EP1370630B1 - Verfahren zur herstellung von entschwefeltem benzin aus einem crackbenzin enthaltendem benzin - Google Patents

Verfahren zur herstellung von entschwefeltem benzin aus einem crackbenzin enthaltendem benzin Download PDF

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Publication number
EP1370630B1
EP1370630B1 EP02701343A EP02701343A EP1370630B1 EP 1370630 B1 EP1370630 B1 EP 1370630B1 EP 02701343 A EP02701343 A EP 02701343A EP 02701343 A EP02701343 A EP 02701343A EP 1370630 B1 EP1370630 B1 EP 1370630B1
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EP
European Patent Office
Prior art keywords
gasoline
stage
sulfur
compounds
process according
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EP02701343A
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English (en)
French (fr)
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EP1370630A1 (de
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Quentin Debuisschert
Jean-Luc Nocca
Denis Uzio
Florent Picard
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including acid treatment as the refining step in the absence of hydrogen
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a diagram for the desulfurization of conversion gasolines and particular gasoline from catalytic cracking, catalytic cracking in a fluid bed (FCC), a coking process (coking in the language of Shakespeare), a visbreaking process (visbreaking in the language of Shakespeare), from a pyrolysis process.
  • This process can also treat straight distillation essences mixed with at least one of the species mentioned above.
  • the process of the present invention achieves high desulfurization rates by limiting the octane loss due to the saturation of olefins observed during hydrodesulfurization reactions.
  • the invention relates to a low sulfur gasoline production process comprising a hydrogenation, a step of transformation of sulfur compounds, a step alkylation of the sulfur compounds not transformed in the previous step, a fractionation into a light fraction and into at least a heavy fraction and optionally one or more intermediate fractions, and hydrodesulfurization a heavy fraction and / or an intermediate fraction.
  • This process makes it possible to enhance a petrol cut possibly also comprising hydrocarbons with two three or four carbon atoms, reducing the total sulfur content of said cuts at very low levels compatible with current or future specifications.
  • This desulfurization is moreover carried out without appreciable reduction in the yield of gasoline and minimizing the decrease in octane number
  • the hydrodesulfurization of the charge sent to catalytic cracking leads to gasolines typically containing 100 ppm of sulfur.
  • the hydrotreating units of catalytic cracking charges however operate under severe conditions of temperature and pressure, which implies a significant consumption of hydrogen and a high investment.
  • the entire feed must be desulphurized, which entails the processing of very large load volumes.
  • the species to be treated generally have an initial point above 70 ° C, and again it is necessary to treat light petrol separately (fraction corresponding to the boiling point compounds between the C5 hydrocarbons with 5 carbon atoms and 70 ° C) for example by means of a softening.
  • the process for desulfurization of a cut naphtha comprising an olefinic essence comprises a step of weighing down the sulfur-containing compounds by alkylation followed by a step of fractionation of the petrol into two cuts, the light petrol being depleted in sulfur.
  • the process for producing gasoline desulfurized includes a separation of the gasoline into a light gasoline and a heavy petrol.
  • the light gasoline is sent to a weighting reactor sulfur compounds by alkylation.
  • Heavy gasoline with reactive olefins added is sent to a weighting reactor for sulfur-containing compounds by alkylation.
  • Heavy and light petrol are mixed and then sent to a distillation which makes it possible to recover, at the head, a gasoline depleted in sulfur.
  • the essence to be desulfurized is treated in a process comprising a step a1) of hydrogenation selective for diolefinic compounds, optionally at least one step a2) aimed at increase the molecular weight of light sulfur products in gasoline initial to be desulfurized, at least one step b) of separation of the gasoline obtained at the exit from step a1) and / or a2) in two separate sections including a light section practically free of sulfur and containing the lightest olefins of the original gasoline and the other heavy cut containing the major part of the compounds sulfur present in the initial gasoline and / or sulfur compounds from the step a2), at least one step c) of processing the heavy cut making it possible to decompose or to hydrogenate the unsaturated sulfur compounds present in this section and in particular cyclic or even aromatic sulfur compounds under conditions limited hydrogenation of olefins present in this cut and at least one step d) gasoline from step c) allowing the sulfur compounds to
  • the present invention makes it possible to produce a desulfurized gasoline while limiting the loss of octane by desulfurization.
  • the scheme of the present invention differs from classic desulphurization schemes which are based on gasoline desulphurization total. In some cases these schemes provide for a separation of the essence into minus two cups: one containing light petrol and one containing heavy petrol i.e. an essence with a final boiling point higher than that of light petrol.
  • Heavy petrol is desulphurized for example by hydrogen treatment or by absorption of sulfur compounds. Schemes including treatment with hydrogen lead to significant saturation of olefins, and therefore, to a high loss of octane
  • Light gasoline can be desulphurized under mild conditions by hydrodesulfurization, washing with a basic solution or adsorption on solid, or softened by an oxidation process such as for example the Merox® process of the Universal Oil Product (UOP) which can be extractable.
  • UOP Universal Oil Product
  • the present invention relates to a process for producing essences with a low sulfur content, which makes it possible to recover the whole of a petrol cut containing sulfur, preferably a petrol cut of catalytic cracking or of coking (coking according to English terminology). , or pyrolysis, or visbreaking (visbreaking according to English terminology), possibly mixed with a direct distillation gasoline, and to reduce the sulfur contents in said gasoline cut to very low levels, without appreciable reduction of the gasoline yield while minimizing the decrease in the octane number due to the hydrogenation of olefins.
  • the feedstock of the process according to the invention may also optionally comprise, in addition to a gasoline cut, a C4 cut - comprising hydrocarbons with two, three or four carbon atoms.
  • stages b) and c) the term “mainly” means that during stage concerned we convert at least 50% of the sulfur compounds which are in the form compounds of the indicated type.
  • step e) is a step of processing at least one of the more fractions heavy separated in step d) on a catalyst making it possible to decompose at least partially sulfur compounds performed under conditions where hydrogenation olefins on this catalyst is limited.
  • polyunsaturated compounds covers the diolefinic hydrocarbon compounds, that is to say containing two double bonds, hydrocarbon compounds containing more than two double bonds but not aromatics and hydrocarbon compounds containing at least one triple bond present in the original essence. Most often the initial essence contains as polyunsaturated compounds essentially diolefinic compounds.
  • the resulting low sulfur gasoline is a gasoline containing less than 150 ppm by weight, often less than 100 ppm and the most often less than 80 ppm by weight of sulfur.
  • Stage b) of transformation of light sulfur compounds usually concerns essentially the transformation of saturated sulfur compounds with a point boiling point below 120 ° C.
  • This step can possibly be carried out simultaneously with step a) on all or part of the initial essence, in the same reactor or in a different reactor. It can also be done in a way separated on all or part of the hydrogenated gasoline in step a).
  • the thiophene and thiophene compounds are little transformed. So this step a) hydrogenation of unsaturated compounds and step b) to increase the weight molecular of light saturated sulfur products initially present in gasoline introduced in step a) are optionally carried out simultaneously in an area single reaction vessel containing one or more beds of a single catalyst.
  • Step c) is a step of alkylation of the sulfur compounds usually belonging to the group comprising thiophene, thiophenic compounds and mercaptans present in the product from step b).
  • Any mercaptans present are either those formed in step a) and / or b), or those present in the initial essence and not converted in step a) and / or b).
  • This step can be carried out in one or more reactors in series or in parallel.
  • the first reactor can act as a guard bed intended to retain the basic compounds possibly present in the starting essence.
  • These basic compounds can also be at least partially removed before the introduction of gasoline in step a) of hydrogenation of the polyunsaturated compounds.
  • This elimination is preferably carried out by treatment with a solution acidic aqueous.
  • the operating conditions can be adjusted so that a part of the starting gasoline olefins is converted into long branched olefins by addition reactions between olefins. Likewise, the operating conditions can be adjusted so that some of the aromatics are weighed down by alkylation with olefins.
  • Step d) of fractionation of the gasoline obtained at the end of step c) comprises the fractionation into at least two fractions (or sections), a slight fraction of preferably practically sulfur-free and containing the lightest olefins initial gasoline (light gasoline or light fraction), and a heavy fraction in which preferably most of the sulfur compounds initially present in the initial essence and / or formed during steps a), b) and c) is concentrated (petrol or heavy fraction). It is also possible to separate the gasoline obtained at step c) in addition to two fractions, that is to say for example a light fraction, minus an intermediate fraction and a heavy fraction. In this case, the fraction (s) intermediates can be sent to a catalytic reforming unit usually after a thorough desulfurization step.
  • Step e) of processing heavy gasoline and / or an intermediate fraction containing a proportion of sulfur compounds very much higher than that contained in the light fraction is a step of processing this fraction on a catalyst making it possible to at least partially decompose the sulfur-containing compounds, in particular cyclic or even aromatic sulfur compounds such as for example thiophenic compounds, by placing themselves in conditions where the hydrogenation of olefins on this catalyst is limited.
  • Step f) is a step for treating the product obtained in step e), without elimination H2S formed during this step e), on a catalyst and under conditions allowing the compounds to be decomposed or at least partially hydrogenated unprocessed sulfur during step e), and preferably to decompose or to hydrogenate unsaturated sulfur compounds and saturated sulfur compounds linear and / or cyclic non-transformed during step e) and in particular the thiophenic compounds and mercaptans, with limited hydrogenation of olefins.
  • Steps e) and f) are most often carried out in at least two zones successive and distinct reactions.
  • the catalytic treatments carried out during steps e) and f) can be carried out either in a single reactor containing the two catalysts, or in at least two different reactors. When the treatment is produced using two reactors, the latter two are placed in series, the second reactor preferably treating fully the effluent leaving the first reactor, preferably without separation of the liquid and the gas between the first and the second reactor.
  • step e it is not necessary to remove the H2S formed during step e) before send the effluent from this step e) to the inlet of the reactor (s) hydrodesulfurization of step f).
  • One of the advantages of the method according to the invention therefore lies in the fact that it is not necessary to adjust the H2S content between step e) and step f).
  • step g) is preferably carried out after step f), this step consists in mixing the light gasoline separated in step d) and at least part of heavy gasoline from step f) to form the overall desulfurized gasoline sought.
  • all of the desulfurized heavy gasoline resulting from step f) is mixed with the light gasoline from step d), without separation of the liquid and the gas contained in heavy petrol after desulfurization, possibly a simple stripping by at least one inert gas can be carried out to remove H2S from heavy petrol largely desulfurized, that is to say usually containing less than 50% by weight and often less than 20% by weight of residual sulfur compounds relative to the content into sulfur-containing compounds of the heavy petrol leaving step d).
  • step g the recovery of light petrol and heavy petrol desulfurization is carried out separately. It is then unnecessary to carry out step g).
  • the operating conditions can be adjusted in order to favor the alkylation reactions of olefins on olefins and aromatics, which leads to, in particular, a drop in gasoline vapor pressure.
  • At least a fraction from the fractionation step, preferably the heavy fraction or a fraction intermediate, can be treated in a transformation step of these compounds sulfur in H2S (hydrogen sulfide) with or without minimization of the saturation of olefins.
  • the heavy petrol or at least one intermediate fraction is treated in a hydrodesulfurization section, preferably in the presence of a hydrodesulfurization catalyst or optionally an absorbent.
  • a hydrodesulfurization catalyst or optionally an absorbent Preferably, no desulfurization of the light fraction is necessary in the process according to the invention, since most of the sulfur compounds initially present in the essence is found in the heavy fraction and possibly in the one or more intermediate fractions of step d) of fractionation which is carried out after the hydrogenation steps, transformation of sulfur compounds (step b), transformation of thiophene compounds and possibly mercaptans, in particular residual mercaptans which are not converted and / or formed in stages a) and b) (step c) by alkylation of at least part of the unconverted sulfur compounds in step b) (step c).
  • This sequence allows to obtain ultimately a desulfurized gasoline without reduction important olefin content or octane number and even for rates high desulphurisation, without the need to treat light petrol with by means of a hydrodesulfurization or softening section, or using processes for restoring the octane number of gasoline. Thanks to this process, significant desulfurization rates are reached, under operating conditions reasonable prices set out below.
  • the sulfur species contained in the feeds treated by the process of the invention can be mercaptans, sulfides, disulfides and / or compounds heterocyclic, such as for example thiophene or alkyl thiophenes, or heavier compounds, such as benzothiophene and / or dibenzothiophene.
  • the petrol fractionation point is preferably limited in order to avoid the presence of sulfur compounds in light gasoline.
  • the process according to the invention is advantageous by carrying out a stage of transformation of the thiophene and more generally thiophenic compounds, for example by means of a alkylation section upstream of the fractionation section or integrated into said section section according to a mode detailed in the following description.
  • step b) To recover a larger fraction of light gasoline while limiting the sulfur content of this fraction without further treatment it is preferably proposed to treat the load in step b) under conditions and on catalysts which transform the light sulfur compounds present in the form of mercaptans and sulphides most often having from 2 to 6 atoms of carbon in their molecule into higher boiling sulfur compounds get finding after separation, possibly in at least a fraction intermediate or heavy gasoline. These intermediate and / or heavy cuts can then be desulfurized.
  • This desulfurization is carried out under conditions defined and by means of a hydrodesulfurization catalyst optionally allowing limit the saturation of olefins or according to a preferred embodiment of the invention, at by means of a chain of catalysts making it possible to achieve levels of high desulfurization while limiting the rate of hydrogenation of olefins and therefore the octane loss.
  • the sulfur content of gasoline cuts produced by catalytic cracking and especially catalytic cracking in a fluid bed depends on the sulfur content of the load processed at the FCC, of the presence or not of a pre-treatment of the load of the FCC, as well as the end point of the cut.
  • the sulfur contents of all of a petrol cut, especially those from the FCC are greater than 150 ppm by weight and most of the time greater than 500 ppm by weight.
  • the contents sulfur are often greater than 1000 ppm by weight, they can even in in some cases reaching values of the order of 4000 to 5000 ppm by weight.
  • the process according to the invention applies in particular when desulfurization rates high gasoline is required, i.e. when the desulfurized gasoline must contain at most 10% of the sulfur of the initial gasoline and possibly at most 5% or even at most 2% of the sulfur of the initial gasoline which corresponds to desulfurization rates greater than 90% or even greater than 95 or 98%.
  • the gasoline at the bottom of the column and / or that contained in an intermediate fraction resulting from stage d) is desulphurized in stage e) on a catalyst and under conditions such as saturation of the olefins is partial in order to limit the loss of octane.
  • the column bottom gasoline and / or that contained in an intermediate fraction resulting from step d) is desulphurized by hydrotreatment according to a process which limits the saturation of olefins.
  • the implementation of a selective hydrodesulfurization makes it possible to limit the saturation of the olefins and thus limit the loss of octane in the gasoline.
  • the heavy gasoline and / or at least one intermediate gasoline thus desulphurized can then be optionally stripped (that is to say that a gas stream, preferably containing one or more inert gases is passed through this gasoline), in order to eliminate the H 2 S possibly produced during the desulfurization.
  • reaction section in place of the fractionation column, i.e. to place at least one of said reaction sections in the fractionation column (reaction section internal to the column), preferably in an area where the reagent concentration is maximum.
  • reaction section should preferably be placed in an area exhibiting the maximum concentration of these compounds.
  • the reaction section internal to the column is chosen from the group formed by the reaction sections following: transformation of sulfur compounds such as thiophene, compounds thiophenics and optionally mercaptans by alkylation (step c)), desulfurization intermediate fractions and / or desulfurization of the heavy fraction ((step e) and / or step f).
  • the reaction section is arranged in the middle of the fractionation column, so as to treat the compounds with intermediate boiling points, i.e. compounds which can constitute an intermediate cut and which are recovered alone or with the fraction heavy at the bottom of the column, at the end of the fractionation step.
  • the heavy fraction is then treated in an external reactor associated or not with the fractionation column.
  • Another variant of the process according to the invention consists both in using a column reactive comprising at least one reaction section and an external coupled reactor or not to the said column.
  • Such variants are for example described in the patent application WO00 / 15319.
  • the variants described above are only illustrations of the variants possible of the method according to the invention.
  • the process according to the invention can indeed be implemented by combining reaction sections (steps a), b), c), e) or f)) either associated with the fractionation column from step d), or internal (s) with said column, is external (s) and not coupled (s) to said column in the sense that the effluent from said or of said reaction section (s) is not recycled to the fractionation column.
  • One of the advantages of the method according to the invention lies in the fact that it is not the most often no need to desulfurize the light fraction of gasoline from splitting.
  • the transformation of sulfur and / or thiophene compounds makes it possible to considerably reduce the content of compounds with a light cut and possibly at least one intermediate cut, and generally recover the essential of these compounds in the heavy fraction, and possibly in the intermediate fraction (s).
  • Steps b) and c) are distinguished, among other things, by the fact that the conversion of thiophenic compounds is generally less than 60% by weight, or even less than 40% by weight in step b), while the conversion is more often than 80% by weight, preferably greater than 90% by weight, very preferably greater than 95% by weight in step c).
  • Step b) essentially performs the weighting of light mercaptans and sulphides while step c) achieves essentially the weighting of thiophenic compounds.
  • the sulfur compound content of the light fraction as well usually obtained is less than 100 ppm, preferably less than 50 ppm, of more preferably less than 20 ppm and very preferably less than 10 ppm.
  • Another advantage is that the residual content of sulfur compounds in the gasoline desulfurized by means of the process according to the invention is particularly low, and that the octane number of the gasoline is maintained at a high level.
  • step a hydrogenation of diolefins
  • the hydrogenation of dienes is a step which makes it possible to eliminate, before hydrodesulfurization, almost all of the dienes present in the gasoline cut containing sulfur to be treated. It preferably takes place in the first stage (step a) of the process according to the invention, generally in the presence of a catalyst comprising at least one group VIII metal, preferably chosen from the group consisting of platinum, palladium and nickel, and a support.
  • a catalyst comprising at least one group VIII metal, preferably chosen from the group consisting of platinum, palladium and nickel, and a support.
  • a catalyst based on nickel or on palladium deposited on an inert support such as for example alumina, silica or a support containing at least 50% alumina.
  • the pressure used is sufficient to maintain more than 60%, preferably 80%, and more preferably 95% by weight of the gasoline to be treated in the liquid phase in the reactor; it is most generally between approximately 0.4 and approximately 5 MPa and preferably greater than 1 MPa, more preferably between 1 and 4 MPa.
  • the hourly space velocity of the liquid to be treated is between approximately 1 and approximately 20 h -1 (volume of charge per volume of catalyst and per hour), preferably between 2 and 10 h -1 , very preferably between 3 and 8 h -1 .
  • the temperature is most generally between about 50 and about 250 ° C, and preferably between 80 and 220 ° C, and more preferably between 100 and 200 ° C, to ensure sufficient conversion of the diolefins. Very preferably it is limited to 180 ° C.
  • the hydrogen to charge ratio expressed in liters is generally between 1 and 50 liters per liter, preferably between 2 and 30 liters, more preferably between 3 and 25 liters per liter.
  • the choice of operating conditions is particularly important. We will operate the most generally under pressure and in the presence of a small amount of hydrogen compared to the stoichiometric value necessary to hydrogenate the diolefins.
  • the hydrogen and the charge to be treated are injected in ascending or descending currents in a reactor preferably comprising a fixed bed of catalyst.
  • Another metal can be combined with the main metal to form a catalyst bimetallic, such as for example molybdenum or tungsten.
  • a catalyst bimetallic such as for example molybdenum or tungsten.
  • Catalytic cracked gasoline can contain up to a few percent (%) of weight of diolefins.
  • the diolefin content is generally reduced to less than 3000 ppm, or even less than 2500 ppm and more preferably less than 1500 ppm. In some cases, it can be obtained less than 500 ppm.
  • the dienes content after selective hydrogenation can even be reduced to less than 250 ppm.
  • the hydrogenation step dienes takes place in a catalytic hydrogenation reactor which includes a catalytic reaction zone crossed by the entire charge and the quantity of hydrogen necessary to carry out the desired reactions.
  • This stage consists in transforming the light sulfur compounds. That is to say the compounds which at the end of step a) of hydrogenation of the dienes would be found (after fractionation in step d)) in light petrol, into sulfur compounds more heavy driven in heavy gasoline.
  • light sulfur compounds are chosen from the families of mercaptans of 1 to 6 carbon atoms and sulfides of 2 to 6 carbon atoms.
  • This transformation is preferably carried out on a catalyst comprising at least one element from group VIII of the classification periodic of the elements (Handbook of Chemistry and Physics 45 th edition 1964-1965) (groups 8, 9 and 10 of the new periodic classification).
  • the choice of catalyst is carried out in particular to promote the reaction between light mercaptans and olefins, which leads to heavier sulfides or mercaptans.
  • Other compounds such that COS or CS2 can optionally also be converted.
  • This step can possibly be carried out at the same time as step a).
  • it can be particularly advantageous to operate, during the hydrogenation of diolefins, under conditions such that at least part of the compounds in the form of mercaptan is transformed.
  • a certain reduction in the content of mercaptans is obtained.
  • Another possibility is to use an identical or different nickel-based catalyst of the catalyst of step a), such as for example the catalyst recommended in the process of patent US-A-3,691,066, which makes it possible to transform the mercaptans (butylmercaptan) into heavier sulfur compounds (sulfides).
  • Another possibility for carrying out this step consists in hydrogenating at least part of the thiophene to thiophane, the boiling point of which is higher than that of thiophene (boiling point 121 ° C).
  • This step can be carried out on a catalyst based on nickel, platinum or palladium.
  • the temperatures are generally between 100 and 300 ° C and preferably between 150 and 250 ° C.
  • the H2 / feed ratio is adjusted between 1 and 20 liters per liter, preferably between 3 and 15 liters per liter, to further promote, if possible, the desired hydrogenation of the thiophenic compounds and minimize the hydrogenation of the olefins present in the feed.
  • the space velocity is generally between 1 and 10 h -1 , preferably between 2 and 4 h -1 and the pressure between 0.5 and 5 MPa, preferably between 1 and 3 MPa.
  • This step consists in preferably passing all of the fraction from step b) on a catalyst having an acid function which makes it possible to carry out the addition of sulfur-containing compounds in the form of mercaptans to the olefins and the alkylation reaction of thiophene and thiophene derivatives by these same olefins.
  • the operating conditions are adjusted to carry out the transformation desired with conversion rates of thiophene and / or thiophene compounds, greater than 80% by weight, preferably greater than 90% by weight, very preferred greater than 95% by weight.
  • Other compounds such as COS or CS2 can possibly also be converted.
  • part of the olefins of the starting gasoline can be converted into long branched olefins, by addition reactions (oligomerization) between olefins, and part of the aromatics made heavier by alkylation with the olefins.
  • oligomerization addition reactions between olefins
  • the essence can be added with a compound known to inhibit the oligomerizing activity of acid catalysts such as alcohols, ethers or water.
  • thiophenic compounds with a boiling point of approximately 60 ° C to around 160 ° C will react with conversion rates higher than 80% weight, preferably greater than 90% by weight, with olefins to form alkyls thiophenes whose boiling point is much higher than that of starting thiophenic compounds.
  • benzene can also be removed by alkylation with olefins. These higher molecular weight compounds are mostly characterized by higher boiling temperatures than they had before alkylation. Thus the theoretical boiling temperature of thiophene which is 84 ° C is shifted to 150 ° C for thiophene alkyls. This reaction is coupled to addition reactions of olefins which therefore most often lead to an increase in the petrol, in particular in the case where the petrol fraction and / or the starting petrol are light, and to a decrease in its vapor pressure.
  • This alkylation step is carried out in the presence of an acid catalyst.
  • This catalyst can be either a resin, a zeolite, a clay, any functionalized silica or any silico-aluminate having an acidity, or any support grafted with groups functional acids.
  • the ratio of the volume of charge injected over the volume of catalyst is between 0.1 and 10 liters / liter / hour and preferably between 0.5 and 4 liter / liter / hour. More specifically, this alkylation step is carried out in the presence at least one catalyst.
  • a particular mode of the invention can consist in using a physical mixture of at least two of the above catalysts in proportions varying from 95/5 to 5/95, preferably from
  • the temperature for this step is generally around 10 to around 350 ° C depending on the type of catalyst or the strength of the acidity. So for an acid type catalyst phosphoric supported, the temperature is usually about 50 to about 250 ° C preferably from about 100 to about 210 ° C
  • the molar ratio of olefins to thiophenic compounds is greater than 10 mole / mole preferably greater than 100 mole / mole.
  • the operating pressure of this step is generally between 0.1 and 3 MPa and preferably such that the filler is in liquid form under the conditions of temperature and pressure, ie at a pressure greater than 0.5 MPa.
  • step d) The effluent from step c) of transformation of the sulfur compounds is at least partially and preferably entirely sent to a fractionation unit (step d)) to be separated into at least two fractions, a light fraction and a heavy fraction which is preferably sent in full optionally after mixing with an intermediate fraction in a desulfurization zone operating in one (step e) or two successive desulfurization stages (stage e) and stage f)).
  • This separation is preferably carried out by means of a distillation column classic also called splitter according to the Anglo-Saxon name.
  • This column of fractionation must separate a light fraction of the gasoline containing a small fraction of sulfur and a heavy fraction preferably containing the major part of the sulfur initially present in the initial gasoline.
  • This column generally operates at a pressure between 0.1 and 2 MPa and of preferably between 0.2 and 1 MPa.
  • the number of theoretical plates in this column of separation is generally between 10 and 100 and preferably between 20 and 60.
  • the reflux rate expressed as the ratio of the liquid flow in the column divided by the distillate flow rate expressed in kg / h, is generally less than unity and preferably less than 0.8.
  • the light gasoline obtained after separation is generally made up of 5, 6 and 7 carbon hydrocarbon cuts. Generally this light fraction has a low sulfur content, i.e. it is not generally necessary treat the light cut before using it as fuel.
  • the light cup L is preferably injected into a liquid gas separation flask in order to separate the unused hydrogen and the H2S, formed during step a) and / or b) and / or c), olefins generally having from 5 to 7 carbon atoms.
  • the so-called heavy cut H1 that is to say the cut whose temperatures are higher than approximately 100 ° C is sent to the desulfurization zone step e) and so preferred steps e) and f).
  • the essence is divided into at least 3 fractions: a light fraction, a heavy fraction and at least a fraction intermediate.
  • the light fraction is identical to that described above.
  • the intermediate fraction I2 whose boiling points as an example are at least 100 ° C and at most about 140 ° C or even about 160 ° C.
  • This cut can be treated in step e) then optionally in step f) of the method according to the invention.
  • the heavy fraction H2 is then a fraction whose boiling points are generally above about 160 ° C or at about 140 ° C. In this case the whole intermediate fraction plus heavy fraction is equivalent to the heavy fraction H1 in the case where the fractionation is limited to two fractions.
  • the heavy cut H2 whose boiling temperatures are generally higher than about 160 ° C or about 140 ° C is sent to the desulfurization zone.
  • step c) fractionate the product from step c) into at least three cuts a light cut (L), at least one intermediate cut (I2) and at least one heavy cut (H2) having the properties described above.
  • the intermediate section I2 whose boiling points are between approximately 100 ° C. and about 120 ° C or about 160 ° C can be sent to a processing unit sulfur compounds according to step c) or recycled in this step c).
  • the section (s) I2 can again be split into a section intermediate I3 and a heavy cut H3
  • the cut H3, thus obtained can optionally be mixed with the H2 cut, preferably before desulphurization and the section I3 can be sent to a sulfur compound processing unit according to step c) or recycled in this step c).
  • step e) includes that in which only one desulphurization step is carried out and those of a preferred embodiment of the invention in which the hydrodesulfurization is carried out in two successive stages e) and f).
  • step e Decomposition of sulfur compounds from heavy fractions and / or intermediaries from step d) (step e):
  • This step which applies to heavy gasoline (heavy fractions and / or intermediate fractions) obtained at the end of step d) of fractionation consists in hydrogenolysing at least partially the sulfur-containing compounds to form H 2 S.
  • the fraction of sulfur compounds thus transformed is a function of the desired degree of desulfurization.
  • This step can, for example, be carried out by passing heavy petrol, in the presence of hydrogen, over a catalyst comprising at least one element from group VIII and / or at least one element from group VIB at least partially in sulphide form, at a temperature between about 210 ° C and about 350 ° C, preferably between 220 ° C and 320 ° C, under a pressure generally between about 1 and about 4 MPa, preferably between 1.5 and 3 MPa.
  • the space velocity of the liquid is between approximately 0.5 and approximately 20 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 0.5 and 10 h-1, very preferably between 1 and 8 a.m.
  • the H 2 / HC ratio is between 100 to 600 liters per liter and preferably between 200 and 500 liters per liter.
  • at least one catalyst comprising at least one element from group VIII (metals from groups 8, 9 and 10 of the new classification, i.e. iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum) and / or at least one element of group VIB (metals of group 6 of the new classification, that is to say chromium, molybdenum or tungsten), on an appropriate support.
  • group VIII metal from groups 8, 9 and 10 of the new classification, i.e. iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum
  • group VIB metal of group 6 of the new classification, that is to say chromium, molybdenum or tungsten
  • the group VIII metal content expressed as oxide is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight.
  • the metal content of group VIB is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight.
  • the element of group VIII, when present, is preferably cobalt, and the element in group VIb, when present, is generally molybdenum or tungsten. Combinations such as cobalt-molybdenum are preferred.
  • the catalyst support is usually a porous solid, such as example an alumina, a silica-alumina or other porous solids, such as by example of magnesia, silica or titanium oxide, alone or in admixture with alumina or silica-alumina.
  • the catalyst according to the invention preferably has a specific surface less than 190 m2 / g, more preferably less than 180m2 / g, and very preferably less than 150 m2 / g.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • the sulphurization step may be carried out by any technique known to a person of art, in-situ or ex-situ.
  • the conversion of the sulfur compounds is greater than 50% and preferably more than 90%.
  • Step e) is carried out under conditions such that the transformation of at least a portion of the unsaturated sulfur compounds such as the thiophenic compounds, into saturated compounds, for example in thiophanes (or thiacyclopentanes) or in transformation, is observed. mercaptans, or alternatively at least partially hydrogenate these unsaturated sulfur compounds to form H 2 S.
  • the conversion of the unsaturated sulfur compounds is greater than 15% and preferably greater than 50%.
  • the hydrogenation rate of the olefins is preferably less than 50%, more preferably less than 40%, and very preferably less than 35%, during this stage.
  • the effluent from this first hydrogenolysis step is then sent, preferably without any separation of the liquid and the gas, to step f) which makes it possible to decompose the sulfur-containing compounds saturated in H 2 S.
  • step f Decomposition of sulfur compounds contained in the product from the step e) (step f):
  • the saturated sulfur compounds are transformed in the presence of hydrogen, on a suitable catalyst.
  • Decomposition of non-unsaturated compounds hydrogenated during step e) can also take place simultaneously.
  • This transformation is carried out, without significant hydrogenation of olefins, that is to say that during this stage the hydrogenation of olefins is generally limited to 20 % by volume relative to the olefin content of the initial gasoline, and preferably, limited to 10% by volume relative to the olefin content of the original gasoline.
  • the catalysts which may be suitable for this stage of the process according to the invention, without that this list is exhaustive, are catalysts generally comprising at least a basic element chosen from elements from group VIII and group VIB, and preferably chosen from the group formed by nickel, cobalt, iron, molybdenum, tungsten. These metals can be used alone or in combination, they are preferably supported and used in their sulfurized form.
  • the catalyst of step f) is preferably of a different nature and / or composition from that used in the step e) .
  • the base metal content of the catalyst according to the invention is generally between approximately 1 and approximately 60% by weight, preferably between 5 and 30% by weight, and very preferably between 10 and 25% by weight.
  • the catalyst is generally shaped, preferably in the form of balls, pellets, of extrudates, for example trilobes.
  • the metal can be incorporated into the catalyst by deposit on the preformed support, it can also be mixed with the front support the shaping stage.
  • the metal is generally introduced in the form of a salt precursor, generally soluble in water, such as for example nitrates, heptamolybdates. This method of introduction is not specific to the invention. Other mode of introduction known to those skilled in the art may be suitable.
  • the catalyst supports used in this stage of the process according to the invention are generally porous solids chosen from refractory oxides, such as, for example, aluminas, silicas and silica-aluminas, magnesia, as well as titanium and zinc oxide, the latter oxides being able to be used alone or in admixture with alumina or silica-alumina.
  • the supports are transition aluminas or silicas whose specific surface is between 25 and 350 m 2 / g. Natural compounds, such as, for example, kieselguhr or kaolin, may also be suitable as supports for the catalysts used in this stage of the process.
  • the catalyst is preferably used at least in part in its sulfurized form. This has the advantage of minimizing the risk of hydrogenation of the compounds unsaturated such as olefins or aromatics during the phase of start-up.
  • the sulfurization step can be carried out by any known technique of those skilled in the art, in-situ or ex-situ.
  • the sulfur content of the catalyst is generally between 0.5 and 25% by weight, preferably between 4 and 20% by weight and very preferably between 4 and 10% by weight.
  • the purpose of the hydrodesulfurization carried out during this step is to convert the saturated sulfur compounds of the gasoline into H 2 S which have already undergone at least one prior hydrogenation of the unsaturated sulfur compounds during step e). It makes it possible to obtain an effluent that meets the desired specifications in terms of content of sulfur compounds.
  • the gasoline thus obtained has only a small loss of octane.
  • the treatment aimed at decomposing the saturated sulfur compounds originating from step e) of the process is carried out in the presence of hydrogen, with the catalyst comprising at least one base metal chosen from the group formed by nickel, cobalt, iron , molybdenum, tungsten, at a temperature between about 280 ° C and about 400 ° C, preferably between about 290 ° C and about 380 ° C, more preferably between 310 ° C and 360 ° C, and very preferably between 320 ° C and 350 ° C, under a pressure generally between about 0.5 and about 5 MPa, preferably between 1 and 3MPa, more preferably between 1.5 and 3 MPa.
  • the catalyst comprising at least one base metal chosen from the group formed by nickel, cobalt, iron , molybdenum, tungsten, at a temperature between about 280 ° C and about 400 ° C, preferably between about 290 ° C and about 380 ° C, more preferably between 310 ° C and 360 ° C, and very
  • the space velocity of the liquid is between approximately 0.5 and approximately 10 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 1 and 8 h -1 .
  • the H 2 / HC ratio is adjusted as a function of the desired hydrodesulfurization rates in the range between approximately 100 and approximately 600 liters per liter, preferably between 100 and 300 liters per liter. All or part of this hydrogen can possibly come from step e) (unconverted hydrogen) or from recycling of the hydrogen not consumed in steps a), b) or c). It has been found that the use of this second catalyst in this step, under specific operating conditions, makes it possible to decompose the saturated compounds, contained in the effluent from step c, into H2S.
  • This implementation makes it possible to achieve a high overall level of hydrodesulfurization at the end of all the stages of the process according to the invention, while minimizing the loss in octane resulting from the saturation of the olefins, since the conversion of olefins during step e) is generally limited to at most 20% by volume of the olefins, preferably at most 10% by volume.
  • the filler of initial essence it is freed from most of its compounds basic nitrogen which are at least partly removed before step c) of alkylation of minus part of the sulfur compounds present in the product resulting from stage b).
  • the basic nitrogen compounds contained in gasoline initial are at least partially eliminated before its introduction in step a) of hydrogenation of polyunsaturated compounds.
  • the elimination of basic nitrogen compounds is carried out by treatment (washing) with a acidic aqueous solution. So when the original essence contains nitrogen compounds basic these are at least partially removed by treatment with a acidic aqueous solution carried out before step c) of alkylation of at least part of the sulfur compounds present in the product resulting from step, b). This washing is usually performed before or after the selective hydrogenation treatment in step a) of the polyunsaturated compounds contained in the initial essence.
  • the catalysts used in steps e) and f) are most often catalysts separate sulfides.
  • Gasoline ( ⁇ ) containing sulfur compounds, diolefins and olefins is injected into line (1).
  • the hydrogen is injected into line (2) in an amount such that the hydrogen / diolefin molar ratio is greater than 1.
  • Petrol and hydrogen are brought into contact in a reactor (A) for selective hydrogenation of diolefins, in optimized conditions to limit the saturation of olefins while hydrogenating the diolefins.
  • the reactor effluent (A) is sent via line (3) to a weighting unit sulfur compounds (B).
  • the reactions carried out in this reactor (B) are essentially reactions of weighting of the mercaptans of 1 to 6 atoms of carbon as well as sulfides of 2 to 6 carbon atoms. There is also a partial conversion of compounds such as CS2 and COS.
  • the gasoline produced is introduced via line (4) into a reactor (C) for weighing down sulfur compounds by addition on olefins.
  • the sulfur compounds mainly weighed down in this reactor are the thiophenic compounds.
  • the gasoline produced in this reactor (C) is therefore both heavier than petrol ( ⁇ ) and depleted in light sulfur compounds.
  • the gasoline produced in the reactor (C) is injected through line (5) into a fractionation column (D) which separates the essence into at least two cuts.
  • Light petrol whose end point can be between 55 ° C and 160 ° C is recovered at the top of the column. This gasoline is desulphurized and does not require additional treatment. The final temperature of this light essence is fixed by the maximum amount of sulfur allowed.
  • the heavy petrol recovered at the bottom of the column by line (7) is sent after mixture with hydrogen introduced via line (8) to a desulfurization section (E + F).
  • This essence has an initial distillation point between 50 ° C and 130 ° C.
  • the hydrodesulfurization section (E + F) is designed to desulfurize petrol while limiting the hydrogenation of olefins, which limits the loss of octane.
  • She is consists of at least 2 reactors in series, the first of which (E) includes a system catalytic optimized to saturate thiophenic compounds and transform partially the sulfur-containing compounds in H2S.
  • the second contains a catalyst which is an optimized catalyst to transform mercaptans into H2S, by limiting hydrogenation of olefins present in gasoline.
  • Heavy petrol recovered by the line (10) and light petrol recovered by the line (6) can be mixed to produce a total desulfurized gasoline recovered by line (11).
  • a cracked gasoline is subjected to a hydrogenation treatment of the diolefins under conditions where the light saturated sulfur compounds present in the feed are partly converted into heavier compounds.
  • This treatment is carried out in a reactor operating continuously.
  • the catalyst is based on nickel and molybdenum (catalyst sold by the company Procatalyse under the reference HR945).
  • the reaction is carried out at 180 ° C under a total pressure of 2.6 MPa, with a space speed of 6 h -1 .
  • the H 2 / charge ratio expressed in liters of hydrogen per liter of charge, is 10.
  • the petrol is separated into two fractions, a light fraction representing 65% by weight of the distilled petrol whose cutting point corresponds to a temperature of 100 ° C. and a heavy fraction.
  • the separation is carried out on a discontinuous distillation column composed of 30 theoretical plates. The characteristics of the two fractions obtained are given in Table 2.
  • the light fraction has diolefin, mercaptan and sulfur contents such that it can be used directly, provided that the specification on the sulfur content is greater than 60 ppm. Heavy fuel must be desulphurized before use. In all cases, this scheme does not make it possible to produce a desulfurized gasoline, containing less than 40 ppm of sulfur, by combining light gasoline and heavy gasoline
  • the catalytic cracking gasoline obtained in Example 1 after the hydrogenation treatment is separated into two fractions, a light fraction representing 20% by weight of the distilled gasoline, the cutting point of which corresponds to a temperature of 55 ° C. and a heavy fraction.
  • the separation is carried out on the same column as in Example 1.
  • the characteristics of the two fractions obtained are given in Table 3.
  • Light fraction Heavy fraction PI-55 55-175 density 15/4 0.65 0.77 Bromine index (gBr / 100g) 130 65 Olefins (GC) 60 36 MAV (mg / g) ⁇ 0.2 ⁇ 0.2 Research octane number 95 90.5 Motor octane number 81.5 80 mercaptans (ppm) ⁇ 1 4 S Total (ppm) 2 437 Cut points (DS) 0.5% 4 52 5% 20 54 10% 22 67 50% 36 102 90% 41 138 95% 54 151 99.5% 72 176
  • the light petrol produced by distillation has mercaptan contents, diolefins and sulfur as it can be used directly.
  • the first catalyst (catalyst A) is obtained by impregnation "without excess solution” of a transition alumina, in the form of beads, with a specific surface of 130 m 2 / g and a pore volume of 0.9 ml / g, with an aqueous solution containing molybdenum and cobalt in the form of ammonium heptamolybdate and cobalt nitrate.
  • the catalyst is then dried and calcined in air at 500 ° C.
  • the cobalt and molybdenum content of this sample is 3% CoO and 14% MoO3.
  • the second catalyst (catalyst B) is prepared from a transition alumina of 140 m 2 / g in the form of beads 2 mm in diameter.
  • the pore volume is 1 ml / g of support.
  • One kilogram of support is impregnated with 1 liter of nickel nitrate solution.
  • the catalyst is then dried at 120 ° C and calcined in an air stream at 400 ° C for one hour.
  • the nickel content of the catalyst is 20% by weight.
  • 100 ml of catalyst A and 200 ml of catalyst B are placed in two reactors in series, so that the feed to be treated (heavy fraction) first meets catalyst A then catalyst B.
  • a sampling zone for the effluent from step e is provided between catalysts A and B.
  • the catalysts are first of all sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a charge containing 2% by weight of sulfur in the form of dimethyldisulfide in n-heptane.
  • the temperature of the catalytic zone comprising catalyst A is 280 ° C.
  • the temperature of the catalytic zone containing catalyst B is 330 ° C.
  • the catalytic cracking gasoline obtained in Example 1 after the treatment of hydrogenation [steps a) and b) according to the invention] is sent to a reactor weighing down the sulfur-containing compounds by alkylation with olefins (step c) according to the invention).
  • the charge is added to isopropanol up to 500 ppm, intended to hydrate the catalyst continuously in the reactor.
  • the effluent thus produced is separated into two sections using a distillation column as described in Example 1.
  • the cutting point of the distillation is set at 100 ° C, the light fraction represents 50% by weight of the starting gasoline.
  • the light gasoline recovered at the end of the fractionation stage has contents in diolefins, mercaptans and total sulfur as it can be used without treatment additional.
  • Heavy petrol requires a desulfurization step.
  • the desulfurization of heavy gasoline (steps e) and f) of the process according to the invention) is carried out using the device described in Example 2.
  • the temperature of the catalytic zone comprising catalyst A is 290 ° C.
  • the temperature of the catalytic zone containing catalyst B is 340 ° C.
  • the gasoline thus produced now only has a sulfur content of 26 ppm. It can be used without further treatment.
  • This gasoline is combined with the light gasoline recovered in step d).
  • the characteristics of the heavy desulfurized gasoline and of the recombined gasoline are given in table 6.
  • step d Desulfurized heavy gasoline (steps e) and f) Light petrol and heavy petrol combined PI-175 PI-100 100-240 PI-240 density 15/4 .7215 .6921 .8134 .7683 Bromine index (gBr / 100g) 80 53 37 45 Olefins (GC)% by weight 44 MAV (mg / g) 12 ⁇ 0.2 ⁇ 0.2 ⁇ 0.2 Research octane number 93 86.2 90.4 88.8 Motor octane number 79.8 79.5 80.2 79.7 mercaptans (ppm) 20 4 12 9 Non-mercaptan sulfur (ppm) 330 14 24 17 S Total (ppm) 350 18 36 26
  • This scheme carried out according to the invention makes it possible to produce a desulfurized petrol with a limited loss of octane, the mercaptan and diolefin contents of which are compatible with the qualities required for petrol.
  • the desulfurization rate is 92.6%
  • the residual sulfur content is 26 ppm
  • the loss of octane calculated by the formula (RON + MON) / 2 is 2.15 points.

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Claims (19)

  1. Verfahren zur Herstellung von Benzinen mit geringem Schwefelgehalt aus einem wenigstens 150 Gew.-ppm schwefelhaltige Verbindungen enthaltendem ursprünglichen Benzin, das wenigstens die folgenden Stufen umfasst:
    eine Stufe a) zur selektiven Hydrierung der nicht aromatischen polyungesättigten Verbindungen, die in dem ursprünglichen Benzin vorliegen,
    wenigstens eine Stufe b), die darauf abzielt, das Molekulargewicht der leichten schwefelhaltigen Produkte zu erhöhen, hauptsächlich von jenen, die in Form von Mercaptanen mit 1 bis 6 Kohlenstoffatomen in deren Molekülen vorliegen und von Sulfiden, die anfänglich in dem in Stufe a) eingeführten Benzin vorliegen und/oder jenen, die in dem Produkt aus Stufe a) enthalten sind,
    wenigstens eine Stufe c) zur Alkylierung von wenigstens einem Teil der schwefelhaltigen Verbindungen, hauptsächlich von jenen, die in Form von thiophenischen Verbindungen vorliegen, die in dem Produkt aus Stufe b) vorliegen, welche darauf abzielt, schwefelhaltige Verbindungen mit höherem Molekulargewicht zu erhalten,
    wenigstens eine Stufe d) zur Fraktionierung des Benzins aus der Stufe c) in wenigstens zwei Fraktionen, eine erste, praktisch von Schwefel befreite Fraktion und welche die leichtesten Olefine des ursprünglichen Benzins enthält, die nicht in der Stufe c) umgewandelt sind (leichtes Benzin), wenigstens eine andere Fraktion, die schwerer ist als diese erste Fraktion und an schwefelhaltigen Verbindungen angereichert ist, und
    wenigstens eine Stufe e) zur Behandlung wenigstens einer der schwereren Fraktionen aus der Stufe d) auf einem Katalysator, der es ermöglicht, wenigstens teilweise die schwefelhaltigen Verbindungen zu zersetzen.
  2. Verfahren nach Anspruch 1, in dem die Stufe e) zur Behandlung von wenigstens einer der Fraktionen, welche schwerer ist und bei der Stufe d) getrennt wurde, auf einem Katalysator, der es ermöglicht, wenigstens teilweise die schwefelhaltigen Verbindungen zu zersetzen, unter Bedingungen durchgeführt wird, wo die Hydrierung der Olefine auf diesen Katalysator begrenzt ist.
  3. Verfahren nach Anspruch 1 oder 2, das wenigstens eine Stufe f) zur Behandlung des aus der Stufe e) erhaltenen Produkts ohne Entfernung von H2S, das bei dieser Stufe e) gebildet ist, auf einem Katalysator und unter Bedingungen umfasst, die es ermöglichen, wenigstens teilweise die nicht in der Stufe e) umgewandelten schwefelhaltigen Verbindungen mit einer begrenzten Hydrierung der Olefine zu zersetzen.
  4. Verfahren nach einem der Ansprüche 1 bis 3, in dem das Ausgangsbenzin ein katalytisches Crackbenzin ist, dessen Endsiedetemperaturen etwa 120°C bis etwa 230°C sind.
  5. Verfahren nach Anspruch 3 oder 4, in dem die Bedingungen der Stufe f) derart gewählt sind, dass die ungesättigten schwefelhaltigen Verbindungen und die linearen gesättigten und/oder zyklischen schwefelhaltigen Verbindungen, die nicht in der Stufe e) umgewandelt sind, mit einer begrenzten Hydrierung der Olefine zersetzt werden.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in dem die Stufe a) zur Hydrierung der ungesättigten Verbindungen und die Stufe b), die darauf abzielt, das Molekulargewicht der leichten schwefelhaltigen Produkte, die anfangs in dem in die Stufe a) eingeführten Benzin vorliegen, zu erhöhen, gleichzeitig in einer einzigen Reaktionszone durchgeführt werden, die ein oder mehrere Betten eines einzigen Katalysators enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 6, in dem das ursprüngliche Benzin basische stickstoffhaltige Verbindungen enthält, die wenigstens teilweise vor der Stufe c) zur Alkylierung wenigstens eines Teils der schwefelhaltigen Verbindungen entfernt werden, die in dem Produkt aus der Stufe b) vorliegen.
  8. Verfahren nach Anspruch 7, in dem die basischen in dem ursprünglichen Benzin enthaltenen stickstoffhaltigen Verbindungen wenigstens teilweise vor dessen Einführung in die Stufe a) zur Hydrierung der polyungesättigten Verbindungen entfernt werden.
  9. Verfahren nach Anspruch 6 oder 7, in dem die Entfernung der basischen stickstoffhaltigen Verbindungen durch eine Behandlung mithilfe einer wässrigen Säurelösung durchgeführt wird.
  10. Verfahren nach einem der Ansprüche 3 bis 9, in dem das schwere entschwefelte Benzin aus der Stufe f) einer Abstreifbehandlung mittels eines Inertgases unterzogen wird.
  11. Verfahren nach einem der Ansprüche 3 bis 10, in dem die Stufen e) und f) in wenigstens zwei aufeinander folgenden unterschiedlichen Reaktionszonen durchgeführt werden.
  12. Verfahren nach einem der Ansprüche 3 bis 11, in dem das leichte Benzin aus der Stufe d) und wenigstens ein Teil des schweren Benzins aus der Stufe f) gemischt werden, um das gewünschte entschwefelte Gesamtbenzin zu bilden.
  13. Verfahren nach einem der Ansprüche 1 bis 12, in dem der Katalysator der Stufe e) wenigstens ein Element der Gruppe VIII und wenigstens ein Element der Gruppe VIB umfasst.
  14. Verfahren nach einem der Ansprüche 3 bis 13, in dem der Katalysator der Stufe f) wenigstens ein Element der Gruppe VIII umfasst.
  15. Verfahren nach einem der Ansprüche 3 bis 14, in dem die in den Stufen e) und f) verwendeten Katalysatoren unterschiedliche geschwefelte Katalysatoren sind.
  16. Verfahren nach einem der Ansprüche 3 bis 15, in dem die Stufen e) und f) in zwei in Reihe angeordneten Reaktoren durchgeführt werden, wobei der zweite Reaktor integral den Abstrom des ersten Reaktors behandelt.
  17. Verfahren nach einem der Ansprüche 1 bis 16, in dem die Alkylierungsstufe c) unter Bedingungen derart durchgeführt wird, dass ein Teil der Olefine des Ausgangsbenzins zu verzweigten langen Olefinen durch Additionsreaktionen zwischen den Olefinen umgewandelt wird und dass ein Teil der Aromaten durch Alkylierung mit den Olefinen schwerer gemacht wird.
  18. Verfahren nach einem der Ansprüche 1 bis 17, in dem die schwere Fraktion aus der Stufe d) in eine Fraktionierungszone geschickt wird, die es ermöglicht, eine schwere, an Schwefel angereicherte Fraktion und eine leichtere, an Schwefel abgereicherte Fraktion zu erhalten.
  19. Verfahren nach einem der Ansprüche 1 bis 17, in dem das Benzin aus der Hydrierentschwefelungsstufe e) oder f) in eine Fraktionierungszone geschickt wird, die es ermöglicht, eine schwere, an Schwefel angereicherte Fraktion und eine leichtere, an Schwefel abgereicherte Fraktion zu erhalten.
EP02701343A 2001-03-12 2002-01-29 Verfahren zur herstellung von entschwefeltem benzin aus einem crackbenzin enthaltendem benzin Expired - Lifetime EP1370630B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR0103358A FR2821850B1 (fr) 2001-03-12 2001-03-12 Procede de production d'essence a faible teneur en soufre comprenant une hydrogenation, un fractionnement, une etape de transformation des composes soufres et une desulfuration
FR0103358 2001-03-12
FR0105538A FR2821852B1 (fr) 2001-03-12 2001-04-23 Procede de production d'une essence desulfuree a partir d'une coupe essence contenant de l'essence de conversion
FR0105538 2001-04-23
PCT/FR2002/000351 WO2002072740A1 (fr) 2001-03-12 2002-01-29 Procede de production d'une essence desulfuree a partir d'une coupe essence contenant de l'essence de craquage

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EP1370630A1 EP1370630A1 (de) 2003-12-17
EP1370630B1 true EP1370630B1 (de) 2004-10-13

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EP02701343A Expired - Lifetime EP1370630B1 (de) 2001-03-12 2002-01-29 Verfahren zur herstellung von entschwefeltem benzin aus einem crackbenzin enthaltendem benzin

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EP (1) EP1370630B1 (de)
JP (1) JP4385178B2 (de)
KR (1) KR100813776B1 (de)
AT (1) ATE279496T1 (de)
BR (1) BR0208050B1 (de)
CA (1) CA2440189C (de)
DE (1) DE60201586T2 (de)
ES (1) ES2231666T3 (de)
FR (1) FR2821852B1 (de)
MX (1) MXPA03008222A (de)
WO (1) WO2002072740A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2884521B1 (fr) * 2005-04-19 2009-08-21 Inst Francais Du Petrole Nouveau procede de desulfuration des essences par alourdissement des composes soufres
FR2885137B1 (fr) * 2005-04-28 2007-07-13 Inst Francais Du Petrole Procede de desulfuration d'essences olefiniques
EP3545052B1 (de) * 2016-11-23 2022-05-04 Haldor Topsøe A/S Verfahren zur entschwefelung von kohlenwasserstoffen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2797639B1 (fr) * 1999-08-19 2001-09-21 Inst Francais Du Petrole Procede de production d'essences a faible teneur en soufre

Also Published As

Publication number Publication date
KR20030080084A (ko) 2003-10-10
ES2231666T3 (es) 2005-05-16
ATE279496T1 (de) 2004-10-15
JP4385178B2 (ja) 2009-12-16
DE60201586D1 (de) 2004-11-18
BR0208050A (pt) 2004-02-25
FR2821852B1 (fr) 2003-05-02
KR100813776B1 (ko) 2008-03-13
WO2002072740A1 (fr) 2002-09-19
CA2440189A1 (fr) 2002-09-19
CA2440189C (fr) 2009-12-15
BR0208050B1 (pt) 2014-11-25
MXPA03008222A (es) 2004-01-29
EP1370630A1 (de) 2003-12-17
JP2004523629A (ja) 2004-08-05
FR2821852A1 (fr) 2002-09-13
DE60201586T2 (de) 2005-02-17

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