EP0904336B1 - Procede de preparation de composes aliphatiques a faible teneur en soufre - Google Patents

Procede de preparation de composes aliphatiques a faible teneur en soufre Download PDF

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Publication number
EP0904336B1
EP0904336B1 EP97929158A EP97929158A EP0904336B1 EP 0904336 B1 EP0904336 B1 EP 0904336B1 EP 97929158 A EP97929158 A EP 97929158A EP 97929158 A EP97929158 A EP 97929158A EP 0904336 B1 EP0904336 B1 EP 0904336B1
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EP
European Patent Office
Prior art keywords
olefin
extractant
sulfur
stage
rich
Prior art date
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Expired - Lifetime
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EP97929158A
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German (de)
English (en)
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EP0904336A1 (fr
Inventor
Maximilian Vicari
Ekkehard Schwab
Marc Walter
Siegmar Maassen
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BASF SE
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BASF SE
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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 production of low sulfur aliphatic compounds and in particular a method for Desulphurization of olefin-rich hydrocarbons by liquid-liquid extraction.
  • Olefin-rich hydrocarbon mixtures are available in large quantities available from cracker plants.
  • so-called Vacuum residue oils in thermal crackers (Visbreaker, Coker) converted to low-boiling fractions, which are characterized by are characterized by a high olefin content.
  • Visbreaker thermal crackers
  • low-boiling fractions which are characterized by are characterized by a high olefin content.
  • FCC fluid catalytic cracking
  • hydrocracking hydrocracking
  • Another example of the large-scale use of this Hydroformylation is an olefin-rich hydrocarbon mixture for the production of higher aldehydes and / or alcohols 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. for the production of plasticizers used.
  • the high sulfur content of these mixtures is a problem, since the sulfur compounds contained are often used as catalyst poisons Act. This applies in particular to thermal Cracking heavy residual oil-rich olefin Hydrocarbon mixtures that have an undesirably high sulfur content may have, the sulfur impurities in essentially as aromatic compounds, such as in particular thiophene, available.
  • the desulfurization of hydrocarbon mixtures is carried out after State of the art catalytically predominantly under hydrogenation / dehydrogenation conditions carried out, e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., 1991, vol. A18, pp. 65-67.
  • the catalytic hydrogenation the so-called Hydrotreating, the sulfur compounds contained in Converted hydrogen sulfide and then with a suitable Washed out solvent.
  • the catalysts used however, also cause the partial hydrogenation of the Olefins, which with regard to further processing, e.g. by Hydroformylation is disadvantageous.
  • EP-A-653 477 desulfurization of light oils by liquid-liquid extraction with nitrogen-containing heterocycles or acid amides, preferably N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone be used.
  • nitrogen-containing heterocycles or acid amides preferably N-methylpyrrolidone and 1,3-dimethyl-2-imidazolidinone be used.
  • the big disadvantage of this The process consists in the low selectivity of the used Extracting agent compared to the starting hydrocarbons, so that also in this process the content of desired olefins is reduced.
  • DE-A-20 40 025 describes a process for the separation of high-purity aromatics from hydrocarbon mixtures by liquid-liquid extraction with downstream extractive distillation, where morpholine and / or N-substituted morpholines in combination be used with water as a solvent. This method finds practical application in the Krupp-Koppers morphylan process, who is also in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., 1995, vol. A3, pp. 491-496.
  • the DE-A-20 40 025 does not deal with the problem of selective Removal of sulfur contaminants from olefin-rich Starting products and the subsequent catalytic processing of desulfurized products.
  • the present invention is therefore based on the object a process for the preparation of low-sulfur aliphatic compounds from olefin-rich intermediate products without significant reduction to provide the olefin content.
  • olefins which are olefin-rich starting products are Olefin mixtures or olefin-rich hydrocarbon mixtures in Question with organic and especially aromatic sulfur compounds are contaminated.
  • Preferred source products are olefin-rich hydrocarbon mixtures, just like them e.g. in the petrochemical industry for thermal cracking processes (Visbreaker, Coker). These hydrocarbon mixtures have a high content of organic, mainly 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 desulphurization of these mixtures with high selectivity, so that poisoning for the subsequent reactions necessary catalysts, e.g. Nickel catalysts at the Alcohol production, is avoided.
  • the selective desulfurization surprisingly succeeds in that an extracting agent containing morpholine used that at a pressure of about 1 atm and a temperature of about 25 ° C a relative depletion ratio of aromatic Sulfur contamination to olefin greater than about 10, such as. from about 10 to 30.
  • the relative depletion ratio is a measure of the selectivity of the extractant used. It is the bigger, ever more aromatic sulfur compounds and the less olefin in the extractant phase are transferred.
  • the depletion ratio can be for a particular extractant reliable, for example by extracting coker gasoline fractions, be determined because of their sulfur contamination consists mainly of aromatic sulfur compounds.
  • the relative depletion ratio is defined by the quotient from percentage decrease in sulfur content, determined by X-ray fluorescence spectroscopy, and percentage decrease in Olefin content, determined according to DIN 51774.
  • the morpholine-containing extraction liquid used according to the invention is preferably selected from morpholine and morpholine derivatives which can carry a C 1 -C 7 -acyl or C 1 -C 7 -alkyl radical on the nitrogen atom, which is optionally substituted by hydroxylamino or mercapto groups or in the alkyl part carries a heteroatom selected from O, N and S, or mixtures thereof, optionally in combination with water or a liquid miscible with the morpholine compound contained.
  • ketones of nitrogen heterocycles such as, for example, pyrrolidones, 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, for example, ethylene and dimethyl sulfoxide, such as ethylene glycol and dimethyl sulfoxide.
  • nitrogen heterocycles such as, for example, pyrrolidones, 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, for example, ethylene and
  • Suitable N-substituted morpholine compounds are in particular NC 1 -C 7 alkyl and NC 1 -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-propionyl, N-butyryl, N-valeryl, N-hexanoyl or N-hetpanoylmorpholine.
  • the amount of morpholine or N-substituted morpholine compounds can vary in a wide range. Generally is the weight ratio of morpholine or morpholine compound to hydrocarbon mixture at least 1: 1. It is particular in the range from 2: 1 to 5: 1. Temperature and pressure at which the extraction is done are not critical. in the generally one works at ambient temperature and normal pressure. However, higher temperatures and pressures can also be used come.
  • the liquid-liquid extraction is carried out in the usual way. Suitable apparatus and procedures are known to the person skilled in the art known and e.g. described in Ullmann, 3rd ed., 1951, Vol. 1, pp. 409-428. Examples are the use of sieve tray columns, Extraction columns with mixing and rest areas, e.g. Stirring columns, and extraction batteries, e.g. Mixer-settler equipment. It is preferred to carry out the extraction in countercurrent. The extractant is preferably recycled.
  • the desulfurized products obtained have essentially one unchanged olefin content and at least 60%, in particular at least 80% and preferably at least 90% reduced Sulfur content.
  • the desulfurized product produced according to the invention can either a single olefin, a mixture of olefins or an olefin rich Be hydrocarbon mixture and as such its intended use be fed.
  • the method according to the invention comprises thus only process steps a) and b) and thus represents a pure desulfurization process.
  • Step c) can, for example, the distillative workup of the prepared olefin mixtures or olefin-rich hydrocarbon mixtures include.
  • Sulfur compounds are removed that act as catalyst poisons are known, e.g. Thiophenes, will be obtained desulfurized olefin mixtures, preferably in catalytic processes, such as. hydroformylation, to higher alcohols or Aldehydes processed.
  • the invention also relates to the use of the above morpholine-containing extracting agent for desulfurization of olefins, olefin mixtures or olefin-rich hydrocarbon mixtures.
  • the invention is illustrated by the following, not limiting Examples and comparative examples explained.
  • the starting hydrocarbon mixture was according to the invention liquid-liquid extraction in a one-step stirring test treated with N-formylmorpholine (NFM) as an extractant.
  • NPM N-formylmorpholine
  • the starting hydrocarbon mixture was by liquid-liquid extraction in a one-step stirring test using N-methyl-2-pyrrolidone (NMP) as an extractant among the same Conditions treated as in Example 1.
  • NMP N-methyl-2-pyrrolidone
  • the starting hydrocarbon mixture was according to the invention liquid-liquid extraction in a six-stage mixer-settler system treated.
  • Example 1 Comparative Example 1 and Example 2 shows that it is using NFM as an extractant is possible to use olefin-rich hydrocarbon mixtures in the desulfurize substantially without reducing the olefin content.
  • the starting hydrocarbon mixture was according to the state of the Technique catalytically treated under dehydrogenation conditions.
  • the starting hydrocarbon mixture was according to the state of the Technology catalyzed under hydrogenation conditions.
  • Example 2 shows that it is contrary to the method of the invention to the hydrogenation and dehydrogenation processes corresponding to the prior art is possible, olefin-rich hydrocarbon mixtures to desulfurize selectively without reducing the olefin content.

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  • 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)

Claims (11)

  1. Procédé de préparation de composés aliphatiques à faible teneur en soufre à partir de produits de départ riches en oléfines, contaminés par des composés organiques de soufre, dans lequel
    a) l'on soumet le produit de départ riche en oléfines et contenant du soufre à une extraction liquide-liquide en une ou plusieurs étapes, à l'aide d'un liquide d'extraction contenant de la morpholine,
    b) on sépare l'agent d'extraction ainsi que les composés soufrés qui y sont contenus, et éventuellement
    c) on retraite le produit aliphatique à faible teneur en soufre.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise un agent d'extraction contenant de la morpholine, qui présente, sous une pression d'environ 1 atmosphère et à une température d'environ 25°C, un taux d'appauvrissement relatif des impuretés soufrées aromatiques à l'oléfine supérieur à 8.
  3. Procédé selon l'une des revendications qui précèdent, caractérisé en ce que le liquide d'extraction contenant de la morpholine est choisi parmi la morpholine et des dérivés de morpholine qui peuvent porter sur l'atome d'azote un reste acyle en C1 à C7 ou alkyle en C1 à C7, qui est éventuellement substitué par des radicaux hydroxyle, amino ou mercapto ou porte dans la partie alkyle un hétéroatome choisi dans le groupe de O, N et S, ou leurs mélanges, éventuellement en combinaison avec de l'eau ou un liquide miscible avec le composé de morpholine présent.
  4. Procédé selon l'une des revendications qui précèdent, caractérisé en ce que l'agent d'extraction est une N-acylmorpholine en C1 à C7.
  5. Procédé selon l'une des revendications qui précèdent, caractérisé en ce que l'agent d'extraction est une N-formylmorpholine.
  6. Procédé selon l'une des revendications qui précèdent, caractérisé en ce que l'agent d'extraction et le produit de départ riche en oléfine et contenant du soufre sont présents en proportion pondérale d'environ 1:1 à environ 5:1 pendant l'étape d'extraction.
  7. Procédé selon l'une des revendications qui précèdent, caractérisé en ce que le produit de départ riche en oléfine et à désulfurer est un mélange d'oléfines qui apparaít lors du craquage thermique d'huiles résiduaires de raffinage.
  8. Procédé selon l'une des revendications qui précèdent, caractérisé en ce qu'à l'étape b), on obtient un produit désulfuré comprenant un mélange d'oléfines, lequel est soumis à une séparation plus poussée dans l'étape c).
  9. Procédé selon l'une des revendications qui précèdent, caractérisé en ce qu'à l'étape b) on obtient un produit désulfuré que l'on soumet dans l'étape c) à une post-réaction catalytique.
  10. Procédé selon la revendication 9, caractérisé en ce que la post-réaction catalytique est une hydroformylation d'oléfine avec réduction catalytique subséquente du produit de carbonylation en l'alcool correspondant.
  11. Utilisation d'un agent d'extraction contenant de la morpholine selon la définition de l'une des revendications 2 à 5 pour la désulfuration d'oléfines, de mélanges d'oléfines ou de mélanges d'hydrocarbures riches en oléfines.
EP97929158A 1996-06-11 1997-06-10 Procede de preparation de composes aliphatiques a faible teneur en soufre Expired - Lifetime EP0904336B1 (fr)

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 (fr) 1996-06-11 1997-06-10 Procede de preparation de composes aliphatiques a faible teneur en soufre

Publications (2)

Publication Number Publication Date
EP0904336A1 EP0904336A1 (fr) 1999-03-31
EP0904336B1 true EP0904336B1 (fr) 2001-08-29

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EP97929158A Expired - Lifetime EP0904336B1 (fr) 1996-06-11 1997-06-10 Procede de preparation de composes aliphatiques a faible teneur en soufre

Country Status (12)

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US (1) US6207043B1 (fr)
EP (1) EP0904336B1 (fr)
JP (1) JP2000511961A (fr)
KR (1) KR20000016545A (fr)
AT (1) ATE204899T1 (fr)
BR (1) BR9709564A (fr)
CA (1) CA2257912A1 (fr)
DE (2) DE19623291A1 (fr)
ES (1) ES2163781T3 (fr)
PT (1) PT904336E (fr)
TW (1) TW449581B (fr)
WO (1) WO1997047707A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1591367A (fr) * 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

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Publication number Publication date
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 (fr) 1997-12-18
PT904336E (pt) 2002-02-28
JP2000511961A (ja) 2000-09-12
WO1997047707A1 (fr) 1997-12-18
BR9709564A (pt) 1999-08-10
ES2163781T3 (es) 2002-02-01
ATE204899T1 (de) 2001-09-15
EP0904336A1 (fr) 1999-03-31

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