Patent Application
20250050305
The present invention relates to the field of hydrotreating gasoline cuts, notably gasoline cuts resulting from fluidized-bed catalytic cracking units. More particularly, the present invention relates to a process for trapping mercaptan-type compounds contained in hydrocarbon feedstocks in the presence of a specific trapping mass.
Automotive fuel specifications call for a significant reduction in the sulfur content in these fuels, and notably in gasolines. This reduction is notably directed toward limiting the content of sulfur and nitrogen oxides in motor vehicle exhaust gases. The specifications currently in force in Europe since 2009 for gasoline fuels set a maximum content of 10 ppm (parts per million) by weight of sulfur. Such specifications are also in force in other countries, for instance the United States and China, where the same maximum sulfur content has been required since January 2017. To achieve these specifications, it is necessary to treat gasolines via desulfurization processes.
The main sources of sulfur in gasoline bases are “cracking” gasolines, and mainly the gasoline fraction obtained from a process of catalytic cracking of an atmospheric or vacuum distillation residue of a crude oil. The gasoline fraction from catalytic cracking, which represents on average 40% of gasoline bases, in fact accounts for more than 90% of the sulfur in gasolines. Consequently, the production of low-sulfur gasolines requires a step of desulfurization of the catalytic cracking gasolines. Among the other sources of gasolines that may contain sulfur, mention may also be made of coker gasolines, visbreaker gasolines or, to a lesser extent, gasolines obtained from atmospheric distillation or steam cracking gasolines.
The removal of sulfur from gasoline cuts consists in specifically treating these sulfur-rich gasolines via desulfurization processes in the presence of hydrogen. These are then referred to as hydrodesulfurization (HDS) processes. However, these gasoline cuts, and more particularly the catalytic cracking (FCC) gasolines, contain a large proportion of unsaturated compounds in the form of monoolefins (about 20% to 50% by weight) which contribute toward a good octane number, diolefins (0.5% to 5% by weight) and aromatics. These unsaturated compounds are unstable and react during the hydrodesulfurization treatment. Diolefins form gums by polymerization during the hydrodesulfurization treatments. This gum formation leads to gradual deactivation of the hydrodesulfurization catalysts or gradual clogging of the reactor. Consequently, the diolefins must be removed by hydrogenation before any treatment of these gasolines. Conventional treatment processes desulfurize gasolines non-selectively by hydrogenating a large portion of the monoolefins, giving rise to a high loss of octane number and high hydrogen consumption. The most recent hydrodesulfurization processes make it possible to desulfurize cracking gasolines rich in monoolefins, while limiting the hydrogenation of the monoolefins and consequently the loss of octane. Such processes are described, for example, in documents EP-A-1077247 and EP-A-1174485.
However, when very deep desulfurization of cracking gasolines needs to be performed, some of the olefins present in the cracking gasolines are hydrogenated, on the one hand, and recombine with H2S to form mercaptans, on the other hand. This family of compounds, of chemical formula R—SH where R is an alkyl group, are generally called recombination mercaptans, and generally represent between 20% by weight and 80% by weight of the residual sulfur in desulfurized gasolines. Reduction of the content of recombination mercaptans may be achieved by catalytic hydrodesulfurization, but this leads to the hydrogenation of a large portion of the monoolefins present in the gasoline, which then leads to a large reduction in the octane number of the gasoline and also to an overconsumption of hydrogen. It is moreover known that the loss of octane due to the hydrogenation of the monoolefins during the hydrodesulfurization step is proportionately greater the lower the targeted sulfur content, i.e. when it is sought to thoroughly remove the sulfur compounds present in the feedstock.
For these reasons, it is thus preferable to treat this partially hydrodesulfurized gasoline via a judiciously chosen adsorption technique which will make it possible simultaneously to remove the sulfur compounds initially present in the cracking gasolines and not converted and the recombination mercaptans, without hydrogenating the monoolefins present, so as to preserve the octane number.
Various solutions are proposed in the literature for extracting these mercaptans from hydrocarbon fractions using adsorption type processes or by combining hydrodesulfurization or adsorption steps. However, there is still a need for more efficient trapping masses for the extraction of mercaptans for the purpose of limiting the hydrogenation reactions responsible in this context for reducing the octane number of the gasolines concerned.
For example, patent application US 2003/0188992 describes a process for desulfurization of an olefinic gasoline by treating the gasoline in a first hydrodesulfurization step and then by removing mercaptan-type sulfur compounds in a polishing step. This polishing step mainly consists of solvent extraction of the mercaptans by scrubbing.
Patent U.S. Pat. No. 5,866,749 proposes a solution for removing the elemental sulfur and mercaptans contained in an olefinic cut by passing the mixture to be treated over a reduced metal chosen from groups IB, IIB and IIIA of the Periodic Table and performed at a temperature below 37° C.
Patent U.S. Pat. No. 6,579,444 discloses a process for removing sulfur present in gasolines or the residual sulfur present in partially desulfurized gasolines using a solid containing cobalt and a group VIB metal.
Patent application US 2003/0226786 describes a process for desulfurizing gasoline by adsorption and also several methods for regenerating the adsorbent. The adsorbent considered is a hydrotreating catalyst and more particularly is based on a group VIII metal alone or mixed with a group VI metal, and containing between 2% and 20% by weight of group VIII metal relative to the total weight of the catalyst.
Patent FR2908781 discloses a process for trapping sulfur compounds from a partially desulfurized hydrocarbon feedstock in the presence of an adsorbent comprising at least one group VIII, IB, IIB or IVA metal, the adsorbent being used in reduced form in the absence of hydrogen and at a temperature above 40° C.
Generally, when they are used in trapping or desulfurization processes, the abovementioned solids use active metals in their reduced form, that is to say in the zero-valent state. During their manufacture, the metals of the active phase of the solids are produced in their oxide forms. A reduction-type activation step is then necessary to convert these oxides, even partially, into reduced metals. Industrially, it is often of little advantage to reduce these solids in an industrial adsorber, due to operating time constraints or else due to the technical impossibility of reaching the temperatures required for the activation step. The activation step is then carried out ex situ, i.e. in another reduction reactor. In order to be able to transport the reduced solid to the industrial reactor, the latter must undergo a passivation treatment. This passivation treatment consists of a surface treatment of the reduced metals in order to reduce their reactivity with respect to air. The passivation treatment must be well controlled. If the passivating treatment is insufficient, there is an industrial risk during the handling, storage or loading of the solid in the adsorber linked to an uncontrolled exothermicity. This exothermicity is linked to the oxidation at the surface of the zerovalent metals or at the core of the particles of zerovalent metals. If the passivating treatment is too strong, there is a risk of damaging the solid and losing all or some of its ability to trap sulfur-containing molecules. These passivation methods are based on a surface protection of the particles of zerovalent metals formed during the reduction step. This surface passivation is generally carried out by mild oxidation, generally with oxygen, but can also be carried out by weak adsorption of molecules on the surface, such as carbon dioxide. These operations are highly controlled to avoid any uncontrolled exothermicity.
The applicant has surprisingly discovered that specific passivation operating conditions applied to the trapping mass make it possible to improve the performance in a mercaptan trapping process when said mass is used, avoiding the formation of soluble sulfur-containing organometallic compounds. Without wishing to be bound to any theory, the use of a step of passivating a trapping mass in the presence of carbon dioxide makes it possible to avoid the formation of metal hydroxythiolate, thus preventing the leaching of the trapping mass and the production of hydrocarbon feedstocks that do not meet specifications.
The present invention relates to a process for trapping mercaptans contained in a sulfur-containing hydrocarbon feedstock at a temperature of between 40° C. and 250° C., a pressure of between 0.2 MPa and 5 MPa, at an hourly space velocity, defined as the volume flow rate of feedstock at the inlet per volume of trapping mass, of between 0.1 h−1 and 50 h−1, in the presence of a trapping mass comprising an active phase comprising at least one group VIII, IB or IIB metal, and an inorganic support selected from the group consisting of alumina, silica, silica-alumina, and clays, said trapping mass having been obtained by a preparation process comprising at least the following steps:
According to one or more embodiments, steps a) to e) of said process for preparing the trapping mass are carried out outside the reaction section of the trapping process.
According to one or more embodiments, the process for preparing the trapping mass further comprises a step f) of activating said trapping mass obtained on conclusion of step e), said step f) being carried out under a stream of reducing gas or under a stream of feedstock to be treated at a temperature of between 100° C. and 300° C.
According to one or more embodiments, step f) of said process for preparing the trapping mass is carried out in the reaction section of the trapping process.
According to one or more embodiments, the reaction section of the trapping process comprises between 2 and 5 reactors.
According to one or more embodiments, step e) of said process for preparing the trapping mass is carried out by a concentration pulse of dilute carbon dioxide at a temperature of between 0° C. and 90° C.
According to one or more embodiments, step d) of said process for preparing the trapping mass is carried out in the presence of hydrogen as reducing gas.
According to one or more embodiments, the content of group VIII, IB or IIB element is between 10% and 80% by weight relative to the total weight of the trapping mass.
According to one or more embodiments, said group VIII, IB or IB metal is chosen from nickel, copper or zinc.
According to one or more embodiments, said metal of the active phase of the trapping mass is nickel.
According to one or more embodiments, the content of aluminum and/or silicon elements in said trapping mass is between 5% and 45% by weight relative to the total weight of the trapping mass.
According to one or more embodiments, said trapping mass comprises a specific surface area of between 150 m2/g and 250 m2/g.
According to one or more embodiments, the trapping mass has a total pore volume, measured by mercury porosimetry, of between 0.20 ml/g and 0.70 ml/g.
According to one or more embodiments, said hydrocarbon feedstock is a feedstock that has been partially desulfurized by a catalytic hydrodesulfurization step.
According to one or more embodiments, said hydrocarbon feedstock to be treated is a partially desulfurized catalytic cracking gasoline having a boiling point below 350° C. and containing between 5% and 60% by weight of olefins and less than 100 ppm by weight of sulfur relative to the total weight of said feedstock.
Subsequently, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor-in-chief D. R. Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
The BET specific surface area is measured by nitrogen physisorption according to the standard ASTM D3663-03, a method described in the work by Rouquerol F., Rouquerol J. and Singh K., “Adsorption by Powders & Porous Solids: Principles, Methodology and Applications”, Academic Press, 1999.
In the present description, according to the IUPAC convention, “micropores” are understood to mean the pores having a diameter of less than 2 nm, i.e. 0.002 μm; “mesopores” are understood to mean the pores having a diameter of greater than 2 nm, i.e. 0.002 μm, and less than 50 nm, i.e. 0.05 μm, and “macropores” are understood to mean the pores having a diameter of greater than or equal to 50 nm, i.e. 0.05 μm.
In the following description of the invention, the “total pore volume” (TPV) of the trapping mass or of the support is understood to mean the volume measured by mercury intrusion porosimetry according to the standard ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne/cm and a contact angle of 140°. The wetting angle was taken equal to 140° following the recommendations of the publication “Techniques de l'ingénieur, traité analyse et caractérisation” [Techniques of the Engineer, Analysis and Characterization Treatise], pages 1050-5, written by Jean Charpin and Bernard Rasneur.
In order to obtain better accuracy, the value of the total pore volume in ml/g that is given in the text which follows corresponds to the value of the total mercury volume (total pore volume measured by mercury intrusion porosimetry) in ml/g measured on the sample minus the value of the mercury volume in ml/g measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).
The contents of metallic elements (group VIII, IB or IIB metals) are measured by X-ray fluorescence.
The invention relates to a process for trapping mercaptans contained in a sulfur-containing hydrocarbon feedstock, said feedstock advantageously having been partially desulfurized by a catalytic hydrodesulfurization step, in the presence of a trapping mass.
The mercaptan trapping process is generally carried out at a temperature of between 40° C. and 250° C., preferably between 100° C. and 250° C., preferably between 130° C. and 240° C.
Said process is generally performed at an hourly space velocity (which is defined as the volume flow rate of feedstock at the inlet per volume of trapping mass) of between 0.1 h−1 and 50 h−1, preferably between 0.5 h−1 and 20 h−1, preferably between 0.5 h−1 and 10 h−1.
Said mercaptan trapping process is generally carried out in the absence of hydrogen. The feedstock must preferably remain liquid, which requires sufficient pressure greater than the vaporization pressure of the feedstock. Said mercaptan trapping process is generally performed at a pressure of between 0.2 MPa and 5 MPa, preferably between 0.2 MPa and 2 MPa.
Advantageously, the reaction section of the trapping process comprises between two and five reactors, which operate in permutable mode, referred to by the term PRS for permutable reactor system or by the term “lead and lag”.
The sulfur-containing hydrocarbon feedstock, which is optionally partially desulfurized, is preferably a gasoline containing olefinic compounds, preferably a gasoline cut obtained from a catalytic cracking process. The treated hydrocarbon feedstock generally has a boiling point below 350° C., preferably below 300° C. and very preferably below 250° C. Preferably, the feedstock contains between 5% and 60% by weight of olefins relative to the total weight of said feedstock. Preferably, the hydrocarbon feedstock contains less than 100 ppm by weight of sulfur and preferably less than 50 ppm by weight of sulfur relative to the total weight of said feedstock, in particular in the form of mercaptans. Preferably, the partially desulfurized hydrocarbon feedstock contains less than 50 ppm by weight of sulfur in the form of mercaptans, relative to the total weight of the feedstock, preferably less than 30 ppm by weight of sulfur in the form of mercaptans.
Preferably, the feedstock to be treated undergoes a partial desulfurization treatment before the mercaptan trapping process: the step consisting in bringing the sulfur-containing feedstock fraction into contact with hydrogen, in one or more hydrodesulfurization reactors in series, containing one or more catalysts suitable for performing the hydrodesulfurization. Preferably, the operating pressure of this step is generally between 0.5 MPa and 5 MPa, and very preferably between 1 MPa and 3 MPa, and the temperature is generally between 200° C. and 400° C., and very preferably between 220° C. and 380° C. Preferably, the amount of catalyst used in each reactor is generally such that the ratio between the flow rate of gasoline to be treated, expressed in m3 per hour under standard conditions, per m3 of catalyst is between 0.5 h−1 and 20 h−1, and very preferably between 1 h−1 and 10 h−1. Preferably, the hydrogen flow rate is generally such that the ratio between the hydrogen flow rate expressed in normal m3 per hour (Nm3/h) and the flow rate of feedstock to be treated expressed in m3 per hour under standard conditions is between 50 Nm3/m3 and 1000 Nm3/m3, very preferably between 70 Nm3/m3 and 800 Nm3/m3. Preferably, this step will be carried out for the purpose of performing hydrodesulfurization selectively, i.e. with a degree of hydrogenation of the monoolefins of less than 80% by weight, preferably less than 70% by weight and very preferably less than 60% by weight.
The degree of desulfurization achieved during this hydrodesulfurization step is generally greater than 50% and preferably greater than 70%, such that the hydrocarbon fraction used in the mercaptan trapping process contains less than 100 ppm by weight of sulfur and preferably less than 50 ppm by weight of sulfur.
Any hydrodesulfurization catalyst may be used in the preliminary hydrodesulfurization step. Preferably, use is made of catalysts which have high selectivity with respect to the hydrodesulfurization reactions, in comparison with the olefin hydrogenation reactions. Such catalysts comprise at least one porous inorganic support, a group VIB metal, a group VIII metal. The group VIB metal is preferentially molybdenum or tungsten and the group VIII metal is preferentially nickel or cobalt. The support is generally selected from the group constituted by aluminas, silica, silica-aluminas, silicon carbide, titanium oxides, alone or as a mixture with alumina or silica-alumina, and magnesium oxides, alone or as a mixture with alumina or silica-alumina. Preferably, the support is selected from the group constituted by aluminas, silica and silica-aluminas. Preferably, the hydrodesulfurization catalyst used in the additional hydrodesulfurization step(s) has the following features:
When the metal is cobalt or nickel, the metal content is expressed as CoO and NiO respectively. When the metal is molybdenum or tungsten, the metal content is expressed as MoO3 and WO3 respectively.
A very preferred hydrodesulfurization catalyst comprises cobalt and molybdenum and has the abovementioned features. Furthermore, the hydrodesulfurization catalyst may comprise phosphorus. In this case, the phosphorus content is preferably between 0.1% and 10% by weight of P2O5, relative to the total weight of catalyst, and the molar ratio of phosphorus to group VIB elements is greater than or equal to 0.25, preferably greater than or equal to 0.27.
Preferably, the feedstock to be treated undergoes a complementary polishing hydrodesulfurization treatment after the partial desulfurization treatment and before the mercaptan trapping process. The polishing hydrodesulfurization step is mainly carried out in order to at least partly decompose the recombination mercaptans formed during the partial desulfurization treatment into olefins and H2S, but it also makes it possible to hydrodesulfurize the more refractory sulfur compounds whereas the first hydrodesulfurization step is mainly carried out in order to convert a large portion of the sulfur compounds into H2S. The remaining sulfur compounds are essentially refractory sulfur compounds and the recombination mercaptans resulting from the addition of the H2S formed.
The polishing hydrodesulfurization process is generally carried out at a temperature of between 280° C. and 400° C., preferably between 300° C. and 380° C., preferably between 310° C. and 370° C. The temperature of this polishing step is generally at least 5° C., preferably at least 10° C. and very preferably at least 20° C. higher than the temperature of the first hydrodesulfurization step. The process is generally carried out at an hourly space velocity (which is defined as the volume flow rate of feedstock at the inlet per volume of catalyst) of between 0.5 h−1 and 20 h−1, preferably between 1 h−1 and 10 h−1. The process is generally carried out at with a hydrogen flow rate such that the ratio between the hydrogen flow rate expressed in normal m3 per hour (Nm3/h) and the flow rate of feedstock to be treated expressed in m3 per hour under standard conditions is between 10 Nm3/m3 and 1000 Nm3/m3, preferably between 20 Nm3/m3 and 800 Nm3/m3.
The process is generally carried out at a pressure of between 0.5 MPa and 5 MPa, preferably between 1 MPa and 3 MPa.
Any hydrodesulfurization catalyst may be used in the polishing hydrodesulfurization step. Preferably, the catalyst comprises at least one porous inorganic support and a group VIII metal. The group VIII metal is preferentially nickel. The support is generally selected from the group constituted by aluminas, silica, silica-aluminas, silicon carbide, titanium oxides, alone or as a mixture with alumina or silica-alumina, and magnesium oxides, alone or as a mixture with alumina or silica-alumina. Preferably, the support is selected from the group constituted by aluminas, silica and silica-aluminas. Preferably, the hydrodesulfurization catalyst used in the polishing hydrodesulfurization step has the following features:
Preferably, the hydrocarbon feedstock after polishing hydrodesulfurization treatment contains less than 100 ppm by weight of sulfur derived from organic compounds and preferably less than 50 ppm by weight of sulfur derived from organic compounds, especially in the form of mercaptans and refractory sulfur compounds.
At the end of the hydrodesulfurization step, the effluent undergoes a step of separation of hydrogen and H2S via any method known to those skilled in the art (disengager, stabilization column, etc.), so as to recover a liquid effluent such that the dissolved H2S represents at most 30% by weight, or even 20% by weight, or even 10% by weight of the total sulfur present in the hydrocarbon fraction to be treated downstream by the mercaptan trapping process.
Said trapping mass used in the context of the process according to the invention comprises an active phase based on at least one group VIII, IB or IIB metal, and an inorganic support chosen from the group consisting of aluminas, silica, silica-aluminas and clays.
The content of group VIII, IB or IIB element is preferably between 10% and 80% by weight relative to the total weight of the trapping mass, preferably between 20% and 70% by weight, very preferably between 30% and 70% by weight.
Preferably, said group VIII, IB or IIB metal is chosen from nickel, copper or zinc. Very preferably, said metal is nickel.
The trapping mass used according to the present invention advantageously has a specific surface area of between 120 m2/g and 350 m2/g, preferably between 150 m2/g and 250 m2/g, more preferentially between 155 and 220 m2/g.
The trapping mass used according to the invention preferably has a total pore volume measured by mercury porosimetry of between 0.20 ml/g and 0.70 ml/g, preferably of between 0.30 ml/g and 0.60 ml/g.
Preferably, the content of aluminum and/or silicon elements in said trapping mass is preferably between 5% and 45% by weight relative to the total weight of the trapping mass, very preferably between 5% and 30% by weight.
Preferably, the inorganic support is an alumina.
According to one variant, said trapping mass used according to the invention may comprise at least one group IA or IIA element, preferably sodium or calcium. When said trapping mass comprises at least one group IA or IIA element, the content thereof is preferably between 0.01% and 5% by weight relative to the total weight of the trapping mass, very preferably between 0.02% and 2% by weight.
Said trapping mass used according to the invention is advantageously in the form of grains having a mean diameter of between 0.5 and 10 mm. The grains may have any shape known to those skilled in the art, for example the shape of beads (preferably having a diameter of between 1 and 6 mm), extrudates, tablets or hollow cylinders. Preferably, the trapping mass is either in the form of extrudates with a mean diameter of between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm, or in the form of beads with a mean diameter of between 0.5 and 10 mm, preferably between 1.4 and 4 mm. The term “mean diameter” of the extrudates is understood to mean the mean diameter of the circle circumscribed in the cross section of these extrudates.
According to the invention, the trapping mass is obtained according to a preparation process comprising the following steps:
Steps a) to e) of the process for preparing the trapping mass are described below.
Steps a) to e) are generally carried out outside the reaction section of the trapping process.
Advantageously, the step of bringing the inorganic support into contact with at least one precursor of the active phase based on at least one group VIII, IB or IIB metal can be carried out by dry impregnation or excess impregnation, or even by deposition-precipitation, or else according to other methods well known to those skilled in the art. By way of example, mention may be made of the methods of dry impregnation of an active phase precursor on a shaped porous inorganic support, or that of co-kneading precursors of active phase and structuring phase and then shaping.
A trapping mass precursor is obtained.
According to step b), the trapping mass precursor obtained in step a) is dried at a temperature below 250° C., advantageously between 50° C. and 180° C., preferably between 70° C. and 150° C., very preferably between 75° C. and 130° C.
The drying step is preferentially performed for a period of from 1 hour to 16 hours, preferably between 4 hours and 14 hours, and preferentially under an inert atmosphere or under an oxygen-containing atmosphere.
The drying step may be carried out by any technique known to a person skilled in the art. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure. It is advantageously carried out using hot air or any other hot gas. Preferably, the gas used is either air or an inert gas, such as argon or nitrogen. Very preferably, the drying is carried out in the presence of nitrogen and/or air.
A dried trapping mass is obtained.
According to the optional step c), the dried trapping mass obtained on conclusion of step b) is preferentially subjected to a calcination treatment at a temperature above or equal to 250° C. and below or equal to 1000° C., preferably between 250° C. and 650° C., and very preferably between 300° C. and 500° C., under an inert atmosphere (nitrogen for example) or under an oxygen-containing atmosphere (air, for example). The duration of this heat treatment is generally less than 16 hours, preferably between 1 hour and 10 hours, more preferentially between 2 and 8 hours. The calcining step may be carried out by any technique known to those skilled in the art. It is advantageously performed in a traversed bed or in a fluidized bed using hot air or any other hot gas.
A calcined trapping mass is obtained.
According to step d), at least one reducing treatment step is performed in the presence of a reducing gas after step b), optionally c), so as to obtain a trapping mass comprising at least one group VIII, IB or IIB metal at least partially in metallic form. This treatment makes it possible to form, at least in part, metallic particles in the zero-valent state. The reducing gas is preferably hydrogen. The hydrogen may be used pure or as a mixture (for example a hydrogen/nitrogen, hydrogen/argon or hydrogen/methane mixture). In the case where the hydrogen is used as a mixture, any proportion may be envisaged.
Said reducing treatment is preferentially performed at a temperature of between 100° C. and 500° C., preferably between 300° C. and 450° C. The duration of the reducing treatment is generally between 1 and 40 hours, preferably between 1 and 24 hours. The rise in temperature up to the desired reduction temperature is generally small, preferably set between 0.1 and 10° C./min, preferably between 0.3 and 7° C./min.
The step of activating the trapping mass is generally carried out ex situ, that is to say outside the reactor of the mercaptan trapping process according to the invention.
A trapping mass at least partially in reduced form is obtained.
The trapping mass, at least partially in reduced form, then undergoes a passivation step in order to protect said trapping mass.
The passivation step can be carried out by various methods, generally in the gas phase. The exothermicity can be controlled by using gas diluted in a gas that is inert with respect to the solid, or else by intermittently sending passivating gas or a gas pulse, or by combining various methods. Said passivation step is carried out in the presence of carbon dioxide, according to any method known to those skilled in the art.
Said passivation step is preferentially carried out by a concentration pulse of dilute carbon dioxide at a temperature of between 0° C. and 90° C., preferably between 5° C. and 50° C., and even more preferably between 15° C. and 30° C.
The trapping mass is obtained.
After the passivation step, a final activation step is advantageously carried out in situ, that is to say in the reactor of the mercaptan trapping process according to the invention, under a stream of reducing gas such as hydrogen or under a stream of feedstock to be treated, at a temperature between 100° C. and 300° C., preferably between 100° C. and 250° C.
The invention is illustrated by the examples that follow without limiting the scope thereof.
An alumina support is provided in the form of beads (sold by Axens®) with a diameter of between 1.4 and 4 mm, having a specific surface area of 205 m2/g and a total pore volume of 0.75 ml/g. An aqueous nickel nitrate solution containing 14% by weight of Ni (Parchem®) is also provided.
The precursor of the trapping mass is prepared by dry impregnation of 50 grams of the alumina support with 30.7 ml of the aqueous nickel nitrate solution, followed by drying in air at 120° C. for 12 hours followed by calcining at 450° C. for 6 hours. The operation of dry impregnation followed by heat treatments is repeated 4 times on the recovered solid.
The trapping mass precursor comprises 34.9% by weight of nickel and 26.8% by weight of aluminum relative to the total weight of the solid. It has a specific surface area of 169 m2/g.
The trapping mass precursor from example 1 is introduced into a reduction reactor. The solid is activated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 400° C. for 2 hours. The solid is then cooled. When the temperature is below 25° C., the solid is recovered without any further measures. Exothermicity is observed during contact with air. The solid is then introduced into a test column 1 cm in diameter. The solid is reactivated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 200° C. for 2 hours.
The trapping mass precursor from example 1 is introduced into a reduction reactor.
The solid is activated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 400° C. for 2 hours.
The solid is then cooled under a nitrogen stream of 1 L per hour and per gram of solid.
When the temperature reaches 25° C., a pulsed passivation program is started, with flow rates of 1 L per hour and per gram of solid. The solid is subjected to a stream of air diluted with nitrogen such that the oxygen concentration is 1 vol %.
If the temperature rises by more than 2° C., the stream is replaced by a stream of pure nitrogen.
When the temperature once again reaches 25° C., the operation is repeated.
The succession of pulses of oxygen diluted to 1% and then of nitrogen is repeated until the reaction exothermicity does not exceed 2° C.
In this case, the solid is subjected to oxygen diluted to 1% for one hour, then a second pulse sequence is carried out with a stream of oxygen diluted to 5%. The succession of pulses of oxygen diluted to 5% and then of nitrogen is repeated until the reaction exothermicity does not exceed 2° C.
In this case, the solid is subjected to air diluted to 5% for one hour, then a second pulse sequence is carried out with a stream of oxygen diluted to 20%. When the reaction exothermicity does not exceed 2° C., the solid is recovered and it is then introduced into a test column 1 cm in diameter.
The solid is reactivated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 200° C. for 2 hours.
The trapping mass from example 1 is introduced into a reduction reactor.
The solid is activated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 400° C. for 2 hours.
The solid is then cooled under a nitrogen stream of 1 L per hour and per gram of solid.
When the temperature reaches 25° C., a pulsed passivation program is started, with flow rates of 1 L per hour and per gram of solid.
The solid is subjected to a stream of carbon dioxide diluted with nitrogen such that the carbon dioxide concentration is 1 vol %.
If the temperature rises by more than 2° C., the stream is replaced by a stream of pure nitrogen.
When the temperature has dropped to a temperature of 25° C., the operation is repeated.
The succession of pulses of carbon dioxide diluted to 1% and then of nitrogen is repeated until the reaction exothermicity does not exceed 2° C.
In this case, the solid is subjected to carbon dioxide diluted to 1% for one hour, then a second pulse sequence is carried out with a stream of carbon dioxide diluted to 5%.
The succession of pulses of carbon dioxide diluted to 5% and then of nitrogen is repeated until the reaction exothermicity does not exceed 2° C.
In this case, the solid is subjected to the 5% carbon dioxide for one hour, then a second pulse sequence is carried out with a stream of carbon dioxide diluted to 20%.
When the reaction exothermicity does not exceed 2° C., the solid is recovered and it is then introduced into a test column 1 cm in diameter.
The solid is reactivated in situ under a stream of 1 L of hydrogen per hour and per gram of solid at 200° C. for 2 hours.
The evaluation of the performance of masses A, B and C is performed by monitoring the performance for the dynamic trapping of hexanethiol in a hydrocarbon matrix.
The test takes place in the test column prefilled with the solid and reactivated in situ as described in the examples. A hydrocarbon matrix referred to as feedstock is prepared beforehand by mixing heptane, 1-hexene and 1-hexanethiol, so as to obtain a matrix containing 2000 ppm by weight of sulfur and 10% by weight of olefin. The column containing the solid is then placed under a stream of heptane at an hourly space velocity of 8 h−1 (80 ml of feedstock per hour per 10 ml of solid), at 150° C. and under a pressure of 1.7 MPa. The experiment begins when the heptane stream is replaced with a feedstock stream at an hourly space velocity of 8 h−1, at 150° C. and under a pressure of 1.7 MPa. The effluents leaving the column are analyzed so as to determine the sulfur concentration of the treated matrix.
The dynamic performance of the solid corresponds to the amount of sulfur retained per gram of solid introduced when the sulfur concentration of the effluents corresponds to one tenth of the concentration of the feedstock. The test is maintained as long as the sulfur concentration in the effluents is less than half the concentration of the feedstock, i.e. a concentration of 1000 ppm by weight. The end-of-test performance corresponds to the amount of sulfur retained per gram of solid when the test is stopped. The results are collated in Table 1 below.
The trapping mass A prepared according to example 2 exhibits poor performance. A colored effluent, containing a sulfur-containing organometallic species, is observed from the start of the test. The end-of-test performance is poor, probably because the uncontrolled passivation was too great and degraded the active phase. Reactivation does not make it possible to restore performance.
The trapping mass B prepared according to example 3 exhibits poor performance. A colored effluent, containing a sulfur-containing organometallic species, is observed from the start of the test, rendering the purification of the hydrocarbon stream insufficient.
The trapping mass C prepared according to example 4 and in accordance with the invention exhibits good performance. The dynamic capacity of the solid is preserved when the solid was subjected to an ex-situ reduction step and a passivation step.
| Number | Date | Country | Kind |
|---|---|---|---|
| FR2113814 | Dec 2021 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/085355 | 12/12/2022 | WO |
