EP0904336A1 - Verfahren zur herstellung von schwefelarmen aliphatischen verbindungen - Google Patents
Verfahren zur herstellung von schwefelarmen aliphatischen verbindungenInfo
- Publication number
- EP0904336A1 EP0904336A1 EP97929158A EP97929158A EP0904336A1 EP 0904336 A1 EP0904336 A1 EP 0904336A1 EP 97929158 A EP97929158 A EP 97929158A EP 97929158 A EP97929158 A EP 97929158A EP 0904336 A1 EP0904336 A1 EP 0904336A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- olefin
- sulfur
- morpholine
- extractant
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
Definitions
- the invention relates to a process for the preparation of low-sulfur aliphatic compounds and, in particular, to a process for the desulfurization of olefin-rich hydrocarbons by liquid-liquid extraction.
- Olefin-rich hydrocarbon mixtures are available in large quantities from cracker plants.
- so-called vacuum residue oils are converted into low-boiling fractions in thermal cracker systems (Visbreaker, Coker), which are characterized by a high olefin content.
- Visbreaker, Coker thermal cracker systems
- These products are e.g. processed into fuels in catalytic processes such as fluid catalytic cracking (FCC) or hydrocracking.
- olefin-rich hydrocarbon mixtures Another example of the industrial use of these olefin-rich hydrocarbon mixtures is hydroformylation for the production of higher aldehydes and / or alcohols by reaction with hydrogen and carbon monoxide in the presence of a catalyst.
- the resulting alcohols serve e.g. as a solvent or are e.g. used to make plasticizers.
- the high sulfur content of these mixtures proves to be a problem, since the sulfur compounds contained often act as catalyst poisons.
- the desulfurization of hydrocarbon mixtures is carried out catalytically predominantly under hydrogenation / dehydration conditions, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1991, vol. A18, pp. 65-67. wrote.
- the so-called hydrotreating the sulfur compounds contained are converted into hydrogen sulfide and then washed out with a suitable solvent.
- the catalysts used also bring about partial hydrogenation of the olefins, which is disadvantageous with regard to further processing, for example by hydroformylation.
- EP-A-653 477 describes the desulfurization of light oils by liquid-liquid extraction with nitrogen-containing heterocycles or acid amides, preference being given to using N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone become.
- the major disadvantage of this process is the low selectivity of the extractants used compared to the starting hydrocarbons, so that the content of desired olefins is also reduced in this process.
- DE-A-20 40 025 describes a process for separating high-purity aromatics from hydrocarbon mixtures by liquid-liquid extraction with subsequent extractive distillation, morpholine and / or N-substituted morpholines being used in conjunction with water as the solvent. This method finds practical application in the Morphylan process by Krupp-Koppers, which is also described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition, 1995, vol. A3, pp. 491-496. However, DE-A-20 40 025 does not deal with the problem of the selective removal of sulfur impurities from olefin-rich starting products and the subsequent catalytic further processing of the desulfurized products.
- the present invention is therefore based on the object of providing a process for the production of low-sulfur aliphatic compounds from olefin-rich precursors without a substantial reduction in the olefin content.
- this object is achieved by providing a process for preparing low-sulfur aliphatic compounds from olefin-rich starting products contaminated with organic sulfur compounds, where a) the sulfur-containing olefin-rich starting product of a one- or multi-stage liquid-liquid Subjected to extraction with an extraction liquid containing morpholine, b) separating the extractant and the sulfur compounds contained therein and, if appropriate, c) further processing the low-sulfur aliphatic product.
- Suitable olefin-rich starting products according to the invention are olefins, olefin mixture or olefin-rich hydrocarbon mixtures which are contaminated with organic and in particular aromatic sulfur compounds.
- preferred starting products are olefin-rich hydrocarbon mixtures, such as those e.g. in the petrochemical industry with thermal cracking processes (Visbreaker, Coker). These hydrocarbon mixtures have a high content of organic, predominantly aromatic sulfur compounds. Because of the high olefin content, such hydrocarbon mixtures are ideal starting products for the catalytic conversion to secondary products, such as aldehydes and alcohols.
- the invention now surprisingly enables desulfurization of these mixtures with high selectivity, so that poisoning of the catalysts required for the subsequent reactions, such as e.g. Nickel catalysts in alcohol production is avoided.
- the selective desulfurization according to the invention is surprisingly achieved by using a morpholine-containing extracting agent which, at a pressure of about 1 atm and a temperature of about 25 ° C., has a relative depletion ratio of aromatic sulfur contamination to olefin of greater than about 10 , such as from about 10 to 30.
- the relative depletion ratio is a measure of the selectivity of the extracting agent used. The larger the aromatic sulfur compounds and the less olefin are converted into the extractant phase, the greater.
- the depletion ratio can be determined reliably for a particular extraction medium, for example by extraction of coker gasoline fractions, since their sulfur contamination consists predominantly of aromatic sulfur compounds.
- the relative depletion ratio is defined by the quotient from the percentage decrease in the sulfur content, determined by X-ray fluorescence spectroscopy and percentage decrease in olefin content, determined according to DIN 51774.
- the morpholin inconvenience Extra Needlessflüs- used in the invention is preferably selected stik linderivaten under morpholine and morpholine having a C ⁇ -C 7 alkyl radical may carry on the nitrogen atom 7 acyl or C ⁇ -C, which is optionally substituted by hydroxyl or amino or mercapto groups in the alkyl part carries a heteroatom, selected from 0, N and S, or mixtures thereof, optionally in combination with water or a liquid miscible with the morpholine compound contained.
- ketones of nitrogen heteroeycles such as, for example, pyrrolidone, imidazolidinones, pyrimidinones, piperidones, pyrazolidinones and piperazinones, certain acid amides, such as, for example, dimethylformamide, diethylformamide and dimethylacetamide, sulfur-containing solvents, such as, for example, tetrahydrothiophene dioxide and dimethyulodioxide, and such as ethylene glycol.
- nitrogen heteroeycles such as, for example, pyrrolidone, imidazolidinones, pyrimidinones, piperidones, pyrazolidinones and piperazinones
- certain acid amides such as, for example, dimethylformamide, diethylformamide and dimethylacetamide
- sulfur-containing solvents such as, for example, tetrahydrothiophene dioxide and dimethyulodioxide, and such as ethylene
- Suitable N-substituted morpholine compounds are in particular N-C ⁇ C 7 alkyl and N-C ⁇ -C 7 acylmorpholine compounds.
- Examples include N-methyl, N-ethyl, Nn-propyl, Nn-butyl, Nn-pentyl, Nn-hexyl, Nn-heptyl, N-formyl, N- Acetyl-, N-pr ⁇ pionyl-, N-butyryl, N-valeryl, N-hexanoyl or N-hetpanoylmorpholine.
- the amount of morpholine or N-substituted morpholine compounds can vary within a wide range.
- the weight ratio of morpholine or morpholine compound to hydrocarbon mixture is at least 1: 1. In particular, it is in the range from 2: 1 to 5: 1.
- the temperature and pressure at which the extraction is carried out are not critical. Generally one works at ambient temperature and normal pressure. However, higher temperatures and pressures can also be used.
- the liquid-liquid extraction is carried out in the usual way. Suitable apparatuses and procedures are known to the person skilled in the art and are described, for example, in Ullmann, 3rd edition, 1951, vol. 1, pp. 409-428. Examples are the use of sieve tray columns, extraction columns with mixing and resting zones, such as, for example, stirring columns, and extraction batteries, such as, for example, mixer-settler apparatus.
- the extraction is preferably carried out in countercurrent.
- the extractant is preferably recycled.
- the desulfurized products obtained have an essentially unchanged olefin content and a sulfur content reduced by at least 60%, in particular at least 80% and preferably at least 90%.
- the desulfurized product produced according to the invention can be either a single olefin, an olefin mixture or an olefin-rich hydrocarbon mixture and can be used as such for its intended use.
- the process according to the invention then only comprises process steps a) and b) and thus represents a pure desulfurization process.
- Process step c) can include, for example, the distillative workup of the olefin mixtures or olefin-rich hydrocarbon mixtures prepared.
- Process step c) can include, for example, the distillative workup of the olefin mixtures or olefin-rich hydrocarbon mixtures prepared.
- the desulfurized olefin mixtures obtained are preferred in catalytic processes, such as e.g. hydroformylation, processed into higher alcohols or aldehydes.
- the invention also relates to the use of the abovementioned morpholine-containing extractants for the desulfurization of olefins, olefin mixtures or olefin-rich hydrocarbon mixtures.
- the invention is illustrated by the following, non-limiting examples and comparative examples.
- a coker-gasoline fraction with a sulfur content (determined by X-ray fluorescence spectroscopy) of 6200 to 7100 ppm was used as the starting hydrocarbon mixture for the liquid-liquid extraction.
- the olefin content was determined in the form of the bromine number in accordance with DIN 51 774 Tl-3, Aug. 1975 and was 64 to 71 g / 100 g.
- the starting hydrocarbon mixture was treated according to the invention by liquid-liquid extraction in a one-stage stirring test using N-formylmorpholine (NFM) as the extractant.
- NPM N-formylmorpholine
- the starting hydrocarbon mixture was treated by liquid-liquid extraction in a one-stage stirring test using N-methyl-2-pyrrolidone (NMP) as extractant under the same conditions as in Example 1.
- NMP N-methyl-2-pyrrolidone
- the starting hydrocarbon mixture was treated according to the invention by liquid-liquid extraction in a six-stage mixer-settler system.
- N-formylmorpholine (NFM) N-formylmorpholine
- NFM / KW mixture 3.5 / 1 ((kg-h " 1 ) / (kg-h” 1 ))
- Example 1 Comparative Example 1 and Example 2 shows that when NFM is used as the extraction agent, it is possible to desulfurize olefin-rich hydrocarbon mixtures essentially without reducing the olefin content.
- NFM NFM
- the sulfur is broken down almost quantitatively.
- the starting hydrocarbon mixture was treated catalytically in accordance with the prior art under dehydrogenation conditions.
- the starting hydrocarbon mixture was treated catalytically in accordance with the prior art under hydrogenation conditions.
- Example 2 shows that, in contrast to the hydrogenation and dehydrogenation processes corresponding to the prior art, it is possible with the process according to the invention to selectively eliminate olefin-rich hydrocarbon mixtures without reducing the olefin content - fine.
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19623291A DE19623291A1 (de) | 1996-06-11 | 1996-06-11 | Verfahren zur Herstellung von schwefelarmen aliphatischen Verbindungen |
DE19623291 | 1996-06-11 | ||
PCT/EP1997/003008 WO1997047707A1 (de) | 1996-06-11 | 1997-06-10 | Verfahren zur herstellung von schwefelarmen aliphatischen verbindungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0904336A1 true EP0904336A1 (de) | 1999-03-31 |
EP0904336B1 EP0904336B1 (de) | 2001-08-29 |
Family
ID=7796647
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97929158A Expired - Lifetime EP0904336B1 (de) | 1996-06-11 | 1997-06-10 | Verfahren zur herstellung von schwefelarmen aliphatischen verbindungen |
Country Status (12)
Country | Link |
---|---|
US (1) | US6207043B1 (de) |
EP (1) | EP0904336B1 (de) |
JP (1) | JP2000511961A (de) |
KR (1) | KR20000016545A (de) |
AT (1) | ATE204899T1 (de) |
BR (1) | BR9709564A (de) |
CA (1) | CA2257912A1 (de) |
DE (2) | DE19623291A1 (de) |
ES (1) | ES2163781T3 (de) |
PT (1) | PT904336E (de) |
TW (1) | TW449581B (de) |
WO (1) | WO1997047707A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6802959B1 (en) * | 2000-06-23 | 2004-10-12 | Conocophillips Company | Separation of olefinic hydrocarbons from sulfur-containing hydrocarbons by use of a solvent |
US20060074598A1 (en) * | 2004-09-10 | 2006-04-06 | Emigholz Kenneth F | Application of abnormal event detection technology to hydrocracking units |
US7720641B2 (en) * | 2006-04-21 | 2010-05-18 | Exxonmobil Research And Engineering Company | Application of abnormal event detection technology to delayed coking unit |
US8862250B2 (en) | 2010-05-07 | 2014-10-14 | Exxonmobil Research And Engineering Company | Integrated expert system for identifying abnormal events in an industrial plant |
CN103945691B (zh) | 2011-11-24 | 2015-10-14 | 阿克佐诺贝尔化学国际公司 | 具有酰胺和酰基吗啉的农业配制剂 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1591367A (de) * | 1967-11-11 | 1970-04-27 | ||
US3639497A (en) * | 1968-08-22 | 1972-02-01 | Badger Co | Extraction and multi-stage fractional distillation with indirect heat exchange of liquid and vapor process and system for recovering aromatic products |
DE2014262C3 (de) * | 1970-03-25 | 1979-08-09 | Krupp-Koppers Gmbh, 4300 Essen | Verfahren zur Abtrennung von Aromaten aus Kohlenwasserstoffgemischen beliebigen Aromatengehaltes |
DE2040025A1 (de) * | 1970-08-12 | 1972-02-24 | Koppers Gmbh Heinrich | Verfahren zur Gewinnung von hochreinen Aromaten aus Kohlenwasserstoffgemischen,die neben diesen Aromaten einen beliebig hohen Gehalt an Nichtaromaten aufweisen |
US4132631A (en) * | 1974-05-17 | 1979-01-02 | Nametkin Nikolai S | Process for petroleum refining |
US4297206A (en) * | 1980-02-01 | 1981-10-27 | Suntech, Inc. | Solvent extraction of synfuel liquids |
DE3135319A1 (de) * | 1981-09-05 | 1983-03-24 | Krupp-Koppers Gmbh, 4300 Essen | "verfahren zur gewinnung reiner aromaten" |
JPH05202367A (ja) * | 1991-10-15 | 1993-08-10 | General Sekiyu Kk | 抽出による軽油の脱硫および脱硝方法 |
US5569788A (en) * | 1995-03-20 | 1996-10-29 | Uop | Process for removal of impurities from etherification feedstocks |
-
1996
- 1996-06-11 DE DE19623291A patent/DE19623291A1/de not_active Withdrawn
-
1997
- 1997-06-10 ES ES97929158T patent/ES2163781T3/es not_active Expired - Lifetime
- 1997-06-10 WO PCT/EP1997/003008 patent/WO1997047707A1/de not_active Application Discontinuation
- 1997-06-10 AT AT97929158T patent/ATE204899T1/de not_active IP Right Cessation
- 1997-06-10 KR KR1019980710133A patent/KR20000016545A/ko not_active Application Discontinuation
- 1997-06-10 BR BR9709564A patent/BR9709564A/pt not_active Application Discontinuation
- 1997-06-10 US US09/194,126 patent/US6207043B1/en not_active Expired - Fee Related
- 1997-06-10 PT PT97929158T patent/PT904336E/pt unknown
- 1997-06-10 CA CA002257912A patent/CA2257912A1/en not_active Abandoned
- 1997-06-10 JP JP10501193A patent/JP2000511961A/ja active Pending
- 1997-06-10 DE DE59704464T patent/DE59704464D1/de not_active Expired - Lifetime
- 1997-06-10 EP EP97929158A patent/EP0904336B1/de not_active Expired - Lifetime
- 1997-06-11 TW TW086108003A patent/TW449581B/zh not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO9747707A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP0904336B1 (de) | 2001-08-29 |
DE19623291A1 (de) | 1997-12-18 |
KR20000016545A (ko) | 2000-03-25 |
US6207043B1 (en) | 2001-03-27 |
TW449581B (en) | 2001-08-11 |
DE59704464D1 (de) | 2001-10-04 |
CA2257912A1 (en) | 1997-12-18 |
PT904336E (pt) | 2002-02-28 |
JP2000511961A (ja) | 2000-09-12 |
WO1997047707A1 (de) | 1997-12-18 |
BR9709564A (pt) | 1999-08-10 |
ES2163781T3 (es) | 2002-02-01 |
ATE204899T1 (de) | 2001-09-15 |
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