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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • 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
• • 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 present invention relates to a method for producing gasolines with low sulfur content, which makes it possible to recover the entire petrol cut containing sulfur, to reduce the total sulfur contents of said petrol cut to very low levels, without appreciable reduction in fuel efficiency, and minimizing the decrease in octane number due to hydrogenation of olefins.
• Hydrotreating (hydrodesulfurization) of the charge sent to the cracking catalytic leads to gasolines typically containing 100 ppm of sulfur.
• catalytic cracking charge hydrotreating units operate in severe temperature and pressure conditions, which requires effort significant investment.
• the entire feed must be desulphurized, which entails the processing of very large load volumes.
• Patent application EP-A-0 725 126 describes a hydrodesulfurization process of a cracked gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds easy to desulfurization and a second fraction rich in compounds difficult to desulfurize. Before to carry out this separation, it is first necessary to determine the distribution of the products sulfur by means of analyzes. These analyzes are necessary to select apparatus and separation conditions.
• US-A-5 318 690 proposes a process with fractionation of the essence and a softening of the light fraction, while the heavy fraction is desulfurized, then converted to ZSM-5 and desulfurized again under conditions sweet.
• This technique is based on a separation of the raw petrol so as to obtain a light cut practically free from sulfur compounds other than mercaptans. This makes it possible to treat said cut only by means of a softening which removes the mercaptans.
• the heavy cut contains a relatively large amount of olefins which are partially saturated during 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 H 2 S present in the medium to reform mercaptans. It is then necessary to carry out additional softening or hydrodesulfurization.
• the present invention relates to a method for producing gasolines with low sulfur content, which makes it possible to recover the entire petrol cut containing sulfur, preferably a gasoline catalytic cracked cut, and reduce sulfur contents in said gasoline cut at very low levels, without reduction appreciable fuel efficiency while minimizing the decrease in octane number due to the hydrogenation of olefins.
• the process according to the invention is a process for producing low-grade petrol in sulfur, from a gasoline cut containing sulfur.
• the method according to the invention comprises at least one treatment of the charge on a first catalyst making it possible to hydrogenate at least partially unsaturated sulfur compounds, especially sulfur compounds cyclic, even aromatic, such as, for example, thiophenic compounds placing in conditions where the hydrogenation of olefins is limited on this catalyst, then a second treatment on a second catalyst allowing decompose the saturated linear and / or cyclic sulfur compounds, with a limited hydrogenation of olefins.
• the two catalytic treatments can be carried out either in a reactor common with a chain of the two catalysts, ie in two reactors different. It is also desirable in some cases to add a step of pretreatment, preferably catalytic, aimed at hydrogenating the diolefins of the charge before the first step of the process according to the invention.
• the charge of the process according to the invention is a petrol cut containing sulfur, preferably a petrol cut from a catalytic cracking unit, whose range of boiling points typically extends from about the points boiling of hydrocarbons with 5 carbon atoms (C5) up to around 250 ° C.
• the end point of the gasoline cut depends on the refinery from which it comes and constraints of the market, but generally remains within the limits indicated above.
• the method according to the invention generally comprises at least a first step (step a), carried out by passing the charge, preferably consisting of the entire gasoline cut, over a catalyst making it possible to at least partially hydrogenate the compounds unsaturated sulfur present in said feed, such as for example thiophenic compounds, in saturated compounds, such as for example thiophanes (or thiacyclopentane), or mercaptans according to a succession of reactions described below:
• This hydrogenation reaction can be carried out on any catalyst which promotes these reactions such as for example a catalyst comprising at least one metal of group VIII and / or at least one metal from group Vlb, preferably at least in part in the form of sulfides.
• a catalyst comprising at least one metal of group VIII and / or at least one metal from group Vlb, preferably at least in part in the form of sulfides.
• the conditions are adjusted in order to be able to at least partially hydrogenate the compounds saturated, such as thiophenic compounds, while limiting the hydrogenation of olefins.
• the method according to the invention comprises a second step (step b) in which the saturated sulfur compounds are converted into H 2 S according to the reactions:
• This treatment can be carried out on any catalyst allowing the conversion of saturated sulfur compounds (mainly thiophanes or mercaptans type). It can for example be carried out on a nickel-based catalyst, molybdenum, or cobalt.
• the gasoline thus desulphurized is then 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 produced. during hydrodesulfurization.
• first step (step a) and second step (step b), do not exclude the possible presence of another stage, in particular a stage of pretreatment of the charge, consisting for example of the selective hydrogenation of dienes present in the charge.
• a stage of pretreatment of the charge consisting for example of the selective hydrogenation of dienes present in the charge.
• Such an optional pretreatment step is to preferably located before step a of the method according to the invention.
• the sulfur species contained in the feeds treated by the process of the invention can be mercaptans or heterocyclic compounds, such as for example thiophenes or alkyl thiophenes, or heavier compounds, such as for example benzothiophene or dibenzothiophene .
• heterocyclic compounds unlike mercaptans, cannot be removed by the extractive processes.
• sulfur-containing compounds are however eliminated by the process according to the invention which leads to their at least partial decomposition into hydrocarbons and H 2 S.
• the sulfur content of gasoline cuts produced by catalytic cracking depends on the sulfur content of the feed treated with FCC, as well as the point end of the cut.
• the sulfur contents of an entire cut gasoline, especially those from the FCC are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight.
• sulfur contents are often greater than 1000 ppm by weight, they can even in some cases reach values of on the order of 4000 to 5000 ppm by weight.
• the hydrogenation of dienes is an optional but advantageous 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 before 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 formed by platinum, palladium and nickel, and a support.
• a catalyst comprising at least one metal from group VIII, preferably chosen from the group formed by platinum, palladium and nickel, and a support.
• a nickel-based catalyst deposited on an inert support, such as, for example, alumina, silica or a support containing at least 50% alumina.
• This catalyst operates under a pressure of 0.4 to 5 MPa, at a temperature of 50 to 250 ° C, with an hourly space velocity of the liquid from 1 to 10 h -1 .
• Another metal can be combined to form a bimetallic catalyst, such as for example molybdenum or tungsten.
• the choice of operating conditions is particularly important. We will operate most generally under pressure in the presence of a small quantity of hydrogen excess over the stoichiometric value required to hydrogenate the diolefins.
• the hydrogen and the charge to be treated are injected in updrafts or descendants in a reactor preferably comprising a fixed bed of catalyst.
• the temperature is more generally between approximately 50 and approximately 250 ° C., and preferably between 80 and 200 ° C, and more preferably between 160 and 190 ° C.
• the pressure used is sufficient to maintain more than 80%, and preferably more than 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, and more preferably between 1 and 4 MPa.
• the space velocity is between approximately 1 and approximately 10 h -1 , preferably between 4 and 10 h -1 .
• the catalytic cracking gasoline can contain up to a few% by weight of diolefins. After hydrogenation, 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. Content dienes after selective hydrogenation can even be reduced to less than 250 ppm.
• the hydrogenation step of the dienes is takes place in a catalytic hydrogenation reactor which includes a zone catalytic reaction crossed by the entire charge and the quantity of hydrogen necessary to carry out the desired reactions.
• step a Hydrogenation of unsaturated sulfur compounds
• This step consists in transforming at least part of the unsaturated compounds sulfur such as thiophenic compounds, in saturated compounds for example in thiophanes (or thiacyclopentanes) or mercaptans.
• This step can for example be carried out by passing the charge, 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 at least partly in sulphide form, to a temperature between about 210 ° C and about 320 ° C, preferably between 220 ° C and 290 ° 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 10 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 3 and 8 h -1 .
• the H 2 / HC ratio is between 100 to 600 liters per liter and preferably between 300 and 600 liters per liter.
• a 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 the group Vlb (metals of group 6 of the new classification, i.e. chromium, molybdenum or tungsten), on a suitable support.
• the element of group VIII, when present, is usually nickel or cobalt, and the group element Vlb, when present, is generally molybdenum or tungsten.
• the catalyst support is usually a porous solid, such as for example a alumina, silica-alumina or other porous solids, such as for example magnesia, silica or titanium oxide, alone or in admixture with alumina or silica-alumina.
• the catalyst After introduction of the element (s) and possibly shaping of the catalyst (when this step is carried out on a mixture already containing the basic elements), the catalyst is in a first activated stage.
• This activation can correspond either to an oxidation, then to a reduction, or to a reduction direct, or to calcination only.
• the calcination step is generally carried out at temperatures ranging from about 100 to about 600 ° C and preferably between 200 and 450 ° C, under an air flow.
• the reduction stage is carried out under conditions allowing at least part of the oxidized forms to be converted metal base metal. Generally, it consists in treating the catalyst under a flow of hydrogen at a temperature preferably at least equal to 300 ° C.
• the reduction can also be achieved in part by 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 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. In this reactor, 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 conversion of unsaturated sulfur compounds is greater than 15% and preferably greater than 50%.
• the hydrogenation rate of olefins is preferably less than 50% and so preferred less than 40% during this step.
• the effluent from this first hydrogenation step is then sent to the level of the catalyst which makes it possible to decompose the saturated sulfur compounds into H2S.
• the saturated sulfur compounds are transformed into presence of hydrogen on a suitable catalyst.
• This transformation is carried out, without significant hydrogenation of olefins, i.e. during this stage the hydrogenation of olefins is generally limited to 20% by volume relative to the olefin content of the starting essence, and preferably limited to 10% by volume relative to the olefin content of gasoline.
• the catalysts which may be suitable for this stage of the process according to the invention, without this list being exhaustive, are catalysts comprising at least one metal base 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 base metal content of the catalyst according to the invention is generally between about 1 and about 60% by weight, preferably between 5 and 20% by weight.
• the catalyst is generally shaped, preferably under in the form of beads, pellets, extrudates, for example trilobes.
• Metal can be incorporated into the catalyst by deposition on the preformed support, it can also be mixed with the support before the shaping step.
• Metal is generally introduced in the form of a precursor salt, generally soluble in water, such as by for example nitrates, heptamolybdates. This method of introduction is not specific of the invention. Any other mode of introduction known to those skilled in the art is suitable for the invention.
• 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 can be used alone or as a mixture 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 After introduction of the base metal and possibly shaping of the catalyst (when this step is carried out from a mixture already containing the base metal), 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 still only to a calcination.
• the calcination step is generally carried out at temperatures ranging from about 100 to about 600 ° C and preferably between 200 and 450 ° C, under an air flow.
• the reduction stage is carried out under conditions allowing at least part of the oxidized forms to be converted metal base metal. Generally, it consists in treating the catalyst under a flow of hydrogen at a temperature at least equal to 300 ° C.
• the reduction can also be carried out in part by chemical reducers.
• the catalyst is preferably used at least in part in its sulfurized form. This has the advantage of minimizing the risk of hydrogenation of unsaturated compounds such as olefins or aromatic compounds during the start-up phase.
• the introduction of sulfur can occur between different activation stages. Preferably, no oxidation step is carried out when the sulfur or a sulfur-containing compound is 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 of the invention. In this reactor, 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 sulfur content of the catalyst is generally understood between 0.5 and 25% by weight, preferably between 4 and 20% by weight and very preferred between 4 and 10% by weight.
• the purpose of the hydrodesulfurization carried out during this stage is to convert into H2S saturated sulfur compounds in gasoline which has already undergone at least one the prior hydrogenation of the unsaturated sulfur compounds, so as to obtain a effluent, which will meet the desired specifications in terms of content of compounds sulfur.
• the gasoline thus obtained has only a small loss of octane.
• this second catalyst in this step, under specific operating conditions, allows the compounds to be broken down saturated, contained in the effluent from the previous step, in H2S.
• This setting work achieves a high overall level of hydrodesulfurization at the end of all the steps of the process according to the invention, while minimizing the loss in octane resulting from the saturation of olefins, because the conversion of olefins during of step b is generally limited to at most 20% by volume of the olefins, of preferably at most 10% by volume.
• the treatment aimed at decomposing the saturated sulfur compounds resulting from the first step 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 250 ° C and about 350 ° C, preferably between about 260 ° C and about 350 ° C, more preferably between about 260 ° C and about 320 ° C, under a low to moderate pressure, generally between approximately 0.5 and approximately 5 MPa, preferably between 0.5 and 3MPa, more preferably between 1 and 3 MPa.
• 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 come from step a or from recycling of the unconsumed hydrogen from step b. This hydrogen resulting from steps a or b may optionally contain unseparated H 2 S.
• One of the possibilities of implementing the method according to the invention consists, for example, in passing the gasoline to be hydrodesulfurized through two separate reactors containing respectively for the first reactor: all or part, preferably all, of a catalyst allowing, at least in part, the hydrogenation of unsaturated sulfur compounds (step a), such as for example thiophenic compounds, into saturated sulfur compounds (such as thiacyclopentanes or mercaptans) and for the second reactor: a catalyst allowing decomposing the saturated sulfur compounds into H 2 S (step b), and optionally another part of the catalyst required in step a, preferably at the head of the bed.
• steps a such as for example thiophenic compounds
• saturated sulfur compounds such as thiacyclopentanes or mercaptans
• the two catalysts can be placed in series in the same reactor.
• the two catalytic zones can operate in different or identical conditions of pressure, temperature, VVH, and H2 / charge ratio
• Example 1 hydrodesulfurization of gasoline on a catalyst allowing the conversion of unsaturated sulfur products.
• HR306C® catalyst sold by the company Procatalyse
• the catalyst is first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a load consisting of 2% by weight of sulfur in the form of dimethyldisulfide in n-heptane.
• Example 2 hydrodesulfurization of gasoline on a catalyst allowing the conversion of saturated sulfur compounds.
• the gasoline whose characteristics are described in Table 1 is subject hydrotreatment on a nickel-based catalyst in a tubular reactor isothermal, with fixed catalyst bed.
• the catalyst is prepared as follows.
• the catalyst 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.
• 1 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.
• the catalyst (100 ml) is then sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a feed containing 2% by weight of sulfur in the form of dimethyldisulphide in n-heptane.
• the test temperature is 300 ° C and 350 ° C.
• the characteristics of the effluents thus obtained are presented in Table 5.
• the nickel-based catalyst therefore makes it possible to desulfurize petrol without consumption of olefins.
• this catalyst it is difficult to achieve high hydrodesulfurization rates, except when working at temperatures significantly above 300 ° C, which results in more octane loss important and imposes constraints at the process level.
• Example 3 hydrodesulfurization with a cobalt-molybdenum catalyst and a recycle of hydrogen.
• the gasoline whose characteristics are described in Table 1 is subject to a hydrodesulfurization on a conventional hydrotreatment catalyst in a reactor insulated tubular.
• 25 ml of HR306C® catalyst, sold by the company Procatalyse, are placed in the hydrodesulfurization reactor.
• the catalyst is everything first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a load consisting of 2% by weight of sulfur in the form of dimethyldisulfide in n-heptane.
• Table 8 presents the results of analysis of the nature and of the concentration of the sulfur-containing compounds obtained after hydrodesulfurization.
• Sulfur compounds identified Charge concentration (ppm) Effluent concentration 8% HDS (ppm) Effluent concentration 20% HDS (ppm) Thiophene 235 10 0 Mercaptans 0 699 631 Methylthiophenes 487 5 0 Thiacyclopentane 82 150 173 Methylthiacyclopentane 40 85 60 C2 Thiophenes 227 18 0 diethylsulfide 11 0 0 C3 Thiophenes 26 0 0 C2 Thiacyclopentanes 46 98 53 C3 Thiacyclopentanes 46 35 36
• Example 4 Hydrodesulfurization with a chain of catalysts for hydrogenation of unsaturated compounds and then for decomposition of saturated sulfur compounds, and with hydrogen recycling.
• the gasoline whose characteristics are described in Table 1 is subject to a hydrodesulfurization on a chain of catalysts in an insulated tubular reactor.
• 25 ml of HR306C® catalyst, sold by the company Procatalyse, and 50 ml of catalyst obtained according to the same protocol as that described in Example 2 are placed in the hydrodesulfurization reactor.
• the catalysts are first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a charge consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
• the temperature of the catalytic zone comprising the HR306C® catalyst is 250 ° C.
• the temperature of the catalytic zone containing the catalyst of Example 2 is 290 ° C.
• an amount of H 2 S corresponding to a partial pressure of 0.023 MPa is injected at the inlet of the reactor.
• Example 5 hydrodesulfurization with a chain of catalysts for hydrogenation of unsaturated compounds and decomposition of saturated sulfur compounds, with recycle of hydrogen.
• the gasoline whose characteristics are described in Table 1 is subject to a hydrodesulfurization on a chain of catalysts in an insulated tubular reactor.
• 25 ml of HR306C® catalyst, sold by the company Procatalyse, and 50 ml of catalyst obtained according to the same protocol as that described in Example 2 are placed in the hydrodesulfurization reactor.
• the catalysts are first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a charge consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
• the temperature of the catalytic zone comprising the HR306C® catalyst is 230 ° C.
• the temperature of the catalytic zone containing the catalyst of Example 2 is 270 ° C.
• an amount of H 2 S corresponding to a partial pressure of 0.023 MPa is injected at the inlet of the reactor.
• Example 6 hydrodesulfurization with a chain of catalysts for hydrogenation of unsaturated compounds and decomposition of saturated sulfur compounds operating at low temperature, with recycle of hydrogen.
• the gasoline whose characteristics are described in Table 1 is subject to a hydrodesulfurization on a chain of catalysts in an insulated tubular reactor.
• 25 ml of HR306C® catalyst, sold by the company Procatalyse, and 50 ml of catalyst obtained according to the same protocol as that described in Example 2 are placed in the hydrodesulfurization reactor.
• the catalysts are first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a charge consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
• the temperature of the catalytic zone comprising the HR306C® catalyst is 230 ° C.
• the temperature of the catalytic zone containing the catalyst of Example 2 is 200 ° C.
• an amount of H 2 S corresponding to a partial pressure of 0.023 MPa is injected at the inlet of the reactor.

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