EP1138749B1 - Benzin Entschwefelungsverfahren mit Entschwefelung von Schwer- und Mittelfraktionen von einen Fraktionierung in mindestens drei Schnitten - Google Patents

Benzin Entschwefelungsverfahren mit Entschwefelung von Schwer- und Mittelfraktionen von einen Fraktionierung in mindestens drei Schnitten Download PDF

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Publication number
EP1138749B1
EP1138749B1 EP01400669A EP01400669A EP1138749B1 EP 1138749 B1 EP1138749 B1 EP 1138749B1 EP 01400669 A EP01400669 A EP 01400669A EP 01400669 A EP01400669 A EP 01400669A EP 1138749 B1 EP1138749 B1 EP 1138749B1
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fraction
gasoline
catalyst
compounds
sulfur
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French (fr)
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EP1138749A1 (de
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Quentin Debuisschert
Blaise Didillon
Jean-Luc Nocca
Denis Uzio
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • 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
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process

Definitions

  • Hydrotreating (hydrodesulphurisation) of the feedstock sent to catalytic cracking leads to gasolines typically containing 100 ppm of sulfur.
  • the hydrotreating units of catalytic cracking feeds operate under severe conditions of temperature and pressure, which implies a high investment.
  • the entire feedstock of the catalytic cracking process must be desulfurized, resulting in the treatment of very large load volumes.
  • the hydrotreating (or hydrodesulphurization) of catalytic cracking gasolines when carried out under standard conditions known to those skilled in the art, makes it possible to reduce the sulfur content of the cut.
  • this method has the major disadvantage of causing a very significant drop in the octane number of the cut, due to the saturation of a significant portion of the olefins during the hydrotreatment.
  • the separation of light gasoline and heavy gasoline before hydrotreatment has already been claimed in US Pat. No. 4,397,739. This type of separation makes it possible to separate a light, olefin-rich, sulfur-containing section.
  • Patent Application EP-A-0 725 126 describes a process for the hydrodesulphurization of a cracking gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds which are easy to desulphurize and a second fraction rich in compounds difficult to desulphurize. Before carrying out this separation, it is necessary to first determine the distribution of the sulfur-containing products by means of analyzes. These analyzes are necessary to select the equipment and the separation conditions.
  • the species to be treated generally have an initial point greater than 70 ° C, and again it is necessary to treat the light petrol separately. (fraction corresponding to compounds of boiling point between C5 (hydrocarbon with 5 carbon atoms) and 70 ° C) for example by a softening.
  • US-A-5,318,690 proposes a process comprising fractionation of gasoline and sweetening of light gasoline, while heavy gasoline is desulfurized, then converted to ZSM-5 and desulphurized again under conditions sweet. This technique is based on a separation of crude gasoline so as to obtain a light cut practically free of sulfur compounds other than mercaptans. This makes it possible to treat said cut only by means of a softening which removes the mercaptans.
  • the heavy cut contains a relatively large amount of olefins which are partly saturated during hydrotreatment.
  • the patent advocates cracking zeolite ZSM-5 which produces olefins, but at the expense of yield.
  • these olefins can recombine with H 2 S present in the medium to reform mercaptans. It is then necessary to perform additional softening or hydrodesulfurization.
  • the present invention relates to a process for the desulphurisation of gasoline, that is to say a process for the production of gasolines with a low sulfur content, which makes it possible to recover the totality of a charge (generally a petrol fraction) containing sulfur, preferably a gasoline cut resulting from a catalytic cracking process, and reduce the sulfur content in said gasoline cut to very low levels, without substantially reducing the gasoline yield, and while minimizing the decrease in gasoline content.
  • a charge generally a petrol fraction
  • a gasoline cut resulting from a catalytic cracking process preferably a gasoline cut resulting from a catalytic cracking process
  • reduce the sulfur content in said gasoline cut to very low levels without substantially reducing the gasoline yield, and while minimizing the decrease in gasoline content.
  • octane number due to the hydrogenation of olefins.
  • the process according to the invention makes it possible to restore at least part of the possible octane losses due to the hydrogenation of the olefins by reforming one
  • steps c1 and / or c2 can be carried out either in a single reactor containing the two catalysts, or in at least two different reactors.
  • the latter two are preferably placed in series, the second reactor preferably treating integrally the effluent at the outlet of the first reactor, preferably without separation of the liquid and the gas between first and second reactor.
  • a step e is preferably carried out after step d, this step consists of mixing the separated essences in step b, whether or not they have undergone desulfurization treatments.
  • the feedstock of the process according to the invention is generally a gasoline cutter containing sulfur, such as, for example, a cut resulting from a coking, visbreaking, steam cracking or catalytic cracking (FCC) fraction.
  • Said filler preferably consists of a gasoline cut from a catalytic cracking unit, whose range of boiling points typically extends from about the boiling points of hydrocarbons containing 5 carbon atoms (C 5 ). up to about 250 ° C.
  • This gasoline can possibly be composed of a significant fraction of gasoline of other origins such as the essences directly resulting from the atmospheric distillation of the crude oil (essence straight run) or process of conversion (essence of coker or steam-cracking for example ).
  • 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.
  • a process for obtaining a gasoline containing sulfur compounds preferably from a catalytic cracking unit, wherein the gasoline first undergoes a selective hydrogenation treatment of diolefins and acetylenic compounds, then optionally a step to weigh down the lighter sulfur compounds, possibly present in the gasoline and which should, in the absence of this step, be in the light gasoline after fractionation, at least one separation of gasoline into at least three fractions, a treatment of at least one of the intermediate fractions to desulphurize and significantly nitrogenize this cut before it undergoes a catalytic reforming treatment, a treatment of heavy gasoline optionally mixed with at least a portion of one of the intermediate fractions, by means of a catalyst known to promote the conversion of unsaturated sulfur compounds present in gasoline, such as for example thiophenic compounds, into sulfur-saturated compounds such as thiophane and mercaptans, and then optionally a second catalyst promoting the selective conversion of saturated sulfur compounds, linear or cyclic already present in the
  • This sequence makes it possible to ultimately obtain a desulphurized gasoline with a control of the olefin content or the octane number, even for high desulphurization rates.
  • significant hydrodesulphurization rates are achieved under reasonable operating conditions specified below.
  • by optimizing the cut points of the intermediate fractions and selecting those which are sent to the catalytic reforming stage it is possible to minimize the benzene content of the final gasoline (for example at contents below 5%). % weight in the final mixture of the desulfurized gasoline fractions), to control the olefin content, and to maintain high research and engine octane values.
  • the search or motor octane loss expressed as the difference between the average value (RON + MON) / 2 observed in this mixture and the average value (RON + MON) / 2 of the initial charge, is limited to less than 2 octane points, preferably less than 1.7 octane points, and more preferably less than 1.5 octane points, and very preferably less than 1 octane point.
  • the average value (RON + MON) / 2 of the desulfurized gasoline by means of the process according to the invention can even decrease by less than 0.5 octane point relative to the average value (RON + MON ) / 2 of the load, or even increase by at least 0.5 point.
  • 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 method according to the invention is particularly applicable when high desulphurization rates of gasoline are required, ie when the desulphurized gas must contain at most 10% of the sulfur of the initial gasoline and possibly at most 5% or even more than 2% of the sulfur of the initial gasoline which corresponds to desulfurization rates greater than 90% or even greater than 95 or 98%.
  • step a1 Hydrogenation of diolefins and acetylenics
  • Hydrogenation of dienes is a step that eliminates, before hydrodesulfurization, almost all the dienes present in the petrol cut. containing sulfur to be treated. It preferably takes place in the first step (step a1) of the process according to the invention, generally in the presence of a catalyst comprising at least one metal of group VIII, preferably chosen from the group formed by platinum, palladium and nickel , and a support.
  • a catalyst comprising at least one metal of group VIII, preferably chosen from the group formed by platinum, palladium and nickel , and a support.
  • a catalyst based on nickel or palladium deposited on an inert support such as, for example, alumina, silica or a support containing at least 50% alumina, will be used.
  • the pressure employed is sufficient to maintain more than 60%, preferably 80%, and more preferably 95% by weight of the gasoline to be treated in the liquid phase in the reactor; it is most generally between about 0.4 and about 5 MPa and preferably greater than 1 MPa, more preferably between 1 and 4 MPa.
  • the hourly space velocity of the liquid to be treated is between about 1 and about 20 h -1 (volume of filler per volume of catalyst per hour), preferably between 3 and 10 h -1 , very preferably between 4 and 8 h -1 .
  • the temperature is most generally between about 50 and about 250 ° C, and preferably between 80 and 230 ° C, and more preferably between 150 and 200 ° C, to ensure sufficient conversion of the diolefins.
  • the hydrogen / charge ratio expressed in liters is generally between 5 and 50 liters per liter, preferably between 8 and 30 liters per liter.
  • the choice of operating conditions is particularly important.
  • the operation will generally be carried out under pressure and in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value necessary for hydrogenating the diolefins and acetylenics.
  • the hydrogen and the feedstock to be treated are injected in ascending or descending streams into a reactor preferably comprising a fixed bed of catalyst.
  • Another metal may be associated with the main metal to form a bimetallic catalyst, such as, for example, molybdenum or tungsten.
  • the catalytic cracked gasoline may contain up to a few weight percent of diolefins. After hydrogenation, 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 hydrogenation stage of the dienes takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the quantity of hydrogen necessary to effect the desired reactions.
  • This optional step consists in transforming the light compounds of the sulfur, which at the end of the separation step b would be in the light gasoline in the absence of this step. It is preferably carried out on a catalyst comprising at least one element of group VIII (groups 8, 9 and 10 of the new periodic classification), or comprising a resin. In the presence of this catalyst, the light sulfur compounds are converted into heavier sulfur compounds, entrained in heavy gasoline.
  • This optional step may possibly be performed at the same time as step a1.
  • nickel-based catalyst that is identical to or different from the catalyst of step a1, such as, for example, the catalyst recommended in the process of US-A-3,691,066, which makes it possible to transform the mercaptans. (butyl mercaptan) to heavier sulfur compounds (methyl thiophene).
  • Another possibility for carrying out this step is to hydrogenate thiophene at least partially to thiophane whose boiling point is greater than that of thiophene (boiling point 121 ° C.).
  • This step can be carried out on a catalyst based on nickel, platinum or palladium. In this case the temperatures are generally between 100 and 300 ° C and preferably between 150 and 250 ° C.
  • the H2 / filler ratio is adjusted to 1 to 20 liters per liter, preferably 2 to 15 liters per liter, to allow the desired hydrogenation of the thiophene compounds while minimizing the hydrogenation of the olefins present in the feedstock.
  • the space velocity is generally between 1 and 10 h -1 , preferably between 2 and 4 h -1 and the pressure between 0.5 and 5 MPa, preferably between 1 and 3 MPa.
  • some of the light sulfur compounds such as sulfides (dimethyl sulfide, methyl-ethylsulfide), CS 2 , COS can also be converted.
  • Another possibility for carrying out this step is to pass the gasoline over a catalyst having an acid function which makes it possible to carry out the addition of the sulfur compounds in the form of mercaptans to the olefins and to carry out the reaction. alkylation of thiophene by these same olefins. It is for example possible to pass the gasoline to be treated on an ion exchange resin, such as a sulfonic resin.
  • the operating conditions will be adjusted to achieve the desired transformation while limiting the olefin oligomerization parasitic reactions.
  • the operation is generally carried out in the presence of a liquid phase, at a temperature of between 10 and 150 ° C. and preferably between 10 and 70 ° C.
  • the operating pressure is between 0.1 and 2 MPa and preferably between 0.5 and 1 MPa.
  • the space velocity is generally between 0.5 and 10 h -1 and preferably between 0.5 and 5 h -1 .
  • the conversion rate of mercaptans is generally greater than 50% and the conversion rate of thiophene is generally greater than 20%.
  • the gasoline can be additive of a compound known to inhibit the oligomerizing activity of acid catalysts such as for example alcohols, ethers or water.
  • This separation is preferably carried out by means of a conventional distillation column also known as a splitter.
  • This fractionation column must make it possible to separate a light fraction of the gasoline containing a small fraction of sulfur, at least an intermediate fraction composed mainly of compounds having from 6 to 8 carbon atoms and a heavy fraction containing most of the sulfur initially. present in the initial essence.
  • This column generally operates at a pressure of between 0.1 and 2 MPa and preferably between 0.2 and 1 MPa.
  • the number of theoretical plates of this separation column is generally between 10 and 100 and preferably between 20 and 60.
  • the reflux ratio, of the column expressed by the ratio between the liquid flow rate in the column and the flow rate of the charge. is generally less than unity and preferably less than 0.8, when these flow rates are measured in kilograms per hour (kg / h).
  • the light gasoline obtained after the separation generally contains at least all the C 5 olefins, preferably the C 5 compounds and at least 20% of the C 6 olefins.
  • this light fraction has a low sulfur content (for example less than 50 ppm), ie it is not generally necessary to treat the light cut before using it as fuel.
  • softening of light gasoline may be considered.
  • This step which applies to the heavy gasoline optionally mixed with at least a portion of an intermediate fraction obtained at the end of the separation step b.
  • this intermediate fraction is composed essentially (that is to say more than 60% by weight, preferably more than 80% by weight) of C 6 or C 7 molecules as well as of most of the sulfur compounds. having a boiling point close to that of the azeotrope of thiophene with paraffins, to about 20%.
  • This step consists in converting at least a portion of the unsaturated sulfur compounds such as the thiophene compounds into saturated compounds, for example thiophanes (or thiacyclopentanes) or in mercaptans, or optionally at least partially hydrogenolysing these unsaturated sulfur compounds to form H 2 S.
  • This step may for example be carried out by passing the heavy fraction, optionally mixed with at least a portion of an intermediate fraction on a catalyst comprising at least one element of group VIII and / or at least one element of group VIb at least part in sulphide form, in the presence of hydrogen, at a temperature between about 200 ° C and about 350 ° C, preferably between 220 ° C and 290 ° C, at a pressure generally between about 1 and about 4 MPa, preferably between 1.5 and 3 MPa.
  • the space velocity of the liquid is between about 1 and about 20 h -1 (expressed as volume of liquid per volume of catalyst per hour), preferably between 1 and 10 h -1 , very preferably between 3 and 8 h -1 .
  • the H 2 / HC ratio is between 50 to 600 liters per liter and preferably between 300 and 600 liters per liter.
  • at least one catalyst comprising at least one group VIII element (Group 8 metals) is generally used.
  • 9 and 10 of the new classification i.e. iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum
  • Group VIb element Group 6 metals of the new classification, ie chromium, molybdenum or tungsten
  • the content of Group VIII metal expressed as oxide is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight.
  • the metal content of the group VIb is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight.
  • the element of group VIII, when present, is preferably cobalt, and the element of group VIb, when present, is usually molybdenum or tungsten. Combinations such as 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 according to the invention preferably has a specific surface area of less than 190 m 2 / g, more preferably less than 180 m 2 / g, and very preferably less than 150 m 2 / g.
  • This activation can correspond to either an oxidation then a reduction, 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 part of the oxidized forms of the metal of group VIII and / or group VI b to the metallic state. Generally, it consists in treating the catalyst under a flow of hydrogen at a temperature preferably 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 may occur before or after any activation step, that is, calcination or reduction.
  • no oxidation step is performed after the sulfur or a sulfur compound has been introduced onto the catalyst. It is therefore for example preferable when the catalyst is sulphurized after drying not to calcine the catalyst, against a reduction step may optionally be carried out after the sulphidation.
  • 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 the 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 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%, more preferably less than 40%, and very preferably less than 35%, during this step.
  • the species treated in stage c1 may optionally contain at least part of at least one intermediate fraction obtained in stage b.
  • step c2 The effluent resulting from this first hydrogenation step is then optionally sent to step c2 which makes it possible to decompose saturated sulfur compounds into H 2 S.
  • the feedstock of this step consists either of only the effluent from step c1, or of a mixture comprising the effluent of step c1 and at least a portion of at least one intermediate fraction.
  • this intermediate fraction is composed essentially (that is to say more than 60% by weight, preferably more than 80% by weight) of C 6 or C 7 molecules as well as of most of the sulfur compounds. having a boiling point close to that of the azeotrope of thiophene with hydrocarbons to 20%.
  • the saturated sulfur compounds are converted to the presence of hydrogen on a suitable catalyst.
  • the decomposition of the non-hydrogenated unsaturated compounds in step c1 can also take place simultaneously.
  • This transformation is carried out without substantial hydrogenation of the olefins, ie during this step the amount of hydrogenated olefins is generally limited to less than 20% by volume relative to the olefin content of the gasoline. initial, and preferably limited to 10% by volume relative to the olefin content of the initial gasoline.
  • the catalysts which may be suitable for this stage of the process according to the invention, without this list being limiting, are catalysts generally comprising at least one basic element (metal) chosen from Group VIII elements, and preferably chosen from group formed by nickel, cobalt, iron, molybdenum, tungsten. These metals can be used alone or in combination, they are preferably supported and used in their sulfurized form. It is also possible to add at least one promoter to these metals, for example tin. Catalysts comprising nickel, or nickel and tin, or nickel and iron, or cobalt and iron, or cobalt and tungsten are preferably used. Said catalysts are more preferably sulfurized, and very preferably presulfided in situ or ex situ.
  • the catalyst of step c2 is preferably of a different nature and / or composition than that used in step c1.
  • the base metal content of the catalyst according to the invention is generally between about 1 and about 60% by weight, preferably between 5 and 20% by weight, and very preferably between 5 and 9% by weight.
  • the catalyst is generally shaped, preferably in the form of beads, pellets, extrudates, for example trilobes.
  • the metal may be incorporated into the catalyst by deposition 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 may be suitable.
  • the supports of the catalysts used in this stage of the process according to the invention are generally porous solids chosen from refractory oxides, such as, for example, aluminas, silicas and silica-aluminas, magnesia, as well as titanium and zinc oxide, these latter oxides can be used alone or mixed 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, such as, for example, kieselguhr or kaolin, may also be suitable as supports for the catalysts used in this step of the process.
  • the catalyst is in a first activated step.
  • This activation can correspond to either an oxidation, then a reduction, or a reduction after drying without calcination, or only to a calcination.
  • the calcination step when present is generally carried out at temperatures of from about 100 ° C to about 600 ° C and preferably from 200 ° C to 450 ° C under an air flow rate.
  • the reduction step is performed under conditions to convert at least a portion of the oxidized forms of the base metal to the metallic state. 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 partly in its sulfurized form, which has the advantage of minimizing the risks of hydrogenation of unsaturated compounds such as olefins or aromatic compounds during the starting phase.
  • the introduction of sulfur can occur between different activation steps. Preferably, no oxidation step is performed when the sulfur or a sulfur compound has been 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. In the latter case, the catalyst is preferably reduced under the conditions described above, then presulfided 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 optionally dried and then transferred to the reactor used to carry out the process of the invention.
  • the catalyst is then treated with hydrogen in order to transform at least one part of the base metal and possibly another sulphide metal.
  • a procedure which is particularly suitable for the invention is that described in 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 and very preferably between 4 and 10% by weight.
  • the hydrodesulfurization carried out during this step c2 is intended to convert to H 2 S saturated sulfur compounds of gasoline which have already undergone at least one prior hydrogenation of unsaturated sulfur compounds in step c1. It makes it possible to obtain an effluent that meets the desired specifications in terms of sulfur compound content.
  • the gasoline thus obtained shows only a slight loss of octane (decrease of the research and / or engine octane number).
  • the treatment for decomposing the saturated sulfur compounds from step c1 of the process is carried out in the presence of hydrogen, with a catalyst comprising at least one base metal selected from the group formed by nickel, cobalt, iron, molybdenum, tungsten, used alone or in a mixture with one another, at a temperature of between about 100 ° C. and about 400 ° C., preferably between about 150 ° C. and about 380 ° C., more preferably between 210 ° C. and 360 ° C, and very preferably between 220 ° C and 350 ° C, at a pressure generally between about 0.5 and about 5 MPa, preferably between 1 and 3MPa, more preferably between 1.5 and 3 MPa.
  • the space velocity of the liquid is between about 0.5 and about 10 h -1 (expressed as 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 of from about 100 to about 600 liters per liter, preferably from 20 to 300 liters per liter. All or part of this hydrogen may possibly come from step c1 (unconverted hydrogen) or a recycling of the hydrogen not consumed in steps a1, a2, c2 or d.
  • this second catalyst in this step makes it possible to decompose the saturated compounds, contained in the effluent from step c1, into H2S.
  • This implementation makes it possible to achieve a high overall level of hydrodesulfurization at the end of all the steps of the process according to the invention, while minimizing the octane loss resulting from the saturation of the olefins, because the conversion of the olefins during step c1 is generally limited to at most 20% by volume of the olefins, preferably at most 10% by volume.
  • step d Hydrotreatment of at least one intermediate cut
  • This treatment of at least one of the intermediate sections aims to eliminate substantially all the sulfur and nitrogen compounds of this fraction and to treat the effluent thus hydrotreated on a reforming catalyst for the isomerization and dehydrocyclization of paraffins.
  • This step applies to at least a portion of an intermediate fraction obtained in step b.
  • This step is generally carried out by passing the fraction over at least one conventional hydrotreating catalyst under conditions which make it possible to eliminate sulfur and nitrogen.
  • Catalysts which are particularly suitable are, for example, catalysts based on a Group VIII metal such as cobalt or nickel and a Group VI metal, such as tungsten or molybdenum.
  • this treatment can be carried out on a type HR 306 or HR448 catalyst sold by the company Procatalyse, at a temperature generally between 250 and 350 ° C., an operating pressure generally of between 1 and 5 MPa, preferably between 2 and 4 MPa, and a space velocity generally between 2 and 8 h -1 (expressed in volume of liquid filler per volume of catalyst and per hour).
  • this treatment almost all the olefins present in this fraction are hydrogenated.
  • the effluent thus obtained is cooled, the decomposition products are then separated by means of any technique known to those skilled in the art. For example, washing processes, stripping or extraction methods may be mentioned.
  • the effluent corresponding to one of the desulphurized and de-nitrogenated intermediate fractions is then treated on a catalyst or a catalyst sequence allowing reforming of the said fraction, that is to say to carry out at least partly the dehydrogenation of the saturated cyclic compounds. isomerization of paraffins and dehydrocyclization of parafines present in the treated intermediate fraction.
  • This treatment aims at increasing the octane number of the fraction considered.
  • This treatment is done by means of a conventional catatalytic reforming process. For example, it may be advantageous to use "fixed bed” or “bed” methods for this purpose.
  • the desulfurized effluent is brought into contact with a reforming catalyst, generally based on platinum supported on alumina, at a temperature of between 400 ° C. and 700 ° C. with a hourly space velocity (kg of treated feedstock per hour and per kg of catalyst) between 0.1 and 10.
  • the operating pressure can be between 0.1 and 4 MPa.A part of the hydrogen produced during the different reactions can be recycled in a ratio of between 0.1 and 10 moles of hydrogen per mole of filler.
  • FIG. 1 shows an embodiment of the method according to the invention.
  • an essence cut (initial essence) containing sulfur is introduced via line 1 into a catalytic hydrogenation reactor 2, which makes it possible to selectively hydrogenate the diolefins and / or the acetylene compounds present in said gasoline cut (step a1 of the process).
  • the effluent 3 of the hydrogenation reactor is sent to a reactor 4, which comprises a catalyst capable of converting the light sulfur compounds with diolefins or olefins into heavier sulfur compounds (step a2).
  • the effluent 5 from the reactor 4 is then sent to the fractionation column 6, which makes it possible to separate the gasoline into 3 fractions (step b).
  • the first fraction obtained is a light cut 7.
  • This light cut preferably comprises less than 50 ppm of sulfur and does not require desulfurization, since the light sulfur compounds present in the initial gasoline have been converted into heavier compounds at the same time. step a2.
  • a second fraction 8 (intermediate fraction) is obtained which is first sent to a catalytic desulphurization reactor 10, then via line 11 to a catalytic reforming reactor (step d).
  • a third fraction (heavy fraction) is obtained via line 9.
  • This cut is first treated in a reactor 14 on a catalyst for converting at least a portion of the unsaturated sulfur compounds present in the feed into saturated sulfur compounds (step c1).
  • the effluent from the reactor 14 is sent to the reactor 16 (step c2) which contains a catalyst promoting the decomposition in H 2 S saturated sulfur compounds initially present in the load and / or formed in the reactor 14.
  • the light section 7 and the effluent 13 (from the reforming reactor 14) and the effluent 17 (from the decomposition reactor 13) are mixed to form the desulfurized gasoline 18 (step e).
  • step c1 it is also possible to send at least part of the non-desulphurized intermediate fraction (line 8), either via line 19 and then mixed with heavy fraction 9 towards the reactor 14 (step c1), either via the line 20 and then mixed with the effluent 15 to the reactor 16 (step c2).
  • a catalytic cracking gasoline whose characteristics are summarized in Table 1 is treated with the objective of reaching a specification of the refinery outlet gasoline pool such that the sulfur content is less than 10 ppm, which requires reducing the Sulfur content of a gasoline from a catalytic cracking unit to less than 20 ppm by weight.
  • the gasoline is separated into three sections in a light section, the distillation range of which is between 35 ° C and 95 ° C, an intermediate cut of which the distillation range is between 95 ° C and 150 ° C and a cut the distillation range is between 150 ° C and 250 ° C.
  • the sulfur content of light gasoline which represents 38% of the total gasoline, is 210 ppm by weight.
  • the intermediate and heavy cuts are treated on a HR306 catalyst of the company Procatalyse.
  • the catalyst (20 ml) is first sulphurized by treatment for 4 hours at a pressure of 3.4 MPa at 350 ° C., in contact with a feed consisting of 2% of sulfur in the form of dimethyl disulphide in n-heptane. .
  • the desulfurization step is carried out at 300 ° C. under 35 bar with an H2 / HC of 150 I / I and a VVh of 3 h -1 . Under these treatment conditions the effluents obtained after stripping of the H 2 S contain 1 ppm of sulfur. Mixing these two desulphurized cups with the lightest cut leads to a gasoline containing 81 ppm by weight of sulfur.
  • the gasoline from a catalytic cracking unit whose characteristics are described in Example 1 is subjected to a hydrogenation treatment of diolefins under conditions in which the sulfur-containing light compounds present in the feed are partly converted into more complex compounds. heavy (steps a1 and a2 simultaneous).
  • This treatment is carried out in a reactor operating continuously and in updraft.
  • the catalyst is based on nickel and molybdenum (HR945 catalyst marketed by the company procatalysis).
  • the catalysts are first sulphurized by treatment for 4 hours at 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 reaction is carried out at 160 ° C.
  • the H2 / feed ratio expressed in liters of hydrogen per liter of feed and 10.
  • the gasoline is then separated into two slices, one having a distillation range between 35 ° C and 80 ° C and representing 29% volume and the other distilling between 80 ° C and 240 ° C representing 71% volume of the product. essence cut.
  • the sulfur content of light gasoline is 22 ppm by weight.
  • the heavy gasoline is subjected to hydrodesulphurization on a series of catalysts in an isothermal tubular reactor.
  • the first catalyst (catalyst A, step c1) is obtained by impregnation "without excess solution" of a transition alumina, in the form of beads, with a specific surface area of 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.
  • the second catalyst (catalyst B, step c2) 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, and 50 ml of catalyst B, are placed in the same hydrodesulfurization reactor, so that the feedstock to be treated (heavy fraction) first meets the catalyst A (step c1) and then the catalyst B (step c2).
  • An effluent sampling zone resulting from step c1 is provided between the catalysts A and B.
  • the catalysts are first sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., contact of a filler consisting of 2% sulfur as dimethyl disulphide in n-heptane.
  • the temperature of the catalytic zone comprising catalyst A is 260 ° C
  • the temperature of the catalytic zone containing catalyst B is 350 ° C.
  • the product obtained contains 19 ppm of sulfur.
  • the desulfurized product is recombined with light gasoline.
  • the measurement of the sulfur content of the gasoline thus obtained leads to a content of 20 ppm by weight. It has a RON of 88.1 and a MON of 79.6, which is a loss of (RON + MON) / 2 compared to the 2.2 point load.
  • the olefin content of this species is 22% vol.
  • the gasoline is heavy and mixed with the second section and is subjected to hydrodesulfurization on a series of catalysts in isothermal tubular reactor.
  • the first catalyst (catalyst A, step c) is obtained by impregnation "without excess solution" of a transition alumina, in the form of beads, with a specific surface area of 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.
  • the second catalyst (catalyst B, step d) 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.
  • step c 25 ml of catalyst A, and 50 ml of catalyst B, are placed in the same hydrodesulphurization reactor, so that the charge to be treated (heavy fraction) first meets the catalyst A (step c) and then the catalyst B (step d).
  • An effluent sampling zone resulting from step c is provided between catalysts A and B.
  • the catalysts are first sulphurized by treatment for 4 hours at a pressure of 3.4 MPa at 350 ° C., contact of a filler consisting of 2% sulfur as dimethyl disulphide in n-heptane.
  • the temperature of the catalytic zone comprising catalyst A is 260 ° C
  • the temperature of the catalytic zone containing catalyst B is 350 ° C.
  • the product obtained contains 37 ppm of sulfur.
  • the third section is treated with an HR306 catalyst from Procatalyse.
  • the catalyst (20 ml) is first sulphurized by treatment for 4 hours at a pressure of 3.4 MPa at 350 ° C., in contact with a feed consisting of 2% of sulfur in the form of dimethyl disulphide in n-heptane. .
  • the desulfurization step is carried out at 300 ° C. under 3.5 MPa with a H2 / HC of 150 I / I and a VVH of 3 h -1 . Under these treatment conditions, the effluent obtained after stripping the H2S contains less than 1 ppm of sulfur.
  • the olefin content is 0.9% by volume and the octane values are 68.7 for the RON and 68.3 for the MON.
  • the gasoline obtained is then treated on a reforming catalyst CR201 marketed by the company Procatalyse.
  • the catalyst (30 ml) is first reduced to 500 ° C under a stream of hydrogen before use.
  • the reforming treatment is carried out at 470 ° C. under a pressure of 7 bar.
  • the ratio H2 / HC is 500 l / l.
  • the VVH is 2 h -1 .
  • the effluent is stabilized by removal of compounds having less than 5 carbon atoms.
  • the reformate obtained, which represents 86% of the treated gasoline fraction has a sulfur content of less than 1 ppm by weight, an RON of 97 and a MON of 86.
  • the fractions from the different treated sections are remixed.
  • the sulfur content is 20 ppm by weight.
  • the average value (RON + MON) / 2 of the total desulphurized gasoline increased by 1.3 points compared to that of the starting gasoline.
  • the hydrogen produced during the catalytic reforming step can be used for the hydrotreatment reaction sections which is an obvious advantage of the process.

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Claims (8)

  1. Verfahren zum Herstellen von Benzin mit geringem Schwefelgehalt aus einem schwefelhaltigen Ausgangsmaterial, das mindestens die folgenden Schritte umfasst:
    a1) mindestens eine selektive Hydrierung von Diolefinen und von Acetylenverbindungen, die im Ausgangsmaterial enthalten sind,
    a2) mindestens ein Schritt vor Schritt b, der auf die Erhöhung der Molmasse der leichten Schwefelprodukte gerichtet ist, die im Ausgangsmaterial und/oder im abfließenden Strom von Schritt a1 enthalten sind,
    b) mindestens eine Auftrennung des abfließenden Stroms, der am Ende von Schritt a1 oder a2 gewonnen wurde, in mindestens drei Fraktionen, eine leichte Fraktion, die so gut wie schwefelfrei ist und die leichtesten Olefine enthält, eine schwere Fraktion, in der der überwiegende Teil der Schwefelverbindungen konzentriert ist, die zu Beginn im Ausgangsbenzin vorhanden waren, und mindestens eine Mittelfraktion, die einen verhältnismäßig geringen Gehalt an Olefinen und Aromaten aufweist,
    c1) mindestens eine Behandlung des Schwerbenzins, das in Schritt b abgetrennt wurde, mit einem Katalysator in Gegenwart von Wasserstoff, wobei dieser Schritt in der Umwandlung mindestens eines Teils der ungesättigten Schwefelverbindungen in gesättigte Verbindungen besteht, wobei gleichzeitig die Umwandlung von Olefinen auf höchstens 20 Volumen% beschränkt ist, und in der zumindest teilweisen hydrogenolytischen Spaltung der ungesättigten Schwefelverbindungen zur Bildung von H2S, wobei diesem Schritt das Stripping des entschwefelten Schwerbenzins folgt, um das entstandene H2S zu entfernen,
    d) mindestens ein Schritt zur Entschwefelung von und Stickstoffentfernung aus mindestens einer Mittelfraktion, gefolgt von einer katalytischen Reformierung.
  2. Verfahren nach Anspruch 1, das außerdem vor dem Strippen einen Schritt c2 zur Behandlung des abfließenden Stroms von Schritt c1 umfasst, wobei die gesättigten Schwefelverbindungen während Schritt c2 in Gegenwart von Wasserstoff und mit einem Katalysator umgewandelt werden, durch den auch die ungesättigten Verbindungen zersetzt werden können, die in Schritt c1 nicht hydriert wurden.
  3. Verfahren nach einem der Ansprüche 1 bis 2, das außerdem einen Schritt e zum Mischen von mindestens zwei Fraktionen umfasst, von denen mindestens eine in Schritt c1 und möglicherweise c2 und/oder in Schritt d entschwefelt wurde.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei ein Teil mindestens einer Mittelfraktion, die in Schritt b gewonnen wurde, vor Schritt c1 mit der Schwerfraktion vermischt wird, die bei Schritt b entstanden ist.
  5. Verfahren nach einem der Ansprüche 1 bis 3, wobei ein Teil mindestens einer Mittelfraktion, die in Schritt b gewonnen wurde, mit dem abfließenden Strom von Schritt c1 vermischt wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei Schritt d zur Entschwefelung und Stickstoffentfernung von einer vollständigen Hydrierung der Olefine begleitet ist.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei das Ausgangsmaterial ein Benzinschnitt aus einer Anlage zum katalytischen Kracken ist.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei Schritt b eine Auftrennung des abfließenden Stroms in vier Fraktionen umfasst, der am Ende von Schritt a1 gewonnen wurde: eine leichte Fraktion, eine schwere Fraktion und zwei Mittelfraktionen, und wobei eine der Mittelfraktionen in Schritt d behandelt wird und die andere mit der schweren Fraktion vermischt wird, die in Schritt b abgetrennt wurde, und anschließend in Schritt c1 und/oder c2 behandelt wird.
EP01400669A 2000-03-29 2001-03-14 Benzin Entschwefelungsverfahren mit Entschwefelung von Schwer- und Mittelfraktionen von einen Fraktionierung in mindestens drei Schnitten Expired - Lifetime EP1138749B1 (de)

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FR0004084 2000-03-29

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FR2807061B1 (fr) 2002-05-31
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FR2807061A1 (fr) 2001-10-05
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