiler, in which a gas phase can separate from a liquid phase, and a heat exchanger, which is located inside or outside the boiler.
- a stripping column is assigned to the evaporator vessel. Since the stripping column and the evaporator boiler is intended only for depletion of high boilers, it is possible to operate the stripping column in a simple manner, without a condenser at the top of the column.
- a typical crude C 4 cut from a naphtha cracker has the following composition in weight percent:
- Raw C 4 cuts from naphtha crackers thus contain predominantly butanes, butenes and 1, 3-butadiene. In addition, small amounts of other hydrocarbons are included. C 4 -acetylenes are frequently present in a proportion of 5% by weight or even up to 2% by weight.
- suitable substances generally include substances or mixtures which have a higher boiling point than the mixture to be separated and a greater affinity for conjugated double bonds and triple bonds than simple double bonds and single bonds, preferably dipolar, particularly preferably dipolar, aprotic solvents , For technical reasons, less or non-corrosive substances are preferred.
- Suitable selective solvents for the process according to the invention are, for example, butyrolactone, nitriles such as acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfurol, N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-formylmorpholine, N-alkyl-substituted cydic acid amides (Lactams) such as N-alkylpyrrolidones, in particular N-methylpyrrolidone.
- nitriles such as acetonitrile, propionitrile, methoxypropionitrile
- ketones such as acetone, furfurol
- N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, die
- N-alkyl substituted lower aliphatic acid amides or N-alkyl substituted cydic acid amides are used. Particularly advantageous are dimethylformamide, acetonitrile, furfurol and in particular N-methylpyrrolidone.
- mixtures of these solvents with one another for example N-methylpyrrolidone with acetonitrile
- mixtures of these solvents with cosolvents such as water and / or tert-butyl ether, for example methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert-butyl ether, n- or iso-butyl tert-butyl ether can be used.
- N-methylpyrrolidone preferably in aqueous solution, in particular with 8 to 10 wt .-% water, particularly preferably with 8.3 wt .-% water.
- N-methylpyrrolidone preferably in aqueous solution, in particular with 8 to 10 wt .-% water, particularly preferably with 8.3 wt .-% water.
- it should be fed as a feed stream, a purified vaporized crude C 4 cut less than 50 Ppm by weight of C 3 hydrocarbons, based on the total weight of the purified vaporous R0h-C4 cut, less than two-thirds of the C 5+ hydrocarbons contained in the feed stream and less than 5% by weight of the C contained in the feed stream 4 -oligomers and polymers.
- the C 3 hydrocarbons in the gaseous purified crude C 4 - cut to less than 10 ppm by weight, based on the total weight of the gaseous purified R0h- C4- Thomase.es, or even more preferably less than 4 wt. -ppm, depleted in a distillation column upstream of the evaporator boiler.
- the C 5+ hydrocarbons are depleted in the gaseous purified crude C 4 cut to less than half of the C 5+ hydrocarbons present in the feed stream.
- the stripping column is preferably operated at a top pressure in the range of 3 to 7 bar absolute, more preferably at a top pressure in the range of 4.5 to 5.5 bar absolute.
- the stripping column has in particular 1 to 15 theoretical plates.
- 1 is a schematic representation of the evaporator boiler with attached stripping column
- Fig. 2 is a schematic representation of an evaporator boiler with associated stripping column.
- the schematic representation in Fig. 1 shows an evaporator vessel, VK, at the upper end of which a stripping column K connects, such that the Evaporator VK and the stripping column K form a single apparatus.
- a sump evaporator is provided at the lower end of the evaporator vessel VK .
- the stripping column K is supplied in the upper region thereof the liquid crude C 4 cut as stream 1, and at the top of the stripping column K, the purified crude C 4 - cut, stream 2, deducted.
- Fig. 2 shows the schematic representation of a further preferred embodiment, in which the evaporator vessel VK and the stripping column K are formed as separate apparatus, and wherein a direct gas and liquid exchange at the upper end of the evaporator vessel VK is provided with the stripping column K.
- the evaporator boiler VK is equipped with a sump evaporator S.
- the stripping column K is fed in the upper region thereof the liquid C 4 cut as stream 1 and withdrawn as overhead stream of the vaporized purified crude C 4 cut , stream 2.
- the starting point is a crude liquid C 4 cut as feed stream for a 100 kt / year plant containing 200 ppm of propane, 400 ppm of propene, 300 ppm of propadiene, 400 ppm of propyne, 2.0% of n-butane, 6.0 % isobutane, 19.0% n-butene, 28.3% isobutene, 5.5% trans-2-butene, 4.4% cis-2-butene, 39.0% butadiene-1, 3 , 0.2% butadiene-1, 2, 1200 ppm butyn-1, 4500 ppm vinyl acetylene and 1000 ppm iso-pentane, 3-methylbutene-1 and 2-methylbutene-2, in each case based on the total weight of the feed stream.
- C 4 oligomers and polymers can be contained in the% range.
- the above crude C 4 cut is subjected to a pre-purification, for comparison in a plant with a distillation column in which the C 3 hydrocarbons are removed overhead and the remaining components are withdrawn via the bottom whereupon the bottoms stream is fed to an evaporator vessel for separation of the high boiling components relative to 1,3-butadiene, ie a single separation apparatus.
- the crude C 4 stream depleted in C 3 components is virtually completely vaporized and discharged under flow control, so that the C 5 components which boil over 1, 3-butadiene in the remaining liquid fraction do not exceed 5% by weight, based on the total weight of the R0h- C4-Schnitten.es supplied to the evaporator vessel, lie to the loss of C 4 components in liquid residue to keep small.
- the proportion of oligomers and polymers contained in the liquid residue is significantly greater because of the lower vapor pressure.
- the liquid stream remaining in the evaporator vessel is discharged as purge stream.
- the same crude C 4 cut is fed as feed stream to an evaporator vessel VK, on which a stripping column K is set up with 5 theoretical plates, to which the liquid C 4 cut 1 is fed in the upper region and from the top End of the same is withdrawn from the gaseous purified crude C 4 cut 2, wherein the stripping column K is operated without a condenser at the top of the column.
- a stripping column K is set up with 5 theoretical plates, to which the liquid C 4 cut 1 is fed in the upper region and from the top End of the same is withdrawn from the gaseous purified crude C 4 cut 2, wherein the stripping column K is operated without a condenser at the top of the column.
- the residue stream (from the evaporator vessel) is according to the prior art 160 kg / h, with a proportion of 1, 3-butadiene of 38.6 wt .-%.
- a purified crude C 4 cut with a higher degree of purity, compared to the method of the prior art is separated by the novel process.
- ppm C 5 components additional proportions of C 6 components as well as oligomers and polymers, which are not taken into consideration here, may be used
- 94.16 kg / h C 5 - fed components according to the prior art extractive distillation In the case according to the invention, on the other hand, only 55.1 kg / h of C 5 components of the extractive distillation are fed in.
- the loss of desired product 1, 3-butadiene is thus greater by about 192 t / year in the process according to the prior art than in the process according to the invention.
- the solvent forming a closed circuit the previous separation of interfering components and impurities keeps the same clean, thereby minimizing the regeneration effort.
- the contamination of the extractive distillation unit (fouling of the beds in the columns) and foaming are kept low. As a result, less antifoam is required with correspondingly lower costs.
- Reduced fouling reduces the cleaning effort for a shutdown. Each shutdown means a production loss of about 2 weeks; this adds to the cleaning effort. This leads to costs in the 7-digit range.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014551607A JP6067748B2 (en) | 2012-01-11 | 2013-01-10 | Steam quality refined crude C4 cut production method as feed stream for extractive distillation using selective solvent |
KR1020147021970A KR102049312B1 (en) | 2012-01-11 | 2013-01-10 | Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent |
EP13700159.0A EP2802637B1 (en) | 2012-01-11 | 2013-01-10 | Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent |
CN201380005242.3A CN104053752B (en) | 2012-01-11 | 2013-01-10 | The gaseous state C of purification is provided4thick fraction is as the method for the feed stream using selective solvent extractive distillation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12150824.6 | 2012-01-11 | ||
EP12150824 | 2012-01-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013104692A1 true WO2013104692A1 (en) | 2013-07-18 |
Family
ID=47553075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2013/050366 WO2013104692A1 (en) | 2012-01-11 | 2013-01-10 | Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2802637B1 (en) |
JP (1) | JP6067748B2 (en) |
KR (1) | KR102049312B1 (en) |
CN (1) | CN104053752B (en) |
WO (1) | WO2013104692A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11697626B2 (en) | 2018-05-18 | 2023-07-11 | Sabic Global Technologies B.V. | Method of producing a fuel additive with a hydration unit |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2877173A (en) * | 1955-03-23 | 1959-03-10 | Standard Oil Co | Hydroforming process |
US4419188A (en) * | 1980-06-02 | 1983-12-06 | Mccall Thomas F | Thermally coupled extractive distillation process |
US20080168797A1 (en) * | 2004-07-06 | 2008-07-17 | Fluor Technologies Corporation | Configurations and Methods for Gas Condensate Separation from High-Pressure Hydrocarbon Mixtures |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58167683A (en) * | 1982-03-29 | 1983-10-03 | Nippon Zeon Co Ltd | Extractive distillation |
DE10022465A1 (en) * | 2000-05-09 | 2001-11-15 | Basf Ag | Processing a four carbon cut from the fractionation of crude oil, useful for the recovery of 1,4-butadiene, comprises extractive distillation, selective hydrogenation and distillation |
DE10333756A1 (en) * | 2003-07-24 | 2005-02-17 | Basf Ag | Process for the separation of a crude C4 cut |
DE102004005930A1 (en) * | 2004-02-06 | 2005-08-25 | Basf Ag | Process for the recovery of crude 1,3-butadiene |
KR101440637B1 (en) * | 2006-07-12 | 2014-09-19 | 바스프 에스이 | Method for separating a c4 fraction by means of extractive distillation using a selective solvent |
CN101492335B (en) * | 2008-01-23 | 2013-07-31 | 中国石油化工股份有限公司 | Combination method for comprehensive utilization of mix C4 |
-
2013
- 2013-01-10 WO PCT/EP2013/050366 patent/WO2013104692A1/en active Application Filing
- 2013-01-10 JP JP2014551607A patent/JP6067748B2/en active Active
- 2013-01-10 EP EP13700159.0A patent/EP2802637B1/en active Active
- 2013-01-10 CN CN201380005242.3A patent/CN104053752B/en active Active
- 2013-01-10 KR KR1020147021970A patent/KR102049312B1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2877173A (en) * | 1955-03-23 | 1959-03-10 | Standard Oil Co | Hydroforming process |
US4419188A (en) * | 1980-06-02 | 1983-12-06 | Mccall Thomas F | Thermally coupled extractive distillation process |
US20080168797A1 (en) * | 2004-07-06 | 2008-07-17 | Fluor Technologies Corporation | Configurations and Methods for Gas Condensate Separation from High-Pressure Hydrocarbon Mixtures |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11697626B2 (en) | 2018-05-18 | 2023-07-11 | Sabic Global Technologies B.V. | Method of producing a fuel additive with a hydration unit |
Also Published As
Publication number | Publication date |
---|---|
JP6067748B2 (en) | 2017-01-25 |
CN104053752B (en) | 2016-08-31 |
KR20140120329A (en) | 2014-10-13 |
JP2015508409A (en) | 2015-03-19 |
KR102049312B1 (en) | 2019-11-28 |
EP2802637A1 (en) | 2014-11-19 |
EP2802637B1 (en) | 2017-03-22 |
CN104053752A (en) | 2014-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2043977B1 (en) | Method for separating a c4 fraction by means of extractive distillation using a selective solvent | |
EP1718585B1 (en) | Method for obtaining raw-1,3-butadiene | |
DE1568902C3 (en) | PRINCIPLES FOR THE SEPARATION OF 13-BUTADIENE, ISOPRENE AND 13-PENTADIENE FROM A C4 or C5 HYDROCARBON MIXTURE | |
EP1501773B1 (en) | Continuous method for obtaining butenes from a c4 fraction | |
DE2724365A1 (en) | PROCESS FOR SEPARATING A C LOW 4 HYDROCARBON MIXTURE BY EXTRACTIVE DISTILLATION | |
EP1628940B1 (en) | Method for obtaining crude 1,3-butadiene from a c4 fraction | |
DE102010011014A1 (en) | Process and apparatus for the distillative recovery of pure 1,3-butadiene from crude 1,3-butadiene | |
EP1656334B1 (en) | Method for the separation of a crude c4 cut | |
EP2788457B1 (en) | Method for performing an extractive distillation using a selective solvent with a vaporous c4 fraction as a feed stream | |
DE2911395C2 (en) | Process for the preparation of a conjugated diolefin from a C 4 or C 5 hydrocarbon mixture | |
EP0284971B1 (en) | Process for the production of 1,3-butadien | |
EP1530555A1 (en) | Method for working up crude 1,3-butadiene | |
EP2496539B1 (en) | Method for separating a c4 fraction by means of extractive distillation using a selective solvent | |
EP2802637B1 (en) | Method for providing a purified crude gaseous c4 fraction as an input stream for an extractive distillation using a selective solvent | |
DE3339157A1 (en) | METHOD FOR OBTAINING A CONJUGATED DIOLEFIN AND / OR OLEFIN FROM A C (DOWN ARROW) 4 (DOWN ARROW) - OR C (DOWN ARROW) 5 (DOWN ARROW) HYDROCARBON MIXTURE | |
EP3573943B1 (en) | Method for obtaining pure 1,3-butadiene | |
EP3596033B1 (en) | Simplified method for obtaining pure 1,3-butadiene | |
WO2019007781A1 (en) | Method and system for separating c4 hydrocarbons by extractive distillation | |
DE3346695A1 (en) | METHOD FOR SEPARATING A C (DOWN ARROW) 4 (DOWN ARROW) HYDROCARBON MIXTURE BY EXTRACTIVE DISTILLATION | |
DE2911393B1 (en) | Process for the production of a conjugated diolefin from a C4 or C5 hydrocarbon mixture | |
DE2911396C2 (en) | Process for the preparation of a conjugated diolefin from a C 4 or C 5 hydrocarbon mixture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13700159 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014551607 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2013700159 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013700159 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147021970 Country of ref document: KR Kind code of ref document: A |