EP1174485B1 - Zweistufiges Benzin Entschwefelungsverfahren mit zwischenzeitlicher Entfernung von H2S - Google Patents

Zweistufiges Benzin Entschwefelungsverfahren mit zwischenzeitlicher Entfernung von H2S Download PDF

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Publication number
EP1174485B1
EP1174485B1 EP01401679A EP01401679A EP1174485B1 EP 1174485 B1 EP1174485 B1 EP 1174485B1 EP 01401679 A EP01401679 A EP 01401679A EP 01401679 A EP01401679 A EP 01401679A EP 1174485 B1 EP1174485 B1 EP 1174485B1
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EP
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Prior art keywords
gasoline
catalyst
stage
sulfur
process according
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English (en)
French (fr)
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EP1174485A1 (de
Inventor
Blaise c/o Inst. Française du Petrole Didillon
Denis c/o Inst. Française du Petrole Uzio
Jean-Luc c/o Inst. Française du Petrole Nocca
Quentin c/o Inst. Franç. du Petrole Debuisschert
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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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/06—Sulfides
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen

Definitions

  • the present invention relates to a process for producing gasolines with a low sulfur content, which makes it possible to recover the whole of a sulfur-containing gasoline fraction, to reduce the total sulfur contents of said gasoline fraction to very low levels, without significant reduction in gasoline yield, and minimizing the decrease in octane number due to the hydrogenation of olefins.
  • This method is particularly applicable when the gasoline to be treated is a catalytic cracking gasoline containing a sulfur content greater than 1000 ppm by weight and / or an olefin content greater than 30% by weight, when the desired sulfur content in the Desulfurized gasoline is less than 50 ppm by weight.
  • Cracking gasolines which can represent 30 to 50% of the gasoline pool, have the disadvantage of containing significant concentrations of sulfur, which means that the sulfur present in the reformulated gasolines is attributable, at nearly 90%, to the gasoline species.
  • cracking catalytic cracking gas in fluidized bed or FCC, steam cracking gasoline, coking gasolines .
  • Desulphurisation (hydrodesulphurisation) of gasolines and mainly cracking gasolines is therefore of obvious importance for achieving specifications.
  • the patent application EP-A-0 725 126 discloses a method for hydrodesulfurizing a cracking gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in easily desulfurized compounds and a second fraction rich in difficult to desulphurize compounds. Before carrying out this separation, it is necessary to first determine the distribution of sulfur-containing products by means of analyzes.
  • the present invention relates to a three-stage desulfurization process for gasolines as defined in the wording of claim 1, and with a hydrogenation pretreatment of diolefins in the feed.
  • This process is particularly particularly suitable for cracking gasolines having a sulfur content greater than 1000 ppm by weight, which it is desired to lower to a level of less than 50 ppm by weight and preferably less than 15 ppm by weight.
  • the selective hydrogenation prior to step A of the diene compounds may optionally hydrogenate acetylenic compounds.
  • the present invention therefore relates to a process for the production of gasolines with a low sulfur content, which makes it possible to recover the whole of a petrol fraction containing sulfur and olefins, to reduce the sulfur contents in said petrol fraction to very low levels. levels and generally at a value of less than 50 ppm or even less than 15 ppm by weight, without a substantial decrease in the yield of gasoline, and by minimizing the reduction in the octane number due to the hydrogenation of the olefins.
  • the process is particularly suitable for the treatment of gasolines with a high sulfur content, ie a sulfur content greater than 1000 ppm by weight and / or when the gasoline has a high olefin content, that is to say greater than 30% weight.
  • the process according to the invention comprises a treatment of the feedstock on a first catalyst making it possible to at least partially hydrogenate aromatic sulfur compounds such as, for example, thiophene compounds by placing under conditions in which the hydrogenation of the olefins is limited on this catalyst (step A), a step for removing at least part of the H2S gasoline thus treated (step B), then a third treatment on at least one catalyst for decomposing at least partially saturated sulfur compounds with limited hydrogenation of olefins (step C).
  • aromatic sulfur compounds such as, for example, thiophene compounds
  • step C is carried out on a chain of catalysts, for example the sequence described in the patent. FR-A-279000 while meeting the criteria for the H2S concentration at the entry of the third step according to the present invention.
  • the feedstock of the process according to the invention is a gasoline cutter containing sulfur and olefins, preferably a petrol cut from a cracking unit, and preferably a gasoline predominantly from a catalytic cracking unit.
  • the treated gasoline can also be a mixture of gasolines from different conversion processes such steam cracking processes, coking or visbreaking (visbreaking according to the English terminology) or even gasoline directly from the distillation of petroleum products.
  • the gasolines having high olefin concentrations are particularly suitable for being subjected to the process according to the invention.
  • the sulfur species contained in the fillers treated by the process of the invention may be mercaptans or heterocyclic compounds, such as, for example, thiophenes or alkylthiophenes, or heavier compounds, such as for example benzothiophene or dibenzothiophene.
  • heterocyclic compounds unlike mercaptans, can not be removed by conventional extractive processes.
  • These sulfur compounds are consequently removed by the process according to the invention which leads to their at least partial decomposition into hydrocarbons and H 2 S.
  • the sulfur content of catalytic cracked gasoline (FCC) gasoline cuts depends on the sulfur content of the FCC treated feed as well as the end point of the cut.
  • the sulfur contents of the entirety of a petrol cut, in particular those coming from the FCC are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight.
  • the sulfur contents are often greater than 1000 ppm by weight, and in some cases they may even reach values of the order of 4000 to 5000 ppm by weight.
  • the gasolines which are particularly suitable for the process according to the invention therefore contain olefin concentrations which are generally between 5 and 60% by weight.
  • the gasoline treated in the process according to the invention preferably contains more than 30% by weight of olefins.
  • the gasolines may also contain significant concentrations of diolefins, that is to say diolefin concentrations of up to 15% by weight. Generally the diolefin content is between 0.1 and 10% by weight. The diolefin content is typically greater than 1% by weight or even greater than 0.5% by weight.
  • the gasoline is, before undergoing stages A, B and C subjected to a selective hydrogenation treatment aimed at hydrogenating at least partly the diolefins present in said gasoline, as described in the wording of claim 1.
  • Gasoline can also naturally contain nitrogen compounds.
  • the nitrogen concentration of the gasoline is generally less than 1000 ppm by weight and is generally between 20 and 500 ppm by weight.
  • This gasoline preferably contains a sulfur content greater than 1000 ppm by weight.
  • the range of boiling points typically extends from about the boiling points of the 5-carbon hydrocarbons (C5) to about 250 ° C.
  • the end point of the gasoline cut depends on the refinery from which it comes and the constraints of the market, but generally remains within the limits indicated above.
  • the gasoline may, for example, undergo splitting or other treatment before being subjected to the process according to the invention without these treatments limiting the scope of the invention.
  • sulfur is essentially present in the form of thiophene compounds (thiophene, methylthiophenes, alkylthiophenes, etc.) and, depending on the end point of the gasoline to treated, benzothiophene compounds, alkylbenzothiophene, or even compounds derived from dibenzothiophene.
  • the method according to the invention firstly comprises a treatment (step A) of the gasoline on a catalyst for hydrogenating at least partly unsaturated sulfur compounds such as for example thiophene compounds, in saturated compounds such as by for example thiophanes (or thiacyclopentane) or mercaptans according to a succession of reactions described below:
  • This hydrogenation reaction can be carried out on a conventional hydrotreating (hydrodesulphurization) catalyst comprising a Group VIII metal and a Group VIb metal partially in the form of sulfides.
  • a conventional hydrotreating (hydrodesulphurization) catalyst comprising a Group VIII metal and a Group VIb metal partially in the form of sulfides.
  • the operating conditions are adjusted so as to be able to hydrogenate at least part of the thiophene compounds while limiting the hydrogenation of the olefins.
  • the thiophene, benzothiophenic and dibenzothiophenic compounds if they are present in the gasoline to be treated, are generally transformed significantly, that is to say that at the end of the first stage, the content of Thiophenic, benzothiophene or dibenzothiophene compounds represent at most 20% of that of the starting gasoline.
  • this hydrogenation step is accompanied by the significant production of H2S by total decomposition of the sulfur compounds initially present in the feedstock.
  • the decomposition rate of the sulfur compounds present in the H2S feed which accompanies the hydrogenation of the unsaturated sulfur compounds, is generally greater than 50%.
  • the method according to the invention comprises a second step where the H2S is at least partly removed from the effluent obtained at the end of step A.
  • This step can be carried out using any techniques known to man of career. It can be carried out directly under the conditions in which the effluent is at the end of step A or after these conditions have been changed in order to facilitate the removal of at least a portion of the H2S.
  • a gas / liquid separation (where the gas is concentrated in H2S and the liquid is depleted in H2S and is sent directly to step C), a step of stripping the gasoline practiced on a liquid fraction of the gasoline obtained after step A, an amine washing step, again performed on a liquid fraction of the gasoline obtained after step A, an uptake of the H2S by an absorbing mass operating on the gaseous or liquid effluent obtained after the step, a separation of the H2S from the gaseous or liquid effluent by a membrane.
  • the sulfur content in the form of H 2 S is generally less than 500 ppm by weight relative to the starting gasoline. In a preferred manner, this content is reduced, at the end of step B, to a value of between 0.2 and 300 ppm by weight and even more preferably to a value of between 0.5 and 150 ppm by weight.
  • step C in which the saturated sulfur compounds are converted into H 2 S according to the reactions:
  • This treatment can be carried out using any catalyst allowing the conversion of saturated sulfur compounds (mainly thiophane or mercaptan type compounds). It may for example be carried out using a catalyst based on nickel, molybdenum, cobalt, iron tungsten or tin. Preferably, the treatment is carried out in the presence of a catalyst based on nickel, nickel and tin, cobalt and iron, cobalt and tungsten.
  • the thus desulphurized gasoline is then optionally stripped in order to remove the H2S produced during step C.
  • step C In the case of gasoline with a high sulfur content and / or when the rate of conversion of unsaturated sulfur compounds to saturated sulfur compounds is not in step A, it may be advantageous to carry out step C with a series of catalysts comprising at least one catalyst described for step A and at least one catalyst described for step C.
  • Hydrogenation of dienes is a step which eliminates, before hydrodesulphurization, almost all the dienes present in the gasoline cutter containing sulfur to be treated. It generally takes place in the presence of a catalyst comprising at least one Group VIII metal, preferably selected from the group consisting of platinum, palladium and nickel, and a support.
  • a catalyst comprising at least one Group VIII metal, preferably selected from the group consisting of platinum, palladium and nickel, and a support.
  • a nickel-based catalyst deposited on an inert support, such as, for example, alumina, silica or a support containing at least 50% alumina. This catalyst operates at a pressure of 0.4 to 5 MPa, at a temperature of 50 to 250 ° C, with a liquid hourly space velocity of 1 to 10 h -1 .
  • Another metal may be combined to form a bimetallic catalyst, such as, for example, molybdenum or tungsten.
  • the choice of operating conditions is particularly important.
  • the operation will generally be carried out under pressure in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value necessary for hydrogenating the diolefins.
  • the hydrogen and the feedstock to be treated are injected in ascending or descending streams into a reactor preferably with a fixed bed of catalyst.
  • the temperature is most generally between about 50 and about 250 ° C, and preferably between 80 and 230 ° C, and more preferably between 120 and 200 ° C.
  • the pressure is sufficient to maintain more than 80%, and preferably more than 95% by weight of the gasoline to be treated in the liquid phase in the reactor; it is most generally between 0.4 and 5 MPa and preferably greater than 1 MPa.
  • the pressure is advantageously between 1 and 4 MPa.
  • the space velocity is from about 1 to about 10 h -1 , preferably from 4 to 10 h -1 .
  • the catalytic cracked gasoline may contain up to a few weight percent of diolefins.
  • the diolefin content is generally reduced to less than 3000 ppm, or even less than 2500 ppm and more preferably less than 1500 ppm. In some cases, it can be obtained less than 500 ppm.
  • the diene content after selective hydrogenation can even if necessary be reduced to less than 250 ppm.
  • the step of hydrogenation of the dienes takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the amount of hydrogen necessary to effect the desired reactions. .
  • This step consists of converting at least a portion of the unsaturated sulfur compounds, such as the thiophene compounds, into saturated compounds, for example thiophanes (or thiacyclopentanes) or mercaptans.
  • This step may, for example, be carried out by passing the feedstock to be treated, in the presence of hydrogen, over a catalyst containing at least one element of group VIII and / or at least one element of group VIb at least partly in sulphide form, at a temperature of between 220 ° C. and 320 ° C. and more preferably between 220 ° C. and 290 ° C., under a pressure generally of between 1 and 5 MPa, preferably between 1 and 4 MPa and more preferably between 1 and 4 MPa. , 5 and 3MPa.
  • the liquid space velocity is between 1 and 10 h -1 (expressed as volume of liquid per volume of catalyst and per hour), preferably between 3 h -1 and 8 h -1.
  • the ratio H 2 / HC is between 100 to 600 liters per liter and preferably 300 to 600 liters per liter.
  • At least one hydrodesulfurization catalyst comprising at least one element of group VIII (metals of groups 8, 9 and 10 of the new classification, ie iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum) and / or at least one element of group VIb (metals of group 6 of the new classification, ie chromium, molybdenum or tungsten), on a suitable support.
  • group VIII metal of groups 8, 9 and 10 of the new classification, ie iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum
  • group VIb metal of group 6 of the new classification, ie chromium, molybdenum or tungsten
  • the group VIII element when present, is generally nickel or cobalt
  • the element of group VIb when present, is generally molybdenum or tungsten.
  • Combinations such as nickel-molybdenum or cobalt-molybdenum are preferred.
  • the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina or other porous solids, such as, for example, magnesia, silica or titanium oxide, alone or in mixture with alumina or silica-alumina.
  • the catalyst After introduction of the element or elements and possibly shaping of the catalyst (when this step is performed on a mixture already containing the base elements), the catalyst is in a first activated step.
  • This activation may correspond to either an oxidation, then a reduction, or a direct reduction, or a calcination only.
  • the calcination step is generally carried out at temperatures of from about 100 to about 600 ° C and preferably from 200 to 450 ° C under an air flow rate.
  • the catalyst preferably used in this step is a catalyst comprising an alumina-based support whose specific surface area is less than 200 m 2 / g, and comprising at least one element selected from the group consisting of cobalt, molybdenum, nickel or tungsten and preferably selected from the group consisting of cobalt, molybdenum and tungsten. Even more preferably, the catalyst according to the invention contains at least cobalt and molybdenum.
  • the molybdenum content, when this element is present is preferably greater than 10% by weight expressed as molybdenum oxide
  • the cobalt content, when this element is present is preferably greater than 1% by weight (expressed as oxide cobalt II).
  • the molybdenum density in the catalyst expressed in grams of MoO3 per square meter of support is greater than 0.05 g / m 2 of support.
  • the reduction step is performed under conditions to convert at least a portion of the oxidized forms of the base metal to metal. Generally, it consists of treating the catalyst under a flow of hydrogen at a temperature of at least 300 ° C. The reduction can also be achieved in part by means of chemical reducers.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • the introduction of sulfur can occur between different activation steps. Preferably, no oxidation step is performed when the sulfur or a sulfur compound is introduced on the catalyst.
  • the sulfur or a sulfur compound can be introduced ex situ, that is to say outside the reactor where the process according to the invention is carried out, or in situ, that is to say in the reactor used for process according to the invention.
  • the catalyst is preferably reduced under the conditions described above, then sulfided by passing a feed containing at least one sulfur compound, which once decomposed leads to the fixation of sulfur on the catalyst.
  • This charge may be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur compound.
  • the sulfur compound is added to the ex situ catalyst .
  • a sulfur compound may be introduced onto the catalyst in the presence of possibly another compound.
  • the catalyst is then dried and then transferred to the reactor for carrying out the process of the invention.
  • the catalyst is then treated in hydrogen to convert at least a portion of the main metal sulfide.
  • a procedure which is particularly suitable for the invention is that described in the patents FR-B-2,708,596 and FR-B-2,708,597 .
  • the conversion of the unsaturated sulfur compounds is greater than 15% and preferably greater than 50%.
  • the degree of hydrogenation of the olefins is preferably less than 50% and preferably less than 40% during this step.
  • stage B which makes it possible to eliminate at least part of the H2S present at the end of stage A.
  • Step B Removal of the H2S from the effluent of step A (Step B):
  • the concentration of H2S is decreased.
  • the removal of the H 2 S can be carried out in various ways, most of which are known to those skilled in the art.
  • This adsorbent mass is preferably regenerable. Its regeneration can be carried out continuously or discontinuously, for example by means of a heat treatment in an oxidizing or reducing atmosphere.
  • the absorbent mass can be used in a fixed bed or in a moving bed.
  • Another method is to perform membrane separation of H2S using a selective membrane operating on a liquid or gaseous effluent from step A.
  • One of the zones of the separation may contain an absorbent mass to promote the transfer H2S through the wall of the membrane.
  • Another method may be to cool the effluent of step A and produce a gas rich in H2S and a liquid phase depleted in H2S.
  • the gas phase can then be treated in an amine washing unit.
  • the liquid phase and the gas phase can then be remixed and sent to step C.
  • the liquid fraction can also undergo other treatments such as stripping with hydrogen, nitrogen or steam. water, extraction of H2S, washing with amines, washing with sodium hydroxide solution in order to reduce its H2S content.
  • the saturated sulfur compounds are converted, in the presence of hydrogen on a suitable catalyst.
  • This transformation is carried out without hydrogenation of the olefins, that is to say that during this step the hydrogenation of the olefins is limited to 20% with respect to the content of the starting gasoline, and preferably limited to 10% in relation to the olefin concentration of gasoline.
  • Catalysts which may be suitable for the invention, without this list being limiting, are catalysts comprising at least one metal selected from the group consisting of nickel, cobalt, iron, molybdenum and tungsten and. More preferably, the catalysts of this step are based on nickel. These metals are preferably supported and used in their sulfurized form.
  • the metal content of the catalyst used according to the invention is generally between about 1 and about 60% by weight and preferably between 5 and 20% by weight.
  • the catalyst is generally shaped, preferably in the form of beads, extrudates, pellets, or trilobes.
  • the metal may be incorporated in the catalyst on the preformed support, it may also be mixed with the support before the shaping step.
  • the metal is generally introduced in the form of a precursor salt, generally soluble in water, such as for example nitrates, heptamolybdates. This mode of introduction is not specific to the invention. Any other mode of introduction known to those skilled in the art is suitable for the implementation of the invention.
  • the supports of the catalysts used in the process of the invention are generally porous solids chosen from refractory oxides, such as, for example, aluminas, silicas and silica-aluminas, magnesia, as well as titanium oxide and zinc oxide, the latter oxides may be used alone or in admixture with alumina or silica-alumina.
  • the supports are transition aluminas or silicas whose specific surface is between 25 and 350 m 2 / g.
  • the natural compounds for example kieselguhr or kaolin may also be suitable as supports for the catalysts of the process according to the invention.
  • the catalyst After introducing the metal and possibly forming the catalyst (when this step is carried out with a mixture already containing the base metal), the catalyst is in a first activated step.
  • This activation may correspond to either an oxidation, then a reduction, or a direct reduction, or a calcination only.
  • the calcination step is generally carried out at temperatures of from about 100 to about 600 ° C and preferably from 200 to 450 ° C under an air flow rate.
  • the reduction step is carried out under conditions making it possible to convert at least a portion of the oxidized forms of the metal basic metal. Generally, it consists of treating the catalyst under a flow of hydrogen at a temperature of at least 300 ° C.
  • the reduction can also be achieved in part by means of chemical reducers.
  • the catalyst is preferably used at least in part in its sulfurized form. This has the advantage of minimizing the risks of hydrogenation of unsaturated compounds such as olefins or aromatic compounds during the start-up phase.
  • the introduction of sulfur can occur between different activation steps. Preferably, no oxidation step is performed when the sulfur or a sulfur compound is introduced on the catalyst.
  • the sulfur or a sulfur compound can be introduced ex situ , that is to say outside the reactor where the process according to the invention is carried out, or in situ , that is to say in the reactor used for process according to the invention.
  • the catalyst is preferably reduced under the conditions described above, then sulfided by passing a feed containing at least one sulfur compound, which once decomposed leads to the fixation of sulfur on the catalyst.
  • This charge may be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur compound.
  • the sulfur compound is added to the ex situ catalyst .
  • a sulfur compound may be introduced onto the catalyst in the presence of possibly another compound.
  • the catalyst is then dried and then transferred to the reactor for carrying out the process according to the invention.
  • the catalyst is then treated in hydrogen to convert at least a portion of the main metal sulfide.
  • a procedure which is particularly suitable for the invention is that described in the patents FR-B-2 708 596 and FR-B-2,708,597 .
  • the sulfur content of the catalyst is generally between 0.5 and 25% by weight, preferably between 4 and 20% by weight.
  • the hydrotreatment carried out during this step is intended to convert the saturated sulfur compounds of gasoline that has already undergone prior treatment to H 2 S, so as to obtain an effluent that will meet the desired specifications in terms of content. in sulfur compounds.
  • the gasoline thus obtained has a slightly higher octane number low, because of the partial but inevitable saturation of olefins, than that of the gasoline to be treated. However this saturation is limited.
  • the operating conditions of the catalyst for decomposing the saturated sulfur compounds into H 2 S must be adjusted to achieve the desired hydrodesulphurization level, and to minimize the octane loss resulting from olefin saturation.
  • the second catalyst (catalyst of step C) used in the process according to the invention generally makes it possible to convert at most 20% of the olefins, preferably at most 10% of the olefins.
  • the treatment for decomposing the saturated sulfur compounds in the first process step (step A) is carried out in the presence of hydrogen, with the metal catalyst, such as more preferably nickel, at a temperature between 200 ° C and 350 ° C, preferably between 250 ° C and 350 ° C, more preferably between 260 ° C and 320 ° C, under a low to moderate pressure generally between 0.5 and 5 MPa, preferably between 0.5 MPa and 3 MPa, more preferably between 1 and 3 MPa.
  • the space velocity of the liquid is generally between 0.5 and 10 h -1 (expressed in volume of liquid per volume of catalyst per hour), preferably between 1 and 8 h -1 .
  • the H 2 / HC ratio is adjusted according to the desired hydrodesulphurization rates in the range generally between about 100 and about 600 liters per liter, preferably between 100 and 300 liters per liter. All or part of this hydrogen can come from stage A or from a recycling of the unconsumed hydrogen resulting from stage C.
  • One of the possibilities of implementing the process according to the invention may, for example, consist in passing the gasoline to be hydrotreated through a reactor containing a catalyst allowing, at least in part, the hydrogenation of the unsaturated sulfur compounds, such as for example the thiophenic compounds, sulfur saturated compounds (step A) and the removal of H 2 S (step B), then through a reactor containing a catalyst for decomposing sulfur saturated compounds into H 2 S (step C) .
  • the step of removing the H2S can also be carried out in the reactor of step C or partly in each of the two reactors.
  • the removal step may also be partly or wholly outside the reactors of steps A and C.
  • the two catalysts of steps A and C are placed in series in the same reactor and an adsorbing mass of H2S is placed between the two catalysts in order to eliminate at least partly the H2S product in the first catalytic zone (step B).
  • the absorbent mass, once saturated with H2S can be either replaced or regenerated. In the latter case the regeneration can be performed discontinuously or continuously depending on the adsorbent mass used.
  • the two catalytic zones can operate under different conditions of pressure, VVH, temperature, H2 / load ratio.
  • Systems can be implanted to dissociate the operating conditions from the two reaction zones.
  • step A it can also be envisaged to carry out a sequence which consists in passing the gasoline to be hydrotreated through a reactor containing a catalyst allowing, at least in part, the hydrogenation of the unsaturated sulfur compounds, into saturated sulfur compounds (stage A). , then separately or simultaneously carry out a step of removing the H 2 S, and then carry out step C in a reactor containing a series of catalysts comprising at least one catalyst of the same type as that used in the first step of the method (step A) and at least one catalyst for decomposing sulfur saturated compounds into H2S (step C).
  • This charge is pretreated by means of a selective hydrogenation step.
  • the hydrogenation of the diolefins is carried out on a HR945® catalyst based on nickel and molybdenum, sold by the company Procatalyse.
  • the test is carried out in a continuous bed-type continuous reactor, the feedstock and the hydrogen being introduced through the bottom of the reactor.
  • 60 ml of catalyst are introduced into the reactor after having been previously sulphurized ex situ for 4 hours, under a pressure of 3.4 MPa, at 350 ° C., in contact with a constituting charge of 2% by weight of sulfur in the form of of dimethylsulfide in n-heptane.
  • the catalyst is then transferred to the reactor where the hydrogenation of the diolefins is carried out.
  • the charge contains // (ppm or% weight) of dienes
  • a catalyst A is obtained by impregnation "without excess solution" of a transition alumina, in the form of beads, with a specific surface area 130 m 2 / g and a pore volume of 0.9 ml / g, with an aqueous solution containing molybdenum and cobalt in the form of ammonium heptamolybdate and cobalt nitrate.
  • the catalyst is then dried and calcined under air at 500 ° C.
  • the cobalt and molybdenum content of this sample is 3% CoO and 10% MoO3. 25 ml of catalyst A are placed in a fixed-bed tubular hydrodesulfurization reactor.
  • the catalyst is first sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a feedstock consisting of 2% of sulfur in the form of dimethyl disulphide in n-heptane.
  • the temperature of the catalytic zone is between 280 ° C and 320 ° C.
  • the hydrogenated gasoline under the conditions of Example 1 is hydrodesulfurized.
  • a second catalyst (catalyst C) is prepared from a transition alumina of 140 m 2 / g in the form of beads 2 mm in diameter. The pore volume is 1 ml / g of support. 1 kilogram of support is impregnated with 1 liter of nickel nitrate solution. The catalyst is then dried at 120 ° C and calcined under a stream of air at 400 ° C for one hour. The nickel content of the catalyst is 20% by weight. 25 ml of catalyst A of Example 1 and 50 ml of catalyst C are placed in the same hydrodesulfurization reactor, so that the feedstock to be treated (heavy fraction) first meets catalyst A and then the Catalyst C.
  • the catalysts are first sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a feedstock consisting of 2% of sulfur in the form of dimethyl disulphide in n-heptane. .
  • the temperature of the catalytic zone comprising catalyst A is 250 ° C to 290 ° C, the temperature of the catalytic zone containing catalyst C is 330 ° C.
  • the hydrogenated gasoline under the conditions of Example 1 is hydrodesulfurized.
  • An experiment is carried out under the same conditions as those of Example 3, except that the two catalysts are placed in two different reactors and that the H2S is separated between these two reactors.
  • the effluent from the first reactor is cooled to room temperature, the liquid phase and the gas phase are separated, the H2S from the liquid phase is stripped by a stream of nitrogen to remove the H2S up to a content of 50 ppm by weight relative to the liquid.
  • the liquid thus obtained is then heated to the temperature of the second catalyst and reinjected in the presence of hydrogen introduced with a hydrogen flow rate of 330 I / I of charge corresponding approximately to the flow rate of hydrogen entering the second reactor of the example 3.
  • Example 5 Another mode of hydrodesulfurization according to steps A, B and C of the process according to the invention.
  • the hydrogenated gasoline under the conditions of Example 1 is hydrodesulfurized. 25 ml of catalyst A are placed in a tubular reactor. This reactor is coupled with a second hydrodesulfurization reactor containing 13 ml of catalyst A of Example 1 and 25 ml of catalyst C of Example 3, so that the feedstock first meets catalyst A and then catalyst C.
  • the effluent of the first reactor is cooled to ambient temperature, the liquid phase and the gas phase are separated, the H2S of the liquid phase is stripped by a stream of nitrogen allowing the H2S to be removed up to at a content of 50 ppm by weight with respect to the liquid.
  • the liquid thus obtained is then heated to the temperature of the second reactor and reinjected in the presence of hydrogen introduced with a flow rate and under a pressure corresponding to that of the second reactor of Example 2.
  • the temperature of the first reactor is indicated in the table. 5.
  • the temperature of the catalyst present in the second zone is raised to 270 ° C and the temperature of the catalyst C present in the second reactor is raised to 330 ° C.

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Claims (10)

  1. Verfahren zur Herstellung von Benzin mit geringem Schwefelgehalt, das mindestens drei Schritte umfasst:
    A) einen ersten Schritt, in dem die schwefelhaltigen Verbindungen, die in dem Benzin vorhanden sind, mindestens teilweise in H2S und in gesättigte schwefelhaltige Verbindungen umgewandelt werden, durch Aufbringen der Beschickung, in Gegenwart von Wasserstoff, auf einen Katalysator, der mindestens ein Element der Gruppe VIII und/oder mindestens ein Element der Gruppe Vlb, mindestens teilweise in Sulfidform, umfasst, wobei der Schritt bei einer Temperatur im Bereich zwischen 220 °C und 320 °C, im Allgemeinen unter einem Druck im Bereich zwischen 1 und 5 MPa, mit einer Raumgeschwindigkeit der Flüssigkeit im Bereich zwischen 1 und 10 h-1 und einem H2/HC-Verhältnis im Bereich zwischen 100 und 600 Litern pro Liter ausgeführt wird.
    B) einen zweiten Schritt, der darauf gerichtet ist, den H2S aus dem in Schritt A produzierten Benzin zu entfernen,
    C) einen dritten Schritt in Gegenwart eines Katalysators, der mindestens teilweise in seiner sulfurierten Form vorliegt, der mindestens ein Nichtedelmetall umfasst, ausgewählt aus der Gruppe gebildet aus Nickel, Cobalt, Eisen, Molybdän und Wolfram, in dem die in dem Benzin verbliebenen gesättigten schwefelhaltigen Verbindungen in H2S umgewandelt werden, wobei der Schritt bei einer Temperatur im Bereich zwischen 200 °C und 350 °C, einem Druck im Bereich zwischen 0,5 und 5 MPa, einer Raumgeschwindigkeit der Flüssigkeit im Bereich zwischen 0,5 und 10 h-1 und einem H2/HC-Verhältnis zwischen 100 und 600 Litern pro Liter ausgeführt wird,
    dadurch gekennzeichnet, dass ein Schritt zur Vorbehandlung, der darauf gerichtet ist, die Diolefine der Beschickung zu hydrieren, vor dem Schritt A ausgeführt wird.
  2. Verfahren nach Anspruch 1, in dem die Beschickung ein Benzin aus dem Cat-Cracker ist.
  3. Verfahren nach einem der Ansprüche 1 oder 2, in dem in Schritt A das Element der Gruppe VIII, wenn es vorhanden ist, Nickel oder Cobalt ist, und das Element der Gruppe VIb, wenn es vorhanden ist, Molybdän oder Wolfram ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, in dem der Nichtedelmetallgehalt des Schritts C im Bereich zwischen 1 und 60 Gew.-% liegt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, in dem das Nichtedelmetall des Schritts C Nickel ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in dem der Schwefelgehalt des Katalysators des Schritts C im Bereich zwischen 0,5 und 25 Gew.-% liegt.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 6, das mittels mindestens zweier getrennter Reaktoren durchgeführt wird, wobei der Reaktor zur Vorbehandlung der Beschickung nicht enthalten ist, wobei der erste Reaktor den Katalysator, der in Schritt A erforderlich ist, und der zweite mindestens den enthält, der in Schritt B erforderlich ist.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 7, das mittels mindestens zweier getrennter Reaktoren durchgeführt wird, wobei der Reaktor zur Vorbehandlung der Beschickung nicht enthalten ist, wobei der erste Reaktor mindestens einen Teil des Katalysators enthält, der in Schritt A erforderlich ist und der zweite mindestens den anderen Teil desjenigen enthält, der in Schritt A erforderlich ist und desjenigen, der in Schritt B erforderlich ist.
  9. Verfahren nach irgendeinem der Ansprüche 1 bis 8, in dem der Schritt B zum Entfernen des H2S durch Adsorption in Gegenwart einer adsorbierenden Masse realisiert wird, ausgewählt aus der Gruppe bestehend aus Zinkoxid, Kupferoxid und Molybdänoxid.
  10. Verfahren nach Anspruch 1 bis 9, in dem der H2S mittels einer Membran abgeschieden wird.
EP01401679A 2000-07-06 2001-06-25 Zweistufiges Benzin Entschwefelungsverfahren mit zwischenzeitlicher Entfernung von H2S Expired - Lifetime EP1174485B1 (de)

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FR3130834A1 (fr) 2021-12-20 2023-06-23 IFP Energies Nouvelles Procédé de traitement d'une essence contenant des composés soufrés
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FR3142362A1 (fr) 2022-11-30 2024-05-31 IFP Energies Nouvelles Catalyseur d’hydrodésulfuration de finition comprenant un métal du groupe VIB, un métal du groupe VIII et du phosphore sur support alumine alpha

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DE60143332D1 (de) 2010-12-09
EP1174485A1 (de) 2002-01-23
FR2811328A1 (fr) 2002-01-11
CA2352408C (fr) 2010-06-15
FR2811328B1 (fr) 2002-08-23
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US6972086B2 (en) 2005-12-06

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