EP1849850A1 - Method of desulphurating olefin gasolines comprising at least two distinct hydrodesulphuration steps - Google Patents

Abstract

The invention relates to a process for the hydrodesulphurisation of gasoline cuts for the production of gasolines with a low sulfur and mercaptan content. This process comprises at least two hydrodesulfurization stages HDS1 and HDS2 operated in parallel on two distinct sections of the gasoline constituting the charge. The flow rate of hydrogen in the hydrodesulphurization step HDS2 is such that the ratio between the hydrogen flow rate and the feed rate to be treated is less than 80% of the ratio of the flow rates used to desulphurize in step d hydrodesulfurization HDS1.

Description

Field of the invention

The invention relates to a process for the production of low sulfur and mercaptan gasolines which comprises at least two hydrodesulfurization stages operated in parallel on two distinct sections of the gasoline. This process optionally comprises a single section for purification and recycling of hydrogen. A hydrodesulfurization step corresponds to one or more hydrodesulfurization sections. A hydrodesulfurization section corresponds to one or more beds.

Description of the problem

The production of fuels for gasoline or diesel engines that meet the new environmental standards notably requires that their sulfur content be significantly reduced. Indeed, the environmental standards oblige refiners to lower the sulfur content in the gasoline and diesel fuel pool to less than or equal to 50 ppm in 2005, which will have to be reduced to 10 ppm by 1 January 2009 within the European community.

The charge to be treated is generally a sulfur-containing gasoline cut such as, for example, a gasoline cut from a coking unit, visbreaking, steam cracking or cracking unit. Catalyst (FCC). Said filler preferably consists of a gasoline cutter from a catalytic cracking unit whose distillation range is between 0 ° C and 300 ° C and preferably between 0 ° C and 250 ° C.
In the rest of the text, we will generally speak of catalytic cracking gasoline by extending this definition to gasolines that may contain, in addition to a portion of catalytic cracking gasoline, gasoline fractions from other conversion units. .
Catalytic cracking gasolines can constitute 30% to 50% by volume of the gasoline pool and generally have high monoolefins and sulfur contents. However, the sulfur present in reformulated gasoline is attributable, to nearly 90%, the gasoline from catalytic cracking. The desulphurisation of gasolines, and mainly of FCC species, is therefore of crucial importance for the respect of current and future standards. However, mono-olefins in gasoline contribute significantly to their octane number. In order to maintain the octane number of the olefinic cracking gasolines at high values, it is necessary to limit the degree of hydrogenation of the mono-olefins during the treatment of gasolines by hydrodesulfurization. For this purpose, so-called selective hydrodesulfurization processes have been developed.

In addition, the desulphurized species must also meet the specifications in terms of corrosive power. The corrosive power of gasolines is essentially due to the presence of acid sulfur compounds such as mercaptans. Desulphurized species must therefore contain few mercaptans to limit their corrosivity. However, it is now known that in the selective hydrodesulfurization units of olefinic species, the H ₂ S present in the reactor can react with unhydrogenated monoolefins to form mercaptans. The fraction of mercaptans in the gasoline produced is generally higher as the sulfur content of the gasoline is low. To minimize the mercaptan content, it is generally preferable to work with a high flow of hydrogen. However, this entails significant costs in terms of compressor, recycling and purification of hydrogen. In order to meet this problem, the present invention presents a solution for limiting the energy consumption of the compressor, while decreasing the mercaptan content and increasing the octane number for a sulfur content of the constant desulphurized gasoline.

Moreover, the contrasting evolution of the world's automotive markets is pushing refiners to seek the maximum flexibility and therefore the possibility of maximizing diesel fuel production for diesel vehicles or gasoline production depending on the circumstances. Thus, it can be very advantageous for a refiner to have the most economical possibility possible to send the heavy fraction of gasoline, either to the gasoline pool or to the middle distillate pool according to his needs.

In summary, the present invention proposes a new solution to economically address the triple problem of reducing the sulfur content in fuels, the limitation of the mercaptan content in gasolines with low sulfur content, and flexibility in fuel production towards gasoline cuts or middle distillates according to market needs. Moreover, in the current context of reducing greenhouse gas emissions, it is important to integrate the issue of controlling energy consumption into any new idea. The process scheme described in the context of this invention is innovative because it makes it possible to simultaneously treat the triple problem described above while limiting the energy consumption due to the necessary compression of the hydrogen which is recycled in the steps of hydrodesulfurization. It is intended to obtain gasolines whose research octane number (RON), sulfur content [S] are such that RON≥90.70 and [S] ≤50ppm, preferably RON≥90.70 and [S] ≤37ppm, more preferably RON≥90.75 and [S] ≤35ppm and very preferably RON≥90.80 and [S] <31 ppm. Preferably, each pair will be associated with a motor octane number (MON) such that MON≥79.45, preferably such as MON≥79.50, even more preferably such as MON≥79.55.

Examination of the prior art.

The patent application EP0725126-A1 discloses a method for desulfurizing catalytic cracking gasoline while limiting octane loss by hydrogenation of mono-olefins. This method consists in distilling the gasoline into several fractions, including at least one fraction rich in difficult to desulphurize compounds selected from thiophene and alkylthiophenes, and a fraction rich in easily desulfurized compounds selected from thiacyclopentane, alkylthiacyclopentanes, benzothiophene and alkylbenzothiophenes. At least one of these two fractions is treated by a hydrodesulfurization process and is then mixed with the untreated fraction.
This method has the disadvantage of requiring an analysis of the different fractions before treatment, and does not describe how to choose the fractions to limit the amount of mercaptans in the final product desulfurized.

The patent US 6596157 B2 describes a process for the desulphurization of petrol cuts from cracking units based on the treatment, in parallel, of the heavy fraction of the gasoline called HCN (Heavy Cat Naphta according to English terminology), under conditions of non-selective hydrodesulfurization and the intermediate fraction of the gasoline called ICN (Anglo-Saxon Intermediate Cat Naphta) under selective hydrodesulfurization conditions, for which the intermediate gasoline (ICN) is heated by the hydrotreated heavy fraction (HCN) stream.
This patent does not describe how to treat the different cuts to limit the fraction of sulfur compounds in the form of mercaptans in the desulfurized gasoline. Moreover, according to the teaching of this patent, the light fraction of the essence called LCN (Light Cat Naphta according to English terminology), must generally be subjected to a complementary desulphurization treatment, for example an extraction of the mercaptans by washing with water. a solution containing sodium hydroxide.

Regarding the problem of extraction of mercaptans in desulfurized cracking gasolines, the solutions currently envisaged described in the patent US 6960291 consist of post treatment species from selective hydrotreatment to deplete mercaptans. The methods envisaged are multiple. For example, the patent WO 01/79391 which describes methods of treatment of partially desulphurized species to reduce the mercaptan content on the basis of various methods such as adsorption, extraction with sodium hydroxide, heat treatments, etc ... However, these methods present disadvantage that they require the implementation of an additional step of gasoline treatment and do not offer the flexibility to send some cuts, either in the gasoline pool or in the middle distillates pool.

The patent application US 2003/0042175 discloses a method of desulphurizing cracking gasolines comprising different treatment steps for decreasing the sulfur content. This process comprises a step of hydrogenation of diolefins, a step of converting the light sulfur compounds by weighting, a step of distillation of the gasoline in several sections and at least one step of desulphurizing at least a portion of the heavy fraction. produced gasoline. However, this patent does not teach how to treat the essences to minimize the mercaptan content of the desulphurized gasoline, nor how to treat the hydrogen from the hydrodesulfurization stages.

Description of the invention

The invention is based on the differentiated treatment of different sections constituting the petrol cut.

It is known that in catalytic cracking gasolines light fractions are rich in mono-olefins and saturated sulfur compounds such as mercaptans and sulphides. By light fraction, we mean the fractions species whose boiling point is below 100 ° C, preferably at 80 ° C and very preferably at 65 ° C. The heavy fraction of the gasoline is in turn rich in benzothiophene sulfur compounds such as benzothiophene and alkylbenzothiophenes and to a lesser degree is rich in alkylthiophenics. Moreover, it is rich in aromatic compounds and poor in olefinic compounds. The heavy fraction of the gasoline consists of hydrocarbons whose boiling point is above 160 ° C, preferably at 180 ° C and very preferably at 207 ° C. This heavy fraction of gasoline is usually the one that contains the most sulfur. The heavy fraction of gasoline can be incorporated either into the gasoline pool or into the middle distillate fraction to produce kerosene or gas oil. The core fraction corresponds to the intermediate fraction between the light fraction and the heavy fraction. The core fraction of the gasoline is rich in mono-olefins and sulfur compounds of thiophene types including thiophene, methyl-thiophenes and other alkylthiophenes.
Generally, the different fractions of the gasoline are obtained by distillation of the effluent of the catalytic cracking unit.

The mixture consisting of the light fraction of the gasoline and the intermediate fraction or the intermediate fraction alone is treated in a first hydrodesulfurization step called HDS1. This step consists in contacting the gasoline to be treated with hydrogen, in one or more series hydrodesulfurization reactors, containing one or more catalysts adapted to carry out the hydrodesulphurization in a selective manner, that is to say with a degree of hydrogenation of mono-olefins of less than 60%, preferably less than 50% and very preferably less than 40%.
The operating pressure of this step is generally between 0.5 MPa and 5 MPa, and preferably between 1 MPa and 3 MPa. The temperature is between 200 ° C and 400 ° C and preferably between 220 ° C and 380 ° C. In the case where the treatment is carried out in several reactors in series, the average operating temperature of each reactor will be higher by at least 5 ° C, preferably at least 10 ° C and very preferably at least 15 ° C at the operating temperature of the reactor which precedes it.
The amount of catalyst used in each reactor is such that the ratio between the gasoline flow to be treated expressed in m ³ per hour at standard conditions, per m ³ of catalyst (also called space velocity) is between 0.5 h ^-1 and 20 h ^-1 and preferably between 1 h ^-1 and 15 h ^-1 . Very preferably, the first reactor will be operated with a space velocity of between 2 h ^-1 and 8 h ^-1 .
The flow rate of hydrogen is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour (Nm ³ / h) and the charge rate to be treated expressed in m ³ per hour at standard conditions is between 50 Nm ³ / m ³ and 1000 Nm ³ / m ³ , preferably between 70 Nm ³ / m ³ and 800 Nm ³ / m ³ .

The desulfurization rate attained during the stage HDS1 is generally greater than 80% and preferably greater than 90%.

After the hydrodesulfurization step, the reaction mixture is cooled to a temperature below 60 ° C in order to condense the hydrocarbons. The gas and liquid phases are separated in a separator. The liquid fraction which contains the desulfurized gasoline and a fraction of the dissolved H ₂ S is sent to a stripping section, the gaseous fraction consisting mainly of hydrogen and containing the majority of the H ₂ S is sent to a purification section.

The heavy fraction of gasoline is treated in a separate hydrodesulfurization step called HDS2. This step consists in contacting the gasoline to be treated with hydrogen, in one or more hydrodesulfurization series reactors containing one or more catalysts adapted to carry out the hydrodesulfurization. Preferably, the hydrodesulfurization of the heavy gasoline will be carried out in a single step, on a single reactor. The hydrodesulfurization may be carried out selectively or non-selectively. In the first case, the hydrogenation rate of the mono-olefins is less than 90%, preferably less than 80% and very preferably less than 60%.

The operating pressure of this step is generally between 0.5 MPa and 10 MPa, and preferably between 1 MPa and 8 MPa. The temperature is between 220 ° C and 450 ° C and preferably between 250 ° C and 380 ° C. In the case where the treatment is carried out in several reactors in series, the average operating temperature of each reactor will be at least 5 ° C., preferably at least 10 ° C. and very preferably at least 10 ° C. minus 15 ° C at the operating temperature of the reactor which precedes it.

The amount of catalyst used in each reactor is such that the ratio between the flow rate of gasoline to be treated expressed in m3 per hour at standard conditions per m3 of catalyst (also called space velocity) is between 0.3 hr ^{. 1} and 20 h ^-1 and preferably between 0.5 h ^-1 and 15 h ^-1 . Very preferably, the first reactor will be operated with a space velocity of between 1 h ^-1 and 8 h ^-1 .

The flow rate of hydrogen is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour (Nm ³ / h) and the charge rate to be treated expressed in m ³ per hour at standard conditions is between 30 Nm ³ / m ³ and 800 Nm ³ / m ³ , preferably between 50 Nm ³ / m ³ and 500 Nm ³ / m ³ . Preferably, this ratio will be less than 80% of the ratio of the flow rates used to desulfurize in the hydrodesulfurization step HDS1, preferably less than 60%, very preferably less than 50% and even more so. preferred less than 40% of the ratio of flow rates used to desulphurize in the hydrodesulfurization step HDS1.

After the hydrodesulfurization step, the reaction mixture is cooled to a temperature below 60 ° C in order to condense the hydrocarbons. The phases gas and liquid are separated in a separator. The liquid fraction containing the desulfurized gasoline and a fraction of the dissolved H ₂ S is sent to a stripping section, the gaseous fraction consisting mainly of hydrogen and containing the majority of the H ₂ S is sent to a purification section.

Any catalyst having good selectivity for hydrodesulfurization reactions can be used in steps HDS1 or HDS2. By way of example, use will be made of catalysts comprising an amorphous and porous mineral support chosen from the group consisting of aluminas, silicon carbide, silica, silica-aluminas or even titanium or magnesium oxides used alone or in admixture with alumina or silica-alumina. It is preferably selected from the group consisting of silica, the family of transition aluminas and silica-aluminas. Very preferably, the support consists essentially of at least one transition alumina, that is to say it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight. % weight, or even at least 90% weight of transition alumina. It may optionally consist solely of a transition alumina.

The specific surface area of the support is generally less than 200 m 2 / g and preferably less than 150 m 2 / g. The porosity of the catalyst before sulfurization is such that it has an average pore diameter greater than 20 nm, preferably greater than 25 nm or even 30 nm and often between 20 and 140 nm, preferably between 20 and 100 nm, and very preferably between 25 and 80 nm. The pore diameter was measured by mercury porosimetry according to ASTM D4284-92 with a wetting angle of 140 °.

The hydrodesulfurization catalyst contains at least one Group VI metal and / or at least one Group VIII metal on a support. The Group VI metal is generally molybdenum or tungsten the Group VIII metal generally nickel or cobalt. The surface density of the group metal VI is understood according to the invention between 2.10 ^-4 and 4.0.10 ^-3 gram of oxide of said metal per m2 of support, preferably between 4.10 ^-4 and 1.6.10 ^-3 g / m ² .

Very preferably, use will be made of a catalyst or a chain of catalysts as described in the patent application. US20060000751 A1 . They are catalysts comprising a support for example chosen from refractory oxides such as aluminas, silicas, silica-aluminas or magnesia, used alone or mixed with one another, a metal of group VI, preferably molybdenum or tungsten promoted or not by a Group VIII metal, preferably cobalt or nickel. These catalysts have an average pore diameter greater than 22 nm. In the eventual case of a catalyst sequence, the process comprises a succession of hydrodesulfurization steps, such that the activity of the catalyst of a step n + 1 is between 1% and 90% of the activity of the catalyst. catalyst of step n.

However, it is possible to use a non-selective catalyst in step HDS2. By way of example, use will be made of catalysts comprising an amorphous and porous mineral support chosen from the group consisting of aluminas, silicon carbide, silica, silica-aluminas or even titanium or magnesium oxides used alone or in admixture with alumina or silica-alumina. It is preferably selected from the group consisting of silica, the family of transition aluminas and silica-aluminas. Very preferably, the support consists essentially of at least one transition alumina, that is to say it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight. % weight, or even at least 90% weight of transition alumina. It may optionally consist solely of a transition alumina. The hydrodesulfurization catalyst contains at least one Group VI metal and / or at least one Group VIII metal on a support. The Group VI metal is generally molybdenum or tungsten and the Group VIII metal is generally nickel or cobalt. The selective or non-selective nature of the hydrodesulfurization catalyst, as defined previously in the description of the invention, generally depends on the composition and the mode for preparing said catalyst. Simple ways of varying the selectivity include, for example, modifying the Group VIII and Group VI metal contents, or possibly the molar ratio between the amounts of Group VIII and Group VI metals for a given or to be donated carrier. vary the surface area of the substrate for constant metal contents.

According to a preferred embodiment of the invention, the excess hydrogen resulting from hydrodesulfurization steps HDS1 and HDS2 can be collected and treated in a single purification section. The hydrogen thus purified is then recycled to at least one of hydrodesulphurization steps HDS1 and HDS2 after a compression step to compensate for pressure losses through the process. An additional charge of fresh hydrogen is made either before or after the compression step in order to compensate for the hydrogen consumption in the hydrodesulfurization reactors.

It is possible to envisage admitting at least all the hydrogen necessary for the reactions occurring in the two hydrodesulphurization stages through only one of the hydrodesulphurization stages, preferably HDS2. For these purposes, all of the hydrogen feed required for steps HDS1 and HDS2 is then sent in only one of these steps, preferably HDS2, and the gas purge of this step is sent to the purification treatment of which the purified gaseous product is recycled at the other hydrodesulfurization stage. This type of scheme makes it possible to minimize the flow of recycled hydrogen passing through the compressor in the case where all the hydrogen consumed in the two hydrodesulfurization stages is sent through the unit HDS2 and the gas purge of this unit is sent the purification treatment of which the purified gas product is recycled only in step HDS1. Indeed, the HDS1 unit requiring a lower hydrogen flow rate compared to HDS2 unit, less hydrogen needs to be recycled by the compressor and thus the energy consumption of the compressor is lower.

It is possible to envisage a combined treatment on the vapor fractions from the two stripping columns dedicated to each hydrodesulfurization step (cooling, recycling of the condensed liquid to each of the stripping columns and combined bleeding of H2S-rich gas sent to a purification step.

In the case where the product of the hydrodesulfurization step HDS2 is sent to the diesel pool, having a step HDS2 dedicated to heavy gasoline makes it possible not to co-mix this gasoline with middle distillate cuts in another hydrotreatment therefore to release capacity in the said hydrotreatment and consequently to increase the production capacity of the refinery.

• d'hydrogéner sélectivement les dioléfines en mono-oléfines
• de transformer les composés soufrés légers saturés et principalement les mercaptans, en sulfures ou mercaptans plus lourds par réaction avec les mono-oléfines

It is possible, while remaining within the scope of the invention, to implement a pretreatment of the charge whose purpose is mainly:

• to selectively hydrogenate diolefins to monoolefins
• to convert saturated light sulfur compounds and mainly mercaptans into heavier sulphides or mercaptans by reaction with mono-olefins

The hydrogenation reactions of the diolefins to monoolefins are illustrated below by the conversion of 1,3 pentadiene, an unstable compound which can readily polymerize, to pent-2-ene by the addition reaction of hydrogen. However, it is sought to limit the secondary reactions of hydrogenation of mono-olefins which in the example below would lead to the formation of n-pentane.

The sulfur compounds that one seeks to transform are mainly mercaptans and sulphides. The main reaction of transformation of mercaptans consists of thioetherification of mono-olefins by mercaptans. This reaction is illustrated below by the addition of propane-2-thiol to pent-2-ene to form a propyl pentyl sulfide.

In the presence of hydrogen, the transformation of the sulfur compounds can also pass through the intermediate formation of hydrogen sulphide which can then be added to the unsaturated compounds present in the feedstock. This route is however a minority in the preferred conditions of the reaction. In addition to the mercaptans, the compounds which can thus be transformed and weighed up are sulphides and mainly dimethyl sulphide, methyl ethyl sulphide, diethyl sulphide, CS ₂ , COS, thiophane and methyl thiophane.

In some cases, weighting reactions of light nitrogen compounds, and mainly nitriles, pyrrole and its derivatives, can also be observed.

This pretreatment step consists in bringing the charge to be treated into contact with a stream of hydrogen and with a catalyst containing at least one metal of group VIb (group 6 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996 ) and at least one Group VIII metal (groups 8, 9 and 10) of said classification, deposited on a porous support.

The catalyst according to the invention may be prepared using any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and VIb on the selected support. This impregnation may for example be carried out according to the known method of preparation of the man of the in the dry-impregnation terminology, in which just the quantity of desired elements is introduced in the form of soluble salts in a chosen solvent, for example deionized water, so as to fill as accurately as possible the porosity of the support. The support thus filled with the solution is preferably dried. The preferred support is alumina which can be prepared from any type of precursors and shaping tools known to those skilled in the art.

The catalyst is usually used in a sulphurized form obtained after treatment in temperature in contact with a decomposable sulfur-containing organic compound and generating hydrogen sulphide (H ₂ S) or directly in contact with a gaseous stream of diluted H ₂ S in H ₂ . This step can be carried out in situ or ex situ (ie inside or outside the hydrodesulfurization reactor) at temperatures between 200 and 600 ° C. and more preferably between 300 and 500 ° C. .

The charge to be treated is mixed with hydrogen before being contacted with the catalyst. The quantity of hydrogen injected is such that the molar ratio between the hydrogen and the diolefins to be hydrogenated is greater than 1 (stoichiometry) and less than 10, and preferably between 1 and 5 mol / mol. Too large an excess of hydrogen can lead to a strong hydrogenation of the mono-olefins and consequently a decrease in the octane number of the gasoline. The entire charge is usually injected at the reactor inlet. However, it may be advantageous in some cases to inject a fraction or the entire charge between two consecutive catalytic beds placed in the reactor. This embodiment makes it possible in particular to continue operating the reactor if the inlet of the reactor is clogged by deposits of polymers, particles, or gums present in the load.

The mixture consisting of gasoline and hydrogen is contacted with the catalyst at a temperature between 80 ° C and 250 ° C, and preferably between 90 ° C and 220 ° C, with a liquid space velocity (LHSV) of between 1 h ^-1 and 10 h ^-1, the unit of the liquid space velocity being per liter of feed per liter of catalyst per hour (ll ^-1 .h ^-1 ). The pressure is adjusted so that the reaction mixture is predominantly in liquid form in the reactor. The pressure is between 0.5 MPa and 5 MPa and preferably between 1 and 4 MPa.

The gasoline treated under the conditions stated above has a reduced diolefin and mercaptan content. Generally, the gasoline produced contains less than 1% by weight of diolefins, and preferably less than 0.5% by weight of diolefins. Light sulfur compounds whose boiling point is lower than that of thiophene (84 ° C) are generally converted to more than 50%. It is therefore possible to separate the light fraction of the gasoline by distillation and to send this fraction directly to the gasoline pool without further processing.

The preferred embodiments of the method of the present invention are illustrated in Figure 1, Figure 2 and Figure 3.

Description of Figure 1:

A core essence, gasoline A flowing through line 1 is mixed with hydrogen from the recycle compressor P1, through line 20. The mixture thus formed is injected into the reaction section R1. The effluent flowing through the line 4 is cooled in the exchanger section E1 in order to condense the hydrocarbons and then the mixture is injected into the separation section S1 via the line 6. The separation section S1 produces a fraction gas extracted by line 8, which consists essentially of hydrogen, H ₂ S and light hydrocarbons and a liquid fraction extracted by line 9. The liquid fraction is then injected into a stabilization section C2 which extracted by line 15, at the top, the H ₂ S dissolved in hydrocarbons. Gasoline recovered at the bottom of column C2 by line 16 can be sent directly to the gasoline pool.
A heavy gasoline, gasoline B flowing through line 3 is mixed with fresh hydrogen supplied by line 2. The mixture thus formed is injected into the reaction section R2. The effluent flowing through the line 5 is cooled in the exchanger section E2 in order to condense the hydrocarbons, then the mixture is injected into the separation section S2 via the line 7. The separation section S2 produces a fraction gaseous extracted from the line 10, which consists essentially of hydrogen, H ₂ S and light hydrocarbons and a liquid fraction extracted by the line 11. The liquid fraction is then injected into a stabilization section C3 which extracts by line 17, at the top, H ₂ S dissolved in hydrocarbons. The desulphurized heavy gasoline recovered via line 18 can be sent either to the gasoline pool or to a pool of middle distillates.
The stabilizing sections C2 and C3 each comprise a distillation column. It is advantageous, in order to limit the operating and investment costs, to collect the distillates from these two columns before cooling them to condense them, and to send them together to the reflux flask. The two columns can thus be operated with a common reflux section.
The hydrogens derived from separators S1 and S2 respectively by lines 8 and 10 are mixed before being treated in a common purification section C1 which consists of washing with an aqueous solution of amine according to a technique well known to humans. of career. After purification, the hydrogen removed from H ₂ S and flowing through line 13 and compressed in a recycle compressor P1 and is then mixed with gasoline A by line 20.
According to another variant of the invention, the makeup hydrogen is injected via the line 12 upstream of the purification section C1. The hydrogen necessary for the treatment of gasoline B is then injected via line 19 into the hydrodesulfurization stage of reaction section R2.

Description of Figure 2

The figures used in this figure correspond to those used for Figure 1.

Another variant of the invention is shown in FIG. 2. According to this variant, a fraction of the hydrogen coming from the separation section S1 via the line 8 is injected, without purification treatment, into the reaction section R2 via the intermediate of line 21.

Description of Figure 3

FIG. 3 illustrates the sequences of the pretreatment stage consisting mainly of hydrogenating the diolefins and weighing down the light sulfur compounds and the selective hydrodesulfurization stage.
The pretreatment step R3 can be carried out either on the total gasoline injected via line 1 or on the gasoline recovered at the distillation head in column C4 via line 3. In the latter case, the essence A is sent directly to column C4 without pre-treatment.

When pretreatment is applied to the total gasoline, the hydrogen is injected via line 10, upstream of the pretreatment step R3, which corresponds to the step of selective hydrogenation and increasing the weight of the saturated light sulfur compounds. The gasoline produced is then distilled in two sections in column C4, a heavy section extracted by line 4 which corresponds to the heavy gasoline described in the text, and a lighter fraction recovered by line 3 which corresponds to the mixture of the essence of heart and light essence described in the text. The light fraction is then distilled in a second column, C5, which separates the essence of the heart that leaves via the line 6 of the light gasoline that leaves via the line 7. The light gasoline recovered by the line 7 is generally low in sulfur and can be sent directly to the gasoline pool without further processing.
The core and heavy gasolines recovered respectively by lines 6 and 4 are treated in one or more hydrodesulfurization sections according to the invention and making it possible to recover a gasoline H via line 8 and a gasoline J via line 9 sent respectively to the gasoline pool and the middle distillate pool.
It may be advantageous to produce the three gasoline cuts described in a single column provided with a side withdrawal from which the essence of heart is extracted. According to another embodiment of the invention, the distillation column of the total gasoline injected via line 1 may be a single column with an inner wall.

When the pretreatment step R3 is applied to the gasoline of the line 3, the hydrogen is injected via the line 11. This embodiment has the advantage of only sending the pre-treatment step R3 fraction of gasoline corresponding to the fraction cleared of heavy gasoline, which decreases the quantities of gasoline to be treated, as well as the presence of potential contaminants of catalysts such as arsenic or silicon which are generally concentrated in the heavy fractions of gasoline.

Examples : Preparation of charges:

• Une coupe a1 correspondant à la fraction 6°C - 188°C
• Une coupe a2 correspondant à la fraction 188°C - 236°C
• Une coupe a3 correspondant à la fraction 6°C - 209°C
• Une coupe a4 correspondant à la fraction 209°C - 236°C

A gasoline a , whose boiling temperatures are between 6 ° C and 236 ° C from a catalytic cracking unit is distilled in a batch distillation column to produce four slices:

• A section a1 corresponding to the fraction 6 ° C - 188 ° C
• A section a2 corresponding to the fraction 188 ° C - 236 ° C
• A cut a3 corresponding to the fraction 6 ° C - 209 ° C
• A cut a4 corresponding to the fraction 209 ° C - 236 ° C

• ppm poids est la teneur pondérale en soufre en partie part millions mesurée selon la méthode ASTM ASTM D-5453.
• BrN (Bromine Number selon la terminologie anglo-saxonne) est l'indice de brome mesuré selon la méthode ASTM D-1159.

The characteristics of the different sections are summarized in Table 1. Table 1: characteristics of distilled cups at a1 a2 a3 a4 100% 85% 15% 92% 8% S ppm weight 390 253 1173 250 1875 BrN g / 100g 41 46.5 11 43 6 RON 91.7 91.5 94.5 92.1 94.3 MY 80 81.3 82.8 81.9 82.9 Chopped off ° C 6-236 6-188 188-235 6-209 209-235

• ppm weight is the weight content of part of part sulfur measured by ASTM method ASTM D-5453.
• BrN (Bromine Number) is the bromine number measured according to the ASTM D-1159 method.

Example 1 (comparative):

A volume of 100 ml of HR806S catalyst (sulfur catalyst based on cobalt and molybdenum) marketed by Axens is charged to the reactor of a pilot unit. This catalyst has the particularity of being presulfided and preactivated ex situ. It does not require a complementary step of sulfurization.

Gasoline a is mixed with hydrogen before being injected into the reactor. The gasoline flow rate is 400 ml / h and the hydrogen flow rate is 116 normal liters per hour. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I. The temperature is adjusted to 260 ° C and the pressure to 2 MPa. The produced essence called c1 is cooled and stripped by a stream of hydrogen to remove dissolved H ₂ S.

After analysis, this gasoline contains 38 ppm of sulfur of which 14.0 ppm are in the form of mercaptans. Its research octane number (RON) is 90.60 and its engine octane number (MON) is 79.40.

Example 2 (according to the invention):

340 ml / h of a1 gasoline are mixed with 98 normal liters per hour of hydrogen and injected onto a volume of 85 ml of HR806S catalyst. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 300 NI / I. The temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa. The gasoline produced called b1 contains 19 ppm of sulfur, of which 8 ppm in the form of mercaptans.

60 ml / h of a2 gasoline are mixed with 14.4 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst. The flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 240 NI / I. The temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa. The gasoline produced called b2 contains 90 ppm of sulfur including 4 ppm in the form of mercaptans.

Overall, for the treatment of cuts a1 and a2, the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
Essences b1 and b2 are mixed at a level of 85% by weight of gasoline b1 and 15% by weight of gasoline b2. The mixture thus formed called c2 is analyzed. It contains 30 ppm sulfur including 8.0 ppm as mercaptans. Its research octane number (RON) is 90.80 and its engine octane number (MON) is 79.50. Fraction b2 can also be sent to the middle distillate pool with very low sulfur content.

By comparing the species c1 and c2 produced in Examples 1 and 2, it appears that the parallel treatment of the separated species in two distinct sections while maintaining, overall, the same hydrogen flow rate makes it possible to improve the octane of the desulfurized gasoline, but especially to significantly reduce the mercaptan content.

Example 3 (according to the invention):

The essence b1 is obtained according to the preparatory mode described in Example 2.

60 ml / h of a2 gasoline are mixed with 6.3 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 105 NI / I. The temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa. The gasoline produced called b5 contains 135 ppm of sulfur including 6 ppm in the form of mercaptans.
Essences b1 and b5 are mixed at a level of 85% by weight of gasoline b1 and 15% by weight of petrol b5 . The mixture thus formed called c4 is analyzed. It contains 36 ppm sulfur including 8.0 ppm as mercaptans. Its research octane number (RON) is 90.90 and its engine octane number (MON) is 79.60. Fraction b5 can also be sent to the middle distillate pool with very low sulfur content.
Overall, for the treatment of cuts a1 and a2, the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 270 NI / I.

Example 4 (according to the invention):

368 ml / h of a3 gasoline are mixed with 108.2 normal liters per hour of hydrogen and injected onto a volume of 92 ml of HR806S catalyst. The flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 294 NI / I. The temperature of the reactor is adjusted to 260 ° C. The gasoline produced called b3 contains 20 ppm of sulfur of which 7 ppm in the form of mercaptans.

32 ml / h of a4 gasoline are mixed with 7.5 normal liters per hour of hydrogen and injected on a volume of 8 ml of HR806S catalyst. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 234 NI / I.
The temperature of the reactor is adjusted to 260 ° C. The gasoline produced called b4 contains 140 ppm of sulfur of which 3 ppm in the form of mercaptans.
Essences b3 and b4 are mixed at a level of 92% by weight of gasoline b3 and 8% by weight of gasoline b4 . The mixture thus formed called c3 is analyzed. It contains 30 ppm of sulfur including 7.0 ppm in the form of mercaptans. Its research octane number (RON) is 91.00 and its engine octane number (MON) is 79.70. Fraction b4 can also be sent to the middle distillate pool with very low sulfur content.

Overall, for the treatment of cuts a3 and a4 , the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.

Comparing Examples 2 and 4, it is clear that it is advantageous to separate from the gasoline a heavy fraction whose boiling point is higher than 209 ° C. to treat it in an independent hydrodesulfurization section, since improves the octane number of the desulfurized gasoline and decreases the mercaptan content.

Example 5 (comparative):

340 ml / h of a1 gasoline are mixed with 98.6 normal liters per hour of hydrogen and injected onto a volume of 85 ml of HR806S catalyst. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I. The temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa. The gasoline produced called b6 contains 22 ppm of sulfur including 9 ppm in the form of mercaptans.
60 ml / h of a2 gasoline are mixed with 17.4 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst. The hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I. The temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa. The gasoline produced called b7 contains 80 ppm of sulfur including 4 ppm in the form of mercaptans.
Overall, for the treatment of cuts a1 and a2 , the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
Essences b6 and b7 are mixed at a level of 85% by weight of gasoline b 6 and 15% by weight of gasoline b7 . The mixture thus formed called c5 is analyzed. It contains 31 ppm of sulfur including 8.3 ppm in the form of mercaptans. Its research octane number (RON) is 90.65 and its engine octane number (MON) is 79.40. Table 2: Comparison of performances obtained Example 1 comparative 2 invention 3 invention 4 invention 5 comparative Cutting point (° C) No 188 188 209 188 H2 / HC (HDS2) versus H2 / HC (HDS1) in% No 80 35 80 100 sulfur content (in ppm) 38 30 36 30 31 mercaptan content (in ppm) 14.0 8.0 8.0 7.0 8.3 RON 90,60 90.80 90.90 91,00 90.65 MY 79.40 79.50 79,60 79.70 79.40 H2 / HC (HDS2) relative to H2 / HC (HDS1) in%: ratio of the flow rate of hydrogen expressed in normal m ³ per hour and the flow rate of the charge to be treated expressed in m ³ per hour at standard conditions as a percentage of the ratio of flow rates used to desulphurize in the hydrodesulfurization step HDS1

The comparison of Examples 1, 2, 4 and 5 shows that the parallel treatment of the separated gasolines in two distinct sections while maintaining, overall, the same hydrogen flow rate makes it possible to improve the octane number of the desulfurized gasoline, and especially to significantly reduce the sulfur and mercaptan contents.

Moreover, when the flow rate of hydrogen in the hydrodesulphurization step HDS2 is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour and the charge flow rate to be treated expressed in m ³ per hour under the conditions standards is less than 80% of the ratio of the flow rates used to desulphurize in the hydrodesulfurization step HDS1 (Example 2 and 4 according to the invention), a significant decrease in the sulfur and mercaptan contents is recorded for octane RON and MON high.

Claims (10)

Process for the production of low sulfur and mercaptan gasolines comprising at least two hydrodesulfurization stages HDS1 and HDS2 operated in parallel on two distinct cuts of the gasoline constituting the charge, the charge corresponding to a gasoline resulting from a catalytic cracking unit distilled into three fractions: a light fraction corresponding to a gasoline fraction whose boiling point is less than 100 ° C. a heavy fraction of the gasoline corresponding to a gasoline fraction whose boiling point is greater than 180 ° C. a core fraction corresponds to the intermediate fraction between the light fraction and the heavy fraction and wherein the flow rate of hydrogen in the hydrodesulphurization step HDS2 is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour and the charge flow rate to be treated expressed in m ³ per hour at standard conditions is less than 80% of the ratio of the flow rates used to desulphurize in the hydrodesulfurization step HDS1. Process according to claim 1 comprising a single section for purifying and recycling the excess hydrogen resulting from the hydrodesulfurization steps HDS1 and HDS2. Process according to one of Claims 1 or 2, in which at least all the hydrogen necessary for the reactions occurring in the two hydrodesulfurization stages is admitted through only one of the hydrodesulphurization stages and in which the purge gas of this hydrodesulfurization step is sent to the purification treatment of which the purified gaseous product is recycled to the other hydrodesulfurization unit. Process according to claim 3 in which at least all the hydrogen necessary for the reactions occurring in the two hydrodesulfurization stages is admitted through the hydrodesulfurization step HDS2. Process according to one of Claims 1 to 4, in which the flow rate of hydrogen in the hydrodesulfurization unit HDS1 is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour and the flow rate of the charge to be treated. expressed in m ³ per hour at standard conditions is between 50 Nm ³ / m ³ and 1000 Nm ³ / m ³ and wherein the hydrogen flow rate in the hydrodesulfurization unit HDS 2 is such that the ratio between the flow rate of hydrogen expressed in normal m ³ per hour and the charge rate to be treated expressed in m ³ per hour at standard conditions is between 30 Nm ³ / m ³ and 800 Nm ³ / m ³ . Process according to one of Claims 1 to 5, in which the mixture consisting of the light fraction of gasoline and the intermediate fraction or the intermediate fraction alone is treated in the hydrodesulfurization step HDS1, this treatment consisting in contacting the gasoline to be treated with hydrogen, in one or more series hydrodesulphurization reactors containing one or more catalysts adapted to carry out the selective hydrodesulfurization with a mono-olefin hydrogenation rate of less than 60%, and wherein the heavy fraction of the gasoline is treated in the hydrodesulfurization step HDS2, which treatment comprises contacting the gasoline to be treated with hydrogen in one or more series hydrodesulfurization reactors containing a or several catalysts adapted to carry out the hydrodesulfurization, the hydrodesulfurization being able to be carried out selectively or non-selectively, the hydrosulfurization rate being ogenation of mono-olefins being less than 90% in the case of selective hydrodesulfurization. Method according to one of claims 1 to 6 wherein the charge is pretreated so as to: selectively hydrogenating diolefins to mono-olefins transforming the saturated light sulfur compounds into heavier sulphides or mercaptans by reaction with the mono-olefins. Process according to one of Claims 1 to 7, in which the catalyst used in hydrodesulfurization steps HDS1 and HDS2 is a catalyst or a chain of catalysts comprising a support, a Group VI metal promoted or not a Group VIII metal. and having an average pore diameter greater than 22 nm. Process according to one of Claims 1 to 8, in which the catalyst used in the hydrodesulfurization steps HDS1 and HDS2 comprises an amorphous and porous mineral support, at least one Group VI metal and / or at least one Group VIII metal, the porosity of the catalyst before sulphurization being such that it has an average pore diameter greater than 20 nm and the density of the Group VI metal is between 2.10 ^-4 and 4.0.10 ^-3 gram of oxide of said metal per m2 of support. Process according to one of claims 8 or 9 wherein the Group VI metal is molybdenum or tungsten and the Group VIII metal is nickel or cobalt.

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