EP1612255B1 - Hydroentschwefelungsverfahren für Benzine unter Verwendung eines Katalysators mit geregelter Porosität. - Google Patents

Hydroentschwefelungsverfahren für Benzine unter Verwendung eines Katalysators mit geregelter Porosität. Download PDF

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Publication number
EP1612255B1
EP1612255B1 EP05291383A EP05291383A EP1612255B1 EP 1612255 B1 EP1612255 B1 EP 1612255B1 EP 05291383 A EP05291383 A EP 05291383A EP 05291383 A EP05291383 A EP 05291383A EP 1612255 B1 EP1612255 B1 EP 1612255B1
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catalyst
process according
activity
range
support
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EP1612255B2 (de
EP1612255A1 (de
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Christophe Bouchy
Nathalie Marchal
Florent Picard
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a desulfurization process using a catalyst containing at least one support, and an active phase comprising for example a metal.
  • the process allows the hydrodesulphurization of gasolines, and especially the gasolines resulting from a catalytic cracking process (FCC Fluid Catalytic Cracking according to English terminology, that is to say catalytic cracking in a fluidized bed).
  • the feedstock to be treated is usually a sulfur-containing gasoline cut such as for example a cut from a coking unit, visbreaking, steam cracking or catalytic cracking (FCC).
  • Said feed is preferably constituted by a gasoline cut from a catalytic cracking unit whose boiling point range typically ranges from that of hydrocarbons with 5 carbon atoms to about 250 ° C.
  • This gasoline can possibly be composed of a significant fraction of gasoline coming from other production processes such as atmospheric distillation (generally called straight run fuel by the refiner) or conversion processes (coker or steam-cracking gasoline).
  • Catalytic cracking gasolines which can constitute 30 to 50% by volume of the gasoline pool, have high olefin and sulfur contents.
  • the sulfur present in the reformulated gasoline is attributable, to nearly 90%, to the gasoline resulting from catalytic cracking.
  • Desulphurisation of species and mainly FCC species is therefore of obvious importance for achieving standards.
  • Hydrotreating or hydrodesulfurization of catalytic cracking gasoline when it is carried out under the conditions conventionally known to those skilled in the art, makes it possible to reduce the sulfur content of the cut.
  • this process has the major disadvantage of causing a very large drop in the octane number of the cut, because of the hydrogenation or saturation of a large part or even all of the olefins under the conditions of the hydrotreatment.
  • the US Patent 5,318,690 proposes a process consisting in splitting the gasoline, softening the light fraction and hydrotraying the heavy fraction on a conventional catalyst and then treating it on a zeolite ZSM5 to recover the initial octane.
  • the WO 01/40409 claims the treatment of an FCC gasoline under conditions of high temperature, low pressure and high hydrogen / charge ratio. Under these particular conditions, the recombination reactions involving H 2 S formed by the desulphurization reaction and the olefins to give rise to mercaptan formation are minimized.
  • the catalysts used for this type of application are sulphide catalysts containing a group VIB element (Cr, Mo, W) and a group VIII element (Fe, Ru, Os, Co, Rh , Ir, Pd, Ni, Pt).
  • the residual sulfur compounds present in the desulfurized gasolines by deep hydrodesulfurization comprise so-called recombinant mercaptans, resulting from the addition of the H 2 S formed during the reaction, on the olefins present, as well as unsaturated sulfur compounds such as thiophene and alkylthiophenes.
  • the presence of the so-called recombination mercaptans explains at least in part that when it is desired to desulphurize in depth gasolines comprising an olefin fraction, a very high growth rate of hydrogenation of olefins is observed for the high levels of desulfurization. .
  • the desired desulfurization rate approaches 100%, the saturation rate of olefins increases very significantly.
  • EP 1 031 622 A1 discloses a process for desulfurizing olefinic gasolines comprising at least two steps, a step of hydrogenation of unsaturated sulfur compounds and a step of decomposition of saturated sulfur compounds.
  • the invention is based on a two-step sequence such that the first step allows the elimination of unsaturated sulfur compounds from saturated sulfur compounds and the second step decomposes the saturated sulfur compounds into H 2 S with hydrogenation of olefins limited.
  • the US Patent 6,231,753 describes a process for the hydrodesulfurization of olefinic gasolines comprising a first hydrodesulphurization step, an H2S extraction step and a second hydrodesulphurization step, the overall desulfurization rate and the temperature of this second step being greater than those from the first.
  • the US Patent 6,231,754 describes a process in which a spent hydrotreatment catalyst is subsequently used in a higher temperature hydrodesulfurization step.
  • the pore diameters of the catalyst are described as between 6 and 20 nm and the surface concentration of MoO 3 between 0.5. 10 -4 and 3.10 -4 g / m 2 .
  • Requirement WO 03/099963 discloses a two-step process wherein the second step is carried out with a catalyst less loaded with metals and having a pore diameter equal to or greater than the catalyst used in the first step.
  • the average pore diameter of the catalysts is between 6 and 20 nm and the surface concentration of MoO 3 is between 0.5. 10 -4 and 3.10 -4 g / m 2 .
  • the hydrodesulfurization process of a gasoline according to the invention uses a catalyst comprising a support and an active phase comprising at least one metal characterized in that the average pore diameter of said catalyst is greater than 20 nanometers, preferably between 20 and 100 nm.
  • the catalyst according to the invention contains at least one Group VI metal, more preferably it additionally contains at least one Group VIII metal.
  • the surface density of the Group VI metal is preferably between 2 ⁇ 10 -4 and 40 ⁇ 10 -4 grams of oxide of said metal per m 2 of support.
  • the support is preferably chosen from the group consisting of aluminas, silica, silica alumina or titanium or magnesium oxides used alone or in admixture with alumina or silica-alumina. . More preferably, the support is at least in part constituted by an alumina. According to a variant of the invention, the specific surface area of the support is less than 200 m 2 / g.
  • the hydrodesulfurization process according to the invention comprises at least two successive stages of hydrodesulfurization and a catalyst whose average pore diameter is greater than 20 nanometers is implemented in at least one of said stages.
  • the successive steps are carried out without intermediate degassing.
  • the process according to the invention comprises a succession of hydrodesulfurization stages and the activity of the catalyst of a step n + 1 is between 1% and 90% of the activity of the catalyst of the step n.
  • the reaction temperature of step n + 1 is greater than that of step n.
  • the catalyst of step n + 1 is the catalyst of step n which has undergone partial deactivation.
  • the deactivation of the catalyst can be achieved by contacting the catalyst with a feed containing a hydrocarbon fraction comprising olefins at a temperature of at least 250 ° C. It is also possible to recycle the catalyst of step n in step n + 1, when its activity has decreased by at least 10%. Another possibility is that the catalyst of step n + 1 comprises a lower metal content than that of the catalyst of step n.
  • the process according to the invention uses at least one hydrodesulfurization catalyst comprising at least one Group VI metal (M VI ) and / or at least one Group VIII metal (M VIII ) on a support.
  • the Group VI metal is generally molybdenum or tungsten the Group VIII metal generally nickel or cobalt.
  • the catalyst support is usually a porous solid selected from the group consisting of aluminas, silicon carbide, silica, silica-aluminas or titanium or magnesium oxides used alone or in admixture with the alumina or silica-alumina. It is preferably selected from the group consisting of silica, the family of transition aluminas and silica-aluminas.
  • the support consists essentially of at least one transition alumina, that is to say it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight. % weight, or even at least 90% weight of transition alumina. It may optionally consist solely of a transition alumina.
  • the specific surface of the support is generally less than 200 m 2 / g, most often less than 150 m 2 / g.
  • the porosity of the catalyst before sulfurization is such that it has an average pore diameter greater than 20 nm, preferably greater than 25 nm or even 30 nm and often between 20 and 140 nm, preferably between 20 and 100 nm, and very preferably between 25 and 80 nm.
  • the pore diameter was measured by mercury porosimetry according to ASTM D4284-92 with a wetting angle of 140 °.
  • the surface density of the Group VI metal is comprised according to the invention between 2.10 -4 and 40.10 -4 gram of oxide of said metal per m 2 of support, preferably between 4.10 -4 and 16.10 -4 g / m 2 .
  • the molar ratio M VIII / (M VI + M VIII ) is typically greater than 0.1, preferably between 0.2 and 0.6 and very preferably between 0.2 and 0. 5.
  • the catalyst according to the invention can be prepared using any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and VIB on the selected support.
  • This impregnation may, for example, be carried out according to the method known to those skilled in the art in the dry-impregnation terminology, in which the quantity of desired elements in the form of soluble salts in the chosen solvent, for example demineralized water, so as to fill the porosity of the support as exactly as possible.
  • the support thus filled with the solution is preferably dried.
  • the preferred support is alumina which can be prepared from any type of precursors and shaping tools known to those skilled in the art.
  • This treatment generally aims to transform the molecular precursors of the elements in the oxide phase. In this case it is an oxidizing treatment, but a direct reduction or even a simple drying of the catalyst can also be carried out.
  • an oxidizing treatment also known as calcination
  • this is generally carried out under air or under dilute oxygen, and the treatment temperature is generally between 200 ° C. and 550 ° C., preferably between 300 ° C. C and 500 ° C.
  • a reducing treatment this is generally carried out under pure hydrogen or preferably diluted, and the treatment temperature is generally between 200 ° C. and 600 ° C., preferably between 300 ° C. and 500 ° C. ° C.
  • Group VIB and VIII metal salts useful in the catalyst preparation process are, for example, cobalt nitrate, nickel nitrate, ammonium heptamolybdate or ammonium metatungstate. Any other salt known to those skilled in the art having sufficient and decomposable solubility during the activation treatment can also be used.
  • the catalyst is usually used in a sulfurized form obtained after treatment in temperature in contact with a decomposable organic sulfur compound and generating H 2 S or directly in contact with a gas stream of H 2 S diluted in H 2 .
  • This step can be carried out in situ or ex situ (inside or outside the reactor) of the hydrodesulfurization reactor at temperatures between 200 and 600 ° C and more preferably between 300 and 500 ° C.
  • the present invention also relates to a process for the desulphurization of gasolines comprising olefins comprising at least two hydrodesulphurization stages and intended to minimize both the content of compounds which are the most refractory to hydrodesulfurization, such as the thiophene compounds and the so-called recombination mercaptans, derived from the addition of H 2 S to the olefins while limiting the degree of hydrogenation of the olefins associated with the removal of the sulfur compounds.
  • At least one of the steps of the hydrodesulfurization process uses a catalyst as previously described.
  • At least partial extraction of the H 2 S between the two reactors by any means known to those skilled in the art is a known solution to achieve high desulfurization rates with a limited olefin hydrogenation rate.
  • this type of diagram can be applied in the context of the present invention.
  • the present method is particularly useful in the case where the hydrodesulphurization reactors are sequenced without removing the H 2 S between the reactors.
  • the method comprises at least two steps.
  • a hydrodesulfurization first stage A is preferably carried out in a fixed bed reactor, generally in the vapor phase, on any catalyst conventionally used for this application.
  • the use of so-called “selective" catalysts is preferred because it makes it possible to limit the hydrogenation of the olefins while maximizing the hydrodesulfurization.
  • This first step is followed by a second step B, for example without operation between steps A and B other than a warming of the effluent of step A.
  • Step B is characterized by the fact that it is carried out on a catalyst having an activity catalytic conversion of thiophene between 1% and 90%, or even between 1% and 70% and preferably between 1% and 50% of the activity of the catalyst of step A.
  • the catalyst used in step B can be either a catalyst whose catalytic formulation has been optimized to achieve the desired catalytic activity, or a partially deactivated catalyst.
  • the use of catalysts which are preferably more selective in series makes it possible to limit the hydrogenation of the olefins to the high levels of desulfurization. It was observed that such a sequence allowed, by an inexpensive device, to significantly improve the selectivity of the desulfurization reaction by minimizing the olefin saturation rate while maintaining a conversion rate of the sulfur compounds into H 2 Gets up. This device also has the advantage that it allows, for a diagram without extraction of the H 2 S between the two reactors, to improve the selectivity of the process compared with a desulphurization performed in a single step.
  • the device is most often based on a set of at least two or three reactors and can be carried out as follows: the reactor of step A contains the fresh catalyst and the reactor of step B contains the spent catalyst.
  • the reactor of step A contains the fresh catalyst
  • the reactor of step B contains the spent catalyst.
  • the reactor containing the catalyst of deactivated step A is used in the second step, a reactor containing fresh catalyst is started and placed in step A.
  • the reactor containing catalyst B is stopped the catalyst is replaced by fresh catalyst and the reactor is put on hold.
  • This embodiment is more particularly of interest for an operation of the low pressure and high temperature hydrodesulphurization section for the two stages, conditions for which the formation of the recombination mercaptans is minimized but which results in a rapid deactivation of the catalysts.
  • hydrodesulfurization By low pressure is meant relative pressures generally less than 2 relative MPa, and preferably less than 1.5 MPa relative or even 1 MPa relative and temperatures generally greater than 250 ° C or 260 ° C and most often greater than 280 ° C.
  • the pressure of steps A and B is generally between about 0.4 MPa and 3 MPa, preferably between 0.6 MPa and 2.5 MPa, the flow rate of hydrogen is such that the ratio of hydrogen flow rates in normal liters per hour on the hydrocarbon flow rate in liters per hour is between 50 and 800 and preferably between 60 and 600.
  • the temperature of step A is between 150 ° C and 450 ° C, preferably between 200 and 200 ° C. ° C and 400 ° C and more preferably between 230 ° C and 350 ° C and the temperature of step B is between 150 ° C and 450 ° C, preferably between 210 ° C and 410 ° C and more preferably between 240 ° C and 360 ° C.
  • Steps A and B are performed according to a preferred mode in sequence without intermediate additional step. It is therefore possible to implement them in the same reactor.
  • the catalytic zone corresponding to step B will be operated at an average temperature above the minimum of 10 ° C to the catalytic zone corresponding to step A.
  • This temperature difference can come either from the heat of reaction released by the hydrogenation of the olefins, or by injection between the catalytic zones A and B of a hotter fluid selected from hydrogen or an inert gas such as nitrogen, the charge or the fluid resulting from the recycling of a fraction of the process effluent.
  • Steps A and B can also be carried out in a catalytic column from which the gaseous compounds are withdrawn at the top under normal conditions of temperature and pressure.
  • the catalytic zone of step A will be arranged higher in the column than the catalytic zone of step B.
  • the catalyst of step B advantageously differs from the catalyst of step A by a catalytic activity of between 1% and 90%, and even between 1% and 70% and preferably between 1% and 50% of the catalytic activity of the catalyst. of Step A.
  • the catalysts of Steps A and B are carried out in sulphide form.
  • the sulphurization procedure can be carried out in situ or ex situ by any sulphurization method known to those skilled in the art.
  • the catalyst used is a new catalyst prepared to exhibit reduced activity
  • the contents of Group VIII and Group VIB metals deposited on the support will not exceed 10.9 and 14% by weight in oxide form and preferably 7.8% and 10% by weight, respectively, in oxide form (for remain consistent with the maximum Co / Co + Mo ratio of 0.6 of the preferred range).
  • the support used generally contains silica, silicon carbide, titanium oxide or magnesium oxide and / or alumina but will preferably be predominantly composed of alumina.
  • the catalyst of step B can also be a deactivated hydrotreatment catalyst.
  • a used catalyst from a distillate hydrodesulfurization unit or any other hydrodesulphurization process present in the refinery could be used, provided that the residual activity measured by the method described in Example 6 did not occur. does not exceed 90%, even 70% and preferably 50% of the activity of the catalyst of step A.
  • the catalyst of step B may finally be identical in formulation to that of step A, but after being deactivated by treatment of a section comprising olefins.
  • the spent catalysts generally have a decreased activity due to the presence of carbon deposition due to the polymerization of the hydrocarbons treated on the catalyst.
  • the present invention can be implemented as follows:
  • the gasoline to be treated is for example characterized by a sulfur content greater than 50 ppm and an olefin content greater than 10% for which it is desired to transform at least 70% of sulfur in H 2 S.
  • This gasoline which presents boiling temperatures generally below 250 ° C can be either directly treated by the device of the present invention, or undergo pretreatment consisting of a selective hydrogenation step and fractionation. These pretreatments are described in detail in the application EP 1 077 247 . In this case, advantageously only the fraction C 6+ (that is to say containing the hydrocarbons whose total carbon number is greater than or equal to 6) of the gasoline can be treated by the process according to the present invention.
  • Gasoline mixed with hydrogen is heated by an exchanger train and / or an oven.
  • the mixture brought to the desired temperature and pressure is generally in the vapor phase. It is sent to a first reactor (stage A) containing a hydrodesulphurization catalyst as described above implemented in a fixed bed.
  • the effluent from this reactor contains hydrocarbons and sulfur compounds which have not reacted, paraffins resulting from the hydrogenation of olefins, H 2 S resulting from the decomposition of sulfur compounds and recombinant mercaptans from H 2 S addition reactions on olefins.
  • This effluent is generally heated in an exchange train and / or an oven so that its temperature is increased by at least 10 ° C.
  • step B a second reactor containing a low-active hydrodesulfurization catalyst such as described above implemented in fixed bed.
  • the effluent from this reactor consists of hydrocarbons and a reduced amount of sulfur compounds which have not reacted during step A, paraffins resulting from the hydrogenation of olefins, the H 2 S from decomposition of sulfur compounds and a decreased amount of recombinant mercaptans from H 2 S addition reactions to olefins.
  • steps A and B allows, with respect to step A alone, to minimize the loss of olefins by hydrogenation, for a given desulfurization rate.
  • the following examples illustrate the advantages of the process in one or two steps as just described. In these examples (as well as in the foregoing description), the contents of sulfur or of sulfur compounds are given in ppm by weight.
  • the catalysts are prepared according to the same method.
  • the synthesis protocol consists in carrying out a dry impregnation of a solution of ammonium heptamolybdate and cobalt nitrate, the volume of the aqueous solution containing the metal precursors being equal to the volume of water recovery (ERV). corresponding to the mass of support to be impregnated.
  • ERP volume of water recovery
  • the concentrations of the precursors in the solution are adjusted so as to deposit on the support the weight contents of desired metal oxides.
  • the solid is then allowed to mature at room temperature for 12 hours and then dried at 120 ° C for 12 hours. Finally, the solid is calcined at 500 ° C. for two hours under an air flow (11 / h / g).
  • the alumina supports used are industrial supports supplied by Axens, the characteristics of which are given in Table 1 below. ⁇ b> Table 1 ⁇ / b>: Characteristics of industrial aluminums.
  • the sulphidation protocol of the catalyst is identical for each catalytic test.
  • the catalyst in its calcined form (oxide), is loaded into the catalytic test unit and then sulphurated by a synthetic filler (4% S in the form of DMDS in n-heptane).
  • the total mercaptan content is measured in potentiometric recipes by the ASTM D3227 method after separation of H 2 S.
  • P 2.7 relative MPa
  • VVH 4 h -1
  • H 2 / load 360 normal liters per liter (nl / I)
  • T 250 - 280 ° C.
  • Each operating condition is maintained for the time necessary for the stabilization of the catalyst, both in hydrogenating activity and in desulfurizing activity (typically 24 to 48 hours).
  • the results obtained on the catalysts A and D are shown in Table 4 below.
  • Catalyst A Catalyst D T (° C) 250 260 270 250 260 S total 160 130 90 130 65 HDS /% 83.5 86.6 90.7 86.6 93.3 % olefins 26.7 26.1 25.5 23.0 21.1 HDO /% 25.2 26.9 28.6 35.6 40.9
  • Example 3 Evaluation of the Performance of Catalysts A and B.
  • the catalysts A (compliant) and B (compliant) are evaluated on FCC No. 2 gasoline with lower sulfur content than FCC No. 1 gasoline, the characteristics of which are given in Table 5 below. .
  • Table 5 ⁇ / b> Characteristics of FCC No. 2 Gasoline.
  • Each operating condition is maintained for the time necessary for the stabilization of the catalyst, both in hydrogenating activity and in desulfurizing activity (typically 24 to 48 hours).
  • the results obtained on the catalysts A and B are shown in Table 6 below. ⁇ b> Table 6 ⁇ / b>: Performance of Catalysts A and B for the Desulfurization of FCC No. 2 Gasoline.
  • Catalyst A Catalyst B T (° C) 270 280 270 280 S total 96 46 92 54 HDS /% 78.7 89.8 79.5 88.0 % olefins 29.7 26.3 30.1 27.5 HDO /% 11.3 21.5 10.1 17.9
  • catalyst B has a lower hydrogenation activity (HDO) than catalyst A.
  • HDO hydrogenation activity
  • Catalyst B (compliant) is therefore also more selective than catalyst D (non-compliant).
  • Example 4 Evaluation of the Performance of Catalysts A and C.
  • Catalyst A and Catalyst C are compared in desulphurization with a depentanized and highly highly sulfurized FCC # 3 gasoline whose characteristics are given in Table 7.
  • Table 7 ⁇ / b> Characteristics of FCC No. 3 Gasoline.
  • a 100 ml sample of catalyst B is subjected to accelerated deactivation on a pilot unit under the following conditions: the catalyst is operated at 300 ° C. under a mixture consisting of the gasoline 4 described in Example 6 and hydrogen injected up to 100 normal liters of hydrogen per liter of gasoline, with a gasoline flow rate of 400 ml / h and under a total pressure of 1 MPa relative. After 800 hours, the reactor is stripped at 120 ° C under nitrogen to remove the adsorbed hydrocarbons. The catalyst thus deactivated is called catalyst G.
  • the activity of the catalysts B, D, E, F, G is evaluated by a hydrodesulfurization test of a mixture of model molecules carried out in a stirred autoclave reactor of 500 ml.
  • a hydrodesulfurization test of a mixture of model molecules carried out in a stirred autoclave reactor of 500 ml.
  • the model charge used for the activity test has the following composition: 1000 ppm of sulfur in thiophene form, 10% by weight of olefins in the form of 2,3-dimethyl-butene-2 in n-heptane.
  • This reaction mixture was chosen because considered representative of a catalytic cracking gasoline.
  • the total system pressure is then adjusted and maintained at 3.5 relative MPa by hydrogen supply and the temperature is adjusted to 250 ° C.
  • the catalyst is contacted with the reaction mixture.
  • Periodic sampling of samples makes it possible to follow the evolution of the composition of the solution over time by gas chromatographic analysis.
  • the duration of the test is chosen so as to obtain final thiophene conversion levels of between 50 and 90%.
  • the activity of the catalyst is defined with respect to the rate constant for conversion of normalized thiophene per volume of catalyst.
  • Gasoline No. 4 described in Table 10 is used to study the performance of catalyst chains. This species is from an FCC unit and has been depentanized. ⁇ b> Table 10 ⁇ / b>: Characteristics of FCC # 4 Gasoline Total sulfur (ppm): 380 Olefins (% by weight): 27.8 Olefins (% by weight): 32.1 Aromatic (% weight): 33.9 ASTM distillation: PI: 55 ° C PF: 219 ° C
  • the chaining tests are carried out in a pilot unit equipped with two reactors in series, each loaded with 100 ml of catalyst.
  • the basic operating conditions used for all the tests are as follows, namely a pressure equal to 1.8 MPa relative and a hydrogen-to-charge ratio of 400 normal liters per liter.
  • VVH (h -1 ) 4 4 4 4 4 4 4 4 S effluent ppm 12 13 14 13 15 12 13 Mercaptans, ppm 9 10 7 8 8 7 10 HDO% 28 32 24.5 21 20.1 21.4 30.6
  • the two reactors placed in series are named respectively reactor 1 and reactor 2.
  • the volume of catalyst in each reactor is 100 ml.
  • Tests 1 and 2 were carried out on catalysts B and D alone. Catalyst D is not in accordance with the invention. Loss of olefins in test 1 is lower than the loss of olefins in Run 2 due to the difference in selectivity between Catalysts B and D.
  • catalysts E, F or G in sequence with catalysts B or D makes it possible to improve the overall selectivity. Indeed, for similar sulfur contents in the recipes, between 12 and 15 ppm, the losses of olefins measured by the HDO level are decreased compared to the tests 1 and 2, carried out on a single catalyst. In addition, it is observed that the best results have been obtained for the sequences 5 and 6 for which the catalysts used in the two steps are in accordance with the invention.
  • Test No. 7 is made from a sequence not according to the invention for which reactor 2 is charged with a more active catalyst than that charged to reactor 1. Compared to tests 3 to 6, , a loss of olefins and a higher residual mercaptan content, for equivalent sulfur content in effluents.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Claims (18)

  1. Hydrodesulfurierungsverfahren von Treibstoffen, umfassend die Anwendung eines Katalysators, der einen Träger und eine aktive Phase umfasst, welche Nickel oder Kobalt umfasst und wobei der mittlere Durchmesser der Poren des Katalysators mehr als 20 Nanometer beträgt.
  2. Verfahren nach Anspruch 1, wobei der mittlere Durchmesser der Poren zwischen 20 und 100 nm liegt.
  3. Verfahren nach Anspruch 1 oder 2, wobei der Katalysator mindestens ein Metall der Gruppe VI enthält.
  4. Verfahren nach Anspruch 3, wobei die Oberflächendichte des Metalls der Gruppe VI zwischen 2, 10-4 und 40, 10-4 Gramm Oxid des Metalls pro m2 des Trägers liegt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Träger aus der Gruppe gewählt ist, gebildet durch Aluminiumoxid, Siliziumdioxid, Siliziumdioxid-Aluminiumoxid oder Titan- oder Magnesiumoxid, verwendet alleine oder als Mischung mit Aluminiumoxid oder Siliziumdioxid-Aluminiumoxid.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Träger mindestens teilweise aus Aluminiumoxid besteht.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei die spezifische Oberfläche des Trägers weniger als 200 m2/g beträgt.
  8. Hydrodesulfurierungsverfahren nach Anspruch 1, umfassend mindestens zwei aufeinanderfolgende Schritte der Hydrodesulfurierung, wobei der Katalysator in mindestens einem der Schritte angewendet wird.
  9. Verfahren nach Anspruch 8, wobei die Reaktionstemperatur der aufeinanderfolgenden Schritte zwischen 150 °C und 450 °C liegt, der Druck zwischen 0,4 und 3 MPa (relativ) liegt und das Volumenverhältnis Wasserstoff zu Kohlenwasserstoffen H2/HC zwischen 50 N I/I und 800 N I/I liegt.
  10. Verfahren nach Anspruch 9, wobei für jeden Schritt der Druck unter 2 MPa (relativ) und die Temperatur über 250 °C liegt.
  11. Verfahren nach einem der Ansprüche 8 bis 10, wobei die aufeinanderfolgenden Schritte ohne Zwischengasung durchgeführt werden.
  12. Verfahren nach einem der Ansprüche 8 bis 11, umfassend eine Aufeinanderfolge von Schritten der Hydrodesulfurierung, dadurch gekennzeichnet, dass die Tätigkeit des Katalysators eines Schritts n+1 zwischen 1 % und 90 % der Tätigkeit des Katalysators des Schritts n liegt.
  13. Verfahren nach Anspruch 12, wobei die Tätigkeit eines Schrittes zwischen 1 % und 50 % der Tätigkeit des Katalysators des vorhergehenden Schrittes liegt.
  14. Verfahren nach einem der Ansprüche 12 oder 13, wobei die Reaktionstemperatur des Schritts n+1 über derjenigen des Schritts n liegt.
  15. Verfahren nach einem der Ansprüche 12 bis 14, wobei der Katalysator des Schritts n+1 der Katalysator des Schritts n ist, der einer teilweisen Deaktivierung unterzogen wurde.
  16. Verfahren nach Anspruch 15, wobei die Deaktivierung des Katalysators durch das Kontaktieren des Katalysators mit einer Charge, welche einen kohlenwasserstoffhaltigen Anteil enthält, welcher Olefine umfasst, bei einer Temperatur von mindestens 250 °C erhalten wird.
  17. Verfahren nach Anspruch 16, wobei der Katalysator des Schritts n zum Schritt n+1 zurückgeführt wird, wenn sich seine Tätigkeit um mindestens 10 % herabgesetzt hat.
  18. Verfahren nach einem der Ansprüche 12 bis 14, wobei der Katalysator des Schritts n+1 einen geringeren Metallgehalt umfasst als derjenige des Katalysators von Schritt n.
EP05291383.7A 2004-07-01 2005-06-27 Hydroentschwefelungsverfahren für Benzine unter Verwendung eines Katalysators mit geregelter Porosität. Active EP1612255B2 (de)

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US20060000751A1 (en) 2006-01-05
BRPI0502597A (pt) 2006-02-14
DK1612255T4 (da) 2016-07-11
FR2872516A1 (fr) 2006-01-06
DE602005003402T2 (de) 2008-02-28
BRPI0502597B1 (pt) 2014-12-30
US20120067780A1 (en) 2012-03-22
DE602005003402T3 (de) 2016-07-21
KR20060049757A (ko) 2006-05-19
US8926831B2 (en) 2015-01-06
DK1612255T3 (da) 2008-03-17
EP1612255B2 (de) 2016-03-30
EP1612255A1 (de) 2006-01-04
CA2510668A1 (fr) 2006-01-01
KR101209347B1 (ko) 2012-12-06
DE602005003402D1 (de) 2008-01-03
FR2872516B1 (fr) 2007-03-09
CA2510668C (fr) 2013-01-29

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