EP1931751B1 - Gasoline desulfurization method comprising adsorption desulfurization of the light fraction and hydrodesulfurization of the heavy fraction - Google Patents

Description

Field of the invention

The present invention relates to a process for producing gasoline with a low sulfur content and high octane number from an initial gasoline comprising olefins and thiophene-type sulfur compounds.

Typically the gasoline concerned by the invention is a catalytic cracking gasoline, but it can also be a gasoline resulting from a conversion process such as coking, or even from a straight-run gasoline, or from even more generally, of any mixture of the said essences.

The present method therefore finds particular application in the desulfurization of gasolines resulting from a catalytic cracking process, fluid catalytic cracking, coking, visbreaking, or pyrolysis.

This process must be considered as a refinement of the demand FR 2,857,973 . The improvement described in the present invention with respect to the patent application FR 2,857,973 is to use an internal process flow to regenerate the adsorbent solid used to desulfurize the light fraction by adsorption. Flow internal process means a flow generated by one of the units forming part of the process object of the invention.

Examination of the prior art

The relevant prior art with respect to the present invention consists of the teachings relating to a gasoline desulphurization with decomposition of the said gasoline into two sections, each being the subject of a specific treatment, an adsorption desulfurization for the so-called light, and a hydrodesulfurization for the so-called heavy cut.

• La demande de brevet FR 2 857 973 décrit un tel procédé dans lequel l'essence à traiter est divisée en une fraction légère envoyée dans une unité de désulfuration par adsorption, et une fraction lourde envoyée dans une unité d'hydrodésulfuration traditionnelle.
• La demande WO 02/36718 propose de séparer l'essence de FCC en une partie légère riche en oléfines et ne comprenant que des composés soufrés du type mercaptans, et en une partie lourde qui concentre le thiophène et ses dérivés (regroupés sous le terme de composés thiophéniques), et les composés soufrés les plus lourds.

The documents US2005 / 0092655 and US2005 / 0061712 describe a process for desulfurization of a hydrocarbon feedstock by adsorption / desorption. The feedstock is separated into two cuts by distillation, the light cut being desulphurized by adsorption, the heavy cut being desulfurized by hydrogenation in the presence of a catalyst and hydrogen. The desorption is carried out by means of a stream of hydrogen resulting from the heavy cut produced by the hydrodesulfurization section. The document US2005 / 0092655 proposes, moreover, to carry out the regeneration by means of a liquid solvent.

• The patent application FR 2,857,973 describes such a process in which the gasoline to be treated is divided into a light fraction sent to an adsorption desulphurization unit, and a heavy fraction sent to a traditional hydrodesulfurization unit.
• Requirement WO 02/36718 proposes to separate the essence of FCC into a light part rich in olefins and comprising only sulfur compounds of the mercaptan type, and a heavy part which concentrates the thiophene and its derivatives (grouped under the term of thiophene compounds), and the heavier sulfur compounds.

The mercaptans present in the light fraction are then removed by a process using an extractive solution of sodium hydroxide. The heavy fraction is desulphurized by a conventional hydrodesulphurization process.

• Le brevet US 6,482,316 B1 propose de désulfurer par adsorption une essence dont la température d'ébullition est comprise entre 10°C et 150°C, et de régénérer le solide adsorbant utilisé par un fluide de la raffinerie dont la température d'ébullition est située dans la même gamme de température. Le brevet en question précise dans une revendication dépendante que le flux préféré pour effectuer la dite régénération est un réformat, donc un flux riche en aromatiques, d'intervalle de distillation typiquement compris entre 10°C et 150°C.

The cutting point of the two fractions is, however, relatively low (below 75 ° C. in the abovementioned application), which limits the interest of such a process, the light fraction comprising a reduced portion of the hydrocarbons contained in the initial gasoline. .

• The patent US 6,482,316 B1 proposes to desulphurize by adsorption a gasoline whose boiling temperature is between 10 ° C and 150 ° C, and to regenerate the adsorbent solid used by a refinery fluid whose boiling point is in the same range of temperature. The patent in question specifies in a dependent claim that the preferred flux for effecting said regeneration is a reformate, thus a rich aromatic stream, distillation range typically between 10 ° C and 150 ° C.

Unlike the patent US 6,482,316 the process which is the subject of the present invention is optionally capable of treating a gasoline whose boiling temperature is between 25 ° C and 300 ° C.

In addition, the said gasoline is separated by distillation into a light gasoline and a heavy gasoline. The light fraction is desulfurized in an adsorption desulfurization unit, and the heavy fraction is desulphurized in a hydrodesulphurization unit.

Regeneration of the adsorbent used to desulphurize the light cut is done with a fraction of the heavy desulphurized cup whose final boiling point can be up to 300 ° C.

This fraction of the heavy desulfurized fraction contains aromatics but is distinct from a reformate by its distillation range.

In the case of the use of reformate as adsorbent solid regenerating agent, as taught in the patent US 6,428,316 , the regeneration of the reformed polluted by the sulfur is generally done by hydrotreatment, but this generates an imbalance of the flows of the refinery that can be expensive and also leads to a decrease in the amount of reformate available for use in eg petrochemicals.

The use of a portion of the heavy desulfurized cut to regenerate the adsorbent solid used in the adsorption treatment of the light cut is therefore an innovative and more economical solution than the solutions of the prior art because it does not disturb the pattern. conventional refinery, and is applicable in all refineries, especially in those that are not equipped with a process of reforming species.

Brief description of Figure 1

the figure 1 represents a diagram of the method according to the invention in which the optional unit E0 is represented in dashed line.

Brief description of the invention

The present invention relates to a process for the desulphurization of a gasoline containing sulfur and unsaturated compounds, generally a catalytic cracking gasoline, comprising at least one separation unit of said gasoline into a light fraction and a heavy fraction, a desulphurization unit by adsorption of said light fraction, and a hydrodesulfurization unit of said heavy fraction, the process being characterized in that the regeneration of the adsorbent solid used in the desulfurization unit by adsorption of the light fraction, is carried out through a portion of said heavy fraction desulphurized, that is to say after its desulfurization in the hydrodesulfurization unit.

1. a) une étape de distillation de l'essence initiale en au moins deux fractions dont:
   • une fraction légère contenant la majorité des oléfines à 5 et 6 atomes de carbone, ainsi que le thiophène, et de préférence les méthylthiophènes,
   • une fraction lourde ne contenant plus d'oléfines à 5 atomes de carbone, et concentrant les composés soufrés lourds tels que les benzothiophènes.
2. b) une étape de désulfuration de la dite fraction légère par adsorption des composés soufrés sur un solide adsorbant, le solide adsorbant utilisé étant choisi dans le groupe constitué par les silices, les alumines, les zéolithes, les charbons actifs, les résines, les argiles, les oxydes de métaux et les métaux réduits,
3. c) une étape d'hydrodésulfuration de la dite fraction lourde sur un catalyseur contenant au moins un métal du groupe VIII et un métal du groupe VIb, dans des conditions classiques d'hydrodésulfuration,

la régénération du solide adsorbant étant réalisée à une température supérieure à 50°C, tout en restant en phase liquide, au moyen d'un solvant de désorption qui est une partie de l'effluent de l'étape d'hydrodésulfuration de la fraction lourde, le solvant comprenant au moins une partie de composés aromatiques, et la partie complémentaire de l'effluent de la dite étape d'hydrodésulfuration étant mélangée avec l'effluent de l'étape de désulfuration par adsorption de la fraction légère pour constituer l'essence désulfurée à haut indice d'octane, le solvant issu de la régénération étant recyclé en étant mélangé à ladite fraction lourde avant d'effectuer l'étape c).More specifically, the process according to the invention is a process for producing a high octane desulfurized gasoline from an initial gasoline comprising olefins and thiophene compounds, said process comprising the following steps:

1. a) a step of distilling the initial gasoline into at least two fractions, including:
   • a light fraction containing the majority of olefins with 5 and 6 carbon atoms, as well as thiophene, and preferably methylthiophenes,
   • a heavy fraction no longer containing 5-carbon olefins, and concentrating heavy sulfur compounds such as benzothiophenes.
2. b) a step of desulfurizing said light fraction by adsorption of the sulfur compounds on an adsorbent solid, the adsorbent solid used being chosen from the group consisting of silicas, aluminas, zeolites, activated carbons, resins, clays , metal oxides and reduced metals,
3. c) a step of hydrodesulfurization of said heavy fraction on a catalyst containing at least one Group VIII metal and a Group VIb metal, under conventional hydrodesulfurization conditions,

the regeneration of the adsorbent solid being carried out at a temperature above 50 ° C., while remaining in the liquid phase, by means of a desorption solvent which is a part of the effluent from the hydrodesulfurization step of the heavy fraction the solvent comprising at least a portion of aromatic compounds, and the complementary portion of the effluent of said hydrodesulfurization step being mixed with the effluent of the desulfurization step by adsorption of the light fraction to form the gasoline; high octane desulfurized, the solvent from the regeneration being recycled by being mixed with said heavy fraction before performing step c).

The present process provides both better adsorption selectivity to the thiophene compounds present in the initial charge, reduced hydrogen consumption, and furthermore achieves future sulfur standards in gasolines.

It should be noted that the process is applicable to gasolines with a very variable sulfur level ranging from a few tens of ppm to a few percent.

The method according to the invention makes it possible to recover a characteristic gasoline very similar to that of the gasoline to be treated with a desulfurization rate which is at least 50%, and preferably at least 80%.

As mentioned in the previous paragraph, the process according to the invention does not disturb the refining scheme, and even applies to refineries that do not have a petrol reforming unit.

On the other hand, the present invention makes it possible to carry out the desulphurization of said hydrocarbon fraction by minimizing the loss of octane by hydrogenation of the olefins since this octane loss is especially sensitive on the heavy fraction of the gasoline to be treated, the light fraction being desulphurized by adsorption, thus preserving the octane number.

As a result, the octane number of the gasoline produced is very little affected by the process, and is less than 10% less than the octane number of the gasoline to be treated, and the most often less than 5% less than the octane number of the gasoline to be treated.

Detailed description of the invention

The following description is given for illustrative purposes and does not limit the scope of the present process. In this description, it has been arbitrarily chosen as the hydrocarbon fraction to treat a gasoline resulting from a catalytic cracking process, representative of the cuts on which the present process can be applied.

Fractionation step of the gasoline to be treated (step a):

• une fraction légère contenant la majorité des oléfines à 5 et 6 atomes de carbone ainsi que le thiophène, et de préférence les méthylthiophènes,
• une fraction lourde ne contenant plus d'oléfines à 5 atomes de carbone, et concentrant les composés soufrés lourds tels que les benzothiophènes.

According to a first embodiment (mode I) of the invention, the essence is split into two fractions:

• a light fraction containing the majority of the olefins with 5 and 6 carbon atoms as well as the thiophene, and preferably the methylthiophenes,
• a heavy fraction no longer containing 5-carbon olefins, and concentrating heavy sulfur compounds such as benzothiophenes.

The light fraction generally has an end point of from about 90 ° C to about 200 ° C, preferably from about 90 ° C to about 160 ° C, most preferably from about 90 ° C to 110 ° C.

This separation is conventionally carried out by means of a distillation column.

• une fraction légère comprenant les composés contenus dans l'essence initiale dont la température d'ébullition est inférieure à la température d'ébullition du thiophène,
• une fraction intermédiaire comprenant au moins le thiophène, et dont le point d'ébullition final est compris entre environ 90°C et environ 200°C, de façon préférée compris entre environ 90°C et environ 160°C, de façon très préférée entre environ 90°C et environ 110°C.
• une fraction lourde concentrant les composés soufrés lourds tels que les benzothiophènes.

According to a second embodiment of the invention (mode II), the essence is distilled into three fractions:

• a light fraction comprising the compounds contained in the initial gasoline, the boiling temperature of which is lower than the boiling point of the thiophene,
• an intermediate fraction comprising at least thiophene, and whose final boiling point is between about 90 ° C and about 200 ° C, preferably between about 90 ° C and about 160 ° C, very preferably between about 90 ° C and about 110 ° C.
• a heavy fraction concentrating heavy sulfur compounds such as benzothiophenes.

The cutting point of the distillation for splitting the gasoline to be treated in two or three fractions is chosen according to the composition of the initial gasoline to be treated and / or depending on the concentration of aromatic hydrocarbons present in the light fraction. (mode I), or in the intermediate fraction (mode II) after fractionation.

It was indeed unexpectedly found by the plaintiff that. during the adsorption step b) described below, the efficiency of the desulfurization is better if the weight percentage of aromatic compounds in said light fraction is less than 25%, and preferably less than 10%, and so still preferred less than 5%.

According to a preferred embodiment of the invention, the cutting point of the light fraction will be chosen according to the composition of the gasoline to be treated so as to have a weight percentage of aromatic compounds present in said light fraction less than 25%, preferably less than 10%, and more preferably less than 5%.

Adsorption / desorption step of the light fraction (step b):

This step consists in eliminating the sulfur compounds present in the light fraction (mode I) or in the intermediate fraction (mode II) resulting from stage a).

According to a preferred embodiment of the invention, said fractions have previously been depleted of mercaptan type compounds, for example by a selective hydrogenation step as described below.

This adsorption step is carried out by contacting the feedstock to be treated with an adsorbent solid having a high affinity with the sulfur compounds, preferably the thiophene compounds.

The solids used as adsorbent can be selected from the following families of adsorbents; silicas, aluminas, zeolites, preferably faujasites, and preferably faujasites partially exchanged with cesium, activated carbons, resins, clays, metal oxides, reduced metals.

It is also possible to use an adsorbent solid having an increased adsorption capacity towards sulfur compounds, by appropriate physical surface treatments, for example temperature treatments, or chemical surface treatments, for example the grafting of molecules. specific surface.

It is also preferable to use solids whose residual acidity is controlled in order to avoid any olefin coking reaction likely to cause rapid aging of the solid used. To avoid this kind of phenomenon, one can for example perform treatments with potash or soda.

Regeneration of the adsorbent solid will be via adsorption / regeneration cycles known per se to those skilled in the art. The experimental conditions of the adsorption and the regeneration will be selected so as to maximize the dynamic capacity of the solid, ie the difference between the quantity of sulfur captured during the adsorption and the quantity of sulfur remaining on the solid after regeneration.

When the adsorption is operated in the liquid phase, it can be done under mild conditions of temperature and pressure to remain in the liquid phase and typically ranging from 0 C. at 200 ° C. under a pressure ranging from 0.1 MPa to 30 MPa (1 MPa = 10 bar) and preferably from 10 ° C. to 100 ° C. under a pressure ranging from 0.2 MPa to 10 MPa.

Regeneration of the adsorbent solid is done using a regeneration fluid or solvent having a sufficiently high desorption power. In general, the regeneration solvent is chosen to replace the gasoline retained in the pores of the adsorbent solid, then to cause the desorption of the other compounds retained on the solid, in particular sulfur compounds.

According to the invention, the regeneration solvent will comprise at least a portion of aromatic compounds. Said part of aromatic compounds will be at least 10% by weight, and preferably at least 25% by weight.

The regeneration solvent is furthermore characterized by a sulfur content lower than the sulfur content of the desulfurized gasoline by adsorption. Generally, the sulfur content of the regeneration solvent is less than 100 ppm, preferably less than 50 ppm, and very preferably less than 20 ppm.

According to the invention, a part of the heavy fraction resulting from the separation of the gasoline to be treated into two fractions according to step a) will be used as regeneration solvent of the adsorbent solid, the said heavy fraction having been desulphurized in the first stage. hydrodesulfurization unit (HDS) subject of step c) of the process according to the invention.

The regeneration solvent according to the invention is therefore a part of the heavy desulfurized fraction, said part being calculated to allow optimum regeneration of the adsorbent solid.

It is moreover preferable to carry out the regeneration at a temperature above 80 ° C., and more preferably above 100 ° C., while remaining in the liquid phase, to promote the desorption of the sulfur-containing molecules, and thus to use a minimal portion of said heavy desulfurized fraction to regenerate the adsorbent solid.

The regeneration effluent containing the sulfur molecules initially retained on the adsorbent solid is recycled to the inlet of the hydrodesulfurization unit of the heavy fraction.

Hydrodesulfurization step of the heavy fraction (step c):

The heavy fraction obtained from step a) of distillation of the gasoline to be treated is subjected to a hydrodesulfurization treatment. This step can be carried out by passing gasoline, in the presence of hydrogen, over a catalyst comprising at least one element of group VIII selected from the group consisting of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum, and at least one group VIB element selected from the group consisting of chromium, molybdenum and tungsten, each of which is at least partly in the form of sulphide.

The reaction temperature is generally between 220 ° C. and 340 ° C. under a pressure of between about 1 MPa and 5 MPa (1 MPa = 10 bars).

The hourly space velocity is between about 1h ^-1 and 20 h ^-1 .

The ratio of the hydrogen flow rate to the feed rate is between 100 liters / liter and 600 liters / liter, expressed as normal liters of hydrogen per liter of gasoline.

The catalyst used to carry out the hydrodesulfurization of the heavy fraction comprises between 0.5% and 15% by weight of Group VIII metal, this percentage expressed in oxide form.

The content by weight of Group VIB metal is generally between 1.5% and 60% by weight and preferably between 2% and 50% by weight.

The element of group VIII is preferably cobalt, and the element of group VIB is preferably molybdenum or tungsten.

The catalyst support is usually a porous solid, such as, for example, magnesia, silica, titanium oxide or alumina, alone or as a mixture.

The effluent from hydrodesulphurization step c) is mixed with the adsorption effluent of step b) to form the high octane desulfurized gasoline.

The sulfur content of said gasoline resulting from the process is reduced by at least 50% and preferably by at least 80% relative to the starting gasoline.

This hydrodesulfurization step c) may furthermore comprise a step of finishing the hydrodesulfurization carried out on a catalyst comprising at least one element of group VIII, preferably chosen from the group formed by nickel, cobalt or iron. .

The metal content of the catalyst of the finishing step is generally from about 1% to about 60% by weight as oxide. This finishing step makes it possible to eliminate the residual sulfur compounds, and mainly the saturated sulfur compounds which will have been formed during the first hydrodesulfurization step.

The temperature of the finishing step is generally between 240 ° C and 360 ° C, and is preferably greater than at least 10 ° C at the inlet temperature of the hydrodesulfurization step.

The pressure is between about 1 MPa and 5 MPa. The hourly space velocity is between about 1 hr ^-1 and 20 hr ^-1 . The ratio of the hydrogen flow rate to the feed rate is between 100 liters / liter and 600 liters / liter, expressed as normal liters of hydrogen per liter of gasoline.

Optional step of selective hydrogenation of the gasoline to be treated:

This optional step, carried out upstream of steps a), b), c), is intended to at least partially remove the diolefins present in the gasoline, and to convert the light sulfur compounds by weighting. Diolefins are in fact precursors of gums which polymerize in hydrodesulphurization or adsorption reactors, especially when the adsorbent solid has an acidity, and thus limit its shelf life. The diolefins are thus hydrogenated to olefins during this step.

This step also makes it possible to convert light sulfur compounds, such as mercaptans, sulphides and CS2, whose boiling point is generally lower than that of thiophene, into heavier sulfur compounds whose boiling point is greater than that of thiophene. by reaction with the olefins present in the feed.

According to the present invention, a majority of said heavy compounds thus formed will be discharged into the heavy fraction after fractionation (step a).

The selective hydrogenation step generally takes place in the presence of a catalyst comprising at least one Group VIII metal, preferably selected from the group consisting of platinum, palladium and nickel, deposited on a support.

For example, a catalyst containing from 1% to 20% by weight of nickel deposited on an inert support, such as, for example, alumina, silica, silica-alumina or a nickel aluminate, will be used. Preferably, the support will contain at least 50% alumina.

Another Group VIB metal such as, for example, molybdenum or tungsten may optionally be combined with the Group VIII metal to form a bimetallic catalyst. This group VIB metal will be deposited at a level of 1% by weight at 20% by weight on the support.

The choice of the operating conditions of the selective hydrogenation step is particularly important. The operation will generally be carried out under pressure in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value necessary for hydrogenating the diolefins. The hydrogen and the feedstock to be treated are injected in ascending or descending streams into a reactor preferably with a fixed bed of catalyst.

The temperature is generally between 50 ° C and 300 ° C, preferably between 80 ° C and 250 ° C, and more preferably between 120 ° C and 210 ° C.

The pressure is chosen 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 from 0.4 MPa to 5 MPa, and preferably from 1 MPa to 4 MPa.

The space velocity is generally between 1 h ^-1 and 12 h ^-1 , preferably between 2 h ^-1 and 10 h ^-1 .

The light fraction of the catalytic cracking gasoline fraction can contain up to a few% by weight of diolefins. After hydrogenation, the diolefin content is reduced to less than 3000 ppm, preferentially less than 2500 ppm, and very preferably less than 1500 ppm.

Concomitantly with the selective hydrogenation reaction of the diolefins, there is an isomerization of the double bond of the external olefins leading to the formation of internal olefins. This isomerization results in a slight gain in the number of octane due to the fact that the internal olefins have an octane number generally higher than that of the terminal olefins.

According to one embodiment of the invention, the selective hydrogenation step takes place in a catalytic hydrogenation reactor comprising a catalytic reaction zone traversed by the entire charge and the quantity of hydrogen necessary to effect the desired reactions. .

The invention will be better understood on reading the following description, in connection with the figure 1 corresponding to one embodiment of the method according to the invention (mode 1).

The gasoline to be treated originating from a catalytic cracking unit (not shown in FIG. 1) is in certain cases sent via line 1 to a selective hydrogenation reactor E0, mixed with a flow of a gas comprising hydrogen (not shown on the figure 1 ).

Recall that the selective hydrogenation unit E0 is optional.

The effluent from reactor E0 is sent via line 2 to a distillation column E1 which produces a light fraction at the top discharged via line (4), and a heavy fraction at the bottom discharged via line (3).

The heavy fraction (3) from the distillation column E1 is mixed with the desorption solvent (8) of the adsorption desulfurization unit (Ad) in the desorption phase to form the charge (3a).

The charge (3a) resulting from the mixing of the lines (3) and (8) is introduced into the hydrodesulfurization reactor E4.

The effluent (5a) of the hydrodesulfurization reactor E4 is separated into a portion (7) which is used for the regeneration of the adsorption desulphurization unit (Ad), and a complementary part (5) which is mixed with the effluent (6) of the adsorption desulfurization unit (Ad) in the adsorption phase to form the desulphurized gasoline (9) which is directed to the gasoline pool.

The light fraction recovered by the line (4) is sent to the desulfurization unit (Ad). The adsorption desulfurization unit (Ad) comprises at least two capacities working alternately in adsorption, on the figure 1 capacity (E2) and desorption, on the figure 1 the capacity (E3).

After a certain time the capacitance (E2) switches to the regeneration phase and the capacitance (E3) switches to the adsorption phase.

The switchover from the adsorption phase to the regeneration phase is done by means of additional lines and valve opening and closing systems not shown on the display. figure 1 .

The capacity E3 is supplied with desorption solvent via the line (7) consisting of a fraction of the desulfurization effluent from the hydrodesulfurization unit E4.

Example

The following nonlimiting example provides a better understanding of the advantages of the present invention.

A representative gasoline I of a catalytic cracking gasoline is synthesized by taking up the proportions of paraffins (n-heptane, isooctane), olefins (1-hexene, 1-dodecene), aromatic compounds (toluene, metaxylene) and of sulfur compounds (thiophene, benzothiophene) usually encountered in a cracking gasoline.

Table 1 gives the characteristics of gasoline I. Table 1 Compound Mass (g) % weight nC7 195.6 24.0 iso octane 142.8 17.5 1 hexene 203.9 25.0 1-dodecene 102.0 12.5 toluene 8.3 1.0 meta xylene 162.6 19.9 thiophene 0.11 0.01 50 ppm S benzothiophene 0.51 0.06 150 ppm S

A gasoline II reproducing the proportions of paraffins (n-heptane), olefins (1-hexene), aromatic compounds (toluene) and sulfur compounds (thiophene) of the light fraction obtained after fractionation at 90 ° C. essence I was synthesized.

Table 2 gives the characteristics of this species II. Table 2 Compound Mass (g) % weight n heptane 195.6 48.0 1 hexene 203.9 50.0 toluene 8.3 2.0 thiophene 0.11 0.03 100 ppm S

A gasoline III reproducing the proportions of paraffins (iso octane), olefins (1-dodecene), aromatic compounds (metaxylene) and sulfur compounds (benzothiophene) of the heavy fraction obtained after fractionation at 90 ° C. essence I was synthesized. Table 3 gives the characteristics of this species III. Table 3 Compound Mass (g) % weight iso octane 142.8 35.0 1-dodecene 102.0 25.0 meta xylene 162.6 39.9 benzothiophene 0.51 0.13 300 ppmS

An IV gasoline reproducing the proportions of paraffins (isooctane), olefins (1-dodecene), aromatic compounds (metaxylene) obtained by hydrodesulfurization of gasoline III was synthesized.

Table 4 gives the characteristics of this species IV. Table 4 Compound Mass (g) % weight iso octane 191.9 47.0 1-dodecene 52.9 13.0 meta xylene 162.6 39.9

Synthetic essence II representing the light fraction to desulfurize by adsorption is sent using a liquid pump on an adsorption column filled with an adsorbent NaCsX type.

This NaCsX solid is obtained by ion exchange carried out dynamically on a NaX zeolite with an aqueous solution of CsCl.sub.1 concentrated to 1.8 mol / l at a temperature of 90.degree.

The adsorption column contains 20 ml of adsorbent solid, and it has been possible to desulphurize at least 100 ml of gasoline II with a sulfur content of less than 5 ppmS.

Regeneration of the adsorbent solid is carried out by passing the synthetic essence IV at a temperature of 60 ° C in the adsorption column.

The sulfur concentration at the output increases sharply at first, then returns to values close to 0 ppm S after the passage of 100 ml of this charge, which indicates the end of the desorption step.

This example demonstrates the capacity of the desulphurized heavy fraction (represented by the synthetic gasoline IV) derived from the gasoline to be desulphurized (represented by the synthetic gasoline I) to desorb the sulfur contained in the adsorbent solid after the desulfurization step. by adsorption of the light fraction represented by synthetic essence II.

Claims (11)

1. Process for the production of a desulfurized gasoline with a high octane number from a starting gasoline that comprises olefins and thiophenic compounds, whereby said process comprises the following stages:

   a) a stage for distillation of the starting gasoline into at least two fractions including:

   - a light fraction containing the majority of olefins with 5 and 6 carbon atoms, as well as thiophene, and preferably methylthiophenes,

   - a heavy fraction that no longer contains olefins with 5 carbon atoms and concentrates the heavy sulfur-containing compounds such as the benzothiophenes,

   b) a stage for desulfurization of said light fraction by adsorption of the sulfur-containing compounds on an adsorbent solid, whereby the adsorbent solid that is used is selected from the group that consists of silicas, aluminas, zeolites, active carbons, resins, clays, metal oxides and reduced metals,

   c) a stage for hydrodesulfurization of said heavy fraction on a catalyst that contains at least one metal of group VIII and a metal of group VIb, under standard hydrodesulfurization conditions,

   whereby the regeneration of the adsorbent solid being realized at a temperature of greater than 50°C, while remaining in liquid phase, is carried out by means of a desorption solvent that is a portion of the effluent of the hydrodesulfurization stage of the heavy fraction, said solvent comprising at least a portion of aromatic compounds, whereby the additional portion of the effluent of said hydrodesulfurization stage is mixed with the effluent of the desulfurization stage by adsorption of the light fraction to constitute the desulfurized gasoline with a high octane number, the solvent resulting from the regeneration being recycled by being mixed with said heavy fraction before realizing step c).
2. Process for the production of a desulfurized gasoline according to claim 1, in which the stage for separation of the gasoline to be treated produces, in addition to the light and heavy fractions, an intermediate fraction that comprises at least the thiophene and whose final boiling point is between 90°C and 160°C.
3. Process for the production of a desulfurized gasoline according to claim 2, in which the stage for desulfurization by adsorption is applied to the intermediate fraction that is obtained from the distillation of the gasoline into three fractions.
4. Process for the production of a desulfurized gasoline according to any of claims 1 to 3, in which the adsorbent solid that is used in the stage for desulfurization by adsorption is selected from among the zeolites, preferably the faujasite-type zeolites, and also preferably is selected from among the faujasites that are partially exchanged with cesium.
5. Process for the production of a desulfurized gasoline according to any of claims 1 to 4, in which the adsorption stage is carried out in liquid phase at a temperature of between 0°C and 200°C and at a pressure of between 0.1 MPa and 30 MPa.
6. Process for the production of a desulfurized gasoline according to any of claims 1 to 5, in which the desorption stage is operated at a temperature of more than 50°C, preferably more than 80°C, and even more preferably more than 100°C.
7. Process for the production of a desulfurized gasoline according to any of claims 1 to 6, in which the hydrodesulfurization stage of the heavy fraction is carried out on a catalyst that comprises between 0.5% and 15% by weight of a metal of group VIII and that comprises between 1.5% and 60% by weight, and preferably between 2 and 50% by weight, of a metal of group VIb.
8. Process for the production of a gasoline according to claim 7, in which the metal of group VIII is preferably cobalt, and the metal of group VIb is selected from the group that is formed by the molybdenum and tungsten.
9. Process for the production of a desulfurized gasoline according to any of claims 1 to 8, in which the stage for separation of the gasoline fraction to be treated is preceded by a stage for selective hydrogenation, carried out on a catalyst that comprises at least one metal of group VIII, preferably selected from the group that is formed by platinum, palladium and nickel.
10. Process for the production of a gasoline according to any of claims 1 to 9, in which the hydrodesulfurization stage of the heavy fraction is followed by a final stage that is carried out on a catalyst that comprises at least one element of group VIII that is preferably selected from the group that is formed by nickel, cobalt or iron.
11. Process for the production of a desulfurized gasoline according to claim 10, in which the temperature at which the final stage is carried out is between 240°C and 360°C and is preferably more by at least 10°C than the initial temperature of the hydrodesulfurization stage.

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