EP1849850A1 - Verfahren zur Raffination von olefinischen Benzinstoffen mit mindestens zwei verschiedenen Phasen der Hydroraffination - Google Patents

Verfahren zur Raffination von olefinischen Benzinstoffen mit mindestens zwei verschiedenen Phasen der Hydroraffination Download PDF

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Publication number: EP1849850A1
Authority: EP; European Patent Office
Prior art keywords: hydrodesulfurization; hydrogen; gasoline; fraction; hds2
Prior art date: 2006-04-24
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP07290436A

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English (en)

French (fr)

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EP1849850B1 (de

Inventor

Annick Pucci

Quentin Debuisschert

Florent Picard

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IFP Energies Nouvelles IFPEN

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IFP Energies Nouvelles IFPEN

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2006-04-24

Filing date

2007-04-10

Publication date

2007-10-31

2007-04-10 Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN

2007-10-31 Publication of EP1849850A1 publication Critical patent/EP1849850A1/de

2022-03-30 Application granted granted Critical

2022-03-30 Publication of EP1849850B1 publication Critical patent/EP1849850B1/de

Status Active legal-status Critical Current

2027-04-10 Anticipated expiration legal-status Critical

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Classifications

- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- 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
- 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
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline

Definitions

the invention relates to a process for the production of low sulfur and mercaptan gasolines which comprises at least two hydrodesulfurization stages operated in parallel on two distinct sections of the gasoline. This process optionally comprises a single section for purification and recycling of hydrogen.
a hydrodesulfurization step corresponds to one or more hydrodesulfurization sections.
a hydrodesulfurization section corresponds to one or more beds.
the charge to be treated is generally a sulfur-containing gasoline cut such as, for example, a gasoline cut from a coking unit, visbreaking, steam cracking or cracking unit.
Catalyst (FCC) Said filler preferably consists of a gasoline cutter from a catalytic cracking unit whose distillation range is between 0 ° C and 300 ° C and preferably between 0 ° C and 250 ° C.
Catalytic cracking gasolines can constitute 30% to 50% by volume of the gasoline pool and generally have high monoolefins and sulfur contents.
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 H 2 S present in the reactor can react with unhydrogenated monoolefins to form mercaptans.
the fraction of mercaptans in the gasoline produced is generally higher as the sulfur content of the gasoline is low. To minimize the mercaptan content, it is generally preferable to work with a high flow of hydrogen.
the present invention presents a solution for limiting the energy consumption of the compressor, while decreasing the mercaptan content and increasing the octane number for a sulfur content of the constant desulphurized gasoline.
the present invention proposes a new solution to economically address the triple problem of reducing the sulfur content in fuels, the limitation of the mercaptan content in gasolines with low sulfur content, and flexibility in fuel production towards gasoline cuts or middle distillates according to market needs.
the process scheme described in the context of this invention is innovative because it makes it possible to simultaneously treat the triple problem described above while limiting the energy consumption due to the necessary compression of the hydrogen which is recycled in the steps of hydrodesulfurization.
each pair will be associated with a motor octane number (MON) such that MON ⁇ 79.45, preferably such as MON ⁇ 79.50, even more preferably such as MON ⁇ 79.55.
MON motor octane number
the patent application EP0725126-A1 discloses a method for desulfurizing catalytic cracking gasoline while limiting octane loss by hydrogenation of mono-olefins.
This method consists in distilling the gasoline into several fractions, including at least one fraction rich in difficult to desulphurize compounds selected from thiophene and alkylthiophenes, and a fraction rich in easily desulfurized compounds selected from thiacyclopentane, alkylthiacyclopentanes, benzothiophene and alkylbenzothiophenes. At least one of these two fractions is treated by a hydrodesulfurization process and is then mixed with the untreated fraction.
This method has the disadvantage of requiring an analysis of the different fractions before treatment, and does not describe how to choose the fractions to limit the amount of mercaptans in the final product desulfurized.
the patent US 6596157 B2 describes a process for the desulphurization of petrol cuts from cracking units based on the treatment, in parallel, of the heavy fraction of the gasoline called HCN (Heavy Cat Naphta according to English terminology), under conditions of non-selective hydrodesulfurization and the intermediate fraction of the gasoline called ICN (Anglo-Saxon Intermediate Cat Naphta) under selective hydrodesulfurization conditions, for which the intermediate gasoline (ICN) is heated by the hydrotreated heavy fraction (HCN) stream.
HCN Heavy Cat Naphta according to English terminology
ICN Anglo-Saxon Intermediate Cat Naphta
HCN hydrotreated heavy fraction
the light fraction of the essence called LCN must generally be subjected to a complementary desulphurization treatment, for example an extraction of the mercaptans by washing with water. a solution containing sodium hydroxide.
the solutions currently envisaged described in the patent US 6960291 consist of post treatment species from selective hydrotreatment to deplete mercaptans.
the methods envisaged are multiple.
the patent WO 01/79391 which describes methods of treatment of partially desulphurized species to reduce the mercaptan content on the basis of various methods such as adsorption, extraction with sodium hydroxide, heat treatments, etc ...
these methods present disadvantage that they require the implementation of an additional step of gasoline treatment and do not offer the flexibility to send some cuts, either in the gasoline pool or in the middle distillates pool.
the patent application US 2003/0042175 discloses a method of desulphurizing cracking gasolines comprising different treatment steps for decreasing the sulfur content. This process comprises a step of hydrogenation of diolefins, a step of converting the light sulfur compounds by weighting, a step of distillation of the gasoline in several sections and at least one step of desulphurizing at least a portion of the heavy fraction. produced gasoline.
this patent does not teach how to treat the essences to minimize the mercaptan content of the desulphurized gasoline, nor how to treat the hydrogen from the hydrodesulfurization stages.
the invention is based on the differentiated treatment of different sections constituting the petrol cut.
light fractions are rich in mono-olefins and saturated sulfur compounds such as mercaptans and sulphides.
light fraction we mean the fractions species whose boiling point is below 100 ° C, preferably at 80 ° C and very preferably at 65 ° C.
the heavy fraction of the gasoline is in turn rich in benzothiophene sulfur compounds such as benzothiophene and alkylbenzothiophenes and to a lesser degree is rich in alkylthiophenics.
it is rich in aromatic compounds and poor in olefinic compounds.
the heavy fraction of the gasoline consists of hydrocarbons whose boiling point is above 160 ° C, preferably at 180 ° C and very preferably at 207 ° C. This heavy fraction of gasoline is usually the one that contains the most sulfur.
the heavy fraction of gasoline can be incorporated either into the gasoline pool or into the middle distillate fraction to produce kerosene or gas oil.
the core fraction corresponds to the intermediate fraction between the light fraction and the heavy fraction.
the core fraction of the gasoline is rich in mono-olefins and sulfur compounds of thiophene types including thiophene, methyl-thiophenes and other alkylthiophenes.
the different fractions of the gasoline are obtained by distillation of the effluent of the catalytic cracking unit.
the mixture consisting of the light fraction of the gasoline and the intermediate fraction or the intermediate fraction alone is treated in a first hydrodesulfurization step called HDS1.
This step consists in contacting the gasoline to be treated with hydrogen, in one or more series hydrodesulfurization reactors, containing one or more catalysts adapted to carry out the hydrodesulphurization in a selective manner, that is to say with a degree of hydrogenation of mono-olefins of less than 60%, preferably less than 50% and very preferably less than 40%.
the operating pressure of this step is generally between 0.5 MPa and 5 MPa, and preferably between 1 MPa and 3 MPa.
the temperature is between 200 ° C and 400 ° C and preferably between 220 ° C and 380 ° C.
the average operating temperature of each reactor will be higher by at least 5 ° C, preferably at least 10 ° C and very preferably at least 15 ° C at the operating temperature of the reactor which precedes it.
the amount of catalyst used in each reactor is such that the ratio between the gasoline flow to be treated expressed in m 3 per hour at standard conditions, per m 3 of catalyst (also called space velocity) is between 0.5 h -1 and 20 h -1 and preferably between 1 h -1 and 15 h -1 .
the first reactor will be operated with a space velocity of between 2 h -1 and 8 h -1 .
the flow rate of hydrogen is such that the ratio between the flow rate of hydrogen expressed in normal m 3 per hour (Nm 3 / h) and the charge rate to be treated expressed in m 3 per hour at standard conditions is between 50 Nm 3 / m 3 and 1000 Nm 3 / m 3 , preferably between 70 Nm 3 / m 3 and 800 Nm 3 / m 3 .
the desulfurization rate attained during the stage HDS1 is generally greater than 80% and preferably greater than 90%.
the reaction mixture is cooled to a temperature below 60 ° C in order to condense the hydrocarbons.
the gas and liquid phases are separated in a separator.
the liquid fraction which contains the desulfurized gasoline and a fraction of the dissolved H 2 S is sent to a stripping section, the gaseous fraction consisting mainly of hydrogen and containing the majority of the H 2 S is sent to a purification section.
the heavy fraction of gasoline is treated in a separate hydrodesulfurization step called HDS2.
This step consists in contacting the gasoline to be treated with hydrogen, in one or more hydrodesulfurization series reactors containing one or more catalysts adapted to carry out the hydrodesulfurization.
the hydrodesulfurization of the heavy gasoline will be carried out in a single step, on a single reactor.
the hydrodesulfurization may be carried out selectively or non-selectively.
the hydrogenation rate of the mono-olefins is less than 90%, preferably less than 80% and very preferably less than 60%.
the operating pressure of this step is generally between 0.5 MPa and 10 MPa, and preferably between 1 MPa and 8 MPa.
the temperature is between 220 ° C and 450 ° C and preferably between 250 ° C and 380 ° C.
the average operating temperature of each reactor will be at least 5 ° C., preferably at least 10 ° C. and very preferably at least 10 ° C. minus 15 ° C at the operating temperature of the reactor which precedes it.
the amount of catalyst used in each reactor is such that the ratio between the flow rate of gasoline to be treated expressed in m3 per hour at standard conditions per m3 of catalyst (also called space velocity) is between 0.3 hr . 1 and 20 h -1 and preferably between 0.5 h -1 and 15 h -1 .
the first reactor will be operated with a space velocity of between 1 h -1 and 8 h -1 .
the flow rate of hydrogen is such that the ratio between the flow rate of hydrogen expressed in normal m 3 per hour (Nm 3 / h) and the charge rate to be treated expressed in m 3 per hour at standard conditions is between 30 Nm 3 / m 3 and 800 Nm 3 / m 3 , preferably between 50 Nm 3 / m 3 and 500 Nm 3 / m 3 .
this ratio will be less than 80% of the ratio of the flow rates used to desulfurize in the hydrodesulfurization step HDS1, preferably less than 60%, very preferably less than 50% and even more so. preferred less than 40% of the ratio of flow rates used to desulphurize in the hydrodesulfurization step HDS1.
the reaction mixture is cooled to a temperature below 60 ° C in order to condense the hydrocarbons.
the phases gas and liquid are separated in a separator.
the liquid fraction containing the desulfurized gasoline and a fraction of the dissolved H 2 S is sent to a stripping section, the gaseous fraction consisting mainly of hydrogen and containing the majority of the H 2 S is sent to a purification section.
any catalyst having good selectivity for hydrodesulfurization reactions can be used in steps HDS1 or HDS2.
catalysts comprising an amorphous and porous mineral support chosen from the group consisting of aluminas, silicon carbide, silica, silica-aluminas or even titanium or magnesium oxides used alone or in admixture with alumina or silica-alumina. It is preferably selected from the group consisting of silica, the family of transition aluminas and silica-aluminas.
the support consists essentially of at least one transition alumina, that is to say it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight. % weight, or even at least 90% weight of transition alumina. It may optionally consist solely of a transition alumina.
the specific surface area of the support is generally less than 200 m 2 / g and preferably less than 150 m 2 / g.
the porosity of the catalyst before sulfurization is such that it has an average pore diameter greater than 20 nm, preferably greater than 25 nm or even 30 nm and often between 20 and 140 nm, preferably between 20 and 100 nm, and very preferably between 25 and 80 nm.
the pore diameter was measured by mercury porosimetry according to ASTM D4284-92 with a wetting angle of 140 °.
the hydrodesulfurization catalyst contains at least one Group VI metal and / or at least one Group VIII metal on a support.
the Group VI metal is generally molybdenum or tungsten the Group VIII metal generally nickel or cobalt.
the surface density of the group metal VI is understood according to the invention between 2.10 -4 and 4.0.10 -3 gram of oxide of said metal per m2 of support, preferably between 4.10 -4 and 1.6.10 -3 g / m 2 .
a catalyst or a chain of catalysts as described in the patent application.
US20060000751 A1 are catalysts comprising a support for example chosen from refractory oxides such as aluminas, silicas, silica-aluminas or magnesia, used alone or mixed with one another, a metal of group VI, preferably molybdenum or tungsten promoted or not by a Group VIII metal, preferably cobalt or nickel.
These catalysts have an average pore diameter greater than 22 nm.
the process comprises a succession of hydrodesulfurization steps, such that the activity of the catalyst of a step n + 1 is between 1% and 90% of the activity of the catalyst.
catalyst of step n is
a non-selective catalyst in step HDS2.
catalysts comprising an amorphous and porous mineral support chosen from the group consisting of aluminas, silicon carbide, silica, silica-aluminas or even titanium or magnesium oxides used alone or in admixture with alumina or silica-alumina. It is preferably selected from the group consisting of silica, the family of transition aluminas and silica-aluminas.
the support consists essentially of at least one transition alumina, that is to say it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight.
the hydrodesulfurization catalyst contains at least one Group VI metal and / or at least one Group VIII metal on a support.
the Group VI metal is generally molybdenum or tungsten and the Group VIII metal is generally nickel or cobalt.
the selective or non-selective nature of the hydrodesulfurization catalyst generally depends on the composition and the mode for preparing said catalyst. Simple ways of varying the selectivity include, for example, modifying the Group VIII and Group VI metal contents, or possibly the molar ratio between the amounts of Group VIII and Group VI metals for a given or to be donated carrier. vary the surface area of the substrate for constant metal contents.
the excess hydrogen resulting from hydrodesulfurization steps HDS1 and HDS2 can be collected and treated in a single purification section.
the hydrogen thus purified is then recycled to at least one of hydrodesulphurization steps HDS1 and HDS2 after a compression step to compensate for pressure losses through the process.
An additional charge of fresh hydrogen is made either before or after the compression step in order to compensate for the hydrogen consumption in the hydrodesulfurization reactors.
step HDS2 dedicated to heavy gasoline makes it possible not to co-mix this gasoline with middle distillate cuts in another hydrotreatment therefore to release capacity in the said hydrotreatment and consequently to increase the production capacity of the refinery.
the sulfur compounds that one seeks to transform are mainly mercaptans and sulphides.
the main reaction of transformation of mercaptans consists of thioetherification of mono-olefins by mercaptans. This reaction is illustrated below by the addition of propane-2-thiol to pent-2-ene to form a propyl pentyl sulfide.
the transformation of the sulfur compounds can also pass through the intermediate formation of hydrogen sulphide which can then be added to the unsaturated compounds present in the feedstock. This route is however a minority in the preferred conditions of the reaction.
the compounds which can thus be transformed and weighed up are sulphides and mainly dimethyl sulphide, methyl ethyl sulphide, diethyl sulphide, CS 2 , COS, thiophane and methyl thiophane.
weighting reactions of light nitrogen compounds and mainly nitriles, pyrrole and its derivatives, can also be observed.
This pretreatment step consists in bringing the charge to be treated into contact with a stream of hydrogen and with a catalyst containing at least one metal of group VIb (group 6 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th Edition, 1995-1996 ) and at least one Group VIII metal (groups 8, 9 and 10) of said classification, deposited on a porous support.
the catalyst according to the invention may be prepared using any technique known to those skilled in the art, and in particular by impregnation of the elements of groups VIII and VIb on the selected support.
This impregnation may for example be carried out according to the known method of preparation of the man of the in the dry-impregnation terminology, in which just the quantity of desired elements is introduced in the form of soluble salts in a chosen solvent, for example deionized water, so as to fill as accurately as possible the porosity of the support.
the support thus filled with the solution is preferably dried.
the preferred support is alumina which can be prepared from any type of precursors and shaping tools known to those skilled in the art.
the catalyst is usually used in a sulphurized form obtained after treatment in temperature in contact with a decomposable sulfur-containing organic compound and generating hydrogen sulphide (H 2 S) or directly in contact with a gaseous stream of diluted H 2 S in H 2 .
This step can be carried out in situ or ex situ (ie inside or outside the hydrodesulfurization reactor) at temperatures between 200 and 600 ° C. and more preferably between 300 and 500 ° C. .
the charge to be treated is mixed with hydrogen before being contacted with the catalyst.
the quantity of hydrogen injected is such that the molar ratio between the hydrogen and the diolefins to be hydrogenated is greater than 1 (stoichiometry) and less than 10, and preferably between 1 and 5 mol / mol. Too large an excess of hydrogen can lead to a strong hydrogenation of the mono-olefins and consequently a decrease in the octane number of the gasoline.
the entire charge is usually injected at the reactor inlet. However, it may be advantageous in some cases to inject a fraction or the entire charge between two consecutive catalytic beds placed in the reactor. This embodiment makes it possible in particular to continue operating the reactor if the inlet of the reactor is clogged by deposits of polymers, particles, or gums present in the load.
the mixture consisting of gasoline and hydrogen is contacted with the catalyst at a temperature between 80 ° C and 250 ° C, and preferably between 90 ° C and 220 ° C, with a liquid space velocity (LHSV) of between 1 h -1 and 10 h -1, the unit of the liquid space velocity being per liter of feed per liter of catalyst per hour (ll -1 .h -1 ).
LHSV liquid space velocity
the pressure is adjusted so that the reaction mixture is predominantly in liquid form in the reactor.
the pressure is between 0.5 MPa and 5 MPa and preferably between 1 and 4 MPa.
the gasoline treated under the conditions stated above has a reduced diolefin and mercaptan content.
the gasoline produced contains less than 1% by weight of diolefins, and preferably less than 0.5% by weight of diolefins.
Light sulfur compounds whose boiling point is lower than that of thiophene (84 ° C) are generally converted to more than 50%. It is therefore possible to separate the light fraction of the gasoline by distillation and to send this fraction directly to the gasoline pool without further processing.
a core essence, gasoline A flowing through line 1 is mixed with hydrogen from the recycle compressor P1, through line 20.
the mixture thus formed is injected into the reaction section R1.
the effluent flowing through the line 4 is cooled in the exchanger section E1 in order to condense the hydrocarbons and then the mixture is injected into the separation section S1 via the line 6.
the separation section S1 produces a fraction gas extracted by line 8, which consists essentially of hydrogen, H 2 S and light hydrocarbons and a liquid fraction extracted by line 9.
the liquid fraction is then injected into a stabilization section C2 which extracted by line 15, at the top, the H 2 S dissolved in hydrocarbons.
Gasoline recovered at the bottom of column C2 by line 16 can be sent directly to the gasoline pool.
a heavy gasoline, gasoline B flowing through line 3 is mixed with fresh hydrogen supplied by line 2.
the mixture thus formed is injected into the reaction section R2.
the effluent flowing through the line 5 is cooled in the exchanger section E2 in order to condense the hydrocarbons, then the mixture is injected into the separation section S2 via the line 7.
the separation section S2 produces a fraction gaseous extracted from the line 10, which consists essentially of hydrogen, H 2 S and light hydrocarbons and a liquid fraction extracted by the line 11.
the liquid fraction is then injected into a stabilization section C3 which extracts by line 17, at the top, H 2 S dissolved in hydrocarbons.
the desulphurized heavy gasoline recovered via line 18 can be sent either to the gasoline pool or to a pool of middle distillates.
the stabilizing sections C2 and C3 each comprise a distillation column. It is advantageous, in order to limit the operating and investment costs, to collect the distillates from these two columns before cooling them to condense them, and to send them together to the reflux flask.
the two columns can thus be operated with a common reflux section.
the hydrogens derived from separators S1 and S2 respectively by lines 8 and 10 are mixed before being treated in a common purification section C1 which consists of washing with an aqueous solution of amine according to a technique well known to humans. of career.
the hydrogen removed from H 2 S and flowing through line 13 and compressed in a recycle compressor P1 and is then mixed with gasoline A by line 20.
the makeup hydrogen is injected via the line 12 upstream of the purification section C1.
the hydrogen necessary for the treatment of gasoline B is then injected via line 19 into the hydrodesulfurization stage of reaction section R2.
FIG. 2 Another variant of the invention is shown in FIG. 2. According to this variant, a fraction of the hydrogen coming from the separation section S1 via the line 8 is injected, without purification treatment, into the reaction section R2 via the intermediate of line 21.
FIG. 3 illustrates the sequences of the pretreatment stage consisting mainly of hydrogenating the diolefins and weighing down the light sulfur compounds and the selective hydrodesulfurization stage.
the pretreatment step R3 can be carried out either on the total gasoline injected via line 1 or on the gasoline recovered at the distillation head in column C4 via line 3. In the latter case, the essence A is sent directly to column C4 without pre-treatment.
the hydrogen is injected via line 10, upstream of the pretreatment step R3, which corresponds to the step of selective hydrogenation and increasing the weight of the saturated light sulfur compounds.
the gasoline produced is then distilled in two sections in column C4, a heavy section extracted by line 4 which corresponds to the heavy gasoline described in the text, and a lighter fraction recovered by line 3 which corresponds to the mixture of the essence of heart and light essence described in the text.
the light fraction is then distilled in a second column, C5, which separates the essence of the heart that leaves via the line 6 of the light gasoline that leaves via the line 7.
the light gasoline recovered by the line 7 is generally low in sulfur and can be sent directly to the gasoline pool without further processing.
the core and heavy gasolines recovered respectively by lines 6 and 4 are treated in one or more hydrodesulfurization sections according to the invention and making it possible to recover a gasoline H via line 8 and a gasoline J via line 9 sent respectively to the gasoline pool and the middle distillate pool. It may be advantageous to produce the three gasoline cuts described in a single column provided with a side withdrawal from which the essence of heart is extracted.
the distillation column of the total gasoline injected via line 1 may be a single column with an inner wall.
This embodiment has the advantage of only sending the pre-treatment step R3 fraction of gasoline corresponding to the fraction cleared of heavy gasoline, which decreases the quantities of gasoline to be treated, as well as the presence of potential contaminants of catalysts such as arsenic or silicon which are generally concentrated in the heavy fractions of gasoline.
HR806S catalyst sulfur catalyst based on cobalt and molybdenum
This catalyst has the particularity of being presulfided and preactivated ex situ. It does not require a complementary step of sulfurization.
Gasoline a is mixed with hydrogen before being injected into the reactor.
the gasoline flow rate is 400 ml / h and the hydrogen flow rate is 116 normal liters per hour.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
the temperature is adjusted to 260 ° C and the pressure to 2 MPa.
the produced essence called c1 is cooled and stripped by a stream of hydrogen to remove dissolved H 2 S.
this gasoline contains 38 ppm of sulfur of which 14.0 ppm are in the form of mercaptans. Its research octane number (RON) is 90.60 and its engine octane number (MON) is 79.40.
340 ml / h of a1 gasoline are mixed with 98 normal liters per hour of hydrogen and injected onto a volume of 85 ml of HR806S catalyst.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 300 NI / I.
the temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa.
the gasoline produced called b1 contains 19 ppm of sulfur, of which 8 ppm in the form of mercaptans.
60 ml / h of a2 gasoline are mixed with 14.4 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst.
the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 240 NI / I.
the temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa.
the gasoline produced called b2 contains 90 ppm of sulfur including 4 ppm in the form of mercaptans.
the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
Essences b1 and b2 are mixed at a level of 85% by weight of gasoline b1 and 15% by weight of gasoline b2.
the mixture thus formed called c2 is analyzed. It contains 30 ppm sulfur including 8.0 ppm as mercaptans. Its research octane number (RON) is 90.80 and its engine octane number (MON) is 79.50.
Fraction b2 can also be sent to the middle distillate pool with very low sulfur content.
60 ml / h of a2 gasoline are mixed with 6.3 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 105 NI / I.
the temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa.
the gasoline produced called b5 contains 135 ppm of sulfur including 6 ppm in the form of mercaptans.
Essences b1 and b5 are mixed at a level of 85% by weight of gasoline b1 and 15% by weight of petrol b5 .
the mixture thus formed called c4 is analyzed.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 270 NI / I.
368 ml / h of a3 gasoline are mixed with 108.2 normal liters per hour of hydrogen and injected onto a volume of 92 ml of HR806S catalyst.
the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 294 NI / I.
the temperature of the reactor is adjusted to 260 ° C.
the gasoline produced called b3 contains 20 ppm of sulfur of which 7 ppm in the form of mercaptans.
32 ml / h of a4 gasoline are mixed with 7.5 normal liters per hour of hydrogen and injected on a volume of 8 ml of HR806S catalyst.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 234 NI / I.
the temperature of the reactor is adjusted to 260 ° C.
the gasoline produced called b4 contains 140 ppm of sulfur of which 3 ppm in the form of mercaptans.
Essences b3 and b4 are mixed at a level of 92% by weight of gasoline b3 and 8% by weight of gasoline b4 .
the mixture thus formed called c3 is analyzed.
Fraction b4 can also be sent to the middle distillate pool with very low sulfur content.
the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
340 ml / h of a1 gasoline are mixed with 98.6 normal liters per hour of hydrogen and injected onto a volume of 85 ml of HR806S catalyst.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
the temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa.
the gasoline produced called b6 contains 22 ppm of sulfur including 9 ppm in the form of mercaptans.
60 ml / h of a2 gasoline are mixed with 17.4 normal liters per hour of hydrogen and injected onto a volume of 15 ml of HR806S catalyst.
the hydrogen flow rate is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
the temperature of the reactor is adjusted to 260 ° C. and the pressure to 2 MPa.
the gasoline produced called b7 contains 80 ppm of sulfur including 4 ppm in the form of mercaptans.
the flow rate of hydrogen is such that the ratio H2 / HC in normal liters of hydrogen per liter of feed is equal to 290 NI / I.
Essences b6 and b7 are mixed at a level of 85% by weight of gasoline b 6 and 15% by weight of gasoline b7 .
the mixture thus formed called c5 is analyzed.

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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)

EP07290436.0A 2006-04-24 2007-04-10 Verfahren zur raffination von olefinischen benzinstoffen mit mindestens zwei verschiedenen phasen der hydroraffination Active EP1849850B1 (de)

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FR0603630A FR2900157B1 (fr)	2006-04-24	2006-04-24	Procede de desulfuration d'essences olefiniques comprenant au moins deux etapes distinctes d'hydrodesulfuration

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EP (1)	EP1849850B1 (de)
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CN (1)	CN101294106B (de)
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- 2007-04-23 US US11/738,647 patent/US7651606B2/en active Active
- 2007-04-24 BR BRPI0701633A patent/BRPI0701633B1/pt active IP Right Grant
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FR3013724A1 (fr) *	2013-11-28	2015-05-29	IFP Energies Nouvelles	Procede d'hydrotraitement d'un gazole dans des reacteurs en parallele avec recyclage d'hydrogene.
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Also Published As

Publication number	Publication date
CN101294106A (zh)	2008-10-29
FR2900157B1 (fr)	2010-09-24
KR20070104843A (ko)	2007-10-29
EP1849850B1 (de)	2022-03-30
KR101441122B1 (ko)	2014-09-17
JP5448305B2 (ja)	2014-03-19
BRPI0701633A (pt)	2007-12-11
US7651606B2 (en)	2010-01-26
US20070246399A1 (en)	2007-10-25
FR2900157A1 (fr)	2007-10-26
BRPI0701633B1 (pt)	2016-12-13
CN101294106B (zh)	2013-03-27
JP2007291392A (ja)	2007-11-08

Publication	Publication Date	Title
EP1849850B1 (de)	2022-03-30	Verfahren zur raffination von olefinischen benzinstoffen mit mindestens zwei verschiedenen phasen der hydroraffination
EP1923452B1 (de)	2017-10-04	Verfahren zur Tiefenentschwefelung von Krack-Benzinstoffen mit einem geringen Oktanzahlverlust
EP2169032B1 (de)	2012-08-15	Katalysator zur teilweise oder ganz Zersetzung oder Hydrierung von ungesättigten schwefelhaltigen Verbindungen
EP1174485B1 (de)	2010-10-27	Zweistufiges Benzin Entschwefelungsverfahren mit zwischenzeitlicher Entfernung von H2S
EP3299441B1 (de)	2019-01-30	Behandlungsverfahren eines benzins durch trennung in drei schnitte
WO2014013153A1 (fr)	2014-01-23	Procede de production d'une essence legere basse teneur en soufre
EP1369468B1 (de)	2017-10-04	Herstellungsverfahren von Kohlenwasserstoffen mit niedrigem Gehalt von Schwefel und von Stickstoff
EP1336649B1 (de)	2011-06-22	Verfahren zur Aufwertung von Aromaten und Nafteno-Aromaten enthaltende Gasölschnitten.
EP2886629B1 (de)	2023-11-01	Verfahren zur hydroentschwefelung von kohlenwasserstoff anteilen
EP3312260B1 (de)	2019-03-27	Verfahren zur hydroentschwefelung einer olefinischen essenz
EP3228683B1 (de)	2018-10-17	Aufbereitungsverfahren einer essenz
WO2014013154A1 (fr)	2014-01-23	Procede de desulfuration d'une essence
WO2016096364A1 (fr)	2016-06-23	Procede d'adoucissement en composes du type sulfure d'une essence olefinique
EP1370627B1 (de)	2011-10-12	Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt
EP4004158A1 (de)	2022-06-01	Verfahren zur herstellung von benzin mit niedrigem gehalt an schwefel und mercaptan
WO2021185658A1 (fr)	2021-09-23	Procédé de production d'une essence a basse teneur en soufre et en mercaptans
EP1370630B1 (de)	2004-10-13	Verfahren zur herstellung von entschwefeltem benzin aus einem crackbenzin enthaltendem benzin
EP1370629B1 (de)	2011-03-23	Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt
EP3283601B1 (de)	2019-04-10	Verfahren zum süssen eines olefinischen benzins von sulphidverbindungen

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