Patent Grant
12018217
The present invention relates to a process for the production of gasoline having a low content of sulfur and of mercaptans.
The production of gasolines meeting new environmental standards requires that their sulfur content be significantly decreased.
It is furthermore known that conversion gasolines, and more particularly those originating from catalytic cracking, which can represent from 30% to 50% of the gasoline pool, have high contents of monoolefins and of sulfur.
The sulfur present in gasolines is for this reason attributable, to close to 90%, to the gasolines resulting from catalytic cracking processes, which will be called FCC (Fluid Catalytic Cracking) gasolines subsequently. FCC gasolines thus constitute the preferred feedstock for the process of the present invention.
Among the possible routes for producing fuels having a low sulfur content, that which has been very widely adopted consists in specifically treating sulfur-rich gasoline bases by catalytic hydrodesulfurization processes in the presence of hydrogen. Conventional processes desulfurize gasolines in a nonselective manner by hydrogenating a large part of the monoolefins, which causes a high loss in octane number and a high consumption of hydrogen. The most recent processes, such as the Prime G+ (trademark) process, make it possible to desulfurize cracked gasolines rich in olefins, while limiting the hydrogenation of the monoolefins and consequently the loss of octane and the high hydrogen consumption which results therefrom. Such processes are, for example, described in the patent applications EP 1 077 247 and EP 1 174 485.
The residual sulfur compounds generally present in desulfurized gasoline can be separated into two distinct families: the unconverted refractory sulfur compounds present in the feedstock, on the one hand, and the sulfur compounds formed in the reactor by secondary “recombination” reactions. Among this last family of sulfur compounds, the predominant compounds are the mercaptans resulting from the addition of H2S formed in the reactor to the monoolefins present in the feedstock.
Mercaptans of chemical formula R—SH, where R is an alkyl group, are also called recombinant mercaptans. Their formation or their decomposition obeys the thermodynamic equilibrium of the reaction between monoolefins and hydrogen sulfide to form recombinant mercaptans. An example is illustrated according to the following reaction:
The sulfur contained in the recombinant mercaptans generally represents between 20% and 80% by weight of the residual sulfur in desulfurized gasolines.
The formation of these recombinant mercaptans is in particular described in the patent U.S. Pat. No. 6,231,754 and the patent application WO01/40409, which teach various combinations of operating conditions and of catalysts making it possible to limit the formation of recombinant mercaptans.
Other solutions to the problem of the formation of recombinant mercaptans are based on a treatment of partially desulfurized gasolines in order to extract therefrom said recombinant mercaptans. Some of these solutions are described in the patent applications WO02/28988 or WO01/79391.
Still other solutions are described in the literature for desulfurizing cracked gasolines using a combination of stages of hydrodesulfurization and of removal of the recombinant mercaptans by reaction to give thioethers or disulfides (also called sweetening) (see, for example, U.S. Pat. Nos. 7,799,210, 6,960,291, US2007114156, EP 2 861 094).
To obtain a gasoline having a very low sulfur content, typically with a content of less than 10 ppm by weight, thus requires the removal of at least a portion of the recombinant mercaptans. Virtually all countries have a very low specification for mercaptans in fuels (typically less than 10 ppm sulfur resulting from RSHs (measurement of content of mercaptans by potentiometry, ASTM D3227 method). Other countries have adopted a “Doctor Test” measurement to quantify the mercaptans with a negative specification to be observed (ASTM D4952 method).
Thus, in some cases, it appears that the most restrictive specification, because it is the most difficult to achieve without harming the octane number, is the specification for mercaptans and not that of the total sulfur.
The publication EP 1 174 485 in particular describes a process for the production of hydrocarbons having a low content of sulfur and of mercaptans comprising a sequence of two hydrodesulfurization reactors with removal of H2S between the two stages. The ratio of the hydrogen flow rate to the flow rate of feedstock to be treated is identical in the two reactors.
One aim of the present invention is to provide a process for the treatment of a gasoline containing sulfur, a portion of which is in the form of mercaptans, which makes it possible to reduce the content of mercaptans of said hydrocarbon fraction while limiting as much as possible the loss of octane and the consumption of reactants such as hydrogen.
A subject matter of the invention is a process for the treatment of a gasoline containing sulfur compounds, olefins and diolefins, the process comprising at least the following stages:
The process according to the invention responds to the problem of desulfurizing an olefinic gasoline, in particular reducing the content of recombinant mercaptans in the desulfurized effluents while limiting the hydrogenation of the olefins by virtue of the combination of the abovementioned stages.
Thus, stage a) is carried out so as to perform a deep desulfurization of the gasoline with a minimal saturation of the olefins (and no aromatic loss), resulting in a maximum octane retention. Deep desulfurization makes it possible to remove almost all of the sulfur compounds initially present in the gasoline. During this stage, new sulfur compounds are formed by recombination of the H2S resulting from the desulfurization and olefins: recombinant mercaptans. The effluent resulting from stage a) thus contains very few sulfur compounds other than recombinant mercaptans.
The H2S separation stage (stage b)) makes it possible to remove the H2S which is produced during desulfurization step a). This stage thus makes it possible to have a concentration of H2S which is thermodynamically favorable to the removal of recombinant mercaptans.
Stage c) has the role of minimizing the amount of recombinant mercaptans remaining. For this, the gasoline is then treated in a “finishing” hydrodesulfurization reactor with a catalyst generally based on nickel which exhibits virtually no olefin hydrogenation activity and is capable of reducing the amount of recombinant mercaptans. This stage is carried out at a higher temperature than that of stage a) in order to thermodynamically promote the removal of the mercaptans. This stage is also carried out with a ratio of the hydrogen flow rate to the flow rate of feedstock to be treated that is less high than that of stage a), which makes it possible to minimize the hydrogenation of the olefins.
Another advantage of the process according to the invention stems from the fact that it makes it possible to achieve a very low content of mercaptans (e.g. less than 10 ppm by weight of sulfur) in the final desulfurized gasoline, with operating conditions for hydrodesulfurization stage a) that are much less severe (for example, significant reduction in the operating pressure and/or temperature), which has the effect of limiting the loss of octane, of increasing the lifetime of the catalyst of the hydrodesulfurization stage and also of reducing the energy consumption.
Another advantage of the process according to the invention comes from the fact that it can easily be installed on existing units (remodeling or revamping).
According to an alternative form, the catalyst of stage a) comprises alumina and an active phase comprising cobalt, molybdenum and optionally phosphorus, said catalyst containing a content by weight, with respect to the total weight of catalyst, of cobalt oxide, in CoO form, of between 0.1% and 10%, a content by weight, with respect to the total weight of catalyst, of molybdenum oxide, in MoO3 form, of between 1% and 20%, a cobalt/molybdenum molar ratio of between 0.1 and 0.8 and a content by weight, with respect to the total weight of catalyst, of phosphorus oxide in P2O5 form of between 0.3% and 10% when phosphorus is present, said catalyst having a specific surface area of between 30 and 180 m2/g.
According to an alternative form, the catalyst of stage c) consists of alumina and of nickel, said catalyst containing a content by weight, with respect to the total weight of catalyst, of nickel oxide, in NiO form, of between 5% and 20%, said catalyst having a specific surface area of between 30 and 180 m2/g.
According to an alternative form, the temperature of stage c) is greater by at least 5° C. than the temperature of stage a).
According to an alternative form, the ratio of ratio of the hydrogen flow rate to the flow rate of feedstock to be treated at the inlet of the reactor of stage a)/ratio of the hydrogen flow rate to the flow rate of feedstock to be treated at the inlet of the reactor of stage c) is greater than or equal to 1.05.
According to an alternative form, the separation stages b) and d) are carried out in a debutanizer or a stripping section.
According to an alternative form, before stage a), a stage of distillation of the gasoline is carried out so as to fractionate said gasoline into at least two, light and heavy, gasoline cuts, and the heavy gasoline cut is treated in stages a), b), c) and d).
According to an alternative form, before stage a) and before any optional distillation stage, the gasoline is brought into contact with hydrogen and a selective hydrogenation catalyst in order to selectively hydrogenate the diolefins contained in said gasoline to give olefins.
According to an alternative form, the gasoline is a catalytic cracking gasoline.
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 content of metals is measured by X-ray fluorescence.
Description of the Feedstock
The process according to the invention makes it possible to treat any type of gasoline cut containing sulfur compounds and olefins, such as, for example, a cut resulting from a coking, visbreaking, steam cracking or catalytic cracking (FCC, Fluid Catalytic Cracking) unit. This gasoline can optionally be composed of a significant fraction of gasoline originating from other production processes, such as atmospheric distillation (gasoline resulting from a direct distillation (or straight run gasoline)), or from conversion processes (coking or steam cracking gasoline). Said feedstock preferably consists of a gasoline cut resulting from a catalytic cracking unit.
The feedstock is a gasoline cut containing sulfur compounds and olefins, the boiling point range of which typically extends from the boiling points of the hydrocarbons having 2 or 3 carbon atoms (C2 or C3) up to 260° C., preferably from the boiling points of the hydrocarbons having 2 or 3 carbon atoms (C2 or C3) up to 220° C., more preferably from the boiling points of the hydrocarbons having 5 carbon atoms up to 220° C. The process according to the invention can also treat feedstocks having lower end points than those mentioned above, such as, for example, a C5-180° C. cut.
The sulfur content of the gasoline cuts produced by catalytic cracking (FCC) depends on the sulfur content of the feedstock treated by the FCC, on the presence or not of a pretreatment of the feedstock of the FCC, and also on the end point of the cut. Generally, the sulfur contents of the whole of a gasoline cut, in particular those originating from the FCC, are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight. For gasolines having end points of greater than 200° C., the sulfur contents are often greater than 1000 ppm by weight; they can even, in certain cases, reach values of the order of 4000 to 5000 ppm by weight.
In addition, the gasolines resulting from catalytic cracking (FCC) units contain, on average, between 0.5% and 5% by weight of diolefins, between 20% and 50% by weight of olefins and between 10 ppm and 0.5% by weight of sulfur, generally including less than 300 ppm of mercaptans.
Description of the Hydrodesulfurization Stage a)
The hydrodesulfurization stage a) is implemented in order to reduce the sulfur content of the gasoline to be treated by converting the sulfur compounds into H2S, which is subsequently removed in stage b). Its implementation is particularly necessary when the feedstock to be desulfurized contains more than 100 ppm by weight of sulfur and more generally more than 50 ppm by weight of sulfur.
The hydrodesulfurization stage a) consists in bringing the gasoline to be treated into contact with hydrogen, in one or more hydrodesulfurization reactors, containing one or more catalysts suitable for carrying out the hydrodesulfurization.
According to a preferred embodiment of the invention, stage a) is implemented with the aim of carrying out a hydrodesulfurization selectively, that is to say with a degree of hydrogenation of the monoolefins of less than 80%, preferably of less than 70% and very preferably of less than 60%.
The temperature is generally between 210 and 350° C., preferably between 220 and 320° C. and particularly preferably between 220 and 290° C. The temperature employed must be sufficient to maintain the gasoline to be treated in the vapor phase in the reactor.
In the case where the hydrodesulfurization stage a) is carried out in several reactors in series, the temperature of each reactor is generally greater by at least 5° C., preferably by at least 10° C. and very preferably by at least 30° C. than the temperature of the reactor which precedes it.
The operating pressure of this stage is generally between 1 and 5 MPa and preferably between 1.5 and 3 MPa.
The amount of catalyst employed in each reactor is generally such that the ratio of 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 1 and 10 h−1 and preferably between 2 and 8 h−1.
The hydrogen flow rate is generally such that the ratio of the hydrogen flow rate, expressed in normal m3 per hour (Nm3/h), to the flow rate of feedstock to be treated, expressed in m3 per hour at standard conditions (15° C., 0.1 MPa), is between 100 and 600 Nm3/m3, preferably between 150 and 300 Nm3/m3. Normal m3 is understood to mean the amount of gas in a volume of 1 m3 at 0° C. and 0.1 MPa.
The hydrogen required for this stage can be fresh hydrogen or recycled hydrogen, preferably freed from H2S, or a mixture of fresh hydrogen and of recycled hydrogen. Preferably, fresh hydrogen will be used.
The degree of desulfurization of stage a), which depends on the sulfur content of the feedstock to be treated, is generally greater than 50% and preferably greater than 70%, so that the product resulting from stage a) contains less than 100 ppm by weight of sulfur and preferably less than 50 ppm by weight of sulfur.
The catalyst used in stage a) must exhibit a good selectivity with regard to the hydrodesulfurization reactions, in comparison with the reaction for the hydrogenation of olefins.
The hydrodesulfurization catalyst of stage a) comprises an oxide support and an active phase comprising a metal from group VIB and a metal from group VIII and optionally phosphorus and/or an organic compound as described below.
The metal from group VIB present in the active phase of the catalyst is preferentially chosen from molybdenum and tungsten. The metal from group VIII present in the active phase of the catalyst is preferentially chosen from cobalt, nickel and the mixture of these two elements. The active phase of the catalyst is preferably chosen from the group formed by the combination of the elements nickel-molybdenum, cobalt-molybdenum and nickel-cobalt-molybdenum and very preferably the active phase consists of cobalt and molybdenum.
The content of metal from group VIII is between 0.1% and 10% by weight of oxide of the metal from group VIII, with respect to the total weight of the catalyst, preferably between 0.6% and 8% by weight, preferably between 2% and 7% by weight, very preferably between 2% and 6% by weight and more preferably still between 2.5% and 6% by weight.
The content of metal from group VIB is between 1% and 20% by weight of oxide of the metal from group VIB, with respect to the total weight of the catalyst, preferably between 2% and 18% by weight, very preferably between 3% and 16% by weight.
The metal from group VIII to metal from group VIB molar ratio of the catalyst is generally between 0.1 and 0.8, preferably between 0.2 and 0.6.
In addition, the catalyst exhibits a density of metal from group VIB, expressed as number of atoms of said metal per unit area of the catalyst, which is between 0.5 and 30 atoms of metal from group VIB per nm2 of catalyst, preferably between 2 and 25, more preferably still between 3 and 15. The density of metal from group VIB, expressed as number of atoms of metal from group VIB per unit area of the catalyst (number of atoms of metal from group VIB per nm2 of catalyst), is calculated, for example, from the following relationship:
with:
X=% by weight of metal from group VIB;
NA=Avogadro's number, equal to 6.022×1023;
S=Specific surface area of the catalyst (m2/g), measured according to the standard ASTM D3663;
MM=Molar mass of the metal from group VIB (for example 95.94 g/mol for molybdenum).
For example, if the catalyst contains 20% by weight of molybdenum oxide MoO3 (i.e. 13.33% by weight of Mo) and has a specific surface area of 100 m2/g, the density d(Mo) is equal to:
Optionally, the catalyst can additionally exhibit a phosphorus content generally of between 0.3% and 10% by weight of P2O5, with respect to the total weight of catalyst, preferably between 0.5% and 5% by weight, very preferably between 1% and 3% by weight. For example, the phosphorus present in the catalyst is combined with the metal from group VIB and optionally also with the metal from group VIII in the form of heteropolyanions.
Furthermore, the phosphorus/(metal from group VIB) molar ratio is generally between 0.1 and 0.7, preferably between 0.2 and 0.6, when phosphorus is present.
Preferably, the catalyst is characterized by a specific surface area of between 5 and 400 m2/g, preferably of between 10 and 250 m2/g, preferably of between 20 and 200 m2/g, very preferably of between 30 and 180 m2/g. The specific surface area is determined in the present invention by the BET method according to the standard ASTM D3663, as described in the work by Rouquerol F., Rouquerol J. and Singh K., Adsorption by Powders & Porous Solids: Principle, Methodology and Applications, Academic Press, 1999, for example by means of an Autopore III™ model device of the Micromeritics™ brand.
The total pore volume of the catalyst is generally between 0.4 and 1.3 cm3/g, preferably between 0.6 and 1.1 cm3/g. The total pore volume is measured by mercury porosimetry according to the standard ASTM D4284 with a wetting angle of 140°, as described in the same work.
The tapped packing density (TPD) of the catalyst is generally between 0.4 and 0.7 g/ml, preferably between 0.45 and 0.69 g/ml. The TPD measurement consists in introducing the catalyst into a measuring cylinder, the volume of which has been determined beforehand, and then, by vibration, in tapping it until a constant volume is obtained. The bulk density of the tapped product is calculated by comparing the mass introduced and the volume occupied after tapping.
Advantageously, the hydrodesulfurization catalyst, before sulfidation, exhibits a mean pore diameter of greater than 20 nm, preferably of greater than 25 nm, indeed even 30 nm and often of between 20 and 140 nm, preferably between 20 and 100 nm, and very preferentially between 25 and 80 nm. The pore diameter is measured by mercury porosimetry according to the standard ASTM D4284 with a wetting angle of 140°.
The catalyst can be in the form of cylindrical or multilobe (trilobe, quadrilobe, and the like) extrudates with a small diameter, or of spheres.
The oxide support of the catalyst is usually a porous solid chosen from the group consisting of: aluminas, silica, silica-aluminas and also titanium or magnesium oxides, used alone or as a mixture with alumina or silica-alumina. It is preferably chosen from the group consisting of silica, the family of the transition aluminas and silica-aluminas; very preferably, the oxide support is constituted essentially of alumina, that is to say that it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight, indeed even at least 90% by weight, of alumina. It preferably consists solely of alumina. Preferably, the oxide support of the catalyst is a “high temperature” alumina, that is to say which contains theta-, delta-, kappa- or alpha-phase aluminas, alone or as a mixture, and an amount of less than 20% of gamma-, chi- or eta-phase alumina.
The catalyst can also additionally comprise at least one organic compound containing oxygen and/or nitrogen and/or sulfur before sulfidation.
A very preferred embodiment of the invention corresponds to the use, for stage a), of a catalyst comprising alumina and an active phase comprising cobalt, molybdenum and optionally phosphorus, said catalyst containing a content by weight, with respect to the total weight of catalyst, of cobalt oxide, in CoO form, of between 0.1% and 10%, a content by weight, with respect to the total weight of catalyst, of molybdenum oxide, in MoO3 form, of between 1% and 20%, a cobalt/molybdenum molar ratio of between 0.1 and 0.8 and a content by weight, with respect to the total weight of catalyst, of phosphorus oxide in P2O5 form of between 0.3% and 10% when phosphorus is present, said catalyst having a specific surface area of between 30 and 180 m2/g. According to one embodiment, the active phase consists of cobalt and molybdenum. According to another embodiment, the active phase consists of cobalt, molybdenum and phosphorus.
Description of the H2S Separation Stage (Stage b)
This stage is carried out in order to separate the excess hydrogen and also the H2S formed during stage a). Any method known to a person skilled in the art can be envisaged.
According to a first embodiment, after the hydrodesulfurization stage a), the effluent is cooled to a temperature generally of less than 80° C. and preferably of less than 60° C. in order to condense the hydrocarbons. The gas and liquid phases are subsequently separated in a separation drum. The liquid fraction, which contains the desulfurized gasoline and also a fraction of the H2S dissolved, is sent to a stabilization column or debutanizer. This column separates a top cut, consisting essentially of residual H2S and of hydrocarbon compounds having a boiling point less than or equal to that of butane, and a bottom cut freed from H2S, called stabilized gasoline, containing the compounds having a boiling point greater than that of butane.
According to a second embodiment, after the condensation stage, the liquid fraction which contains the desulfurized gasoline and also a fraction of the H2S dissolved is sent to a stripping section, while the gaseous fraction, consisting mainly of hydrogen and of H2S, is sent to a purification section. The stripping can be carried out by heating the hydrocarbon fraction, alone or with an injection of hydrogen or steam, in a distillation column in order to extract, at the top, the light compounds which were entrained by dissolution in the liquid fraction and also the residual dissolved H2S. The temperature of the stripped gasoline recovered at the column bottom is generally between 120° C. and 250° C.
Preferably, the separation stage b) is carried out in a stabilization column or debutanizer. This is because a stabilization column makes it possible to separate the H2S more efficiently than a stripping section.
Stage b) is preferably carried out in order for the sulfur in the form of H2S remaining in the desulfurized gasoline, before stage c), to represent less than 30%, preferably less than 20% and more preferably less than 10% of the total sulfur present in the treated hydrocarbon fraction.
The desulfurized gasoline resulting from stage b) contains sulfur compounds in a content of sulfur excluding mercaptans of less than 10 ppm and a content of sulfur in the form of mercaptans of less than 200 ppm, preferably of less than 100 ppm and particularly preferably of less than 50 ppm.
Description of Stage c)
“Finishing” hydrodesulfurization stage c) consists in bringing the effluent depleted in H2S resulting from stage b), hydrogen and a catalyst comprising an oxide support and an active phase consisting of at least one metal from group VIII into contact in at least one reactor at a temperature of between 200 and 350° C., at a pressure of between 1 and 5 MPa, with a space velocity of between 1 and 10 h−1 and a ratio of the hydrogen flow rate to the flow rate of feedstock to be treated which is lower than that of stage a), said temperature of stage c) being greater than the temperature of stage a).
Just as with the previous hydrodesulfurization stage a), stage c) is implemented with the aim of minimizing hydrogenation of the monoolefins in order to preserve the octane number, that is to say with a degree of hydrogenation of the monoolefins of less than 80%, preferably of less than 70% and very preferably of less than 60%.
The temperature of this stage is generally between 215° C. and 390° C., preferably between 250 and 380° C., and more preferably between 260° C. and 370° C.
The temperature of this stage c) is preferably greater by at least 5° C., preferably by at least 10° C., and very preferably by at least 30° C. than the temperature of stage a).
The operating pressure of this stage is generally between 1 and 5 MPa and preferably between 1 and 3 MPa.
The amount of catalyst employed in each reactor is generally such that the ratio of 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 1 and 10 h−1 and preferably between 2 and 8 h−1.
The ratio of the hydrogen flow rate to the flow rate of feedstock to be treated, also called H2/HC ratio, of stage c) is lower than the H2/HC ratio of stage a). The ratio of the hydrogen flow rate to the flow rate of feedstock to be treated is understood to mean the ratio at the inlet of the reactor of the stage concerned. The ratio or adjustment factor defined by F=(H2/HCinlet of the reactor of stage a))/(H2/HCinlet of the reactor of stage c)) is greater than or equal to 1.05, preferably greater than 1.1 and preferably between 1.1 and 6 and preferentially between 1.2 and 4.
The hydrogen flow rate is generally such that the ratio of the hydrogen flow rate, expressed in normal m3 per hour (Nm3/h), to the flow rate of feedstock to be treated, expressed in m3 per hour at standard conditions, is between 25 and 400 Nm3/m3, preferably between 40 and 250 Nm3/m3, and particularly preferably between 50 and 150 Nm3/m3.
The hydrogen required for this stage can be fresh hydrogen or recycled hydrogen, preferably freed from H2S, or a mixture of fresh and recycled hydrogen. Preferably, fresh hydrogen will be used. According to one embodiment, the hydrogen can originate from a hydrogen feed dedicated to this stage, for example a hydrogen compressor.
According to another embodiment, and by virtue of the relatively low H2 flow rate/feedstock flow rate ratio required in stage c), the fresh hydrogen may originate from the hydrogen feed of stage a), which makes it possible to save on a hydrogen compressor.
According to another embodiment, it is also possible to inject fresh hydrogen into stage c), to separate the hydrogen from the gasoline produced in stage d) and to inject this hydrogen, which contains little H2S, into stage a). This makes it possible to reduce the partial pressure of H2S at the inlet to stage c), which promotes the removal of the mercaptans.
In stage c), the degree of removal of the mercaptans is generally greater than 50% and preferably greater than 70%, so that the product resulting from stage c) contains less than 10 ppm sulfur and preferably less than 5 ppm sulfur resulting from the recombinant mercaptans, with respect to the total weight of the feedstock.
The degree of hydrogenation of the olefins of this stage is generally less than 5% and preferably less than 2%.
The catalyst of stage c) is different in nature and/or in composition from that used in stage a). The catalyst of stage c) is in particular a very selective hydrodesulfurization catalyst: it makes it possible to hydrodesulfurize without hydrogenating the olefins and thus to preserve the octane number.
The catalyst which may be suitable for this stage c) of the process according to the invention, without this list being limiting, is a catalyst comprising an oxide support and an active phase consisting of at least one metal from group VIII and preferably chosen from the group formed by nickel, cobalt and iron. These metals can be used alone or in combination. Preferably, the active phase consists of a metal from group VIII, preferably nickel. Particularly preferably, the active phase consists of nickel.
The content of metal from group VIII is between 1% and 60% by weight of oxide of the metal from group VIII, with respect to the total weight of the catalyst, preferably between 5% and 30% by weight, very preferably between 5% and 20% by weight.
Preferably, the catalyst is characterized by a specific surface area of between 5 and 400 m2/g, preferably of between 10 and 250 m2/g, preferably of between 20 and 200 m2/g, very preferably of between 30 and 180 m2/g. The specific surface area is determined in the present invention by the BET method according to the standard ASTM D3663, as described in the work by Rouquerol F., Rouquerol J. and Singh K., Adsorption by Powders & Porous Solids: Principle, Methodology and Applications, Academic Press, 1999, for example by means of an Autopore III™ model device of the Micromeritics™ brand.
The pore volume of the catalyst is generally between 0.4 and 1.3 cm3/g, preferably between 0.6 and 1.1 cm3/g. The total pore volume is measured by mercury porosimetry according to the standard ASTM D4284 with a wetting angle of 140°, as described in the same work. The tapped packing density (TPD) of the catalyst is generally between 0.4 and 0.7 g/ml, preferably between 0.45 and 0.69 g/ml.
The TPD measurement consists in introducing the catalyst into a measuring cylinder, the volume of which has been determined beforehand, and then, by vibration, in tapping it until a constant volume is obtained. The bulk density of the tapped product is calculated by comparing the mass introduced and the volume occupied after tapping.
Advantageously, the catalyst of stage c), before sulfidation, exhibits a mean pore diameter of greater than 20 nm, preferably of greater than 25 nm, indeed even 30 nm and often of between 20 and 140 nm, preferably between 20 and 100 nm, and very preferentially between 25 and 80 nm. The pore diameter is measured by mercury porosimetry according to the standard ASTM D4284 with a wetting angle of 140°.
The catalyst can be in the form of cylindrical or multilobe (trilobe, quadrilobe, and the like) extrudates with a small diameter, or of spheres.
The oxide support of the catalyst is usually a porous solid chosen from the group consisting of: aluminas, silica, silica-aluminas and also titanium or magnesium oxides, used alone or as a mixture with alumina or silica-alumina. It is preferably chosen from the group consisting of silica, the family of the transition aluminas and silica-aluminas; very preferably, the oxide support is constituted essentially of alumina, that is to say that it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight, indeed even at least 90% by weight, of alumina. It preferably consists solely of alumina. Preferably, the oxide support of the catalyst is a “high temperature” alumina, that is to say which contains theta-, delta-, kappa- or alpha-phase aluminas, alone or as a mixture, and an amount of less than 20% of gamma-, chi- or eta-phase alumina.
A very preferred embodiment of the invention corresponds to the use, for stage c), of a catalyst consisting of alumina and of nickel, said catalyst containing a content by weight, with respect to the total weight of catalyst, of nickel oxide, in NiO form, of between 5% and 20%, said catalyst having a specific surface area of between 30 and 180 m2/g.
The catalyst of stage c) is characterized by a hydrodesulfurization catalytic activity generally of between 1% and 90%, preferentially of between 1% and 70% and very preferably of between 1% and 50% of the catalytic activity of the catalyst of stage a).
Description of the Preparation of the Catalysts and of the Sulfidation
The preparation of the catalysts of stages a) and c) is known and generally comprises a stage of impregnation of the metals from group VIII and from group VIB, when it is present, and optionally of phosphorus and/or of the organic compound on the oxide support, followed by a drying operation and then by an optional calcination making it possible to obtain the active phase in their oxide forms. Before its use in a process for the hydrodesulfurization of a sulfur-containing olefinic gasoline cut, the catalysts are generally subjected to a sulfidation in order to form the active entity as described below.
The impregnation stage can be carried out either by slurry impregnation, or by impregnation in excess, or by dry impregnation, or by any other means known to a person skilled in the art. The impregnation solution is chosen so as to be able to dissolve the metal precursors in the desired concentrations.
Use may be made, by way of example, among the sources of molybdenum, of the oxides and hydroxides, molybdic acids and salts thereof, in particular the ammonium salts, such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid (H3PMo12O40), and salts thereof, and optionally silicomolybdic acid (H4SiMo12O40) and salts thereof. The sources of molybdenum can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin, Dawson, Anderson or Strandberg type, for example. Use is preferably made of molybdenum trioxide and the heteropolycompounds of Keggin, lacunary Keggin, substituted Keggin and Strandberg type.
The tungsten precursors which can be used are also well known to a person skilled in the art. For example, use may be made, among the sources of tungsten, of the oxides and hydroxides, tungstic acids and salts thereof, in particular the ammonium salts, such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid and salts thereof, and optionally silicotungstic acid (H4SiW12O40) and salts thereof. The sources of tungsten can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin or Dawson type, for example. Use is preferably made of the oxides and the ammonium salts, such as ammonium metatungstate, or the heteropolyanions of Keggin, lacunary Keggin or substituted Keggin type.
The cobalt precursors which can be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example. Use is preferably made of cobalt hydroxide and cobalt carbonate.
The nickel precursors which can be used are advantageously chosen from the oxides, hydroxides, hydroxycarbonates, carbonates and nitrates, for example.
The preferred phosphorus precursor is orthophosphoric acid H3PO4, but salts and esters thereof, such as ammonium phosphates, are also suitable. The phosphorus can also be introduced at the same time as the element(s) from group VIB in the form of Keggin, lacunary Keggin, substituted Keggin or Strandberg-type heteropolyanions.
After the impregnation stage, the catalyst is generally subjected to a drying stage at a temperature of less than 200° C., advantageously of between 50° C. and 180° C., preferably between 70° C. and 150° C., very preferably between 75° C. and 130° C. The drying stage is preferentially carried out under an inert atmosphere or under an oxygen-containing atmosphere. The drying stage can 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 stage is carried out at atmospheric pressure. It is advantageously carried out in a traversed bed using hot air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is either air or an inert gas, such as argon or nitrogen. Very preferably, the drying is carried out in a traversed bed in the presence of nitrogen and/or of air. Preferably, the drying stage has a duration of between 5 minutes and 15 hours, preferably between 30 minutes and 12 hours.
According to an alternative form of the invention, the catalyst has not undergone calcination during its preparation, that is to say that the impregnated catalytic precursor has not been subjected to a stage of heat treatment at a temperature of greater than 200° C. under an inert atmosphere or under an oxygen-containing atmosphere, in the presence or absence of water.
According to another alternative form of the invention, which is preferred, the catalyst has undergone a calcination stage during its preparation, that is to say that the impregnated catalytic precursor has been subjected to a stage of heat treatment at a temperature of between 250° C. and 1000° C. and preferably between 200° C. and 750° C., for a period of time typically of between 15 minutes and 10 hours, under an inert atmosphere or under an oxygen-containing atmosphere, in the presence or absence of water.
Before bringing into contact with the feedstock to be treated in a process for the hydrodesulfurization of gasolines, the catalysts of the process according to the invention generally undergo a sulfidation stage. The sulfidation is preferably carried out in a sulforeducing medium, that is to say in the presence of H2S and of hydrogen, in order to transform the metal oxides into sulfides, such as, for example, MoS2, Co9S6 or Ni3S2. The sulfidation is carried out by injecting, onto the catalyst, a stream containing H2S and hydrogen, or else a sulfur compound capable of decomposing to give H2S in the presence of the catalyst and of hydrogen. Polysulfides, such as dimethyl disulfide (DMDS), are H2S precursors commonly used to sulfide catalysts. The sulfur can also originate from the feedstock. The temperature is adjusted in order for the H2S to react with the metal oxides to form metal sulfides. This sulfidation can be carried out in situ or ex situ (inside or outside the reactor) of the reactor of the process according to the invention at temperatures of between 200° C. and 600° C. and more preferentially between 300° C. and 500° C.
The degree of sulfidation of the metals constituting the catalysts is at least equal to 60%, preferably at least equal to 80%. The sulfur content in the sulfided catalyst is measured by elemental analysis according to ASTM D5373. A metal is regarded as sulfided when the overall degree of sulfidation, defined by the molar ratio of the sulfur (S) present on the catalyst to said metal, is at least equal to 60% of the theoretical molar ratio corresponding to the complete sulfidation of the metal(s) under consideration. The overall degree of sulfidation is defined by the following equation:
(S/metal)catalyst≥0.6×(S/metal)theoretical
in which:
(S/metal)catalyst is the molar ratio of sulfur (S) to metal present on the catalyst
(S/metal)theoretical is the molar ratio of sulfur to metal corresponding to the complete sulfidation of the metal to give sulfide.
This theoretical molar ratio varies according to the metal under consideration:
(S/Fe)theoretical=1
(S/CO)theoretical=8/9
(S/Ni)theoretical=2/3
(S/Mo)theoretical=2/1
(S/W)theoretical=2/1
When the catalyst comprises several metals, the molar ratio of S present on the catalyst to the combined metals also has to be at least equal to 60% of the theoretical molar ratio corresponding to the complete sulfidation of each metal to give sulfide, the calculation being carried out in proportion to the relative molar fractions of each metal.
For example, for a catalyst comprising molybdenum and nickel with a respective molar fraction of 0.7 and 0.3, the minimum molar ratio (S/Mo+Ni) is given by the relationship:
(S/Mo+Ni)catalyst=0.6×{(0.7×2)+(0.3×(2/3)}
Description of the H2S Separation Stage (Stage d)
At the end of stage c), the gasoline treated under the conditions set out hereinabove thus exhibits a reduced content of mercaptans.
In accordance with the invention, a stage of separation of the H2S formed and present in the effluent resulting from stage c) is performed (stage d). Any method known to a person skilled in the art can be envisaged.
According to a first embodiment, after stage c), the effluent is cooled to a temperature generally of less than 80° C. and preferably of less than 60° C. in order to condense the hydrocarbons. The gas and liquid phases are subsequently separated in a separation drum. The liquid fraction, which contains the desulfurized gasoline and also a fraction of the H2S dissolved, is sent to a stabilization column or debutanizer. This column separates a top cut, consisting essentially of residual H2S and of hydrocarbon compounds having a boiling point less than or equal to that of butane, and a bottom cut freed from H2S, called stabilized gasoline, containing the compounds having a boiling point greater than that of butane.
According to a second embodiment, after the condensation stage, the liquid fraction which contains the desulfurized gasoline and also a fraction of the H2S dissolved is sent to a stripping section, while the gaseous fraction, consisting mainly of hydrogen and of H2S, is sent to a purification section. The stripping can be carried out by heating the hydrocarbon fraction, alone or with an injection of hydrogen or steam, in a distillation column in order to extract, at the top, the light compounds which were entrained by dissolution in the liquid fraction and also the residual dissolved H2S. The temperature of the stripped gasoline recovered at the column bottom is generally between 120° C. and 250° C.
Preferably, the separation stage d) is carried out in a stabilization column or debutanizer. This is because a stabilization column makes it possible to separate the H2S more efficiently than a stripping section.
Stage d) is preferably carried out in order for the sulfur in the form of H2S remaining in the effluent from stage c) to represent less than 30%, preferably less than 20% and more preferably less than 10% of the total sulfur present in the treated hydrocarbon fraction.
It should be noted that stage c) and the H2S separation stage (stage d) can be carried out simultaneously by means of a catalytic column equipped with at least one catalytic bed containing the hydrodesulfurization catalyst. Preferably, the catalytic distillation column comprises two beds of hydrodesulfurization catalyst and the effluent from stage b) is sent into the column between the two beds of catalyst.
Schemes which can be Employed within the Scope of the Invention
Different schemes can be employed in order to produce, at a lower cost, a desulfurized gasoline having a reduced content of mercaptans. The choice of the optimum scheme depends in fact on the characteristics of the gasolines to be treated and to be produced and also on the constraints specific to each refinery.
The schemes described below are given by way of illustration without limitation.
According to a first alternative form, a stage of distillation of the gasoline to be treated is carried out in order to separate two cuts (or fractions), namely a light cut and a heavy cut, and the heavy cut is treated according to the process of the invention. The light cut generally has a boiling point range of less than 100° C. and the heavy cut a temperature range of greater than 65° C. This first alternative form has the advantage of not hydrotreating the light cut which is rich in olefins and generally comprises a low sulfur content, which makes it possible to limit the loss of octane through hydrogenation of the olefins.
According to a second alternative form, the gasoline to be treated is subjected, before the hydrodesulfurization process according to the invention, to a preliminary stage consisting of a selective hydrogenation of the diolefins present in the feedstock, as described in the patent application EP 1 077 247.
The gasoline to be treated is treated beforehand in the presence of hydrogen and of a selective hydrogenation catalyst so as to at least partially hydrogenate the diolefins and to carry out a reaction for increasing the molecular weight of a portion of the light mercaptan (RSH) compounds present in the feedstock to give thioethers, by reaction with olefins.
To this end, the gasoline to be treated is sent to a selective hydrogenation catalytic reactor containing at least one fixed or moving bed of catalyst for the selective hydrogenation of the diolefins and for increasing the molecular weight of the light mercaptans. The reaction for the selective hydrogenation of the diolefins and for increasing the molecular weight of the light mercaptans is preferentially carried out on a sulfided catalyst comprising at least one element from group VIII and optionally at least one element from group VIB and an oxide support. The element from group VIII is preferably chosen from nickel and cobalt and in particular nickel. The element from group VIB, when it is present, is preferably chosen from molybdenum and tungsten and very preferably molybdenum.
The oxide support of the catalyst is preferably chosen from alumina, nickel aluminate, silica, silicon carbide or a mixture of these oxides. Use is preferably made of alumina and more preferably still of high-purity alumina. According to a preferred embodiment, the selective hydrogenation catalyst contains nickel at a content by weight of nickel oxide, in NiO form, of between 1% and 12%, and molybdenum at a content by weight of molybdenum oxide, in MoO3 form, of between 6% and 18% and a nickel/molybdenum molar ratio of between 0.3 and 2.5, the metals being deposited on a support consisting of alumina. The degree of sulfidation of the metals constituting the catalyst is preferably greater than 60%.
During the optional selective hydrogenation stage, the gasoline is brought into contact with the catalyst at a temperature of between 50 and 250° C., preferably between 80 and 220° C. and more preferably still between 90 and 200° C., with a liquid space velocity (LHSV) of between 0.5 and 20 h−1, the unit of the liquid space velocity being the liter of feedstock per liter of catalyst and per hour (l/l/h). The pressure is between 0.4 and 5 MPa, preferably between 0.6 and 4 MPa and more preferably still between 1 and 3 MPa. The optional selective hydrogenation stage is typically carried out with a ratio of the hydrogen flow rate, expressed in normal m3 per hour, to the flow rate of feedstock to be treated, expressed in m3 per hour at standard conditions, of between 2 and 100 Nm3/m3, preferably between 3 and 30 Nm3/m3.
After selective hydrogenation, the content of diolefins, determined via the maleic anhydride value (MAV), according to the UOP 326 method, is generally reduced to less than 6 mg maleic anhydride/g, indeed even less than 4 mg MA/g and more preferably less than 2 mg MA/g. In some cases, there may be obtained less than 1 mg MA/g.
The selectively hydrogenated gasoline is subsequently distilled into at least two cuts, a light cut and a heavy cut and optionally an intermediate cut. In the case of the fractionation into two cuts, the heavy cut is treated according to the process of the invention. In the case of the fractionation into three cuts, the intermediate and heavy cuts can be treated separately by the process according to the invention.
It should be noted that it is possible to envisage carrying out the stages of hydrogenation of the diolefins and of fractionation in two or three cuts simultaneously by means of a catalytic distillation column which includes a distillation column equipped with at least one catalytic bed.
Other characteristics and advantages of the invention will now become apparent on reading the description which will follow, given solely by way of illustration and without limitation, and with reference to the appended
With reference to
An effluent (gasoline) containing H2S is withdrawn from said hydrodesulfurization reactor 9 via the line 10. The effluent subsequently undergoes a stage of removal of the H2S (stage b)) which consists, in the embodiment of
The stabilized gasoline is sent via the line 36 into a hydrodesulfurization unit 11 of stage c) in order to reduce the content of residual mercaptans in the stabilized gasoline by hydrodesulfurization. As specified above, the unit 11 employs a lower H2 flow rate/feedstock flow rate ratio than that of stage a), and a higher temperature than that of stage a). Stage c) is carried out in the presence of a suitable hydrodesulfurization catalyst. Fresh hydrogen can be supplied via the line 12. By virtue of the relatively low H2 flow rate/feedstock flow rate ratio required in stage c), the hydrogen needed for stage c) in the unit 11 may also be taken directly from the hydrogen feed of the unit 9 via the line 13. This makes it possible to save on a hydrogen compressor.
The effluent from stage c) subsequently undergoes a stage of removal of the H2S (stage d)) which consists, in the embodiment of
Table 1 gives the characteristics of an FCC gasoline treated by the process according to the prior art (EP 1 077 247) and illustrated by
The FCC gasoline (line 1) is treated in the selective hydrogenation reactor 2 in the presence of a catalyst A (optional stage). The catalyst A is a catalyst of NiMo type on gamma-alumina. The metal contents are respectively 7% by weight NiO and 11% by weight MoO3 with respect to the total weight of the catalyst, that is to say an Ni/Mo molar ratio of 1.2. The specific surface area of the catalyst is 230 m2/g. Prior to use thereof, the catalyst A is sulfided at atmospheric pressure in a sulfidation bed under an H2S/H2 mixture consisting of 15% by volume of H2S at 1 l/g·h of catalyst and at 400° C. for two hours. This protocol makes it possible to obtain a degree of sulfidation of greater than 80%.
The gasoline (line 1) is brought into contact with hydrogen (line 3) in a reactor which contains the catalyst A. This stage of the process implements the selective hydrogenation of the diolefins and the conversion (increase in the molecular weight) of a portion of the light mercaptan (RSH) compounds present in the feedstock. The content of diolefins is directly proportional to the MAV (maleic anhydride value). The diolefins are undesirable compounds since they are precursors to gums in gasolines.
The operating conditions employed in the selective hydrogenation reactor are: Temperature: 140° C., total pressure: 2.5 MPa, added H2/gasoline feedstock volume ratio: 5 normal liters of hydrogen per liter of gasoline at standard conditions (vol/vol), hourly space velocity (HSV): 3 h−1.
The effluent from the selective hydrogenation stage (line 4) having a low content of conjugated diolefins (MAV=0.6 mg/g) and a low content of light sulfur compounds (the molecular weight of which was increased in the selective hydrogenation stage) is sent to a fractionating column (5) in order to separate at the top a light gasoline (line 6) and at the bottom of the column a first heavy gasoline cut (line 7). The characteristics of the light gasoline and of the first heavy gasoline cut are indicated in table 2. As indicated in table 2, the light gasoline obtained (line 6) has a low sulfur content (10 ppm by weight). The first heavy gasoline cut, which corresponds to approximately 72% by mass of the gasoline, has a high sulfur content (600 ppm) and requires additional treatment before being incorporated into the gasoline pool.
This example makes reference to the prior art (EP 1 077 247) and to
The effluent from the reactor 11 (line 14) is sent to a separation drum (15) in order to withdraw a gas phase containing H2S and hydrogen via the line 16 and a liquid fraction. The liquid fraction, which contains the desulfurized gasoline and also a fraction of the H2S dissolved, is sent via the line 17 to a stabilization column or debutanizer (18) in order to separate, at the top of the column via the line 19, a stream containing C4− hydrocarbons and the residual H2S and, at the bottom, via the line 20 of the column, a heavy “stabilized” gasoline obtained from the second reactor, the characteristics of which are illustrated in table 3. The loss of olefins is given in table 4.
The process according to example 2 makes it possible to obtain a heavy gasoline having a low sulfur content (10 ppm by weight). The loss of olefins between the first heavy gasoline cut and the stabilized heavy gasoline obtained after the second hydrodesulfurization stage is 27.3% by mass (in absolute terms).
This example makes reference to the present invention, according to
The first hydrodesulfurization stage (stage a)) is conducted in the presence of a CoMo catalyst supported on alumina. The temperature is 260° C., the pressure is 2 MPa, the liquid space velocity (expressed in volume of liquid per volume of catalyst and per hour) is 3 h−1, the ratio of the hydrogen flow rate to the feedstock flow rate is 200 normal m3 per m3 under standard conditions. The effluent from the reactor (line 10) is partially condensed in order to be introduced into the gas/liquid separator (31). The gas phase produced (line 32) contains essentially hydrogen and H2S, possibly along with light hydrocarbons. The bottom of the separator (line 33) contains a partially desulfurized hydrocarbon cut.
The characteristics of the heavy gasoline obtained after stage a) of the present invention are illustrated in table 5. The loss of olefins after stage a) is given in table 6.
In stage b) according to the invention, a stage of removal of the H2S present in the effluent from stage a) is carried out. The effluent from the reactor (9) is partially condensed in order to be introduced into the gas/liquid separator (31). The gas phase produced (line 32) contains essentially hydrogen and H2S, possibly along with light hydrocarbons. The bottom of the separator contains a partially desulfurized heavy hydrocarbon cut. After condensation of the effluent from stage a) (line 33), the separation is carried out in a stabilization column (34) so as to produce a stabilized heavy gasoline cut (line 36) and a gas phase containing C4− hydrocarbons and residual H2S (line 35).
The characteristics of the stabilized heavy gasoline cut obtained after stage b) of the present invention are illustrated in table 7.
In stage c) according to the invention, the stabilized heavy gasoline cut which is depleted in H2S is brought into contact with hydrogen in the hydrodesulfurization reactor (11) and in the presence of a “finishing” Ni catalyst supported on alumina. The temperature is 350° C., the pressure is 2 MPa, the liquid space velocity (expressed in volume of liquid per volume of catalyst and per hour) is 3 h−1. The ratio of the hydrogen flow rate expressed in normal m3 per hour to the flow rate of the feedstock to be treated expressed in m3 per hour at standard conditions is less than that of stage a), specifically 80 Nm3/m3. Under these operating conditions, the hydrogenation of the olefins is negligible.
The characteristics of the effluent (14) obtained after stage c) of the present invention are illustrated in table 8.
The desulfurized heavy cut (line 14) is then separated (stage d)). It is partially condensed in order to be introduced into the gas/liquid separator (15). The gas phase produced (line 16) contains essentially hydrogen and H2S, possibly along with light hydrocarbons. The bottom of the separator (line 17) contains a partially desulfurized hydrocarbon cut, which is sent to a stabilization column (18) in order to recover, at the top of the column, hydrogen and H2S (line 19), possibly along with light hydrocarbons, and, at the bottom of the column (line 20), a desulfurized heavy gasoline cut. The characteristics of the heavy gasoline cut obtained after stabilization (line 20) of the present invention are illustrated in tables 9 and 10.
Very advantageously, the process according to the invention makes it possible to produce a gasoline having a low sulfur content (10 ppm S) while at the same time reducing the absolute loss of olefins compared to the desulfurized heavy gasoline HCN after the second desulfurization stage (presented in comparative example 2).
Specifically, in example 2 the loss of olefins (in % by mass) between the first heavy gasoline cut (7) and the gasoline obtained after the second hydrodesulfurization stage (14) is 6.8% and in example 3 according to the invention the loss of olefins between the first heavy gasoline cut (7) and the desulfurized and stabilized heavy gasoline HCN (20) is 4.7%. Thus, example 3 according to the invention makes it possible to retain a relative 31% of the olefins present in the first heavy gasoline cut (7) while producing a gasoline with the same low sulfur content (10 ppm). The retention of the olefins present in the first heavy gasoline cut HCN has a positive impact on the octane numbers of the gasoline produced.
The process according to the invention thus makes it possible to obtain, after stabilization, a gasoline cut having a low content of organic sulfur (10 ppm). This gasoline may, with the light gasoline LCN obtained in example 1, be profitably exploited in the gasoline pool for formulating vehicle fuel.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1908343 | Jul 2019 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/069033 | 7/6/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/013527 | 1/28/2021 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3809644 | Johnson | May 1974 | A |
| 9505993 | Gornay et al. | Nov 2016 | B2 |
| 20050133410 | Li | Jun 2005 | A1 |
| 20100236979 | Fan | Sep 2010 | A1 |
| 20150166907 | Gornay | Jun 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 3014896 | Jun 2015 | FR |
| Entry |
|---|
| International Search Report dated Jul. 27, 2020 issued in corresponding PCT/EP2020/069033 application (2 pages). |
| Number | Date | Country | |
|---|---|---|---|
| 20220325191 A1 | Oct 2022 | US |
