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
  • 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
  • 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
  • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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 process for producing gasoline with a low sulfur content comprising hydrogenation, fractionation, a step of transformation of the sulfur compounds and desulfurization.
• This process makes it possible to enhance a gasoline cut possibly comprising also hydrocarbons with two three or four carbon atoms, by reducing the total sulfur content of said cut to very low levels compatible with current or future specifications.
• This desulfurization is moreover carried out without appreciable reduction in the gasoline yield and while minimizing the reduction in the octane number.
• the production of reformulated gasolines meeting the new environmental standards notably requires that their concentration of olefins be reduced slightly, but significantly their concentration of aromatics (especially benzene) and sulfur.
• the catalytic cracked gasolines which can represent 30 to 50% of the gasoline pool, have high olefin and sulfur contents.
• the sulfur present in reformulated gasolines is attributable, to almost 90%, to catalytic cracking gasoline (FCC, "Fluid Catalytic Cracking" or catalytic cracking in a fluidized bed). Desulfurization (hydrodesulfurization) of gasolines and mainly FCC gasolines is therefore of obvious importance for the achievement of specifications.
• the hydrotreatment (hydrodesulfurization) of the feed sent to catalytic cracking leads to gasolines typically containing 100 ppm of sulfur.
• the catalytic cracking charge hydroprocessing units operate under severe temperature and pressure conditions, which implies a high consumption of hydrogen and a high investment.
• the entire charge must be desulphurized, which entails the treatment of very large charge volumes.
• Hydrotreating (or hydrodesulfurization) of catalytic cracking gasolines when carried out under conventional conditions known to those skilled in the art, makes it possible to reduce the sulfur content of the cut.
• this process has the major drawback of causing a very significant drop in the octane number of the cut, due to the saturation of all of the olefins during the hydrotreatment.
• US Pat. No. 4,131,537 teaches the advantage of dividing petrol into several cuts, preferably three, according to their boiling point, and of desulfurizing them under conditions which can be different and in the presence of a catalyst comprising at least one metal from group VIB and / or group VIII. It is stated in this patent that the greatest benefit is obtained when the gasoline is divided into three cuts, and when the cut having intermediate boiling points is treated under mild conditions.
• Patent application EP-A-0 755 995 describes a process for desulfurization of FCC gasolines comprising at least two steps.
• the first is a catalytic hydrodesulfurization at a temperature between 200 and 350 ° C, with a desulfurization rate between 60 and 90% and is carried out in the presence of a feed containing less than 0.1% by volume of sulfide hydrogen (H2S).
• the second, and possibly the following ones, are also catalytic hydrodesulfurization stages carried out between 200 and 300 ° C. and in the presence of a feed comprising less than 0.05% by volume of H2S.
• the desulfurization rate is between 60 and 90% in this step. In this process, the H2S concentration must be kept at a very low level.
• Patent application EP-A-0 725 126 describes a process for hydrodesulfurization of cracked gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds which are easy to desulfurize and a second fraction rich in compounds difficult to desulfurize. Before carrying out this separation, it is first necessary to determine the distribution of the sulfur-containing compounds by means of analyzes. These analyzes are necessary to select the apparatus and the separation conditions.
• the essences to be treated generally have an initial point greater than 70 ° C., and again it is necessary to treat the light essence separately (fraction corresponding to the compounds with a boiling point comprised between the C5 hydrocarbons with 5 carbon atoms and 70 ° C) for example by means of a softening.
• US-A-5 318 690 proposes a process comprising a fractionation of the gasoline and a softening of the light gasoline, while the heavy gasoline is desulphurized, then converted on a zeolite ZSM-5 and desulphurized again in mild conditions.
• This technique is based on a separation of the crude gasoline so as to obtain a light cut preferably practically devoid of sulfur compounds other than mercaptans. This makes it possible to treat said cut only by means of a softening which removes the mercaptans.
• the olefins present in a relatively large amount in the heavy cut, are partially saturated during the hydrotreatment.
• the patent recommends cracking on zeolite ZSM-5 which produces olefins, but to the detriment of the yield.
• these olefins can recombine with the H2S present in the medium to reform mercaptans. It is then necessary to carry out additional softening or hydrodesulfurization.
• Patent application WO 00/15319 describes a method making it possible to simultaneously carry out the fractionation and the treatment of a light naphtha.
• the light cut contains mercaptans generally ranging from methyl-mercaptan to hexyl-mercaptan.
• These sulfur compounds are eliminated from the light fraction only in the case where the fractionation column contains a hydrodesulfurization section at the top of the column. In the absence of this section, it is therefore not possible to eliminate the mercaptans which either end up in the desulfurized gasoline when the light fraction is recombined with the heavy desulfurized fraction, or can be eliminated with the whole. of the light fraction, which generates a loss of gasoline yield after desulfurization.
• US Pat. No. 6,083,379 describes a process for the desulphurization and improvement of the octane number of gasolines comprising a fractionation of the gasoline in at least two cuts, the treatment of the light fraction in the presence of a zeolite, a fractionation of the light fraction thus treated, the mixture of heavy fractions obtained during the two stages of fractionation and hydrodesulfurization of the mixture of these fractions.
• Patent application WO 94/22980 describes a gasoline desulfurization process comprising a fractionation into two sections, the heaviest section is desulfurized in a hydrodesulfurization reactor and then treated in the presence of an acid catalyst which makes it possible to compensate for the loss of octane.
• the lightest cut is also desulphurized by means of a non-hydrogenating extraction of the mercaptans.
• the patent US Pat. No. 5,968,346 describes a process for the hydroconversion of a hydrocarbon charge, making it possible to remove impurities such as compounds comprising heteroatoms.
• This process comprises a first step of hydroconversion of the entire feed, followed by a separation of the liquid and the vapor present in the effluent from this first step and of contacting the gas with a liquid.
• the mixture of the two liquid fractions resulting from the contacting and the fractionation is then treated in a second hydroconversion stage in the presence of a catalyst.
• 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 coking (coking according to English terminology). , or pyrolysis, or visbreaking (visbreaking according to English terminology), and reduce the sulfur contents in said gasoline cut to very low levels, without appreciable reduction in gasoline efficiency while minimizing the decrease in the index octane 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.
• the process according to the invention is a process for producing gasoline with a low sulfur content, from a gasoline cut containing sulfur (initial gasoline). It includes at least the following steps: a) at least one selective hydrogenation of the diolefins present in the initial gasoline. b) optionally at least one step of chemical transformation of the light sulfur compounds present in the gasoline, preferably this chemical transformation aims to weigh down, that is to say to increase the molecular weight of said sulfur compounds, preferably essentially compounds sulfur having a lower boiling point than thiophene.
• This step can optionally be carried out simultaneously with step a on all or part of the initial gasoline, in the same reactor or a different reactor. It can also be carried out separately on all or part of the hydrogenated gasoline in step a.
• step c) at least one fractionation of the gasoline obtained in step a or b into at least two fractions (or cuts), a light fraction preferably practically free of sulfur and containing the lightest olefins of the initial gasoline ( light gasoline or light fraction), and a heavy fraction in which preferably the major part of the sulfur compounds initially present in the initial gasoline is concentrated (gasoline or heavy fraction). It is also possible to separate the gasoline obtained in step a or b in addition to two fractions, that is to say for example a light fraction, at least an intermediate fraction and a heavy fraction.
• step d) optionally a step of transformation of the sulfur compounds different from step b. It is preferably an alkylation or adsorption step of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans, preferably mercaptans having 1 to 6 carbon atoms, present in at least one cut obtained in step c, preferably in the light cut and / or in at least one intermediate cut.
• the mercaptans possibly present are either formed in step a and / or b, or present in the initial gasoline and not converted in step a and / or b.
• step e) optionally at least one step comprising a desulfurization treatment of at least part of at least one intermediate fraction resulting from the fractionation in step c or from step d of transformation of the compounds sulfur, in the presence of at least one hydrodesulfurization catalyst or an absorbent.
• step g) optionally a step of mixing the light fraction from step c or d, and optionally at least one intermediate fraction, from step c or d or e, with the desulfurized heavy fraction from step f.
• all of the heavy gasoline desulfurized from step f is mixed with the light gasoline from step c or d, without separation of the liquid and the gas contained in the heavy gasoline after desulfurization, optionally a simple stripping with an inert gas can be carried out to remove the H2S from the heavy gasoline which is completely desulphurized.
• a simple stripping with an inert gas can be carried out to remove the H2S from the heavy gasoline which is completely desulphurized.
• the recovery of light petrol, desulfurized heavy petrol, and possibly at least one intermediate petrol is carried out separately. It is then unnecessary to carry out step g.
• the charge of the process according to the invention is a gasoline cutter containing sulfur, preferably a gasoline cutter coming from a catalytic cracking unit, the range of boiling points of which typically extends from approximately the boiling points of the hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to about 250 ° C, preferably from about the boiling points of hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to about 220 ° C, more preferably from about the boiling points of hydrocarbons with 5 carbon atoms to about 220 ° C.
• the end point of the gasoline cut depends on the refinery from which it comes and market constraints, but generally remains within the limits indicated above.
• a method for obtaining a gasoline preferably from a catalytic cracking unit, coking or visbreaking and having a limited sulfur content in which the gasoline " undergoes first a selective hydrogenation treatment of the diolefins, then possibly a step of transformation of the lighter sulfur compounds of the gasoline which should after the fractionation be found in light petrol so that they are essentially in the heavy fraction after the fractionation stage of the process according to the invention.
• the petrol thus treated then undergoes fractionation in at least two cuts.
• at least one fraction resulting from the fractionation stage preferably the light fraction or an intermediate fraction, can be treated in a stage of transformation of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans. is preferably an alkylation or adsorption step.
• Heavy gasoline is treated in a desulfurization section, preferably in the presence of a hydrodesulfurization catalyst or an absorbent.
• 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 gasoline are found in the heavy fraction and possibly in the intermediate fraction or fractions after the stages of hydrogenation, transformation of light sulfur compounds (step b), fractionation (step c), and optionally transformation of sulfur compounds in particular thiophenics and optionally mercaptans, in particular residual mercaptans that are not converted and / or formed in steps a and b ( step d).
• This sequence makes it possible in the end to obtain a desulfurized gasoline without significant reduction in the olefin content or in the octane number, even for high desulfurization rates, and this without it being necessary to treat the light gasoline by means of a hydrodesulfurization or softening section, or by using methods allowing the octane number of the gasoline to be restored. Thanks to this process, significant desulfurization rates are reached, under reasonable operating conditions specified below.
• the petrol fractionation point is preferably limited in order to avoid the presence of thiophene in light petrol.
• the latter forming azeotropes with a certain number of hydrocarbons, it will be possible to separate in light gasoline only the olefins in C5 and a small part of the olefins in C6 under penalty of causing a too much fraction of thiophene in this cut.
• step b and / or d in conditions and on catalysts which make it possible to transform the sulfur compounds, preferably the light sulfur compounds, into sulfur compounds with higher boiling point found after separation, optionally in at least one intermediate fraction or in heavy gasoline .
• These intermediate and / or heavy cuts can then be desulfurized.
• the sulfur content of gasoline cuts produced by catalytic cracking depends on the sulfur content of the feed treated with the FCC, on the presence or not of a pretreatment of the feed of the FCC, as well as on the end point of the cut. .
• the sulfur contents of an entire gasoline cut, in particular those originating from the FCC are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight.
• the sulfur contents are often greater than 1000 ppm by weight, they can even in certain cases reach values of the order of 4000 to 5000 ppm by weight.
• the process according to the invention applies in particular when high rates of desulphurization of the petrol are required, that is to say when the desulphurized petrol must contain at most 10% of the sulfur of the initial petrol and possibly at most 5% or even at most 2% of the sulfur of the initial gasoline which corresponds to desulfurization rates higher than 90% or even higher than 95 or 98%.
• the method according to the invention comprises at least the following steps: a) at least one step carried out by passing the charge, preferably consisting of the entire gasoline cut, over a catalyst making it possible to selectively hydrogenate the diolefins of l without hydrogenating olefins. b) optionally at least one optional step consisting in passing all or part of the initial gasoline or of the hydrogenated gasoline in step a, preferably all of the initial or hydrogenated gasoline in step a, on a catalyst making it possible to transform at least partly the light sulfur compounds (for example: ethylmercaptan, propyl mercaptan), by reaction with all or part of the olefins, into heavier sulfur compounds.
• This step is preferably carried out simultaneously with step a, for example by passing the initial gasoline over a catalyst capable of both hydrogenating the diolefins and of converting the light sulfur compounds, preferably with the olefins, into more sulfur compounds. heavy, or on a separate catalyst but allowing this transformation to be carried out in the same reactor as step a. It is possibly possible to observe on certain types of charges a formation of certain mercaptans at the end of stage a or b, this formation is probably due to a hydrogenolysis of the disulfides of high molecular weight. c) at least one step aimed at separating the initial gasoline into a light gasoline and a heavy gasoline.
• the cutting point of light petrol and heavy petrol is determined in order to limit the sulfur content of the light petrol and to allow its use in the petrol pool preferably without additional post-treatment. It is also possible to separate the gasoline obtained in step a or b in addition to two fractions, that is to say for example a light fraction, at least one or even several intermediate fractions and a heavy fraction. d) optionally a step of transformation of the sulfur-containing compounds, preferably of alkylation or of adsorption of the compounds chosen from the group consisting of thiophene, thiophene compounds and optionally the mercaptans present in at least one cut obtained in step c , preferably in the light cut and / or in at least one intermediate cut.
• step e) optionally at least one step comprising a desulfurization treatment of at least part of at least one intermediate fraction resulting from the fractionation in step c or from step d of transformation of the sulfur-containing compounds in particular of thiophene, of the compounds thiophenics and optionally mercaptans, in the presence of at least one hydrodesulfurization catalyst or an absorbent.
• a stripping can also be carried out between two hydrodesulfurization zones or reactors, optionally used to desulfurize said intermediate fraction.
• 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 H2S possibly produced during the desulfurization.
• step g optionally a step of mixing the light fraction from step c or d with optionally at least one intermediate fraction from step c, d or e and with the heavy desulfurized fraction from step f.
• These fractions can also be valued separately without being mixed.
• reaction section with the fractionation column.
• Said reaction section (s) then operate on at least one fraction taken from inside the fractionation column and the effluent from the reaction section is returned to the fractionation column.
• the reaction section or sections thus coupled to the fractionation column of step c can be chosen from the group consisting of the reaction sections of the following steps:
• step a hydrogenation of diolefins
• step f Such devices comprising a fractionation column associated with an external reactor and which can be used in the process according to the invention have for example been described for applications in the field of refining and petrochemistry in US Patents 5,1777,283, US 5,817,227 and US 5,888,355
• reaction section in place of the fractionation column, that is to say to place at least one of said reaction sections in the column of fractionation (reaction section internal to the column), preferably in an area where the reagent concentration is maximum.
• reaction section will preferably be placed in an area having the maximum concentration of these compounds. Since the light fraction of gasoline does not require a desulfurization treatment, when a desulfurization section is internal to the fractionation column, said reaction section will generally not be placed at the top of the column.
• the reaction section internal to the column is chosen from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (optional step b), transformation of compounds sulfur such as thiophene, thiophene compounds and optionally mercaptans (optional step d), desulfurization of intermediate fractions (optional step e), desulfurization of the heavy fraction (step f).
• the reaction section is placed in the middle of the fractionation column, so as to treat the compounds having intermediate boiling points, that is to say the compounds which can constitute a intermediate cut and which are recovered alone or with the heavy fraction 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.
• Such reactive columns are known to a person skilled in the art and have for example been described in patents or patent applications US 5,368,691, US 5,523,062, FR 2,737 131, FR 2,737,132, EP-A-0461 855.
• Another variant of the process according to the invention consists both in using a reactive column comprising at least one reaction section and an external reactor coupled or not coupled to said column. Such variants are for example described in patent application WO00 / 15319.
• the variants described above are only illustrations of the possible variants of the method according to the invention.
• the method according to the invention can indeed be implemented by combining reaction sections (steps a, b, d, e or f) either associated with the fractionation column from step c, or internal (s ) to said column, either external (s) and not coupled (s) to said column in the sense that the effluent from said reaction section (s) is not recycled to the fractionation column.
• One of the advantages of the process according to the invention lies in the fact that it is not necessary to desulfurize the light fraction of the gasoline resulting from the fractionation.
• the transformation of sulfur and / or thiophene compounds makes it possible to considerably reduce the content of sulfur compounds in the light cut and possibly at least one intermediate cut, and generally to recover the essentials of these compounds in the heavy fraction, and optionally in the intermediate fraction (s).
• Steps b and d are distinguished, inter alia, by the fact that the conversion of thiophene compounds is generally less than 60% by weight, or even less than 40% by weight in step b, while the conversion or adsorption of said compounds is the more often greater than 80% by weight, preferably greater than 90% by weight, very preferably greater than 95% by weight in step d.
• Step b essentially effects the weighting of light mercaptans.
• This operation is carried out while maintaining most of the olefins in the light fraction, possibly in at least one intermediate fraction which does not require extensive desulfurization.
• the content of sulfur compounds in the light fraction thus obtained is generally less than 50 ppm, preferably less than 20 ppm, more preferably less than 10 ppm and very preferably less than 5 ppm.
• Another advantage lies in the fact that the residual content of sulfur-containing compounds in the desulfurized petrol by means of the process according to the invention is particularly low, and that the octane number of the petrol 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 fraction containing sulfur to be treated. It preferably takes place in the first step (step a) of the process according to the invention, generally in the presence of a catalyst comprising at least one metal from group VIII, preferably chosen from the group consisting of platinum, palladium and nickel. , and a support.
• a catalyst comprising at least one metal from group VIII, preferably chosen from the group consisting of platinum, palladium and nickel.
• a catalyst based on nickel or on palladium deposited on an inert support for example such as alumina, silica or a support containing at least 50% alumina, will be used.
• 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 - ' ' (volume of charge per volume of catalyst and per hour), preferably between 2 and 10 h - ' ', very preferably between 3 and 8 a.m. ⁇ 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.
• the hydrogen to charge ratio expressed in liters is generally between 1 and 50 liters per liter, preferably between 3 and 30 liters per liter, more preferably between 8 and 25 liters per liter.
• the choice of operating conditions is particularly important. Most generally, it will be operated under pressure and in the presence of a quantity of hydrogen in slight excess relative to the stoichiometric value necessary to hydrogenate the diolefins.
• the hydrogen and the feedstock to be treated are injected in upward or downward streams into a reactor preferably comprising a fixed bed of catalyst.
• Another metal can be combined with the main metal to form a bimetallic catalyst, such as for example molybdenum or tungsten.
• the catalytic cracking gasoline can contain up to a few% by weight of diolefins. After hydrogenation, the content of diolefins is generally reduced to less than 3000 ppm, even less than 2500 ppm and more preferably less than 1500 ppm. In some cases it can be obtained less than 500 ppm. The content of dienes after selective hydrogenation can even be reduced to less than 250 ppm if necessary.
• the hydrogenation step of the dienes takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the quantity of hydrogen necessary to effect desired reactions.
• This optional step consists of transforming the light sulfur compounds. That is to say the compounds which, at the end of step b of separation, would be found in light petrol, in heavier sulfur compounds entrained in heavy petrol. Preferably, the transformed light compounds have a lower boiling point than that of thiophene.
• This transformation is preferably carried out on a catalyst comprising at least one element from group VIII (groups 8, 9 and 10 of the new periodic classification), or comprising a resin. The choice of catalyst is carried out in particular so as to promote the reaction between the light mercaptans and the olefins, which leads to heavier mercaptans.
• This optional step can optionally be carried out at the same time as step a.
• Another possibility is to use a catalyst based on nickel identical or different from the catalyst of stage 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. In this case 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 thiophene 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.
• the gasoline is fractionated into two fractions: - a light fraction containing a limited residual sulfur content, preferably less than about 200 ppm, more preferably less than
• step d of treatment of thiophene and / or thiophene compounds is optionally step d of treatment of thiophene and / or thiophene compounds.
• This separation is preferably carried out by means of a conventional distillation column also called a splitter.
• This fractionation column must make it possible to separate a light fraction of the gasoline containing a small fraction of the 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 preferably between 0.2 and 1 MPa.
• the number of theoretical plates of this separation column is generally between 10 and 100 and preferably between 20 and 60.
• the reflux rate expressed as being the ratio of the liquid flow rate in the column divided by the distillate flow rate expressed in kg / h, is generally less than one and preferably less than 0.8.
• the light gasoline obtained at the end of the separation generally contains at least all of the C5 olefins, preferably the C5 compounds and at least 20% of the C6 olefins.
• this light fraction has a low sulfur content, that is to say that it is not generally necessary to treat the light cut before using it as fuel.
• the essence is divided into at least 3 fractions: a light fraction, a heavy fraction and at least an intermediate fraction.
• step d of transformation of the sulfur-containing compounds, in particular of the thiophenic compounds is present in the process according to the invention, the essence is preferably fractionated into at least two cuts having the following properties:
• cut H1 at least one so-called heavy cut (cut H1) whose boiling points are (for information) greater than approximately 60 ° C.
• the light section L is preferably injected into a liquid gas separation flask in order to separate the unconsumed hydrogen and I ⁇ 2S, formed during step a and or b, from the olefins generally having 5 to 7 carbon atoms.
• the so-called heavy cut H1 that is to say the cut whose temperatures are above about 60 ° C., is sent to a distillation column or any other separation process capable of separating this cut into at least two cuts:
• the heavy fraction H2 whose boiling temperatures are generally higher than approximately 160 ° C. or approximately 120 ° C. is sent to step f) of desulfurization.
• the intermediate section 12 the boiling points of which are, for example, between approximately 60 ° C. and approximately 120 ° C. or approximately 160 ° C. can be sent to a unit for processing the sulfur-containing compounds according to step d.
• the sections 12 can again be split into an intermediate section 13 and a heavy section H3, in particular when step d is an alkylation step of the thiophene compounds.
• the H3 cut thus obtained can optionally be mixed with the H2 cut, preferably before desulfurization.
• step d transformation of the sulfur-containing compounds, in particular of the thiophenic compounds, preferably by alkylation or adsorption
• Step d is a step for transforming the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans present in the light cut and / or in at least one intermediate fraction.
• This step consists in preferably passing the light fraction and / or possibly at least one intermediate fraction resulting from the fractionation (step c) over an absorbent or over a catalyst having an acid function which makes it possible to carry out the addition of the sulfur-containing compounds in the form of mercaptans on olefins and the alkylation reaction of thiophene and thiophene derivatives with these same olefins.
• the operating conditions are adjusted to carry out the desired transformation with conversion or adsorption rates of thiophene and / or thiophenics and / or light mercaptans, preferably mercaptans having from 1 to 6 carbon atoms, greater than 80% by weight, preferably greater than 90% by weight, very preferably greater than 95% by weight.
• Other compounds such as COS or CS2 can optionally also be adsorbed or converted.
• the essence can be added with a compound known to inhibit the oligomerizing activity of acid catalysts such as alcohols, ethers or water.
• the light cut or the intermediate cut obtained in step c is treated in a section making it possible to transform, preferably by alkylation or adsorption, the compounds chosen from the group consisting by thiophene, thiophene compounds and mercaptans.
• the thiophene compounds contained in the 60 ° C-160 ° C cut will react with conversion rates greater than 80% by weight, preferably greater than 90% by weight, with the olefins to form alkyls thiophenes according to the following reaction for thiophene:
• 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 which is 80 ° C is shifted to 250 ° C for thiophene alkyls and this reaction therefore most often leads to an increase in the gasoline, especially in the case where the gasoline fraction and / or the starting essence are light.
• 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 acid functional groups.
• the ratio of the volume of feed injected to the volume of catalyst is between 0.1 and 10 liters / liter / hour and preferably between 0.5 and 4 liters / liter / hour.
• this alkylation step is carried out in the presence of at least one acid catalyst chosen from the group consisting of silicoaluminates, titanosilicates, mixed alumina titanium, clays, resins, mixed oxides obtained by grafting of at least one organosoluble organosoluble or water-soluble compound (chosen from the group consisting of alkys. and / or alkoxy.
• at least one acid catalyst chosen from the group consisting of silicoaluminates, titanosilicates, mixed alumina titanium, clays, resins, mixed oxides obtained by grafting of at least one organosoluble organosoluble or water-soluble compound (chosen from the group consisting of alkys. and / or alkoxy.
• metals of at least one element such as titanium, silicon zirconium, germanium, tin, tantalum, niobium ...) on at minus an oxide such as alumina (gamma, delta, eta forms, alone or as a mixture) silica, alumina silicas, titanium silicas, zirconia silicas or any other solid having any acidity.
• a particular embodiment of the invention may 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 85/15 to 15/85 and very preferably from 70/30 to 30/70 ".
• the temperature for this stage is generally between 10 and 350 ° C. depending on the type of catalyst or the strength of the acidity.
• the temperature is between 50 and 150 ° C. preferably between 50 and 120 ° C.
• the molar ratio of olefin to thiophene compounds is between 0.1 and 1000 mole / mole, preferably between 0.5 and 500 mole / mole.
• the operating pressure of this step is generally between 0.1 and 3 MPa and preferably such that the charge is in liquid form under the temperature and pressure conditions, ie at a pressure greater than 0.5 MPa.
• the effluent resulting from stage d, of transformation of the sulfur-containing compounds, preferably of alkylation or adsorption can optionally be mixed at least in part with a heavy cut resulting from the fractionation in stage c.
• the effluent from stage d of transformation of the sulfur compounds can also optionally be sent to a new fractionation unit to be separated into two fractions, an untreated intermediate fraction or optionally desulfurized without being mixed, and a heavy fraction which is preferably mixed with the heavy fraction from step d before being desulphurized in step f.
• effluent D1 resulting from an alkylation can be separated into:
• section D2 devoid of any thiophenic compound which is collected
• step d can optionally be advantageously carried out on the light fraction resulting from step c.
• the alkylation of the light mercaptans present in this fraction then facilitates the desired elimination of the sulfur compounds, but also makes it possible to reduce the vapor pressure (RVP index or Reid Vapor Pressure according to English terminology) of the final desulfurized gasoline.
• RVP index Reid Vapor Pressure according to English terminology
• All of the effluent D1 from said alkylation unit (step d) or the cut D3 from fractionation after alkylation can preferably be mixed at least in part with a heavy cut (for example the cut H2) and sent to the desulfurization section of step f. - desulfurization of the heavy fraction (step f) and optionally of at least one intermediate fraction (step e):
• This step can for example be a hydrodesulfurization step carried out by passing heavy or intermediate gasoline, in the presence of hydrogen, over a catalyst comprising at least one element from group VIII and / or at least one element from group Vlb to less partially in sulfide 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 1 and approximately 20 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 1 and 10 h -1, very preferably between 3 and 8 h
• the H 2 / HC ratio is between 100 to 600 liters per liter and preferably between 300 and 600 liters per liter.
• the content of group VIII metal expressed as oxide is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight.
• the metal content of group Vlb is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight.
• the element of group VIII, when it is present, is preferably cobalt, and the element of group Vlb, when it is present, is generally molybdenum or tungsten. Combinations such as cobalt-molybdenum are preferred.
• the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina or other porous solids, such as for example magnesia, silica or titanium oxide, alone or in combination. mixture with alumina or silica-alumina.
• the catalyst according to the invention preferably has a specific surface of less than 190 m2 / g, more preferably less than 180 m2 / g, and very preferably less than 150 m2 / g.
• the catalyst is in a first activated stage. This activation can correspond either to an oxidation then to a reduction, or to a direct reduction, or to a calcination only.
• the calcination step is generally carried out at temperatures ranging from approximately 100 to approximately 600 ° C. and preferably between 200 and 450 ° C., under an air flow.
• the reduction step is carried out under conditions which make it possible to convert at least part of the oxidized forms of the base metal to metal. Generally, it consists in treating the catalyst under a stream of hydrogen at a temperature preferably at least equal to 300 ° C. The reduction can also be carried out in part by means of chemical reducers.
• the catalyst is preferably used at least in part in its sulfurized form.
• the introduction of sulfur can occur before or after any activation step, that is to say calcination or reduction.
• no oxidation step of the catalyst is carried out when the sulfur or a sulfur-containing compound has been introduced onto the catalyst.
• the sulfur or a sulfur-containing compound can be introduced ex situ, that is to say outside the reactor where the process according to the invention is carried out, or in situ, that is to say in the reactor used for the method according to the invention.
• the catalyst is preferably reduced under the conditions described above, then sulphurized by passing a charge containing at least one sulfur compound, which once decomposed leads to the fixing of sulfur on the catalyst.
• This charge can be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur-containing compound.
• the sulfur-containing compound is added to the catalyst ex situ.
• a sulfur-containing compound can be introduced onto the catalyst in the optional presence of another compound.
• the catalyst is then dried, then transferred to the reactor used to carry out the process according to the invention.
• the catalyst is then treated under hydrogen in order to transform at least part of the main metal into sulphide.
• a procedure which is particularly suitable for the invention is that described in patents FR-B- 2,708,596 and FR-B- 2,708,597.
• the desulfurization of heavy petrol and / or at least one intermediate petrol can also be carried out by means of an absorber comprising an absorbent mass, for example based on zinc oxide.
• Said desulfurization can also be carried out by means of a combination between a hydrodesulfurization section and an absorber, preferably located after the hydrodesulfurization section.
• the desulphurization section preferably comprises only a single absorber and / or a single reactor.
• Said reactor contains only one type (in terms of chemical formulation) of hydrodesulfurization catalyst, possibly arranged in several separate beds.
• said catalyst is based on cobalt, more preferably it is a catalyst comprising cobalt and molybdenum or tungsten.
• the catalyst used in this section is sulfurized.
• the optional section for treating at least one intermediate section may comprise several reactors possibly associated with one or more absorbers.
• Said section can comprise two reactors in series, with a possible separation of the gas containing I ⁇ 2S and the liquid between the two reactors.
• two different catalysts arranged in at least two beds inside said reactors, possibly with an intermediate addition of hydrogen (also called quench according to English terminology).
• a catalyst comprising cobalt and molybdenum or tungsten combined with a catalyst comprising nickel.
• said catalysts are sulfurized.
• FIG. 1 illustrates certain preferred variants of the method according to the invention.
• the charge is admitted via line 1 and mixed with hydrogen arriving via line 2.
• the mixture 3 is introduced into the reactor 4 containing a catalyst for the selective hydrogenation of diolefins (step a).
• the effluent from this reactor is introduced into a reactor 7, optionally after addition of hydrogen via line 6.
• the reactor 7 contains a catalyst which makes it possible to weigh down light sulfur compounds, such as light mercaptans, by reaction with olefins (step b).
• the effluent 8 from the reactor 7 is introduced into a fractionation column (9) making it possible to separate the petrol into at least 2 sections: a light section 10 which is not treated, and a heavy section 13 which is desulphurized in a reactor 20 containing a hydrodesulphurization catalyst, after mixing with hydrogen supplied via line 19.
• the heavy desulphurized fraction 21 is mixed with the light fraction 10 to yield desulfurized gasoline 22.
• the fractionation column 9 makes it possible to separate the effluent 8 from the reactor 7 into 4 sections: a light section 10 untreated, a first intermediate section 11 introduced into a reactor alkylation 14 which makes it possible to carry out the alkylation of thiophene, thiophene compounds and optionally mercaptans and the effluent of which is returned to the fractionation column 9 via line 15, a second intermediate fraction 12 treated in the presence of hydrogen brought via line 16 in a reactor containing a hydrodesulfurization catalyst, and a heavy cut 13 which is also desulfurized in the presence of hydrogen supplied via line 19 in a reactor 20 containing a hydrodesulfurization catalyst.
• the desulfurized heavy fraction 21 and the desulfurized intermediate fraction 18 are mixed with the light fraction 10 to give the desulfurized gasoline 22.
• the method according to the invention is a method for producing gasoline with a low sulfur content comprising at least the following steps: at least one selective hydrogenation of the diolefins present in the initial gasoline (step a) , at least one step of transformation of the light sulfur compounds present in the gasoline (step b), at least one fractionation (step c) of the gasoline obtained in step a or b into at least two fractions a light fraction and a heavy fraction, a desulfurization treatment in one step (step f) of at least part of the heavy fraction resulting from the fractionation in step c.
• the process according to the invention is a process for producing petrol with a low sulfur content comprising at least the following stages: at least a selective hydrogenation of the diolefins present in the initial petrol (stage a), at minus a fractionation (step c) of the gasoline obtained in step a into at least two fractions, a light fraction and a heavy fraction, a step (step d) of transformation of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans present in at least one cut obtained in step c, a desulfurization treatment in one step (step f) of at least part of the heavy fraction resulting from the fractionation in step c .
• it can also further comprise at least one step of transformation of the light sulfur compounds present in the gasoline (step b).
• steps a and b are carried out simultaneously in the same reactor.
• steps b and / or d make it possible to increase the molecular weight of the sulfur-containing compounds, in order to mainly separate them in the heavy fraction of step c.
• the gasoline resulting from stages a or b can also, according to a variant, be fractionated into a light fraction, at least an intermediate fraction and a heavy fraction.
• the method according to the invention may also comprise at least one step d of transformation of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans present in the light cut and / or in at least an intermediate fraction.
• step d of transformation of the sulfur compounds is an alkylation or an adsorption.
• the method according to the invention can also further comprise a step e of desulphurization of at least part of at least one intermediate fraction resulting from the fractionation in step c or from step d of transformation of the sulfur-containing compounds.
• the heavy gasoline is desulfurized in step f in the presence of a hydrodesulfurization catalyst or an absorbent, and more preferably the heavy gasoline desulfurized in step f is stripped by means of an inert gas.
• the process according to the invention can also comprise a step g of mixing the light fraction resulting from step c or d and optionally at least one fraction intermediate from step c or d or e with the desulfurized heavy fraction from step f.
• the method according to the invention comprises at least one reaction section internal to the column and chosen from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (optional step b), transformation of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans (optional step d), desulfurization of the intermediate fractions (optional step e) and desulfurization of the heavy fraction (step f).
• At least one reaction section of the process according to the invention is coupled to the column and chosen from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (optional step b) , transformation of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans (optional step d), desulfurization of the intermediate fractions (optional step e) and desulfurization of the heavy fraction (step f).
• the effluent from step d of transformation of the sulfur-containing compounds can optionally be mixed at least in part with a heavy cut resulting from the fractionation in step c.
• Said effluent can also be sent to a new fractionation unit to be separated into two fractions, an untreated or optionally desulphurized intermediate fraction without being mixed, and a heavy fraction which is preferably mixed with the heavy fraction from step c before being desulphurized in step f.
• a catalytic cracking gasoline whose characteristics are presented in Table 1 is separated into two fractions (step c), a light fraction whose cutting point corresponds to a temperature of 63 ° C and a heavy fraction.
• the light fraction represents 25% by weight of the starting gasoline and groups together 88% of the compounds olefins having 5 carbon atoms which were present in the starting gasoline and 23% of olefins having 6 carbon atoms.
• the light fraction has a sulfur, mercaptan and diolefin content such that it is no longer necessary to carry out an additional treatment of this fraction before using it.
• the heavy fraction is subjected to hydrodesulfurization on a catalyst in an insulated tubular reactor.
• the catalyst is obtained by impregnating “without excess solution” with 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 a solution aqueous 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 of catalyst A is 3% CoO and 14% MoO3.
• the catalyst is sulphurized beforehand by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a load containing 2% by weight of S in the form of dimethylsulfide diluted in n-heptane.
• the heavy desulfurized gasoline is then mixed with the light gasoline, the composition of which is given in Table 1.
• the gasoline thus formed contains 185 ppm of sulfur including 100 ppm of mercaptans. Such a essence will therefore require additional treatment before its use.
• Example 2 (according to the invention): The gasoline whose characteristics are described in Example 1 is subjected to a hydrogenation treatment of the diolefins (step a) under conditions such that the light sulfur compounds present in the feed are partly converted into heavier compounds (stage b carried out simultaneously with stage a. This treatment is carried out in a continuous reactor operating in updraft.
• the catalyst is an HR945 catalyst sold by the company Procatalyse. The reaction is carried out at 160 ° C. under a total pressure of 13 bar, with a space velocity of 6 h "1. The H2 / charge ratio, expressed in liters of hydrogen per liter of charge and 10.
• step c the essence is separated into two fractions (step c) under the conditions described in Example 1.
• the characteristics of the two fractions obtained are specified in Table 4.
• the light fraction contains a sulfur, mercaptan and diolefin content such that it is no longer necessary to carry out an additional treatment of this fraction before using it.
• the heavy fraction is subjected to hydrodesulfurization on catalyst A of Example 1 in an insulated tubular reactor.
• the catalyst is sulphurized beforehand 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 S in the form of dimethyl sulphide diluted in n-heptane.
• the heavy desulfurized gasoline is then mixed with the untreated light gasoline, the composition of which is given in table 4.
• the desulfurized gasoline thus formed contains 147 ppm of sulfur, of which 68 ppm of mercaptans.

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