EP0991736A1 - Verfahren zur abtrennung benzothiophen-verbindungen aus einem kohlenwasserstoffgemisch kohlenwasserstoffgemisch - Google Patents

Verfahren zur abtrennung benzothiophen-verbindungen aus einem kohlenwasserstoffgemisch kohlenwasserstoffgemisch

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Publication number
EP0991736A1
EP0991736A1 EP98930834A EP98930834A EP0991736A1 EP 0991736 A1 EP0991736 A1 EP 0991736A1 EP 98930834 A EP98930834 A EP 98930834A EP 98930834 A EP98930834 A EP 98930834A EP 0991736 A1 EP0991736 A1 EP 0991736A1
Authority
EP
European Patent Office
Prior art keywords
mixture
complexing agent
reagent
accepting
complex
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
Application number
EP98930834A
Other languages
English (en)
French (fr)
Other versions
EP0991736B8 (de
EP0991736B1 (de
Inventor
Marc Lemaire
Michèle MONNET
Michel Vrinat
Valérie LAMURE
Emmanuelle Sanson
Alexandra Milenkovic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
IFP Energies Nouvelles IFPEN
TotalEnergies Marketing Services SA
Original Assignee
Elf Antar France
Centre National de la Recherche Scientifique CNRS
IFP Energies Nouvelles IFPEN
Total Raffinage Distribution SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Elf Antar France, Centre National de la Recherche Scientifique CNRS, IFP Energies Nouvelles IFPEN, Total Raffinage Distribution SA filed Critical Elf Antar France
Publication of EP0991736A1 publication Critical patent/EP0991736A1/de
Application granted granted Critical
Publication of EP0991736B1 publication Critical patent/EP0991736B1/de
Publication of EP0991736B8 publication Critical patent/EP0991736B8/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms

Definitions

  • the present invention relates to the separation of benzothiophenic compounds from a mixture of hydrocarbons containing them, for example from a fuel. like diesel.
  • a fuel like diesel.
  • the importance of such separation has increased in recent years following the introduction or planned application of various laws around the world aimed at lowering the rate of sulfur products in diesel.
  • benzothiophenic compounds is meant both benzothiophene and its counterparts, for example dibenzothiophene, and derivatives mono-, di-, or trisubstituted thereof, for example dial yl, trialkyl, alkenyl, and aryl
  • electro-attractor is meant any organic compound deficient or poor in electrons, and in particular substituted by groups themselves electro-attractors, for example the sulfo, nitro, halo, haloalkyl groups, for example trifluoromethyl, cyano, carbonyl, carboxyl, amido, carba ido or a combination thereof
  • diesel means for example a fuel for a diesel engine, kerosene, fuel oil, and other fuel oils having a boiling point generally between about 175 ° C to about 400 ° C.
  • the benzothiophenic compounds in particular the dialkyldibenzothiophenes, for example 4, 6-dimethyl-dibenzothiophene (DMDBT), are known to be among the most resistant to the usual catalytic processes deep hydrodesulfurization. Therefore, the present invention will be more particularly described and explained with respect to the separation of this molecule.
  • US Patent US-A-5,454,933 describes an approach for reducing the content or selective separation of dibenzothiophene (DBT), or its derivatives, in a diesel fuel supply, by adsorption of dibenzothiophene molecules on solid supports such as activated carbon, zeolites, silica-alumina, etc.
  • DBT dibenzothiophene
  • solid supports such as activated carbon, zeolites, silica-alumina, etc.
  • the selection made is based essentially on the form of the molecule to be eliminated, that is to say that only steric factors are taken into account for the application of this process.
  • This method has proved effective, but its practical and economic interest is limited by two characteristics of the materials used as adsorbents.
  • the present invention has posed the problem of separating at least partially, even completely, and this in an inexpensive manner, the benzothiophenic compounds as defined above, from a mixture of hydrocarbons containing them, for example diesel, by the application of another treatment route which is independent of the only steric factors mentioned above for the aforementioned American patent.
  • This problem has been surprisingly resolved by applying, not the principle of shape selectivity as described in the aforementioned patent, but by applying the principle of a donor-acceptor type interaction (or charge transfer), to effect the separation of benzothiophenic compounds.
  • an object of the present invention is a process for the separation of at least one benzothiophenic compound from a mixture of hydrocarbons containing it, the process being more particularly characterized in that said mixture is brought into contact, or a fraction obtained from the latter, with a reagent comprising an acceptor complexing agent ⁇ , to obtain a donor-acceptor complex between the acceptor complexing agent and said benzothiophenic compound, and in that said complex is separated from said mixture, or said fraction, to obtain a fraction depleted or purified of said benzothiophenic compound.
  • a process according to the present invention makes it possible to obtain a mixture of desulphurized hydrocarbons having a sulfur content of between 0 ppm and 2000 ppm, preferably between 0 ppm and 500 ppm.
  • a method according to the present invention makes it possible to reduce the load of benzothiophenic compounds, to a value between 0% and 75%, and preferably between 0% and 15%, relative to the initial weight of said compounds.
  • the process is carried out in a homogeneous phase, that is to say without the intervention of a solid phase for fixing or supporting the accepting complexing agent ⁇ .
  • the process is carried out in a heterogeneous phase, that is to say with the intervention of a solid phase as defined above.
  • the process for the separation of benzothiophenic compounds can also be carried out before or after a step of deep catalytic hydrodesulfurization, known per se.
  • a deep catalytic hydrodesulfurization step in which case the fraction depleted in benzothiophenic compound is subjected to a deep catalytic hydrodesulfurization.
  • the process according to the invention makes it possible in particular to eliminate the dibenzothiophene compounds, and thus makes it possible to carry out the deep catalytic hydrodesulfurization step under milder conditions of temperature and pressure, and thus to prolong the duration life of the catalyst.
  • the complex is separated from the mixture, by extraction with an organic solvent, for example chloroform.
  • organic solvent for example chloroform.
  • regenerate the reagent by separating the complex into benzothiophenic compounds and complexing agent.
  • the separation of the complex is done chemically, but can also be done by application of physicochemical means.
  • the reagent can be regenerated: - by reducing the complex separated from the mixture, to form a salt of the acceptor agent ⁇ ; - And by reoxidizing the salt to regenerate the acceptor complexing agent ⁇ .
  • the accepting complexing agent ⁇ comprises an electro-attracting compound, or poor in electrons.
  • This agent is called " ⁇ acceptor” because in general it has a ⁇ or ⁇ type electron system.
  • the accepting complexing agent ⁇ comprises an aromatic compound substituted by at least one electro-attracting group, and more preferably chosen from the group consisting of sulfo, nitro, fluoro, trifluoromethyl, cyano, carbonyl, carboxyl, a ido groups. , carbamido.
  • a preferred example of such an acceptor complexing agent ⁇ is chosen from a group consisting of the family of quinones, substituted or not, more preferably dichloro-dicyano-benzoquinone, anthraquinone, benzoquinone, or tetracyanoquinodimethane, or the family of fluorenones, substituted or not, more preferably tetranitro-fluorenone or dinitrofluorenone.
  • tetranitrofluorenone and tetracyanodiquinodimethane are even more preferred for constituting the acceptor complexing agent ⁇ , because of their capacities and their increased separation factors.
  • the reagent comprises a support on which is fixed the accepting complexing agent ⁇ , which is in divided form or not, and which is chosen from the group consisting of inorganic oxides, such than alumina and silica, activated carbon, ion exchange resins, and zeolites.
  • in divided form is meant that the support can in particular be in the form of beads, for example made of glass, or of granules.
  • the accepting complexing agent ⁇ can be supported and on the reagent by any suitable means, for example by adsorption, absorption, covalent bond.
  • the reagent consists essentially of the accepting complexing agent ⁇ , and is more preferably in this case a polymer of the latter.
  • polymer is understood to mean both homopolymers constituted solely from monomers of the accepting complexing agent ⁇ , as well as copolymers of the latter with other polymers.
  • the time for bringing the mixture of hydrocarbons into contact with the complexing agent can vary quite widely.
  • the contacting period can be between approximately 10 minutes and 150 hours, and preferably between 2.5 hours to 115 hours.
  • the contacting between the mixture of hydrocarbons comprising the benzothiophenic compounds and the reagent can be carried out continuously, methodically or fractionally, for example in a column.
  • the application rate of the mixture or of the fraction containing the benzothiophenic compounds to be separated can be between 0.5 ml / min to 50 ml / min per cm3 of column volume, and preferably between 0.5 ml / min to 10 ml / min per cm3 of column volume.
  • the contacting temperature can be between 10 ° C and 60 ° C, and preferably between 15 ° C and 30 ° C.
  • the separation process according to the present invention can be carried out batchwise, semi-continuously or continuously. Preferably, however, and in particular for reasons of economy, it is carried out continuously.
  • the mixture of hydrocarbons is brought into contact with stirring with the reagent.
  • the mixture of hydrocarbons is a gas oil, as defined above, and more preferably a fuel for a diesel engine.
  • - Figure 1 represents a visible UV spectrum of a donor-acceptor complex in solution, namely between dichlorodicyanobenzoquinone, as ⁇ accepting complexing agent, and 4, 6-dimethyl-dibenzothiophene, as benzothiophenic compound;
  • FIG. 1 shows a visible UV spectrum of another donor-acceptor complex in solution, namely between dichlorodicyanobenzoquinone, as a complexing acceptor agent ⁇ , and 1-methylnaphthalene;
  • - Figure 3 shows a graph showing the evolution of the concentration of 4, 6-dimethyl-dibenzothiophene in a solution consisting of it and heptane, as a function of the volume of eluent, when the process of the invention to such a solution;
  • FIG. 1 shows a visible UV spectrum of another donor-acceptor complex in solution, namely between dichlorodicyanobenzoquinone, as a complexing acceptor agent ⁇ , and 1-methylnaphthalene
  • - Figure 3 shows a graph showing the evolution of the concentration of 4, 6-dimethyl-dibenzothiophene in a solution consisting of it and heptane, as a function of the volume of eluent, when the process of the invention to such a solution
  • the a___ part corresponds to an FPD of a diesel fuel with a sulfur content of 360 ppm.
  • Part b_ ⁇ corresponds to an FPD of the same diesel after complexation-filtration with TNF (320 ppm residual).
  • the part ç ⁇ _ corresponds to an FID of the aromatic compounds trapped by TNF.
  • the dj_ part corresponds to an FPD of aromatic compounds trapped by TNF;
  • FIG. 5 shows the gas chromatography analyzes (FID and FDP) of a diesel containing 860 ppm of sulfur.
  • Part a ⁇ corresponds to an FID of a diesel fuel with a sulfur content of 860 ppm.
  • Part b. corresponds to an FPD of the same diesel.
  • the part ç ⁇ . corresponds to an FPD of diesel after complexation-filtration with TNF (720 ppm residual).
  • the part d ⁇ _ corresponds to an FID of the aromatic compounds trapped by TNF.
  • the part e _; _ corresponds to an FPD of the aromatic compounds trapped by TNF;
  • FIG. 6 represents the gas chromatography analyzes (FID and FDP) of a diesel containing
  • Part a ⁇ _ corresponds to an FID of a diesel fuel with a sulfur content of 11,300 ppm.
  • the part ⁇ . corresponds to an FPD of the same diesel.
  • Part c. corresponds to an FPD of diesel after complexation-filtration with TNF (9700 ppm residual).
  • the part d ⁇ _ corresponds to an FPD of the aromatic compounds trapped by TNF.
  • the part e ⁇ corresponds to the FID of the aromatic compounds trapped by TNF.
  • dichlorodicyanobenzoquinone was chosen as the ⁇ accepting complexing agent.
  • This commercial compound is known to easily form donor-acceptor complexes (CDA) with electron-rich aromatics.
  • CDA donor-acceptor complexes
  • the DDQ / DMDBT complex was extracted with chloroform, then this solution washed with an aqueous solution of sodium bisulfite (10%) and sodium carbonate.
  • This solution has the effect of reducing 3a DDQ to DDHQ (hydroquinone), which makes it possible to extract this hydroquinone in the form of phenate.
  • DDHQ was recovered by neutralization of the aqueous solution, and DMDBT by evaporation of the chloroform solution. In in both cases, the regeneration yields are greater than 90%.
  • Example 2 shows that it is possible to completely separate the DMDBT contained in an alkane solution, by simple filtration of the alkane solution on silica supporting DDQ. Almost all of the DDQ is used to form a 1/1 complex with DMDBT, which is thus removed from the hydrocarbon mixture.
  • the complex can be separated, for example, by reducing DDQ to DDHQ.
  • the two components can be recovered, separated, and DDHQ can be recycled to DDQ by oxidation according to known methods.
  • This example describes the separation of DMDBT from an alkane solution also containing a product "mimicking" the aromatic derivatives contained in diesel.
  • 100 ml of a 0.04% sulfur solution in heptane were prepared, containing equimolar amounts of DMDBT (196 mg), MN (131 mg) and dodecane (157 mg) as an internal standard.
  • An equimolar amount of reagent was added and the mixture stirred at 20 ° C.
  • a gas oil conventionally desulfurized by heterogeneous catalysis was diluted in an amount of 15 ml in 200 ml of heptane.
  • the solution obtained had a sulfur content (measured by X-ray fluorescence) of 214 ppm, about half of which consisted of DMDBT and other benzothiophenic compounds, and the other half of non aromatic or weakly aromatic sulfur compounds.
  • 328 mg of tetranitrofluorenone was added, which corresponded to an equivalent of tetranitrofluorenone relative to the amount of DMDBT and other benzothiophenic compounds contained in this solution.
  • Samples of this suspension were taken, then after filtration the sulfur content was determined by X-ray fluorescence. The results are given below in Table 3.
  • the sulfur aromatics represent 25% by weight of the total mass of the retained compounds.
  • Analysis by mass spectrometry indicates that the structure of these ar Oomatic which compete for complexation with TNF are fluorene, 1 • anthracene, phenanthrene and the corresponding alkylated derivatives.
  • the molecular mass of the trapped aromatic compounds varies between 166 and 220 mol / g.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP98930834A 1997-06-12 1998-06-11 Verfahren zur abtrennung benzothiophen-verbindungen aus einem kohlenwasserstoffgemisch kohlenwasserstoffgemisch Expired - Lifetime EP0991736B8 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9707538 1997-06-12
FR9707538A FR2764610B1 (fr) 1997-06-12 1997-06-12 Procede de separation de composes benzothiopheniques d'un melange d'hydrocarbures les contenant, et melange d'hydrocarbures obtenu par ce procede
PCT/FR1998/001218 WO1998056875A1 (fr) 1997-06-12 1998-06-11 Procede de separation de composes benzothiopheniques d'un melange d'hydrocarbures les contenant, et melange d'hydrocarbures obtenu par ce procede

Publications (3)

Publication Number Publication Date
EP0991736A1 true EP0991736A1 (de) 2000-04-12
EP0991736B1 EP0991736B1 (de) 2003-01-29
EP0991736B8 EP0991736B8 (de) 2003-05-07

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EP98930834A Expired - Lifetime EP0991736B8 (de) 1997-06-12 1998-06-11 Verfahren zur abtrennung benzothiophen-verbindungen aus einem kohlenwasserstoffgemisch kohlenwasserstoffgemisch

Country Status (9)

Country Link
US (1) US6441264B1 (de)
EP (1) EP0991736B8 (de)
JP (1) JP4040696B2 (de)
AT (1) ATE231906T1 (de)
CA (1) CA2293550C (de)
DE (1) DE69811075T2 (de)
ES (1) ES2192327T3 (de)
FR (1) FR2764610B1 (de)
WO (1) WO1998056875A1 (de)

Cited By (1)

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US6441264B1 (en) * 1997-06-12 2002-08-27 Total Raffinage Distribution S.A. Method for separating benzothiophene compounds from hydrocarbon mixture containing them, and hydrocarbon mixture obtained by said method

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FR2814172A1 (fr) * 2000-09-19 2002-03-22 Total Raffinage Distribution Procede de deazotation de coupes petrolieres par formation de complexes de transfert de charge
WO2003020850A2 (en) * 2001-09-04 2003-03-13 The Regents Of The University Of Michigan Selective sorbents for purification of hydrocarbons
US7094333B2 (en) 2001-09-04 2006-08-22 The Regents Of The University Of Michigan Selective sorbents for purification of hydrocarbons
US7053256B2 (en) 2001-09-04 2006-05-30 The Regents Of The University Of Michigan Selective sorbents for purification of hydrocarbons
US7029574B2 (en) 2002-09-04 2006-04-18 The Regents Of The University Of Michigan Selective sorbents for purification of hydrocarbons
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Also Published As

Publication number Publication date
ATE231906T1 (de) 2003-02-15
CA2293550A1 (fr) 1998-12-17
WO1998056875A1 (fr) 1998-12-17
ES2192327T3 (es) 2003-10-01
FR2764610A1 (fr) 1998-12-18
FR2764610B1 (fr) 1999-09-17
DE69811075D1 (de) 2003-03-06
US6441264B1 (en) 2002-08-27
CA2293550C (fr) 2009-10-13
JP4040696B2 (ja) 2008-01-30
DE69811075T2 (de) 2004-01-29
EP0991736B8 (de) 2003-05-07
EP0991736B1 (de) 2003-01-29
JP2002511895A (ja) 2002-04-16

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