EP1746144A1 - Neues Verfahren zur Entschwefelung eines olefinischen Benzins zur Begrenzung von Mercaptan. - Google Patents

Neues Verfahren zur Entschwefelung eines olefinischen Benzins zur Begrenzung von Mercaptan. Download PDF

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Publication number
EP1746144A1
EP1746144A1 EP06291025A EP06291025A EP1746144A1 EP 1746144 A1 EP1746144 A1 EP 1746144A1 EP 06291025 A EP06291025 A EP 06291025A EP 06291025 A EP06291025 A EP 06291025A EP 1746144 A1 EP1746144 A1 EP 1746144A1
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Prior art keywords
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hydrodesulfurization
reactor
gasoline
catalyst
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English (en)
French (fr)
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EP1746144B1 (de
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Florent Picard
Christophe Bouchy
Nathalie Marchal
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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
    • 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
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline

Definitions

  • the production of reformulated species that meet the new environmental standards requires a much greater reduction in their sulfur content.
  • the environmental standards force refiners to lower the sulfur content in the gasoline pool to values of less than or equal to 50 ppm in 2005, which will have to be reduced to 10 ppm by January 1, 2009 within the community. European.
  • the desulphurized species must also meet the specifications in terms of corrosive power.
  • the corrosive power of gasolines is essentially due to the presence of acid sulfur compounds such as mercaptans.
  • Desulphurized species must therefore contain few mercaptans to limit their corrosivity.
  • the feedstock to be treated is generally a sulfur-containing gasoline cut such as, for example, a petrol cut from a coking unit, visbreaking, steam cracking or catalytic cracking unit (FCC).
  • Said feedstock is preferably composed of a gasoline cutter from a catalytic cracking unit whose distillation range is typically between 70 ° C and about 250 ° C.
  • Catalytic cracking gasolines can make up 30% to 50% by volume of the gasoline pool and generally have high olefin and sulfur contents.
  • sulfur present in the reformulated gasoline is attributable, to nearly 90%, to gasoline from catalytic cracking.
  • the desulphurisation of gasolines, and mainly of FCC species, is therefore of crucial importance for the respect of current and future standards.
  • Hydrotreating or hydrodesulfurization of catalytic cracking gasolines when carried out under conventional conditions, makes it possible to reduce the sulfur content of the cut.
  • these processes have the major disadvantage of causing a very large drop in the octane number of the cut, due to the hydrogenation of a large part, indeed of all the olefins under the usual conditions of hydrotreating.
  • the method described in the present invention makes it possible to significantly reduce the formation of recombinant mercaptans, and to limit the loss of octane during the desulphurization step, without resorting to a complementary step of treating gasoline. Indeed, it has been found by the inventors that it was possible to improve the performance of selective desulphurisation processes of gasolines, by recycling a fraction of the desulfurized gasoline.
  • the patent US 2,431,920 relates to gasoline fractions which contain more than 0.1% by weight of sulfur (ie more than 1000 ppm by weight) in order to desulphurize these fractions and to saturate at least a part of the olefins.
  • the present invention differs from the prior art in that it is intended to desulphurize in a very thorough manner gasolines which contain less than 0.1% by weight of sulfur, while precisely limiting the degree of hydrogenation of the olefins as well as the formation of mercaptans.
  • FIG. 1 represents a diagram of the process according to the invention in which the optional elements of the process are shown in dotted lines.
  • the invention can be described as a process for the hydrodesulfurization of a gasoline containing less than 0.1% by weight of sulfur, from a catalytic cracking unit, or a gasoline from other conversion units, and containing preferably at least one part of catalytic cracking gasoline, comprising at least one hydrodesulfurization reactor using a bimetallic catalyst working at a VVH between 0.1 h -1 and 20 h -1 , a temperature of between 220 ° C.
  • the hydrodesulfurization reactor used in the process according to the invention will generally be a fixed bed reactor, the size of the catalyst grains being of the order of a few millimeters, and preferably between 1 and 4 mm.
  • the catalyst used in the process comprises at least one group VIII element and a group VIb element, deposited on a porous support, the group VIII element preferably being iron, cobalt or nickel, preferably cobalt and the group VIb element preferably being molybdenum or tungsten, preferably molybdenum.
  • the hydrodesulfurization catalyst consists of a porous support having a specific surface area of less than 200 m 2 / gram.
  • the process according to the invention can in certain cases use a finishing reactor located downstream of the hydrodesulfurization reactor, the said finishing reactor using either a monometallic catalyst or a bimetallic catalyst of the same type as that used in the reactor. hydrodesulfurization.
  • the process comprises a finishing reactor
  • the invention relates to a process for the desulfurization of gasolines containing less than 0.1% by weight of sulfur in the form of any type of sulfur compounds (1000 ppm by weight), preferably less than 950 ppm by weight of sulfur, more preferably less than 900 ppm of sulfur and very preferably less than 850 ppm of sulfur, and including any type of chemical compounds including olefins.
  • the present process finds particular application in the conversion of conversion gasolines, and in particular the species from catalytic cracking, fluid-bed catalytic cracking (FCC), a coking process, a visbreaking process, or a pyrolysis process.
  • FCC fluid-bed catalytic cracking
  • the process according to the invention makes it possible to produce a gasoline with a very low sulfur content and improved octane number.
  • the sulfur content of the gasoline obtained by means of the process according to the invention is thus generally less than 30 ppm by weight, preferably less than 28 ppm by weight, and very preferably less than 25 ppm by weight.
  • the mercaptan content of said gasoline is preferably less than 25 ppm by weight, more preferably less than or equal to 22 ppm by weight and very preferably less than or equal to 20 ppm by weight.
  • the process according to the invention comprises at least one step of hydrodesulfurization of the gasoline to be treated possibly followed by a step of finishing the hydrodesulfurization.
  • the hydrodesulphurization is carried out in at least one fixed-bed reactor which may comprise a plurality of catalytic beds separated by an injection zone for a cold fluid called a cooling zone, making it possible to control the rise in temperature along the reactor.
  • the finishing step is also carried out in at least one fixed-bed reactor which may comprise several catalytic beds.
  • the desulfurized gasoline can be recycled at the inlet of the hydrodesulfurization reactor, or between two consecutive beds of catalyst at the cooling zone, or between the hydrodesulfurization reactor and the finishing reactor. .
  • the total flow rate of recycled gasoline corresponds to a flow rate of between 0.1 and 3 times the flow rate of gasoline to be desulphurized, preferably between 0.2 and 2 times the flow rate.
  • gasoline to desulfurize and very preferably between 0.2 and 1 times the gasoline flow to desulphurize.
  • the recycled gasoline is characterized in that it has a sulfur content lower than the sulfur content of the gasoline to be desulphurized, and preferably, a sulfur content at least two times lower than the sulfur content of the essence to desulphurize.
  • the operating conditions of the hydrodesulphurization reactor are those typically used to selectively desulphurize olefinic species.
  • the operation will be carried out, for example, at a temperature of between 220 ° C. and 350 ° C., under a general pressure of between 0.1 and 5 MPa, preferably between 1 MPa and 3 MPa.
  • the space velocity will generally be between about 0.1 h -1 and 20 h -1 (expressed as the volume of liquid gas to be desulfurized per volume of catalyst per hour), preferably between 0.1 h -1 and 10 h - 1 , and very preferably between 0.5 h -1 and 8 h -1 .
  • the ratio of the hydrogen flow rate on the gasoline flow to be desulphurized will generally be between 50 liters / liter and 800 liters / liter, and preferably between 100 liters / liter and 400 liters / liter.
  • the hydrodesulfurization reactor contains at least one bed of hydrodesulfurization catalyst comprising at least one group VIII element, and a group VIb element, deposited on a porous support.
  • the group VIII element is preferably iron, cobalt or nickel.
  • the group VIb element is preferably molybdenum or tungsten.
  • the content of group VIII element expressed as oxide is generally between 0.5% by weight and 15% by weight, and preferably between 0.7% by weight and 10% by weight.
  • the metal content of the group VIb is generally between 1.5% by weight and 60% by weight, and preferably between 2% by weight and 50% by weight.
  • the porous support of the hydrodesulfurization catalyst is selected from the group consisting of silica, alumina, silicon carbide or any mixture of said elements of the group.
  • an alumina-based support whose specific surface area is less than 200 m 2 / g, preferably less than 150 m 2 / g, and very preferably lower at 100 m 2 / g.
  • the surface density of the metal of group VIB is preferably 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 of support.
  • the Group VIb and VIII elements being active in hydrodesulfurization in their sulfurized form the catalyst generally undergoes a sulphurization step before it comes into contact with the feedstock to be treated.
  • this sulphurization is obtained by a heat treatment of the solid during which it is brought into contact with a decomposable sulfur compound and hydrogen sulphide generator.
  • the catalyst can also be directly contacted with a gas stream comprising hydrogen sulfide.
  • This sulphurization step may be carried out ex situ or in situ, ie inside or outside the hydrodesulfurization reactor.
  • the sulfurized catalyst may also have been subjected to a carbon deposition step so as to deposit a certain carbon content, preferably less than or equal to 2.8% by weight.
  • This carbon deposition step aims at improving the selectivity of the catalyst by preferentially reducing the hydrogenating activity of the catalyst.
  • the carbon content deposited is between 0.5% and 2.6% by weight.
  • This carbon deposition step can be carried out before, after, or during the step of sulphurizing the catalyst.
  • the method may use a hydrodesulfurization finishing step using a catalyst comprising at least one element selected from group VIII elements, deposited on a porous support such as for example alumina or silica.
  • the element content of group VIII is between 1% and 60% by weight, and preferably between 2% and 20% by weight.
  • the said group VIII element is introduced in the form of a metal oxide, then it is sulphurized before use.
  • This finishing step is mainly used to decompose saturated sulfur compounds such as mercaptans or sulphides contained in the hydrodesulphurization effluent.
  • this finishing step is carried out at a temperature higher than the hydrodesulfurization step.
  • the finishing step will be carried out on a hydrodesulphurization catalyst comprising at least one group VIII element and a Group VIb element, deposited on a porous support.
  • the group VIII element is preferably iron, cobalt or nickel.
  • the group VIb element is preferably molybdenum or tungsten.
  • the content of group VIII element expressed as oxide is between 0.5% by weight and 10% by weight and preferably between 0.7% by weight and 5% by weight.
  • the metal content of group VIb is between 1.5% by weight and 50% by weight, and preferably between 2% by weight and 20% by weight.
  • the porous support is selected from the group consisting of silica, alumina, silicon carbide or any mixture of said constituent elements.
  • an alumina-based support whose specific surface area is less than 200 m 2 / g, preferably less than 150 m 2 / g, and very preferably lower at 100 m 2 / g.
  • the porosity of the catalyst used in the finishing step is such that the average pore diameter is greater than 20 nm, and preferably between 20 nm and 100 nm.
  • the surface density of the group VIb metal is preferably 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 catalyst of the finishing step is characterized by a catalytic activity generally of between 1% and 90%, preferably between 1% and 70%, and very preferably between 1% and 50% of the catalytic activity of the catalyst.
  • main catalyst of hydrodesulfurization is characterized by a catalytic activity generally of between 1% and 90%, preferably between 1% and 70%, and very preferably between 1% and 50% of the catalytic activity of the catalyst.
  • Figure 1 shows a hydrodesulphurization reactor divided into two catalytic beds, and a finishing reactor divided into two catalytic beds.
  • the gasoline to be treated is introduced via line (1) and then mixed with hydrogen introduced via line (2) and heated by an exchanger train and / or an oven (11).
  • the hydrogen of the line (2) consists of a mixture of the hydrogen recycled by the line (10) and the additional hydrogen introduced by the line (23).
  • the mixture brought to the temperature and the pressure necessary to reach the desired desulfurization rate is generally in the vapor phase in the line (3).
  • the effluent from the reactor (12) contains hydrocarbons and sulfur compounds that have not reacted, paraffins from the hydrogenation of olefins, H 2 S from the decomposition of sulfur compounds, and recombinant mercaptans. from the addition reactions of H 2 S on olefins.
  • the reactor effluent (12) is sent via line (4) in an exchange train (13) in order to condense the hydrocarbon fraction (the part of FIG. 1 in the dashed rectangle is then absent from the flow diagram). process according to this variant).
  • the mixture of liquid hydrocarbons and hydrogen is then separated in a separator tank (14) which makes it possible to recover a liquid fraction in bottom by the line (6) constituted mainly of the desulfurized gasoline, and at the top, a gaseous fraction. by line (5) consisting mainly of hydrogen and H 2 S.
  • the gaseous effluent is directed by line (5) to a washing section (15) to separate H 2 S from hydrogen.
  • the liquid effluent brought by the line (6) is expanded and injected into a stripping column (17) which makes it possible to extract at the top, via the line (9), the residual H 2 S dissolved in the hydrocarbons.
  • the desulfurized gasoline is recovered at the bottom of the stripping column by the line (7).
  • a fraction of this desulfurized gasoline is withdrawn via line (8) and mixed with the feedstock introduced via line (1).
  • the hydrodesulfurization carried out in the reactor (12) is followed by a step of finishing the hydrodesulfurization carried out in the finishing reactor (19).
  • the reaction mixture recovered at the line (4) can be reheated by an exchange train or an oven (18) and then sent into the finishing reactor (19) (implementation of the part of Figure 1 located in the rectangle in broken lines).
  • the recycling of a fraction of the desulphurized gasoline can be carried out either by the line (1), at the inlet of the hydrodesulphurization reactor, or by the line (20) between two catalyst beds of the hydrodesulfurization reactor ( 12), either by the line (22) between two catalyst beds of the finishing reactor (19), or by the line (21) between the hydrodesulfurization reactor (12) and the finishing reactor (19).
  • the combination of recycling means that some of the desulfurized gasoline can be recycled at each of the various recycling points previously listed. In this case, the distribution of the recycling flow between the different recycling points can be absolutely arbitrary.
  • a continuously operating hydrodesulfurization reactor is charged with 100 ml (ml is the abbreviation of milliliter) of HR806 catalyst marketed by the company Axens.
  • This catalyst based on cobalt and molybdenum oxides is sulfided with a mixture of H 2 and DMDS under conventional sulfurization conditions, in order to convert at least 80% of the metal oxides of molybdenum and cobalt into sulfides.
  • the reaction mixture is cooled and the gasoline is separated from the hydrogen in a gas / liquid separator.
  • Recovered gasoline is stripped by a nitrogen flow to remove residual H 2 S and analyzed.
  • the gasoline produced contains 32 ppm of sulfur, of which 22 ppm in the form of mercaptans, and a bromine value of 30 mg / 100ml.
  • a test is conducted on gasoline A under conditions similar to Example 1.
  • a fraction of the liquid recipe from the stripper is returned to the charging pot using a pump.
  • the recycle rate is calculated as the recycle rate divided by the fresh charge rate.
  • the temperature is adjusted in increments of 1 ° C to obtain about 30 ppm of sulfur in the recipe.
  • the recycle rate is adjusted to obtain recycle rates in a range of 0.2 to 3. For each recycle rate, a sample of desulphurized gasoline is recovered and analyzed. Table 2 presents the analyzes performed on the different samples. Recycling rate 0.2 0.5 1 2 3 total flow l / h 0.48 0.6 0.8 1.2 1.6 Temperature, ° C 285 285 286 289 291
  • the operation of the reactor with recycling of a fraction of the recipe makes it possible, for the same sulfur content in the recipe, to produce a gasoline having a lower mercaptan content and a higher olefin content.

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  • Chemical & Material Sciences (AREA)
  • 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)
EP06291025A 2005-07-18 2006-06-22 Neues Verfahren zur Entschwefelung eines olefinischen Benzins zur Begrenzung von Mercaptan. Revoked EP1746144B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0507685A FR2888583B1 (fr) 2005-07-18 2005-07-18 Nouveau procede de desulfuration d'essences olefiniques permettant de limiter la teneur en mercaptans

Publications (2)

Publication Number Publication Date
EP1746144A1 true EP1746144A1 (de) 2007-01-24
EP1746144B1 EP1746144B1 (de) 2008-11-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06291025A Revoked EP1746144B1 (de) 2005-07-18 2006-06-22 Neues Verfahren zur Entschwefelung eines olefinischen Benzins zur Begrenzung von Mercaptan.

Country Status (6)

Country Link
US (1) US8034233B2 (de)
EP (1) EP1746144B1 (de)
JP (1) JP5138907B2 (de)
CN (1) CN1900230B (de)
DE (1) DE602006003482D1 (de)
FR (1) FR2888583B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343562B (zh) * 2007-07-09 2011-09-21 中国石油化工股份有限公司 一种汽油加氢脱硫、降烯烃方法
FR3116740A1 (fr) * 2020-11-27 2022-06-03 IFP Energies Nouvelles Procédé de préparation d’un catalyseur d’hydrodésulfuration d’une coupe essence comprenant un métal du groupe VIB, un métal du groupe VIII et du carbone graphitique

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130056391A1 (en) * 2010-03-17 2013-03-07 Indian Oil Corporation Limited Catalytical hydrodesulfurization of kerosene in two steps on cobalt-molybdenum catalyst and intermediate stripping
CN102465025B (zh) * 2010-11-05 2014-05-21 中国石油化工股份有限公司 一种劣质汽油加工方法
CN202717753U (zh) * 2011-06-22 2013-02-06 北京金伟晖工程技术有限公司 一种低成本制造低硫高辛烷值汽油的装置
US9017545B2 (en) * 2011-11-10 2015-04-28 China Petroleum & Chemical Corporation Process for hydrotreating inferior naphtha fraction
US9806164B1 (en) * 2013-03-26 2017-10-31 The Penn State Research Foundation Controlled synthesis and transfer of large area heterostructures made of bilayer and multilayer transition metal dichalocogenides
US10144883B2 (en) 2013-11-14 2018-12-04 Uop Llc Apparatuses and methods for desulfurization of naphtha
FR3035117B1 (fr) 2015-04-15 2019-04-19 IFP Energies Nouvelles Procede d'adoucissement en composes du type sulfure d'une essence olefinique
CN109415638A (zh) 2016-10-07 2019-03-01 托普索公司 一种用于加氢处理含有大于4％的烯烃的燃料气流的方法
FR3130834A1 (fr) * 2021-12-20 2023-06-23 IFP Energies Nouvelles Procédé de traitement d'une essence contenant des composés soufrés
FR3142487A1 (fr) * 2022-11-30 2024-05-31 IFP Energies Nouvelles Procédé d’hydrodésulfuration de finition des essences mettant en œuvre un catalyseur à base de métaux du groupe VIB et VIII et du phosphore sur support alumine à faible surface spécifique
FR3142486A1 (fr) * 2022-11-30 2024-05-31 IFP Energies Nouvelles Procédé d’hydrodésulfuration de finition des essences mettant en œuvre un enchaînement de catalyseurs

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431920A (en) 1944-12-21 1947-12-02 Shell Dev Catalytic treatment of sulfurbearing hydrocarbon distillates
US5968346A (en) * 1998-09-16 1999-10-19 Exxon Research And Engineering Co. Two stage hydroprocessing with vapor-liquid interstage contacting for vapor heteroatom removal
US6126814A (en) * 1996-02-02 2000-10-03 Exxon Research And Engineering Co Selective hydrodesulfurization process (HEN-9601)
US6231754B1 (en) 1996-02-02 2001-05-15 Exxon Research And Engineering Company High temperature naphtha desulfurization using a low metal and partially deactivated catalyst
WO2001040409A1 (en) 1999-12-03 2001-06-07 Exxon Research And Engineering Company Naphtha desulfurization with reduced mercaptan formation
WO2001079391A1 (en) 2000-04-18 2001-10-25 Exxonmobil Research And Engineering Company Selective hydroprocessing and mercaptan removal
WO2002028988A1 (en) 2000-09-29 2002-04-11 Exxonmobil Research And Engineering Company Catalytic stripping for mercaptan removal
EP1369466A1 (de) * 2002-06-03 2003-12-10 Institut Francais Du Petrole Hydroentschwefelungsverfahren für Schwefel und Olefine enthaltende Schnitten in Anwesenheit eines Träger-Katalysators welcher Metalle von den Gruppen VIII und VIB enthält
US20040226863A1 (en) * 2003-01-29 2004-11-18 Denis Uzio Partially coked catalysts that can be used in the hydrotreatment of fractions that contain sulfur-containing compounds and olefins

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2746907A (en) * 1952-01-11 1956-05-22 Union Oil Co Process for hydro-desulfurization of light hydrocarbons using a nickel oxide catalyst
US4113603A (en) * 1977-10-19 1978-09-12 The Lummus Company Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes
JPH07102266A (ja) * 1993-11-17 1995-04-18 Tonen Corp 石油蒸留物の低イオウ化方法
JP3269900B2 (ja) * 1993-12-06 2002-04-02 日石三菱株式会社 分解ガソリン留分の脱硫処理方法
JP3291164B2 (ja) * 1995-06-02 2002-06-10 日石三菱株式会社 接触分解ガソリンの脱硫方法
US5968466A (en) * 1995-06-07 1999-10-19 Asec Manufacturing Copper-silver zeolite catalysts in exhaust gas treatment
JP3387700B2 (ja) * 1995-07-26 2003-03-17 新日本石油株式会社 接触分解ガソリンの脱硫方法
US6231753B1 (en) * 1996-02-02 2001-05-15 Exxon Research And Engineering Company Two stage deep naphtha desulfurization with reduced mercaptan formation
US6824673B1 (en) * 1998-12-08 2004-11-30 Exxonmobil Research And Engineering Company Production of low sulfur/low aromatics distillates
CA2393753C (en) * 1999-12-22 2010-07-20 Bruce Randall Cook High temperature depressurization for naphtha mercaptan removal
FR2811328B1 (fr) * 2000-07-06 2002-08-23 Inst Francais Du Petrole Procede comprenant deux etapes d'hydrodesulfuration d'essence et une elimination intermediaire de l'h2s forme au cours de la premiere etape
US7153415B2 (en) * 2002-02-13 2006-12-26 Catalytic Distillation Technologies Process for the treatment of light naphtha hydrocarbon streams

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431920A (en) 1944-12-21 1947-12-02 Shell Dev Catalytic treatment of sulfurbearing hydrocarbon distillates
US6126814A (en) * 1996-02-02 2000-10-03 Exxon Research And Engineering Co Selective hydrodesulfurization process (HEN-9601)
US6231754B1 (en) 1996-02-02 2001-05-15 Exxon Research And Engineering Company High temperature naphtha desulfurization using a low metal and partially deactivated catalyst
US5968346A (en) * 1998-09-16 1999-10-19 Exxon Research And Engineering Co. Two stage hydroprocessing with vapor-liquid interstage contacting for vapor heteroatom removal
WO2001040409A1 (en) 1999-12-03 2001-06-07 Exxon Research And Engineering Company Naphtha desulfurization with reduced mercaptan formation
WO2001079391A1 (en) 2000-04-18 2001-10-25 Exxonmobil Research And Engineering Company Selective hydroprocessing and mercaptan removal
WO2002028988A1 (en) 2000-09-29 2002-04-11 Exxonmobil Research And Engineering Company Catalytic stripping for mercaptan removal
EP1369466A1 (de) * 2002-06-03 2003-12-10 Institut Francais Du Petrole Hydroentschwefelungsverfahren für Schwefel und Olefine enthaltende Schnitten in Anwesenheit eines Träger-Katalysators welcher Metalle von den Gruppen VIII und VIB enthält
US20040226863A1 (en) * 2003-01-29 2004-11-18 Denis Uzio Partially coked catalysts that can be used in the hydrotreatment of fractions that contain sulfur-containing compounds and olefins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343562B (zh) * 2007-07-09 2011-09-21 中国石油化工股份有限公司 一种汽油加氢脱硫、降烯烃方法
FR3116740A1 (fr) * 2020-11-27 2022-06-03 IFP Energies Nouvelles Procédé de préparation d’un catalyseur d’hydrodésulfuration d’une coupe essence comprenant un métal du groupe VIB, un métal du groupe VIII et du carbone graphitique

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EP1746144B1 (de) 2008-11-05
JP2007023285A (ja) 2007-02-01
US20070012596A1 (en) 2007-01-18
FR2888583B1 (fr) 2007-09-28
US8034233B2 (en) 2011-10-11
CN1900230A (zh) 2007-01-24
JP5138907B2 (ja) 2013-02-06
DE602006003482D1 (de) 2008-12-18
CN1900230B (zh) 2012-10-31
FR2888583A1 (fr) 2007-01-19

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