EP0661371A1 - Process for the production of an internal combustion engine fuel by hydro treatment and extraction and final product - Google Patents

Process for the production of an internal combustion engine fuel by hydro treatment and extraction and final product Download PDF

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Publication number
EP0661371A1
EP0661371A1 EP94403024A EP94403024A EP0661371A1 EP 0661371 A1 EP0661371 A1 EP 0661371A1 EP 94403024 A EP94403024 A EP 94403024A EP 94403024 A EP94403024 A EP 94403024A EP 0661371 A1 EP0661371 A1 EP 0661371A1
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EP
European Patent Office
Prior art keywords
product
weight
solvent
sulfur
boiling point
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EP94403024A
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German (de)
French (fr)
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EP0661371B1 (en
Inventor
Frédéric Morel
Massimo Zuliani
Paul Mikitenko
Marc Boulet
Roben Loutaty
Jean Claude Company
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IFP Energies Nouvelles IFPEN
Total Marketing Services SA
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IFP Energies Nouvelles IFPEN
Total Raffinage Distribution SA
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0409—Extraction of unsaturated hydrocarbons
    • C10G67/0418—The hydrotreatment being a hydrorefining
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • 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
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to a petroleum product and a process for obtaining said petroleum product which can optionally be used for the formulation of a fuel for an internal combustion engine and the product obtained by the process.
  • the gas oils that are currently on the market either in the form of fuels for internal combustion engines, or in the form of fuel, are most often products resulting from refining which contain sulfur in a quantity (expressed by weight of sulfur) of about 0.3%.
  • hydrodesulfurization treatment from a feed which can come from the direct distillation of a crude oil or from a specific treatment of a crude oil (for example a pyrolysis or a distillation followed by pyrolysis of the fraction recovered during distillation, or thermal or catalytic cracking) generally containing at least 0.8% by weight of sulfur.
  • sulfur and cetane content standards are in place or will be implemented in the very near future. These standards are becoming more and more stringent, particularly for diesel oils intended to be used as fuel for engines. Thus in France, in particular from 1995, the sulfur content of these gas oils must be at most equal to 0.05% by weight (500 ppm) while gas oils which comply with the standards in force have a content of sulfur up to 0.3%.
  • gas oils used in France as fuel for internal combustion engines must currently have a cetane number at least equal to 48 and the gas oils used as fuel a cetane number at least equal to 40. We can expect in a near future to a tightening of these standards and in particular those concerning the diesel oils used as fuel in the engines.
  • the present invention therefore relates to a simple implementation process, consuming little hydrogen.
  • This process uses industrial hydrotreatment units (hydrodesulfurization in particular). It makes it possible to improve the qualities of the diesel fuel produced and to comply with future standards and in particular that concerning the sulfur content.
  • the method of the invention also makes it possible to improve the cetane engine index of diesel, to reduce its content of aromatic compounds not containing sulfur heteroatom in their molecule, to reduce its content of nitrogenous compounds, d '' improve its color and odor and finally reduce the formation of solid particles when used in an internal combustion engine.
  • the present invention provides a solution to the specific problem of obtaining, in as large a quantity as possible relative to the starting product, a petroleum product entering into the composition of an engine quality diesel or diesel engine from a particular hydrocarbon cut having characteristics which makes it difficult to recover in the form of engine diesel.
  • the invention also relates to the process for obtaining a petroleum product used in the composition of a domestic fuel oil.
  • hydrodesulfurization (HDS) will be used in the following description instead of hydrotreatment.
  • polyaromatic compounds compounds having at least two aromatic rings, sulfur or not.
  • the initial and final boiling point temperatures are TBP cut points.
  • the hydrocarbon feed which is treated according to the process of the invention is most often called a diesel cut and it preferably has an initial boiling point of approximately 150 ° C. and a final boiling point of approximately 400 ° C., its sulfur content is usually greater than 0.1% and most often greater than 0.5% by weight, its content of n- and iso-alkanes is approximately 30 to 45% by weight, its aromatic content is usually from about 15% to about 65% by weight.
  • This feedstock is most often a direct distillation gas oil, a pyrolysis gas oil or a mixture of the two.
  • This charge can advantageously be mixed with an L.C.O. (light cycle oil) from a catalytic cracking unit and preferably in an LCO / diesel ratio of 1: 4 to 1: 1.
  • L.C.O. light cycle oil
  • the color of this filler measured according to the ASTM D 1500 method is usually greater than or equal to 2.
  • the cetane number according to ISO 5165 of this filler is most often less than around 60 and it is for example around 50 to about 55.
  • the nitrogen content of this feed is very often about 100 to about 1000 ppm expressed by weight of nitrogen relative to the weight of the feed.
  • the product Q1 obtained is a new product taking into account all of its characteristics (cutting point, cetane, paraffin content and sulfur content) which is particularly advantageous for obtaining, by formulation with other diesel cuts, quality fuels.
  • the product (Q1) obtained by the process of the present invention usually has a nitrogen content expressed by weight of nitrogen 2 times less than that of the initial charge and often 4 to 5 times less.
  • This product (Q1) most often has a color measured according to ASTM 1500 standard less than 1 and the cetane number of this product is generally at least 3 points higher and often at least 5 points higher than the cetane number of the initial charge (for example from 3 to 14 points).
  • Its sulfur content compared to that of load is usually less than or equal to 5% by weight.
  • Its net iso-alkane content generally increases by at least 4 points, advantageously by 5 to 20 points and most often by 6 to 11 points, compared to that of the filler.
  • the content of aromatic compounds containing no sulfur atom in their molecule in this product (Q1) is usually reduced by at least 10% by weight relative to that of the initial charge and often by at least 30% by weight. weight.
  • the odor of this product is less strong than that of the initial charge.
  • the invention advantageously relates to a petroleum product characterized in that the distillation cut corresponds to 95% by weight distilled between 320 ° C and 460 ° C, its cetane number is greater than 60, its content of n- and iso-alkanes is at least equal to 48% by weight, and its sulfur content less than or equal to 500 ppm (weight).
  • the hydrodesulfurization is advantageously carried out in a hydrodesulfurization unit under mild conditions making it possible to desulfurize the sulfur molecules by hydrogenating as little as possible.
  • This approach is not obvious to a person skilled in the art of the 1990s, who is rather led to the solution of severifying the conditions of a hydrotreatment in order to simultaneously decrease the sulfur content and increase the cetane of the charges.
  • the temperature is 320 to 370 ° C
  • the hourly space velocity is from 1 to 5
  • the pressure from 1 to 5 MPa
  • the volume ratio H2 on load from 50 to 350 Nm3 / m3.
  • the charge dearomatization rate is then at most equal to around 15%. We can thus distinguish two particularly advantageous cases of implementation of this hydrodesulfurization making it possible to obtain an excellent charge for the following extraction step.
  • the operation is carried out in the presence of a selective catalyst for the hydrodesulfurization of the sulfur molecules with respect to the hydrogenation of aromatics, adapted to limit the hydrogenation, for example one of those marketed by the PROCATALYSE, under a partial pressure of hydrogen at the outlet of the hydrodesulfurization reactor advantageously between approximately 1.0 MPa and approximately 3.0 MPa and a product (P) containing an amount of sulfur from 2 to 30 times less, ie between 0.1 and 0.3% by weight depending on the charge, for example, and most often from 3 to 10 times less than that of the initial charge.
  • the charge dearomatization rate is then significantly less than 10%.
  • the other conditions for carrying out this hydrodesulfurization step are conventional conditions for hydrodesulfurization qualified by those skilled in the art of simple and gentle hydrodesulfurization.
  • the operation is carried out in the presence of a conventional catalyst adapted to limit the hydrogenation, for example one of those sold by the company PROCATALYSE, under a partial pressure of hydrogen at the outlet of the hydrodesulfurization reactor, advantageously included.
  • a conventional catalyst adapted to limit the hydrogenation for example one of those sold by the company PROCATALYSE
  • a partial pressure of hydrogen at the outlet of the hydrodesulfurization reactor advantageously included.
  • P product
  • the rate of dearomatization of the charge is at most equal to approximately 15%.
  • the other conditions for carrying out this hydrodesulfurization step are conventional conditions for more severe hydrodesulfurization.
  • This hydrodesulfurization is carried out using a larger volume of catalyst than in the case of simple hydrodesulfurization, for example a volume of catalyst 2 times greater, as well as a higher hydrogen pressure, calculated to carry out a more hydrodesulfurization. thrust.
  • the separation step generally comprises a steam stripping of the total liquid hydrotreatment effluent, followed or not by an additional distillation step. This last step is generally required when you want to send to extracting a fraction P2 whose initial boiling point is higher than that of the hydrotreatment effluent once stripped.
  • the liquid / liquid extraction step is a step carried out under conventional conditions.
  • This extraction can for example be carried out against the current in a conventional device, for example a filling column, with trays or with mechanical agitation (RDC: rotating disc contactor) generally having an efficiency of 3 to 20 theoretical stages and preferably of 5 to 10 theoretical stages, at a temperature generally between 0 ° C and 140 ° C, advantageously between 30 ° C and 80 ° C and under a pressure allowing to operate in the liquid phase and therefore between 0.1 and 1 MPa , preferably between 0.1 and 0.6 MPa.
  • RDC rotating disc contactor
  • the volume ratio of the solvent (S1) to the volume of the product (P2), obtained in step b), is preferably from approximately 0.2: 1 to approximately 5: 1, advantageously 0.5: 1 to 2 : 1 and most often about 1: 1.
  • the solvent is preferably chosen from the group of solvents making it possible also to extract at least part of the aromatic compounds, not containing a sulfur atom in their molecule, present in the product (P2) obtained in step b).
  • the extraction conditions are preferably chosen so as to obtain a raffinate (R1) containing by weight at most 90% and preferably at most 70% of the total weight of the aromatic compounds, not containing a sulfur atom in their molecule , present in the product (P2) obtained in step b).
  • the extract (E1) under these conditions will contain at least 10% and often at least 30% by weight of the total weight of the aromatic compounds, not containing a sulfur atom in their molecule, present in the product (P2) obtained at step b), as well as preferably at least 30% and often at least 50% and frequently at least 80% by weight of the total weight of the sulfur-containing compounds, most often dibenzothiophenic and naphthobenzothiophenic initially contained in the product (P2).
  • the product (Q1) thus obtained usually contains from 2 to 10 times less sulfur than the product (P2) from step b) and most often from 4 to 10 times less.
  • the extraction solvent is most often a single solvent, but mixtures of solvent can also be used.
  • This solvent generally contains less than 20% and often less than 10% by weight of water.
  • This solvent can be an anhydrous solvent. It is often chosen from the group formed by methanol, acetonitrile, monomethylformamide, dimethylformamide, dimethylacetamide, furfural, N-methylpyrolidone and dimethylsulfoxide. Very often a solvent containing no nitrogen is used and most often an oxygenated non-nitrogenous solvent.
  • the preferred solvent is furfural.
  • At least one cosolvent which may be, an alcohol of 1 to 6 carbon atoms, for example a linear or branched alcohol, or furfuryl alcohol.
  • the feed to be treated has a high final boiling point and is particularly rich in nitrogen compounds, especially basic, it may be advantageous to introduce with the extraction solvent alone or in mixture, a minor amount of acids, in particular carboxylic (less than 1% by weight relative to the solvent for example).
  • carboxylic acids of 1 to 6 carbon atoms and more particularly, acids having a boiling point below 250 ° C., in particular formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, maleic acid, crotonic acid, isobutyric acid, valeric acid, trimethylacetic acid, benzoic acid, and 2-furoic acid .
  • the solvent can be recovered from the raffinate by stripping or distillation, preferably by steam stripping, the conditions of which have been described above.
  • the raffinate (R1) obtained in step c) is then sent to step d) for example in a steam stripping zone in which it is separated under conditions making it possible to recover an enriched head fraction, and preferably highly enriched in solvent (S1) and a bottoms product (Q1) preferably highly depleted in solvent (S1).
  • the conditions of this separation are chosen so as to obtain a overhead fraction containing almost all of the solvent, that is to say for example, more than 95% by weight of the amount of solvent contained in the raffinate (R1) and introduced into this stripping zone. There is thus preferably recovered at least about 99% by weight of the amount of solvent contained in the raffinate (R1).
  • the extract (E1) obtained in step c) is then sent to a solvent recovery zone (S1) used in step c) in which a product enriched in is recovered.
  • the separation of the solvent from the extract is generally carried out by distillation and / or steam stripping and preferably by distillation followed by steam stripping under the conditions set out above. This extract is therefore separated under conditions making it possible to recover a fraction of the head enriched, and preferably highly enriched, in solvent (S1) and a bottom product (Q2) depleted in solvent (S1).
  • this separation Most often the conditions of this separation are chosen so as to obtain a top fraction containing almost all of the solvent, that is to say for example more than 95% by weight of the amount of solvent contained in the extract ( E1) and introduced into this separation zone. At least about 99% by weight of the amount of solvent contained in the extract (E1) is thus preferably recovered.
  • step a) When operating in step a) under substantially more severe hydrodesulfurization conditions, that is to say in particular in the presence of a very large quantity of catalyst, the product (Q2) which is obtained by distillation of the extract (E1) will most often have a sulfur content of less than or equal to about 0.3% by weight.
  • This product (Q2) will of course not be usable as fuel for the engines, since it most often contains a quantity of sulfur greater than the future standard; on the other hand, it can probably be used as fuel.
  • the top product (s), obtained by separation of the raffinate (R1) and optionally of the extract (E1), enriched in solvent, are recycled in step c) d liquid / liquid extraction.
  • At least part of the product (Q2) obtained from the extract (E1) after separation of the solvent (S1) can be sent to a hydrodesulfurization zone separate from the hydrodesulfurization zone of the initial charge or even be returned to the hydrodesulfurization zone of step a).
  • the part of the product (Q2) is subjected to hydrodesulfurization under conditions making it possible to obtain a product (P3) having a sulfur content less than or equal at 0.3% by weight and preferably less than or equal to 0.2% by weight.
  • the hydrocarbon feedstock having an initial boiling point of at least 150 ° C and a final boiling point of at most 500 ° C
  • a distillation zone in which a fraction (F1) having a final boiling point of at least 250 ° C is separated at the head and a fraction (F2) having an initial boiling point of at least 250 ° C at the bottom.
  • the fraction (F2) is treated according to the process described above for the hydrocarbon feed 150-500 ° C. steps a) to d).
  • the fraction (F1) is sent to a hydrodesulfurization zone separate from that of step a) in which it is hydrodesulfurization under conventional conditions and for example under the simple conditions described above, then the product (P ') hydrodesulfurized obtained is sent to a separation zone, for example by stripping or by distillation, of the product (P ') in a fraction (P10) having a final boiling point below 150 ° C, and in a fraction (P20) having an initial boiling point higher than the final boiling point of the fraction (P10).
  • This product (P20) can, at least in part, be mixed with the product (Q1) obtained from the fraction (F2) to form a product (Q10) having the qualities required as engine fuel.
  • the fraction (P10) is essentially formed of compounds resulting from side reactions during hydrodesulfurization. This fraction (P10) generally represents less than 2% by volume relative to the total volume of the fraction (F1).
  • the main advantages of the invention are as follows: in the raffinate (table) a higher content of n- and iso-alkanes is obtained than according to the hydrocracking or hydrodesaromatization processes, a cetane number higher, despite an aromatic hydrocarbon content greater than 10%.
  • the consumption of hydrogen in hydrotreatment is lower. It can be reduced for example to 0.15% by weight with respect to the charge, when the hydrogenation is limited to the maximum.
  • FIGS 1 and 2 schematically represent the main variants for the implementation of the method according to the present invention.
  • similar bodies are designated by the same numbers and reference letters.
  • the hydrocarbon feedstock to be treated is sent by line (1) to the hydrodesulfurization zone (HDS1) at the outlet of which recover by line 2 a product (P) which is sent to a separation zone (SEP. 1) from which we recover by line 3 a product (P1) and by line 4 a product (P2) whose initial boiling point is higher than the final boiling point of the product (P1).
  • This product (P2) is sent via line 4 to an extraction zone (EXT.)
  • an extraction solvent (S1) is also introduced via line 5 and from which an extract (E1) is recovered. by line 7 and a raffinate (R1) by line 6.
  • This raffinate (R1) is sent by line 6 to a zone (D1) for recovering the solvent (S1) by line 8 and a petroleum product ( Q1) possibly being used as a base in the composition of an engine diesel of improved qualities, by line 9.
  • the extract (E1) is sent by line 7 to a zone (D2) for recovering the solvent (S1) by line 10 and a product (Q2) through line 11.
  • This product (Q2) can be, at least in part, recovered by line 11a when the valve V4 is open, or be, at least in part, sent by line 11b when the valve V1 is open either in a hydrodesulfurization zone (HDS3) not shown diagrammatically or in the hydrodesulfurization zone (HDS1).
  • HDS3 hydrodesulfurization zone
  • this product (Q2) is recovered by line 11a it can be valued as fuel but does not meet future standards on engine diesel fuel and cannot be used as such as fuel.
  • the hydrocarbon feedstock to be treated is sent by the line (100) to a zone (TOP) from which a heavy fraction (F2) of initial boiling point greater than about 250 ° C. is recovered which is treated as the hydrocarbon feedstock according to the description above made in connection with FIG. 1.
  • the product (Q1) can be, at least partly recovered by line 9 and line 9a when the valve V2 is open, or be, at least in part sent by line 9b in line 140 when the valve V3 is open.
  • this petroleum product partially forms a base used in the composition of an engine diesel of improved qualities.
  • a light fraction (F1) of final boiling point greater than about 250 ° C. is recovered via line 110.
  • This fraction (F1) is sent by line 110 to a hydrodesulfurization zone (HDS2) at the outlet of which a hydrodesulfurized product (P ') is recovered by line 120 which is sent to a separation zone (SEP 2) from which we recover by line 130 a product (P10) and by line 140 a product (P20) whose initial boiling point is higher than the final boiling point of the product (P10).
  • This product (P20) is optionally mixed with the product (Q1) arriving via line 9b.
  • This mixture or the product (P20) forms a base used in the composition of a diesel engine of improved qualities which is recovered by line 149.
  • the feed used in this example is a straight-run diesel cut having a cetane number of 55, a total content of aromatic compounds, sulfur and non-sulfur, of 30% by weight, a content of n and iso -alkanes of 39% by weight, a naphthenes content of 31%, a sulfur content of 1.22% by weight, a nitrogen content expressed by weight of nitrogen of 255 ppm and a color measured according to the ASTM D standard 1500 equal to 2.
  • This diesel cut has an initial distillation point of 150 ° C and a final distillation point of 400 ° C.
  • This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C., the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 2, 5 h ⁇ 1. The amount of hydrogen consumed is 0.25% by weight relative to the charge.
  • a product (P) containing 0.2% by weight of sulfur, 28% by weight of sulfur and non-sulfur aromatic compounds and a content of n- and iso-alkanes of 40% is recovered via line 2.
  • This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 175 ppm by weight.
  • the cetane number of the product (P) is 56.
  • This product has a final distillation point of 400 ° C. It is sent to a steam stripping zone of water (SEP1) from which a product (P1) having a final distillation point of 220 ° C is recovered via line 3 and a product (P2) having an initial distillation point of 220 ° via line 4 C and a final distillation point of 400 ° C.
  • SEP1 steam stripping zone of water
  • This zone is an extraction column comprising a packing formed by Pall rings with an overall efficiency substantially equal to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C.
  • a raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for possible recycling at extraction zone and at the bottom a raffinate (Q1) containing less than 5 ppm of furfural for example, having a sulfur content of 0.04% by weight, a cetane number of 67, a content by weight of sulfur-containing aromatic compounds and non-sulfur of 12%, an n- and iso-alkane content of 49%, a nitrogen content of 40 ppm and a Saybolt color of 30 and which can be introduced into the diesel tank (pool).
  • an extract (E1) is also recovered which is sent to a distillation zone (D2) followed by a steam stripping zone in which the furfural which is recovered is separated at the head. via line 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.6% by weight, a cetane number of 25 , a content by weight of sulfur and non-sulfur aromatic compounds of 77% and a nitrogen content of 500 ppm.
  • This product Q2 can be sent via lines 11 and 11b to a hydrodesulfurization zone (HDS3) distinct from that into which the initial charge has been introduced.
  • This hydrodesulfurization is carried out in the presence of the HR 306C catalyst, under a partial hydrogen pressure of 2.5 MPa, at a temperature of 330 ° C. with a hydrogen recycling of 200 liters per liter of charge and an hourly space velocity of 2.5 h ⁇ 1.
  • a product is obtained having a sulfur content of 0.2% by weight. Its other characteristics are practically unchanged.
  • This product can be mixed with domestic fuel, that is to say introduced into what those skilled in the art call the domestic fuel pool.
  • the charge used in this example is the same as that used in Example 1.
  • This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.5 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen is equal to 200 liters per liter of charge and the hourly space speed is 1 h ⁇ 1. The amount of hydrogen consumed is 0.4% by weight relative to the charge.
  • a product (P) containing 0.05% by weight of sulfur, 27% by weight of sulfur and non-sulfur aromatic compounds and a content of n- and iso-alkanes of 40% by weight is recovered via line 2.
  • This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 130 ppm by weight.
  • the cetane number of the product (P) is 57.
  • This product has a final distillation point of 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P1) is recovered by line 3 having an end point of distillation of 220 ° C.
  • a raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for recycling possible at the extraction zone and at the bottom a raffinate (Q1) containing practically no more furfural, having a sulfur content of 0.01% by weight, a cetane number of 69, a content by weight of aromatic sulfur compounds and non-sulfur of 10%, an n- and iso-alkane content of 50% by weight, a nitrogen content of 20 ppm and a Saybolt color of 30.
  • This raffinate is sent by line 9 to the diesel pool.
  • an extract (E1) is also recovered which is sent to a distillation zone followed by a steam stripping zone D2 in which the furfural which is recovered by the head is separated. line 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.15% by weight, a cetane number of 26, a content by weight of sulfur and non-sulfur aromatic compounds of 77% and a nitrogen content of 500 ppm.
  • This product Q2 can be sent via lines 11 and 11a to the domestic fuel pool.
  • the charge used in this example is the same as that used in Example 1.
  • This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.5 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 1 h ⁇ 1. The amount of hydrogen consumed is 0.4% by weight relative to the charge.
  • a product (P) containing 0.05% by weight of sulfur, 27% by weight of sulfur and non-sulfur aromatic compounds is recovered via line 2.
  • This product has a color measured by the ASTM D-1500 method less than 1 and a nitrogen content of 130 ppm by weight.
  • the cetane number of the product (P) is 57.
  • This product has a final distillation point of 400 ° C.
  • Product P is stripped with steam to remove the light fractions ( ⁇ 150 ° C) and the hydrogen sulfide formed in the hydrodesulfurization reactor (less than 2% of the initial charge).
  • a raffinate (R1) is obtained which is sent via line 6 to the distillation zone D1 in which the furfural which is recovered at the head is separated by line 8 for possible recycling to the extraction zone and at the tail, by line 9, a raffinate (Q1) containing practically no more furfural. At least part of this product (Q1) is mixed with at least part of the product (P1) stripped of its light fraction and one then obtains a fraction (F) having a sulfur content of 0.01% by weight, a cetane number of 62, a content by weight of sulfur and non-sulfur aromatic compounds of 15%, its content of n- and isoalkanes is 49% by weight, a nitrogen content of 30 ppm and a Saybolt color of 20.
  • This fraction 7 is mixed with the diesel pool.
  • an extract (E1) is also recovered which is sent to a distillation zone D2 in which the furfural which is recovered at the top is separated by line 10 for possible recycling at the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.25% by weight, a cetane number of 25, a content by weight of aromatic sulfur compounds and not 82% sulfur and a nitrogen content of 700 ppm.
  • This product Q2 can be treated as described above in Example 1.
  • the charge used in this example is the same as that used in Example 1. It is introduced via line 100 into a distillation zone from which a fraction (F1) having a point of recovery is recovered via line 110. initial boiling point of 150 ° C and a final boiling point of 300 ° C. This fraction is introduced via line 110 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 150 liters per liter of charge and the hourly space speed is 4 h ⁇ 1.
  • a product (P ′) containing 0.005% by weight of sulfur, 20% by weight of sulfur and non-sulfur aromatic compounds is recovered via line 120.
  • This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 20 ppm by weight.
  • the cetane number of the product (P ') is 57.
  • This product has a final distillation point of 300 ° C. It is sent to a stripping zone with water vapor (SEP2) from which a product (P10) is recovered by line 130 having an end point of distillation of 150 ° C. and by line 140 a product ( P20) having an initial distillation point of 150 ° C and a final distillation point of 300 ° C.
  • This product (P20) is sent by line 140 and line 149 to the engine fuel pool.
  • a fraction (F2) is recovered via line 1 having an initial boiling point of 300 ° C and a final boiling point of 400 ° C. Its aromatic hydrocarbon content is 37% by weight and its content of n- and iso-alkanes is 34% by weight.
  • This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 3.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 316C, the temperature is maintained at 350 ° C., the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 1h ⁇ 1. The amount of hydrogen consumed is 0.45% relative to the feed.
  • a product (P) containing 0.15% by weight of sulfur, 34% by weight of sulfur and non-sulfur aromatic compounds and a content of n and iso-alkanes of 35% is recovered via line 2.
  • This product has a color measured according to the ASTM D-1500 method less than 2 and a nitrogen content of 300 ppm by weight.
  • the cetane number of the product (P) is 56.
  • This product has a final distillation point of 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P1) is recovered by line 3 having an end point of distillation of 300 ° C. and by line 4 a product ( P2) having an initial distillation point of 300 ° C and a final distillation point of 400 ° C.
  • SEP1 stripping zone with water vapor
  • This product after having been cooled to 70 ° C., (P2) is sent to an extraction zone (EXT.) By line 4 into which is also introduced by line 5 an amount of furfural equal in volume to the amount of product (P2) introduced into this zone.
  • This zone is an extraction column comprising a packing formed by Pall rings of an efficiency substantially equivalent to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C.
  • a raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone D1 in which the furfural which is recovered at the head is separated by line 8 with a view to its possible recycling to zone d extraction and tail a raffinate (Q1) containing practically no more furfural, having a sulfur content of 0.04% by weight, a cetane number of 67, a content by weight of aromatic sulfur and non-sulfur compounds of 20 %, an n- and iso-alkane content of 48% by weight, a nitrogen content of 30 ppm and a Saybolt color of 20.
  • an extract (E1) is also recovered that the we send to a distillation zone D2 in which the furfural which is recovered at the head is separated at the head 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.5% by weight, a cetane number of 25, a e content by weight of aromatic sulfur and non-sulfur compounds of 80% and a nitrogen content of 1000 ppm.
  • the product (Q1) is sent via lines 9, 9b, and 149 to the engine fuel pool.
  • the mixture of P20 and Q1 is a product having a cetane number of 61, a content by weight of sulfur and non-sulfur aromatic compounds of 23%, a sulfur content of 0.02% by weight, a nitrogen content of 30 ppm and a Saybolt color of 25. This mixture can also be mixed, at least in part, with at least part of the product P1, once stripped.
  • a charge of direct distillation diesel fuel with an initial distillation point of 150 ° C. and a final distillation point of 400 ° C. containing 35% by weight of aromatics and sulfur compounds and 10% of di- and polyaromatics is treated according to the Example 1 under hydrotreatment conditions defined below.
  • Hydrogen partial pressure (MPa) Product P Aromatics + sulfur compounds% by weight
  • the feed used in this example is a mixture of direct distillation diesel cut and diesel cut resulting from catalytic cracking, LCO type.
  • the direct distillation diesel cut has a density at 15 ° C of 857, a refractive index at 60 ° C of 1.4617, a cetane index of 55, a total content of aromatic compounds, sulfur and non-sulfur, of 35 , 4% by weight, a content of n- and iso-alkanes and naphthenes of 64.6% by weight, a sulfur content of 1.33% by weight and a nitrogen content expressed by weight of nitrogen of 124 ppm.
  • the LCO diesel cut has a density at 15 ° C of 944.1, a refractive index at 60 ° C of 1.5245, a cetane index of 23, a total content of aromatic, sulfur and non-sulfur compounds of 67.4 % by weight, a content of n- and iso-alkanes and naphthenes of 32.6% by weight, a sulfur content of 3.13% by weight and a nitrogen content expressed by weight of nitrogen of 930 ppm.
  • load C1 the load containing 80% of direct distillation diesel cut and 20% of LCO cut
  • load C2 the load containing 50% of direct distillation diesel cut and 50% of LCO cut.
  • the sections C1 and C2 have an initial distillation point of 200 ° C and a final distillation point of 400 ° C.
  • the charge C1 is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 200 liters of charge and the hourly space speed is 2.5 h ⁇ 1. The amount of hydrogen consumed is 0.25% by weight relative to the charge.
  • a product (P ′) with a density at 15 ° C. of 862.2 and containing 0.051% of sulfur, 31% by weight of sulfur and non-sulfur aromatic compounds, 61% by weight of n- is recovered via line 2 and iso-alkanes and 285 ppm nitrogen.
  • the cetane number of the product (P ') is 53 and its final point of distillation is 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P'1) having a final distillation point of 230 ° C. is recovered via line 3, and through line 4 a product (P'2) having an initial distillation point of 230 ° C and a final distillation point of 400 ° C.
  • SEP1 stripping zone with water vapor
  • P'2 having an initial distillation point of 230 ° C and a final distillation point of 400 ° C.
  • This product (P'2) after cooling to 70 ° C, that is to say at the temperature of the extraction zone, is sent to an extraction zone (EXT.)
  • line 4 in which line 5 is also introduced with an amount of furfural equal in volume to the amount of product (P'2) introduced into this zone.
  • This zone is an extraction column comprising a packing formed of Pall rings with an overall efficiency substantially equal to three theoretical stages.
  • the extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C.
  • a raffinate is obtained (R'1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for possible recycling.
  • an extract (E'1) is also recovered which is sent to a distillation zone (D2) followed by a steam stripping zone in which the furfural which is separated at the head is separated.
  • an extract (Q'2) containing practically no more furfural having a sulfur content of 0.14% by weight, a content by weight of sulfur and non-sulfur aromatic compound of 87.2%, a nitrogen content of 800 ppm, a content of n- and iso-alkanes and naphthenes of 12.8% by weight and a density at 15 ° C. of 1002, 8.
  • the load C2 undergoes the same treatment as the load C1.
  • Line 2 is used to recover a product (P '') with a density at 15 ° C of 888.1 and containing 0.067% by weight of sulfur, 44.6% by weight of aromatic sulfur and non-sulfur compounds, 47, 4% by weight of n- and iso-alkanes and naphthenes and 527 ppm of nitrogen.
  • the cetane number of the product (P '') is 43 and its final point of distillation is 400 ° C.
  • the product (P''1) recovered by line 3 has a final distillation point of 230 ° C
  • the product (P''2) recovered by line 4 has an initial distillation point of 230 ° C and a 400 ° C final distillation point.
  • the raffinate (R''1) obtained after extraction is sent via line 6 to the steam stripping zone (D1) in the same way as the raffinate (R'1).
  • the raffinate (Q''1) obtained at the tail contains less than 5 ppm of furfural, for example, 0.02% by weight of sulfur, a cetane number of 66.1, 17% by weight of aromatic sulfur and non-sulfur compounds , 83% by weight of n- and isoalkanes and naphthenes, 150 ppm of nitrogen and a density at 15 ° C of 883.9.
  • the extract (E''1) obtained after extraction is sent to the distillation zone (D2) followed by steam stripping.
  • the extract (Q''2) obtained at the tail contains practically no more furfural, 0.12% by weight of sulfur, 87.9% by weight of sulfur and non-sulfur aromatic compounds, 900 ppm of nitrogen, 12, 1% by weight of n- and iso-alkanes and naphthenes, and a density at 15 ° C of 985.3.
  • the products Q'2 and Q''2 can be sent via lines 11 and 11b to a hydrodesulfurization zone (HDS3) distinct from that into which the initial charge has been introduced.
  • This hydrodesulfurization is carried out in the presence of the HR 306C catalyst, under partial hydrogen pressure of 2.5 MPa, at a temperature of 330 ° C. with a hydrogen recycling of 200 liters per liter of charge and an hourly space speed of 2 , 5 h ⁇ 1.
  • a product is obtained having a sulfur content of 0.2% by weight. Its other characteristics are practically unchanged.
  • This product can be mixed with domestic fuel, that is to say introduced into what those skilled in the art call the domestic fuel pool.

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Abstract

Petroleum product and process for obtaining the said petroleum product which can optionally be used for the formulation of an internal combustion engine fuel, including a stage a) of hydrotreatment in which a hydrocarbon feedstock is treated in hydrocarbon conditions under a partial pressure of hydrogen leaving the reactor of approximately 0.5 MPa to approximately 6 MPa, a stage b) of separation of the product (P) originating from stage a) into a product (P1) of initial boiling point lower than approximately 300 DEG C and a product (P2) of final boiling point higher than the final boiling point of product (P1), a stage c) of liquid/liquid extraction with the aid of a solvent (S1), in which an extract (E1) and a raffinate (R1) are obtained from the product (P2), a stage d) of recovery of the solvent (S1) from the raffinate (R1) making it possible to obtain a product (Q1) depleted in solvent (S1), having improved properties and containing less than 500 ppm by weight of sulphur. According to a particular embodiment the extract (E1) is distilled so as to obtain a tail product (Q2) which is subsequently conveyed into a hydrotreatment zone so as to obtain a product (P3) preferably containing less than 0.3 % by weight of sulphur. The solvent (S1) recovered at the head of the distillation is recycled to the extraction stage c). This solvent is chosen from the group consisting of dimethylformamide, dimethylacetamide, furfural, N-methylpyrrolidone and dimethyl sulphoxide.

Description

L'invention concerne un produit pétrolier et un procédé d'obtention dudit produit pétrolier pouvant éventuellement servir à la formulation d'un carburant pour moteur à combustion interne et le produit obtenu par le procédé. Les gazoles que l'on trouve actuellement sur le marché, soit sous forme de carburants pour moteurs à combustion interne, soit sous forme de combustible, sont le plus souvent des produits issus du raffinage qui contiennent du soufre en une quantité (exprimée en poids de soufre) d'environ 0,3 %. Ils sont habituellement obtenus à la suite d'un traitement d'hydrodésulfuration à partir d'une charge pouvant provenir de la distillation directe d'un pétrole brut ou d'un traitement particulier d'un pétrole brut (par exemple une pyrolyse ou une distillation suivie d'une pyrolyse de la fraction récupérée lors de la distillation, ou un craquage thermique ou catalytique) contenant généralement au moins 0,8 % en poids de soufre.The invention relates to a petroleum product and a process for obtaining said petroleum product which can optionally be used for the formulation of a fuel for an internal combustion engine and the product obtained by the process. The gas oils that are currently on the market, either in the form of fuels for internal combustion engines, or in the form of fuel, are most often products resulting from refining which contain sulfur in a quantity (expressed by weight of sulfur) of about 0.3%. They are usually obtained following a hydrodesulfurization treatment from a feed which can come from the direct distillation of a crude oil or from a specific treatment of a crude oil (for example a pyrolysis or a distillation followed by pyrolysis of the fraction recovered during distillation, or thermal or catalytic cracking) generally containing at least 0.8% by weight of sulfur.

L'art antérieur est illustré par le brevet US 5 059 303 qui décrit un procédé pour stabiliser des fractions hydrocarbonées (syncrude oils) très sensibles aux effets de la lumière, de la chaleur et de l'oxygène par exemple. Ces hydrocarbures sont généralement des huiles de schistes dont la principale caractéristique, qui les rend inacceptables en tant que charges de procédés de traitement conventionnels, est leur haute teneur en composés azotés, particulièrement basiques (teneur en azote comprise entre 1 et 3% au moins). Ces fractions hydrocarbonées particulières doivent donc être prétraitées avant leur utilisation, dans des conditions sévères d'hydrotraitement.The prior art is illustrated by US Pat. No. 5,059,303 which describes a process for stabilizing hydrocarbon fractions (syncrude oils) very sensitive to the effects of light, heat and oxygen for example. These hydrocarbons are generally shale oils, the main characteristic of which, which makes them unacceptable as fillers for conventional treatment processes, is their high content of particularly basic nitrogen compounds (nitrogen content of between 1 and 3% at least). . These particular hydrocarbon fractions must therefore be pretreated before their use, under severe hydrotreatment conditions.

Dans un certain nombre de pays industriels, des normes de teneur en soufre et de cétane sont en place ou vont être mises en place dans un très proche avenir. Ces normes sont de plus en plus sévères particulièrement pour les gazoles destinés à être employés comme carburant pour les moteurs. C'est ainsi qu'en France, en particulier dès 1995, la teneur en soufre de ces gazoles devra être au plus égale à 0,05 % en poids (500 ppm) alors que les gazoles conformes aux normes en vigueur ont une teneur en soufre pouvant atteindre 0,3 %.In a number of industrial countries, sulfur and cetane content standards are in place or will be implemented in the very near future. These standards are becoming more and more stringent, particularly for diesel oils intended to be used as fuel for engines. Thus in France, in particular from 1995, the sulfur content of these gas oils must be at most equal to 0.05% by weight (500 ppm) while gas oils which comply with the standards in force have a content of sulfur up to 0.3%.

De même les gazoles employés en France comme carburant pour les moteurs à combustion interne doivent actuellement avoir un indice de cétane au moins égal à 48 et les gazoles employés comme combustible un indice de cétane au moins égal à 40. On peut s'attendre dans un proche avenir à une sévérisation de ces normes et en particulier de celles concernant les gazoles utilisés comme carburant dans les moteurs.Likewise the gas oils used in France as fuel for internal combustion engines must currently have a cetane number at least equal to 48 and the gas oils used as fuel a cetane number at least equal to 40. We can expect in a near future to a tightening of these standards and in particular those concerning the diesel oils used as fuel in the engines.

Par ailleurs, étant donné la diversité des charges à traiter (bruts de différentes origines, de viscoréduction, de cokage, d'hydroconversion, de distillation ou de craquage catalytique) pour produire du gazole, il est souhaitable de pouvoir proposer au raffineur un procédé flexible, susceptible d'adapter les produits formés à la demande et de répondre aux futures spécifications aussi bien au niveau du soufre, de l'azote, de l'indice de cétane, de la couleur que de la teneur en aromatiques.In addition, given the diversity of the charges to be treated (crudes of different origins, visbreaking, coking, hydroconversion, distillation or catalytic cracking) to produce diesel, it is desirable to be able to offer the refiner a flexible process , capable of adapting the products formed to demand and of meeting future specifications in terms of sulfur, nitrogen, cetane number, color and aromatic content.

Enfin tous les procédés existants tels que l'hydrodésaromatisation ou l'hydrocraquage qui permettent d'obtenir des produits pétroliers à basse teneur en soufre et à indice de cétane relativement élevés consomment des quantités d'hydrogène importantes. Par exemple, le procédé d'hydrodésaromatisation d'une charge de distillation directe dont les intervalles de distillation (ASTM D86) sont 180°C < T 5% < 300°C, 260°C < T 50% < 350 , 350°C < T 95% < 460°C, consomme de 0,6 à 1,1 % d'hydrogène par rapport à la charge tandis que le procédé d'hydrocraquage nécessite plus de 2% d'hydrogène par rapport à sa charge. Or, la charge d'hydrogène de la raffinerie qui est généralement l'unité de reformage catalytique tendra à devenir insuffisante dans le contexte actuel de sévérisation des normes gazoles qui ont pour conséquence une augmentation des hydrotraitements.Finally, all existing processes such as hydrodesaromatization or hydrocracking which make it possible to obtain petroleum products with a low sulfur content and a relatively high cetane number consume significant quantities of hydrogen. For example, the hydrodearomatization process of a direct distillation charge whose distillation intervals (ASTM D86) are 180 ° C <T 5% <300 ° C, 260 ° C <T 50% <350, 350 ° C <T 95% <460 ° C, consumes 0.6 to 1.1% of hydrogen with respect to the feed while the hydrocracking process requires more than 2% of hydrogen with respect to its feed. However, the hydrogen charge of the refinery, which is generally the catalytic reforming unit, will tend to become insufficient in the current context of harsher diesel standards which result in an increase in hydrotreatments.

De plus, ces procédés existants conduisent à l'obtention d'un produit pétrolier dont l'indice de cétane ne dépasse pas 63, ce dernier n'étant atteint qu'au prix d'une hydrogénation des hydrocarbures aromatiques de la charge, réaction qui est consommatrice d'hydrogène. (voir tableau).In addition, these existing processes lead to the production of a petroleum product whose cetane number does not exceed 63, the latter being reached only at the cost of hydrogenation of the aromatic hydrocarbons in the feed, a reaction which consumes hydrogen. (See table).

Il est donc souhaitable de proposer au raffineur un procédé qui lui permette de produire un produit pétrolier répondant aux diverses normes qui entreront en application dans un avenir très proche et dès 1995, pour ce qui est de la teneur en soufre. Il est de même souhaitable de pouvoir produire un produit pétrolier ayant une odeur la moins prononcée possible.It is therefore desirable to propose to the refiner a process which allows him to produce a petroleum product meeting the various standards which will come into application in the very near future and from 1995, as far as is sulfur content. It is likewise desirable to be able to produce a petroleum product having the least pronounced odor possible.

La présente invention concerne donc un procédé de mise en oeuvre simple, consommant peu d'hydrogène. Ce procédé utilise les unités industrielles d'hydrotraitement (hydrodésulfuration notamment). Il permet d'améliorer les qualités du gazole produit et de respecter les futures normes et en particulier celle qui concerne la teneur en soufre. Le procédé de l'invention permet en outre, d'améliorer l'indice de cétane moteur du gazole, de réduire sa teneur en composés aromatiques ne contenant pas d'hétéroatome de soufre dans leur molécule, de réduire sa teneur en composés azotés, d'améliorer sa couleur et son odeur et enfin de diminuer la formation de particules solides lors de son utilisation dans un moteur à combustion interne. La présente invention propose une solution au problème spécifique d'obtention, en une quantité la plus importante possible par rapport au produit de départ, d'un produit pétrolier entrant dans la composition d'un gazole de qualité moteur ou gazole moteur à partir d'une coupe hydrocarbonée particulière ayant des caractéristiques qui la rende difficile à valoriser sous forme de gazole moteur.The present invention therefore relates to a simple implementation process, consuming little hydrogen. This process uses industrial hydrotreatment units (hydrodesulfurization in particular). It makes it possible to improve the qualities of the diesel fuel produced and to comply with future standards and in particular that concerning the sulfur content. The method of the invention also makes it possible to improve the cetane engine index of diesel, to reduce its content of aromatic compounds not containing sulfur heteroatom in their molecule, to reduce its content of nitrogenous compounds, d '' improve its color and odor and finally reduce the formation of solid particles when used in an internal combustion engine. The present invention provides a solution to the specific problem of obtaining, in as large a quantity as possible relative to the starting product, a petroleum product entering into the composition of an engine quality diesel or diesel engine from a particular hydrocarbon cut having characteristics which makes it difficult to recover in the form of engine diesel.

L'invention concerne, en outre, le procédé d'obtention d'un produit pétrolier entrant dans la composition d'un fuel domestique.The invention also relates to the process for obtaining a petroleum product used in the composition of a domestic fuel oil.

Plus particulièrement, l'invention concerne un procédé d'obtention d'une base entrant dans la composition d'un carburant pour moteur à combustion interne à allumage par compression présentant notamment un indice de cétane et une teneur en soufre améliorés, à partir d'une charge hydrocarbonée ayant un point initial d'ébullition d'au moins 150 °C et de point final d'ébullition d'au plus 500 °C, contenant environ 0,05 % à environ 5 % en poids de soufre, environ 10 à environ 60 % en poids de n- et isoalcanes, environ 10 % à environ 85 % en poids d'hydrocarbures aromatiques au moins en partie sous forme de composés polyaromatiques (soufrés ou non), ayant un indice de cétane d'environ 20 à environ 60 et ayant une teneur en azote d'environ 50 à environ 5 000 ppm (partie par million) en poids, ledit procédé étant caractérisé en ce qu'il comprend les étapes suivantes :

  • une étape a) d'hydrotraitement dans laquelle on effectue l'hydrotraitement de ladite charge dans des conditions permettant d'obtenir un produit (P) contenant une quantité de soufre de 2 à 50 fois moindre, et le plus souvent de 3 à 30 fois moindre que celle de la charge initiale, ledit hydrotraitement étant généralement effectué sous une pression partielle d'hydrogène en sortie de réacteur d'environ 0,5 MPa (mégapascal) à environ 6MPa, telle que le taux de désaromatisation de la charge est au plus égale à 30%.
  • une étape b) de séparation, par exemple par strippage ou par distillation, du produit (P) en un produit (P2) ayant un point d'ébullition initial supérieur à la température d'ébullition du solvant d'extraction de l'étape suivante c) et de préférence au moins supérieur de 20°C, et en un produit (P1) ayant un point d'ébullition final inférieur au point d'ébullition initial du produit P2,
  • une étape c) d'extraction liquide/liquide dans laquelle on met en contact, à une température d'extraction d'au plus 140°C, par exemple 0 - 80°C, dans des conditions d'extraction des composés polyaromatiques, le produit (P2) obtenu à l'étape b) avec un solvant ou un mélange de solvants (S1) permettant d'extraire au moins en partie les composés polyaromatiques qu'il contient, ledit solvant ou mélange de solvants ayant un point initial d'ébullition inférieur, et de préférence inférieur d'au moins 20 °C, au point initial d'ébullition du produit (P2) obtenu à l'étape b), et au cours de laquelle on récupère un extrait (E1) enrichi en composés polyaromatiques et un raffinat (R1) et,
  • une étape d) de récupération du solvant (S1) employé à l'étape c), par exemple par distillation ou par strippage, à partir du raffinat (R1) obtenu à l'étape c) dans laquelle on récupère un produit enrichi en solvant (S1) et un produit (Q1) appauvri en solvant (S1) ayant des qualités améliorées et contenant moins de 500 ppm en poids de soufre.
More particularly, the invention relates to a process for obtaining a base used in the composition of a fuel for an internal combustion engine with compression ignition having in particular an improved cetane number and a sulfur content, starting from a hydrocarbon feedstock having an initial boiling point of at least 150 ° C and an end boiling point of at most 500 ° C, containing from about 0.05% to about 5% by weight of sulfur, from about 10 to approximately 60% by weight of n- and isoalkanes, approximately 10% to approximately 85% by weight of aromatic hydrocarbons at least in part in the form of polyaromatic compounds (sulfur or not), having a cetane number of approximately 20 to approximately 60 and having a nitrogen content of about 50 to about 5,000 ppm (parts per million) by weight, said method being characterized in that it comprises the following steps:
  • a hydrotreatment stage a) in which the hydrotreatment of said feed is carried out under conditions making it possible to obtain a product (P) containing a quantity of sulfur from 2 to 50 times less, and most often from 3 to 30 times less than that of the initial charge, said hydrotreatment generally being carried out under a partial pressure of hydrogen at the outlet of the reactor of approximately 0.5 MPa (megapascal) to approximately 6MPa, such that the rate of dearomatization of the charge is at most equal to 30%.
  • a step b) of separation, for example by stripping or by distillation, of the product (P) into a product (P2) having an initial boiling point higher than the boiling point of the extraction solvent of the following step c) and preferably at least 20 ° C. higher, and in a product (P1) having a final boiling point lower than the initial boiling point of the product P2,
  • a step c) of liquid / liquid extraction in which is brought into contact, at an extraction temperature of at most 140 ° C., for example 0 - 80 ° C., under conditions of extraction of the polyaromatic compounds, the product (P2) obtained in step b) with a solvent or a mixture of solvents (S1) making it possible to extract at least partially the polyaromatic compounds which it contains, said solvent or mixture of solvents having an initial point of lower boiling, and preferably at least 20 ° C lower, than the initial boiling point of the product (P2) obtained in step b), and during which an extract (E1) enriched in polyaromatic compounds is recovered and a raffinate (R1) and,
  • a step d) of recovery of the solvent (S1) used in step c), for example by distillation or by stripping, from the raffinate (R1) obtained in step c) in which a product enriched in solvent is recovered (S1) and a product (Q1) depleted in solvent (S1) having improved qualities and containing less than 500 ppm by weight of sulfur.

Par souci de simplicité, on utilisera dans la suite de la description, le terme d'hydrodésulfuration (HDS) à la place d'hydrotraitement.For the sake of simplicity, the term hydrodesulfurization (HDS) will be used in the following description instead of hydrotreatment.

Par composés polyaromatiques, on entend des composés ayant au moins deux cycles aromatiques, soufrés ou non.By polyaromatic compounds is meant compounds having at least two aromatic rings, sulfur or not.

Les températures de points d'ébullition initial et final sont des points de coupe TBP.The initial and final boiling point temperatures are TBP cut points.

La charge hydrocarbonée que l'on traite selon le procédé de l'invention est le plus souvent dénommée coupe gazole et elle a, de préférence, un point d'ébullition initial d'environ 150 °C et un point d'ébullition final d'environ 400 °C, sa teneur en soufre est habituellement supérieure à 0,1 % et le plus souvent supérieure à 0,5 % en poids, sa teneur en n- et iso-alcanes est d'environ 30 à 45 % en poids, sa teneur en composés aromatiques est habituellement d'environ 15 % à environ 65 % en poids. Cette charge est le plus souvent un gazole de distillation directe, un gazole de pyrolyse ou un mélange des deux. Cette charge peut être avantageusement mélangée à une coupe L.C.O. (light cycle oil) provenant d'une unité de craquage catalytique et préférentiellement dans un rapport LCO/gazole de 1:4 à 1:1. La couleur de cette charge mesurée selon la méthode ASTM D 1500 est habituellement supérieure ou égale à 2. L'indice de cétane selon la norme ISO 5165 de cette charge est le plus souvent inférieur à environ 60 et il est par exemple d'environ 50 à environ 55. La teneur en azote de cette charge est très souvent d'environ 100 à environ 1000 ppm exprimée en poids d'azote par rapport au poids de la charge.The hydrocarbon feed which is treated according to the process of the invention is most often called a diesel cut and it preferably has an initial boiling point of approximately 150 ° C. and a final boiling point of approximately 400 ° C., its sulfur content is usually greater than 0.1% and most often greater than 0.5% by weight, its content of n- and iso-alkanes is approximately 30 to 45% by weight, its aromatic content is usually from about 15% to about 65% by weight. This feedstock is most often a direct distillation gas oil, a pyrolysis gas oil or a mixture of the two. This charge can advantageously be mixed with an L.C.O. (light cycle oil) from a catalytic cracking unit and preferably in an LCO / diesel ratio of 1: 4 to 1: 1. The color of this filler measured according to the ASTM D 1500 method is usually greater than or equal to 2. The cetane number according to ISO 5165 of this filler is most often less than around 60 and it is for example around 50 to about 55. The nitrogen content of this feed is very often about 100 to about 1000 ppm expressed by weight of nitrogen relative to the weight of the feed.

Le produit Q1 obtenu est un produit nouveau compte-tenu de l'ensemble de ses caractéristiques (point coupe, cétane, teneur en paraffine et teneur en soufre) particulièrement intéressant pour obtenir par formulation avec d'autres coupes gazoles des carburants de qualité.The product Q1 obtained is a new product taking into account all of its characteristics (cutting point, cetane, paraffin content and sulfur content) which is particularly advantageous for obtaining, by formulation with other diesel cuts, quality fuels.

Le produit (Q1) obtenu par le procédé de la présente invention a habituellement une teneur en azote exprimée en poids d'azote 2 fois moindre que celle de la charge initiale et souvent 4 à 5 fois moindre. Ce produit (Q1) a le plus souvent une couleur mesurée selon la norme ASTM 1500 inférieure à 1 et l'indice de cétane de ce produit est en général supérieur d'au moins 3 points et souvent d'au moins 5 points à l'indice de cétane de la charge initiale (par exemple de 3 à 14 points). Sa teneur en soufre par rapport à celle de la charge est habituellement inférieure ou égale à 5% en poids. Sa teneur en net iso-alcanes augmente en général d'au moins 4 points, avantageusement de 5 à 20 points et le plus souvent de 6 à 11 points, par rapport à celle de la charge. La teneur en composés aromatiques ne contenant pas d'atome de soufre dans leur molécule dans ce produit (Q1) est habituellement réduite d'au moins 10 % en poids par rapport à celle de la charge initiale et souvent d'au moins 30 % en poids. L'odeur de ce produit est moins forte que celle de la charge initiale.The product (Q1) obtained by the process of the present invention usually has a nitrogen content expressed by weight of nitrogen 2 times less than that of the initial charge and often 4 to 5 times less. This product (Q1) most often has a color measured according to ASTM 1500 standard less than 1 and the cetane number of this product is generally at least 3 points higher and often at least 5 points higher than the cetane number of the initial charge (for example from 3 to 14 points). Its sulfur content compared to that of load is usually less than or equal to 5% by weight. Its net iso-alkane content generally increases by at least 4 points, advantageously by 5 to 20 points and most often by 6 to 11 points, compared to that of the filler. The content of aromatic compounds containing no sulfur atom in their molecule in this product (Q1) is usually reduced by at least 10% by weight relative to that of the initial charge and often by at least 30% by weight. weight. The odor of this product is less strong than that of the initial charge.

L'invention concerne avantageusement un produit pétrolier caractérisé en ce que la coupe de distillation correspond à 95% poids distillés entre 320° C et 460° C, son indice de cétane est supérieur à 60, sa teneur en n- et iso-alcanes est au moins égale à 48 % poids, et sa teneur en soufre inférieure ou égale à 500 ppm (poids).The invention advantageously relates to a petroleum product characterized in that the distillation cut corresponds to 95% by weight distilled between 320 ° C and 460 ° C, its cetane number is greater than 60, its content of n- and iso-alkanes is at least equal to 48% by weight, and its sulfur content less than or equal to 500 ppm (weight).

Selon la présente invention, I'hydrodésulfuration est avantageusement effectuée dans une unité d'hydrodésulfuration sous des conditions douces permettant de désulfurer les molécules soufrées en hydrogénant le moins possible. Cette démarche n'est pas évidente pour l'homme du métier des années 1990 qui est plutôt conduit à la solution de sévériser les conditions d'un hydrotraitement pour simultanément diminuer la teneur en soufre et augmenter le cétane des charges. Dans ces conditions, la température est de 320 à 370°C, la vitesse spatiale horaire est de 1 à 5, la pression de 1 à 5 MPa et le rapport volumique H₂ sur charge de 50 à 350 Nm³/m³. Le taux de désaromatisation de la charge est alors au plus égal à 15% environ. On peut ainsi distinguer deux cas particulièrement avantageux de mise en oeuvre de cette hydrodésulfuration permettant d'obtenir une excellente charge pour l'étape d'extraction suivante.According to the present invention, the hydrodesulfurization is advantageously carried out in a hydrodesulfurization unit under mild conditions making it possible to desulfurize the sulfur molecules by hydrogenating as little as possible. This approach is not obvious to a person skilled in the art of the 1990s, who is rather led to the solution of severifying the conditions of a hydrotreatment in order to simultaneously decrease the sulfur content and increase the cetane of the charges. Under these conditions, the temperature is 320 to 370 ° C, the hourly space velocity is from 1 to 5, the pressure from 1 to 5 MPa and the volume ratio H₂ on load from 50 to 350 Nm³ / m³. The charge dearomatization rate is then at most equal to around 15%. We can thus distinguish two particularly advantageous cases of implementation of this hydrodesulfurization making it possible to obtain an excellent charge for the following extraction step.

Selon la première possibilité qui est préférée, on opère en présence d'un catalyseur sélectif de l'hydrodésulfuration des molécules soufrées par rapport à l'hydrogénation des aromatiques, adapté à limiter l'hydrogénation, par exemple l'un de ceux commercialisés par la société PROCATALYSE, sous une pression partielle d'hydrogène en sortie de réacteur d'hydrodésulfuration avantageusement comprise entre environ 1,0 MPa et environ 3,0 MPa et on récupère un produit (P) contenant une quantité de soufre de 2 à 30 fois moindre soit entre 0,1 et 0,3% poids en fonction de la charge, par exemple, et le plus souvent de 3 à 10 fois moindre que celle de la charge initiale. Le taux de désaromatisation de la charge est alors sensiblement inférieur à 10%. Les autres conditions de mise en oeuvre de cette étape d'hydrodésulfuration sont des conditions classiques d'une hydrodésulfuration qualifiée par les hommes de métier d'hydrodésulfuration simple et douce.According to the first possibility which is preferred, the operation is carried out in the presence of a selective catalyst for the hydrodesulfurization of the sulfur molecules with respect to the hydrogenation of aromatics, adapted to limit the hydrogenation, for example one of those marketed by the PROCATALYSE, under a partial pressure of hydrogen at the outlet of the hydrodesulfurization reactor advantageously between approximately 1.0 MPa and approximately 3.0 MPa and a product (P) containing an amount of sulfur from 2 to 30 times less, ie between 0.1 and 0.3% by weight depending on the charge, for example, and most often from 3 to 10 times less than that of the initial charge. The charge dearomatization rate is then significantly less than 10%. The other conditions for carrying out this hydrodesulfurization step are conventional conditions for hydrodesulfurization qualified by those skilled in the art of simple and gentle hydrodesulfurization.

Selon la deuxième possibilité, on opère en présence d'un catalyseur classique adapté à limiter l'hydrogénation, par exemple l'un de ceux commercialisés par la société PROCATALYSE, sous une pression partielle d'hydrogène en sortie de réacteur d'hydrodésulfuration avantageusement comprise entre environ 2 MPa et environ 5 MPa et on récupère un produit (P) contenant une quantité de soufre de 5 à 60 fois moindre, soit inférieure à 0,1% poids, par exemple entre 0,02 et 0,05%, et le plus souvent de 10 à 40 fois moindre que celle de la charge initiale. Par ailleurs, le taux de désaromatisation de la charge est au plus égal à 15% environ. Les autres conditions de mise en oeuvre de cette étape d'hydrodésulfuration sont des conditions classiques d'une hydrodésulfuration plus sévère. Cette hydrodésulfuration est effectuée en utilisant un volume de catalyseur plus important que dans le cas de l'hydrodésulfuration simple, par exemple un volume de catalyseur 2 fois plus important, ainsi qu'une pression d'hydrogène plus élevée, calculée pour effectuer une hydrodésulfuration plus poussée.According to the second possibility, the operation is carried out in the presence of a conventional catalyst adapted to limit the hydrogenation, for example one of those sold by the company PROCATALYSE, under a partial pressure of hydrogen at the outlet of the hydrodesulfurization reactor, advantageously included. between approximately 2 MPa and approximately 5 MPa and a product (P) containing a quantity of sulfur of 5 to 60 times less, ie less than 0.1% by weight, for example between 0.02 and 0.05%, is recovered, and most often 10 to 40 times less than that of the initial charge. Furthermore, the rate of dearomatization of the charge is at most equal to approximately 15%. The other conditions for carrying out this hydrodesulfurization step are conventional conditions for more severe hydrodesulfurization. This hydrodesulfurization is carried out using a larger volume of catalyst than in the case of simple hydrodesulfurization, for example a volume of catalyst 2 times greater, as well as a higher hydrogen pressure, calculated to carry out a more hydrodesulfurization. thrust.

Une description de plusieurs catalyseurs commerciaux d'hydrodésulfuration et des conditions industrielles de mise en oeuvre des hydrodésulfurations peut par exemple être trouvée dans le volume 1 du livre de P. WUITHIER, édité par les éditions TECHNIP sous le titre Le PÉTROLE, RAFFINAGE ET GÉNIE CHIMIQUE, pages 816 à 831. On peut choisir avantageusement par exemple un catalyseur contenant du molybdène et du cobalt, connu pour limiter l'hydrogénation.A description of several commercial hydrodesulfurization catalysts and of the industrial conditions for implementing hydrodesulfurization can for example be found in volume 1 of the book by P. WUITHIER, edited by TECHNIP editions under the title PETROLEUM, REFINING AND CHEMICAL ENGINEERING , pages 816 to 831. One can advantageously choose, for example, a catalyst containing molybdenum and cobalt, known to limit hydrogenation.

L'étape de séparation, bien connue de l'homme de l'art comprend en règle générale un strippage à la vapeur de l'effluent liquide total d'hydrotraitement, suivi ou non d'une étape de distillation complémentaire. Cette dernière étape est en général requise lorsqu'on veut envoyer à l'extraction une fraction P2 dont le point d'ébullition initial est supérieur à celui de l'effluent d'hydrotraitement une fois strippé. Les conditions opératoires sont en général : pression réduite inférieure à 1 bar, avantageusement 10 à 100 mbar, de préférence 20 à 50 mbar (1 bar = 10⁵Pa) et température comprise entre 80 et 250°C.The separation step, well known to those skilled in the art generally comprises a steam stripping of the total liquid hydrotreatment effluent, followed or not by an additional distillation step. This last step is generally required when you want to send to extracting a fraction P2 whose initial boiling point is higher than that of the hydrotreatment effluent once stripped. The operating conditions are generally: reduced pressure less than 1 bar, advantageously 10 to 100 mbar, preferably 20 to 50 mbar (1 bar = 10⁵Pa) and temperature between 80 and 250 ° C.

L'étape d'extraction liquide/liquide est une étape réalisée dans des conditions classiques. Cette extraction pourra par exemple être effectuée à contre-courant dans un dispositif classique par exemple une colonne à remplissage, à plateaux ou à agitation mécanique (R.D.C. : rotating disc contactor) ayant en général une efficacité de 3 à 20 étages théoriques et de préférence de 5 à 10 étages théoriques, à une température généralement comprise entre 0 °C et 140 °C, avantageusement entre 30 °C et 80 °C et sous une pression permettant d'opérer en phase liquide et donc comprise entre 0,1 et 1 MPa, de préférence entre 0,1 et 0,6 MPa. Le rapport en volume du solvant (S1) au volume du produit (P2), obtenu à l'étape b), est de préférence d'environ 0,2 : 1 à environ 5 : 1, avantageusement 0,5 : 1 à 2 : 1 et le plus souvent d'environ 1 : 1. Le solvant est de préférence choisi dans le groupe des solvants permettant d'extraire également au moins une partie des composés aromatiques, ne contenant pas d'atome de soufre dans leur molécule, présents dans le produit (P2) obtenu à l'étape b). Les conditions d'extraction sont de préférence choisies de manière à obtenir un raffinat (R1) contenant en poids au plus 90 % et de préférence au plus 70 % du poids total des composés aromatiques, ne contenant pas d'atome de soufre dans leur molécule, présents dans le produit (P2) obtenu à l'étape b). L'extrait (E1) dans ces conditions contiendra au moins 10 % et souvent au moins 30 % en poids du poids total des composés aromatiques, ne contenant pas d'atome de soufre dans leur molécule, présents dans le produit (P2) obtenu à l'étape b), ainsi que de préférence au moins 30 % et souvent au moins 50 % et fréquemment au moins 80 % en poids du poids total des composés soufrés, le plus souvent dibenzothiophéniques et naphtobenzothiophéniques contenus initialement dans le produit (P2). Le produit (Q1) ainsi obtenu contient habituellement de 2 à 10 fois moins de soufre que le produit (P2) issu de l'étape b) et le plus souvent de 4 à 10 fois moins .The liquid / liquid extraction step is a step carried out under conventional conditions. This extraction can for example be carried out against the current in a conventional device, for example a filling column, with trays or with mechanical agitation (RDC: rotating disc contactor) generally having an efficiency of 3 to 20 theoretical stages and preferably of 5 to 10 theoretical stages, at a temperature generally between 0 ° C and 140 ° C, advantageously between 30 ° C and 80 ° C and under a pressure allowing to operate in the liquid phase and therefore between 0.1 and 1 MPa , preferably between 0.1 and 0.6 MPa. The volume ratio of the solvent (S1) to the volume of the product (P2), obtained in step b), is preferably from approximately 0.2: 1 to approximately 5: 1, advantageously 0.5: 1 to 2 : 1 and most often about 1: 1. The solvent is preferably chosen from the group of solvents making it possible also to extract at least part of the aromatic compounds, not containing a sulfur atom in their molecule, present in the product (P2) obtained in step b). The extraction conditions are preferably chosen so as to obtain a raffinate (R1) containing by weight at most 90% and preferably at most 70% of the total weight of the aromatic compounds, not containing a sulfur atom in their molecule , present in the product (P2) obtained in step b). The extract (E1) under these conditions will contain at least 10% and often at least 30% by weight of the total weight of the aromatic compounds, not containing a sulfur atom in their molecule, present in the product (P2) obtained at step b), as well as preferably at least 30% and often at least 50% and frequently at least 80% by weight of the total weight of the sulfur-containing compounds, most often dibenzothiophenic and naphthobenzothiophenic initially contained in the product (P2). The product (Q1) thus obtained usually contains from 2 to 10 times less sulfur than the product (P2) from step b) and most often from 4 to 10 times less.

Le solvant d'extraction est le plus souvent un solvant unique, mais on peut également employer des mélanges de solvant. Ce solvant contient généralement moins de 20 % et souvent moins de 10 % en poids d'eau. Ce solvant peut être un solvant anhydre. Il est souvent choisi dans le groupe formé par le méthanol, I'acétonitrile, la monométhylformamide, la diméthylformamide, la diméthylacétamide, le furfural, la N-méthylpyrolidone et le diméthylsulfoxyde. On emploie très souvent un solvant ne contenant pas d'azote et le plus souvent un solvant non azoté oxygéné. Le solvant préféré est le furfural.The extraction solvent is most often a single solvent, but mixtures of solvent can also be used. This solvent generally contains less than 20% and often less than 10% by weight of water. This solvent can be an anhydrous solvent. It is often chosen from the group formed by methanol, acetonitrile, monomethylformamide, dimethylformamide, dimethylacetamide, furfural, N-methylpyrolidone and dimethylsulfoxide. Very often a solvent containing no nitrogen is used and most often an oxygenated non-nitrogenous solvent. The preferred solvent is furfural.

On peut également ajouter au solvant d'extraction au moins un cosolvant qui peut être, un alcool de 1 à 6 atomes de carbone, par exemple un alcool linéaire ou ramifié, ou le furfuryl alcool.It is also possible to add to the extraction solvent at least one cosolvent which may be, an alcohol of 1 to 6 carbon atoms, for example a linear or branched alcohol, or furfuryl alcohol.

Si la charge à traiter a un point d'ébullition final élevé et est particulièrement riche en composés azotés, surtout basiques, il peut être avantageux d'introduire avec le solvant d'extraction seul ou en mélange, une quantité mineure d'acides, notamment carboxyliques (moins de 1% poids par rapport au solvant par exemple). Parmi ceux-ci, on peut avantageusement citer les acides carboxyliques de 1 à 6 atomes de carbone et plus particulièrement, les acides ayant une température d'ébullition inférieure à 250°C, notamment l'acide formique, l'acide acétique, l'acide propionique, l'acide butanoïque, l'acide pentanoïque, l'acide maléïque, l'acide crotonique, l'acide isobutyrique, l'acide valérique, l'acide triméthylacétique, l'acide benzoïque, et l'acide 2-furoïque.If the feed to be treated has a high final boiling point and is particularly rich in nitrogen compounds, especially basic, it may be advantageous to introduce with the extraction solvent alone or in mixture, a minor amount of acids, in particular carboxylic (less than 1% by weight relative to the solvent for example). Among these, mention may advantageously be made of carboxylic acids of 1 to 6 carbon atoms and more particularly, acids having a boiling point below 250 ° C., in particular formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, maleic acid, crotonic acid, isobutyric acid, valeric acid, trimethylacetic acid, benzoic acid, and 2-furoic acid .

La récupération du solvant à partir du raffinat peut être faite par un strippage ou une distillation, de préférence par un strippage à la vapeur dont les conditions ont été décrites ci-avant.The solvent can be recovered from the raffinate by stripping or distillation, preferably by steam stripping, the conditions of which have been described above.

Le raffinat (R1) obtenu à l'étape c) est ensuite envoyé à l'étape d) par exemple dans une zone de strippage à la vapeur dans laquelle il est séparé dans des conditions permettant de récupérer une fraction de tête enrichie, et de préférence fortement enrichie, en solvant (S1) et un produit de queue (Q1) de préférence fortement appauvri en solvant (S1). Le plus souvent, les conditions de cette séparation sont choisies de manière à obtenir une fraction de tête contenant la quasi totalité du solvant, c'est-à-dire par exemple, plus de 95 % en poids de la quantité de solvant contenu dans le raffinat (R1) et introduit dans cette zone de strippage. On récupère ainsi, de préférence, au moins environ 99 % en poids de la quantité de solvant contenu dans le raffinat (R1).The raffinate (R1) obtained in step c) is then sent to step d) for example in a steam stripping zone in which it is separated under conditions making it possible to recover an enriched head fraction, and preferably highly enriched in solvent (S1) and a bottoms product (Q1) preferably highly depleted in solvent (S1). Most often, the conditions of this separation are chosen so as to obtain a overhead fraction containing almost all of the solvent, that is to say for example, more than 95% by weight of the amount of solvent contained in the raffinate (R1) and introduced into this stripping zone. There is thus preferably recovered at least about 99% by weight of the amount of solvent contained in the raffinate (R1).

De même dans une forme de réalisation particulière, l'extrait (E1) obtenu à l'étape c) est ensuite envoyé dans une zone de récupération du solvant (S1) employé à l'étape c) dans laquelle on récupère un produit enrichi en solvant (S1) et un produit (Q2) appauvri en solvant (S1). La séparation du solvant de l'extrait est réalisée en général par une distillation et/ou un strippage à la vapeur et de préférence par une distillation suivie d'un strippage à la vapeur dans des conditions énoncées ci-avant. Cet extrait est donc séparé dans des conditions permettant de récupérer une fraction de tête enrichie, et de préférence fortement enrichie, en solvant (S1) et un produit de queue (Q2) appauvri en solvant (S1). Le plus souvent les conditions de cette séparation sont choisies de manière à obtenir une fraction de tête contenant la quasi totalité du solvant c'est-à-dire par exemple plus de 95 % en poids de la quantité de solvant contenu dans l'extrait (E1) et introduit dans cette zone de séparation. On récupère ainsi de préférence au moins environ 99 % en poids de la quantité de solvant contenu dans l'extrait (E1).Similarly, in a particular embodiment, the extract (E1) obtained in step c) is then sent to a solvent recovery zone (S1) used in step c) in which a product enriched in is recovered. solvent (S1) and a product (Q2) depleted in solvent (S1). The separation of the solvent from the extract is generally carried out by distillation and / or steam stripping and preferably by distillation followed by steam stripping under the conditions set out above. This extract is therefore separated under conditions making it possible to recover a fraction of the head enriched, and preferably highly enriched, in solvent (S1) and a bottom product (Q2) depleted in solvent (S1). Most often the conditions of this separation are chosen so as to obtain a top fraction containing almost all of the solvent, that is to say for example more than 95% by weight of the amount of solvent contained in the extract ( E1) and introduced into this separation zone. At least about 99% by weight of the amount of solvent contained in the extract (E1) is thus preferably recovered.

Lorsqu'on opère dans l'étape a) dans des conditions d'hydrodésulfuration sensiblement plus sévères, c'est-à-dire en particulier en présence d'une très importante quantité de catalyseur, le produit (Q2) que l'on obtient par distillation de l'extrait (E1) aura une teneur en soufre le plus souvent inférieure ou égale à environ 0,3 % en poids. Ce produit (Q2) sera bien entendu non utilisable comme carburant pour les moteurs, puisqu'il contient le plus souvent une quantité de soufre supérieure à la future norme ; par contre on pourra vraisemblablement l'utiliser comme combustible.When operating in step a) under substantially more severe hydrodesulfurization conditions, that is to say in particular in the presence of a very large quantity of catalyst, the product (Q2) which is obtained by distillation of the extract (E1) will most often have a sulfur content of less than or equal to about 0.3% by weight. This product (Q2) will of course not be usable as fuel for the engines, since it most often contains a quantity of sulfur greater than the future standard; on the other hand, it can probably be used as fuel.

Dans une forme particulièrement avantageuse de réalisation de l'invention, le ou les produits de tête, obtenus par séparation du raffinat (R1) et éventuellement de l'extrait (E1), enrichis en solvant, sont recyclés à l'étape c) d'extraction liquide/liquide.In a particularly advantageous embodiment of the invention, the top product (s), obtained by separation of the raffinate (R1) and optionally of the extract (E1), enriched in solvent, are recycled in step c) d liquid / liquid extraction.

Selon une forme particulière de mise en oeuvre du procédé selon l'invention, au moins une partie du produit (Q2) obtenu à partir de l'extrait (E1) après séparation du solvant (S1) peut être envoyée dans une zone d'hydrodésulfuration distincte de la zone d'hydrodésulfuration de la charge initiale ou même être renvoyée dans la zone d'hydrodésulfuration de l'étape a). Dans cette zone, distincte de la zone d'hydrodésulfuration de l'étape a), la partie du produit (Q2) est soumise à une hydrodésulfuration dans des conditions permettant d'obtenir un produit (P3) ayant une teneur en soufre inférieure ou égale à 0,3 % en poids et de préférence inférieure ou égale à 0,2 % en poids.According to a particular form of implementation of the method according to the invention, at least part of the product (Q2) obtained from the extract (E1) after separation of the solvent (S1) can be sent to a hydrodesulfurization zone separate from the hydrodesulfurization zone of the initial charge or even be returned to the hydrodesulfurization zone of step a). In this zone, distinct from the hydrodesulfurization zone of step a), the part of the product (Q2) is subjected to hydrodesulfurization under conditions making it possible to obtain a product (P3) having a sulfur content less than or equal at 0.3% by weight and preferably less than or equal to 0.2% by weight.

Selon une variante du procédé selon la présente invention, la charge hydrocarbonée, ayant un point initial d'ébullition d'au moins 150 °C et un point final d'ébullition d'au plus 500 °C, est envoyée dans une zone de distillation dans laquelle on sépare en tête une fraction (F1) ayant un point final d'ébullition d'au moins 250 °C et en queue une fraction (F2) ayant un point initial d'ébullition d'au moins 250 °C. Selon la présente variante, la fraction (F2) est traitée selon le procédé décrit ci-devant pour la charge hydrocarbonée 150-500 °C étapes a) à d). La fraction (F1) est envoyée dans une zone d'hydrodésulfuration distincte de celle de l'étape a) dans laquelle elle est hydrodésulfurée dans des conditions classiques et par exemple dans les conditions simples décrites ci-devant, puis le produit (P') hydrodésulfuré obtenu est envoyé dans une zone de séparation, par exemple par strippage ou par distillation, du produit (P') en une fraction (P10) ayant un point d'ébullition final inférieur à 150 °C, et en une fraction (P20) ayant un point d'ébullition initial supérieur au point d'ébullition final de la fraction (P10). Ce produit (P20) peut, au moins en partie être mélangé au produit (Q1) obtenu à partir de la fraction (F2) pour former un produit (Q10) ayant les qualités requises comme carburant moteur. La fraction (P10) est essentiellement formée de composés résultant de réactions secondaires au cours de l'hydrodésulfuration. Cette fraction (P10) représente en général moins de 2 % en volume par rapport au volume total de la fraction (F1).According to a variant of the process according to the present invention, the hydrocarbon feedstock, having an initial boiling point of at least 150 ° C and a final boiling point of at most 500 ° C, is sent to a distillation zone in which a fraction (F1) having a final boiling point of at least 250 ° C is separated at the head and a fraction (F2) having an initial boiling point of at least 250 ° C at the bottom. According to the present variant, the fraction (F2) is treated according to the process described above for the hydrocarbon feed 150-500 ° C. steps a) to d). The fraction (F1) is sent to a hydrodesulfurization zone separate from that of step a) in which it is hydrodesulfurization under conventional conditions and for example under the simple conditions described above, then the product (P ') hydrodesulfurized obtained is sent to a separation zone, for example by stripping or by distillation, of the product (P ') in a fraction (P10) having a final boiling point below 150 ° C, and in a fraction (P20) having an initial boiling point higher than the final boiling point of the fraction (P10). This product (P20) can, at least in part, be mixed with the product (Q1) obtained from the fraction (F2) to form a product (Q10) having the qualities required as engine fuel. The fraction (P10) is essentially formed of compounds resulting from side reactions during hydrodesulfurization. This fraction (P10) generally represents less than 2% by volume relative to the total volume of the fraction (F1).

Les principaux avantages de l'invention sont les suivants : on obtient dans le raffinat (tableau) une teneur en n- et iso-alcanes plus élevée que selon les procédés d'hydrocraquage ou d'hydrodésaromatisation, un indice de cétane plus élevé, en dépit d'une teneur en hydrocarbures aromatiques supérieure à 10%. Par ailleurs, la consommation en hydrogène dans l'hydrotraitement est moindre. Elle peut être réduite par exemple à 0,15% poids par rapport à la charge, lorsque l'hydrogénation est limitée au maximum.

Figure imgb0001
Figure imgb0002
 The main advantages of the invention are as follows: in the raffinate (table) a higher content of n- and iso-alkanes is obtained than according to the hydrocracking or hydrodesaromatization processes, a cetane number higher, despite an aromatic hydrocarbon content greater than 10%. In addition, the consumption of hydrogen in hydrotreatment is lower. It can be reduced for example to 0.15% by weight with respect to the charge, when the hydrogenation is limited to the maximum.
Figure imgb0001
Figure imgb0002

La comparaison des profils de chromatogrammes des composés soufrés (détecteur spécifique de chromatographie en phase gazeuse : Sievers) montre que pour le schéma HDS et extraction (raffinat) les composés soufrés recueillis dans le raffinat sont sous forme essentiellement benzothiophénique, les composés dibenzothiophéniques et naphtobenzothiophéniques se retrouvant essentiellement dans l'extrait alors que pour les schémas conventionnels, que ce soit par hydrodésulfuration profonde ou hydrodésaromatisation les composés soufrés restant dans le produit pétrolier sont essentiellement sous forme dibenzothiophénique et naphtobenzothiophénique.The comparison of the chromatogram profiles of the sulfur compounds (specific gas chromatography detector: Sievers) shows that for the HDS and extraction scheme (raffinate) the sulfur compounds collected in the raffinate are in essentially benzothiophenic form, the dibenzothiophenic and naphthobenzothiophenic compounds are essentially found in the extract whereas for the conventional schemes, whether by deep hydrodesulfurization or hydrodesaromatization, the sulfur compounds remaining in the petroleum product are essentially in the dibenzothiophenic and naphthobenzothiophenic form.

Les figures 1 et 2 représentent schématiquement les principales variantes pour la mise en oeuvre du procédé selon la présente invention. Sur ces figures les organes similaires sont désignés par les mêmes chiffres et lettres de référence.Figures 1 and 2 schematically represent the main variants for the implementation of the method according to the present invention. In these figures, similar bodies are designated by the same numbers and reference letters.

Selon la figure 1 la charge hydrocarbonée à traiter est envoyée par la ligne (1) dans la zone d'hydrodésulfuration (HDS1) à la sortie de laquelle on récupère par la ligne 2 un produit (P) que l'on envoie dans une zone de séparation (SEP. 1) à partir de laquelle on récupère par la ligne 3 un produit (P1) et par la ligne 4 un produit (P2) dont le point initial d'ébullition est supérieur au point final d'ébullition du produit (P1). Ce produit (P2) est envoyé par la conduite 4 dans une zone d'extraction (EXT.) dans laquelle on introduit également un solvant (S1) d'extraction par la ligne 5 et à partir de laquelle on récupère un extrait (E1) par la ligne 7 et un raffinat (R1) par la ligne 6. Ce raffinat (R1) est envoyé par la ligne 6 dans une zone (D1) de récupération du solvant (S1) par la ligne 8 et d'un produit pétrolier (Q1) pouvant servir éventuellement de base dans la composition d'un gazole moteur de qualités améliorées, par la ligne 9. L'extrait (E1) est envoyé par la ligne 7 dans une zone (D2) de récupération du solvant (S1) par la ligne 10 et d'un produit (Q2) par la ligne 11. Ce produit (Q2) peut être, au moins en partie, récupéré par la ligne 11a lorsque la vanne V4 est ouverte, ou être, au moins en partie, envoyé par la ligne 11b lorsque la vanne V1 est ouverte soit dans une zone d'hydrodésulfuration (HDS3) non schématisée soit dans la zone d'hydrodésulfuration (HDS1). Lorsque ce produit (Q2) est récupéré par la ligne 11a il peut être valorisé comme combustible mais ne répondant pas aux futures normes sur les gazoles moteur il ne pourra pas être utilisé tel quel comme carburant.According to FIG. 1, the hydrocarbon feedstock to be treated is sent by line (1) to the hydrodesulfurization zone (HDS1) at the outlet of which recover by line 2 a product (P) which is sent to a separation zone (SEP. 1) from which we recover by line 3 a product (P1) and by line 4 a product (P2) whose initial boiling point is higher than the final boiling point of the product (P1). This product (P2) is sent via line 4 to an extraction zone (EXT.) Into which an extraction solvent (S1) is also introduced via line 5 and from which an extract (E1) is recovered. by line 7 and a raffinate (R1) by line 6. This raffinate (R1) is sent by line 6 to a zone (D1) for recovering the solvent (S1) by line 8 and a petroleum product ( Q1) possibly being used as a base in the composition of an engine diesel of improved qualities, by line 9. The extract (E1) is sent by line 7 to a zone (D2) for recovering the solvent (S1) by line 10 and a product (Q2) through line 11. This product (Q2) can be, at least in part, recovered by line 11a when the valve V4 is open, or be, at least in part, sent by line 11b when the valve V1 is open either in a hydrodesulfurization zone (HDS3) not shown diagrammatically or in the hydrodesulfurization zone (HDS1). When this product (Q2) is recovered by line 11a it can be valued as fuel but does not meet future standards on engine diesel fuel and cannot be used as such as fuel.

Selon la figure 2, la charge hydrocarbonée à traiter est envoyée par la ligne (100) dans une zone (TOP) à partir de laquelle on récupère une fraction (F2) lourde de point d'ébullition initial supérieur à environ 250 °C qui est traitée comme la charge hydrocarbonée selon la description ci-devant faite en liaison avec la figure 1. A partir de la zone (D1) le produit (Q1) peut être, au moins en partie récupéré par la ligne 9 et la ligne 9a lorsque la vanne V2 est ouverte, ou être, au moins en partie envoyé par la ligne 9b dans la ligne 140 lorsque la vanne V3 est ouverte. Lorsqu'il est récupéré par la ligne 9a ce produit pétrolier forme partiellement une base entrant dans la composition d'un gazole moteur de qualités améliorées. A partir de la zone (TOP) on récupère par la ligne 110 une fraction (F1) légère de point d'ébullition final supérieur à environ 250 °C. Cette fraction (F1) est envoyée par la ligne 110 dans une zone d'hydrodésulfuration (HDS2) à la sortie de laquelle on récupère par la ligne 120 un produit (P') hydrodésulfuré que l'on envoie dans une zone de séparation (SEP. 2) à partir de laquelle on récupère par la ligne 130 un produit (P10) et par la ligne 140 un produit (P20) dont le point initial d'ébullition est supérieur au point final d'ébullition du produit (P10). Ce produit (P20) est éventuellement mélangé au produit (Q1) arrivant par la conduite 9b. Ce mélange ou le produit (P20) forme d'une base entrant dans la composition d'un gazole moteur de qualités améliorées qui est récupéré par la ligne 149.According to FIG. 2, the hydrocarbon feedstock to be treated is sent by the line (100) to a zone (TOP) from which a heavy fraction (F2) of initial boiling point greater than about 250 ° C. is recovered which is treated as the hydrocarbon feedstock according to the description above made in connection with FIG. 1. From zone (D1) the product (Q1) can be, at least partly recovered by line 9 and line 9a when the valve V2 is open, or be, at least in part sent by line 9b in line 140 when the valve V3 is open. When it is recovered by line 9a, this petroleum product partially forms a base used in the composition of an engine diesel of improved qualities. From zone (TOP), a light fraction (F1) of final boiling point greater than about 250 ° C. is recovered via line 110. This fraction (F1) is sent by line 110 to a hydrodesulfurization zone (HDS2) at the outlet of which a hydrodesulfurized product (P ') is recovered by line 120 which is sent to a separation zone (SEP 2) from which we recover by line 130 a product (P10) and by line 140 a product (P20) whose initial boiling point is higher than the final boiling point of the product (P10). This product (P20) is optionally mixed with the product (Q1) arriving via line 9b. This mixture or the product (P20) forms a base used in the composition of a diesel engine of improved qualities which is recovered by line 149.

Les exemples suivants illustrent l'invention sans en limiter la portée.The following examples illustrate the invention without limiting its scope.

EXEMPLE 1EXAMPLE 1

La charge utilisée dans cet exemple est une coupe gazole de distillation directe (straight-run) ayant un indice de cétane de 55, une teneur totale en composés aromatiques, soufrés et non soufrés, de 30 % en poids, une teneur en n et iso-alcanes de 39% en poids, une teneur en naphtènes de 31%, une teneur en soufre de 1,22 % en poids, une teneur en azote exprimée en poids d'azote de 255 ppm et une couleur mesurée selon la norme ASTM D 1500 égale à 2. Cette coupe gazole a un point initial de distillation de 150 °C et un point final de distillation de 400 °C.The feed used in this example is a straight-run diesel cut having a cetane number of 55, a total content of aromatic compounds, sulfur and non-sulfur, of 30% by weight, a content of n and iso -alkanes of 39% by weight, a naphthenes content of 31%, a sulfur content of 1.22% by weight, a nitrogen content expressed by weight of nitrogen of 255 ppm and a color measured according to the ASTM D standard 1500 equal to 2. This diesel cut has an initial distillation point of 150 ° C and a final distillation point of 400 ° C.

Cette charge est introduite par la conduite 1 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 2,0 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 306C, la température est maintenue à 330 °C, la quantité d'hydrogène introduit est égale à 200 litres par litre de charge et la vitesse spatiale horaire est de 2,5 h⁻¹. La quantité d'hydrogène consommé est de 0,25% poids par rapport à la charge.This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C., the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 2, 5 h⁻¹. The amount of hydrogen consumed is 0.25% by weight relative to the charge.

On récupère par la ligne 2 un produit (P) contenant 0,2 % en poids de soufre, 28 % en poids de composés aromatiques soufrés et non soufrés et une teneur en n- et iso-alcanes de 40%. Ce produit a une couleur mesurée selon la méthode ASTM D-1500 inférieure à 1 et une teneur en azote de 175 ppm en poids. L'indice de cétane du produit (P) est de 56. Ce produit a un point final de distillation de 400 °C. Il est envoyé dans une zone de strippage à la vapeur d'eau (SEP1) à partir de laquelle on récupère par la ligne 3 un produit (P1) ayant un point final de distillation de 220 °C et par la ligne 4 un produit (P2) ayant un point initial de distillation de 220 °C et un point final de distillation de 400 °C. Ce produit (P2) après avoir refroidi à 70°C, c'est-à-dirc à la température de la zone d'extraction, est envoyé dans une zone d'extraction (EXT.) par la ligne 4 dans laquelle on introduit également par la ligne 5 une quantité de furfural égale en volume à la quantité de produit (P2) introduite dans cette zone. Cette zone est une colonne d'extraction comportant un garnissage formé d'anneaux de Pall d'une efficacité globale sensiblement égale à trois étages théoriques. L'extraction s'effectue à contre-courant, sous pression atmosphérique et à la température de 70 °C. On obtient un raffinat (R1) que l'on envoie par la conduite 6 dans la zone de strippage à la vapeur (D1) dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 8 en vue de son recyclage éventuel à la zone d'extraction et en queue un raffinat (Q1) contenant moins de 5 ppm de furfural par exemple, ayant une teneur en soufre de 0,04 % en poids, un indice de cétane de 67, une teneur en poids de composés aromatiques soufrés et non soufrés de 12 %, une teneur en n- et iso-alcanes de 49%, une teneur en azote de 40 ppm et une couleur Saybolt de 30 et qui peut être introduit dans le réservoir (pool) gazole. A partir de cette zone d'extraction on récupère également un extrait (E1) que l'on envoie dans une zone de distillation (D2) suivie d'une zone de strippage à la vapeur dans lesquelles on sépare en tête le furfural qui est récupéré par la conduite 10 en vue de son recyclage éventuel à la zone d'extraction et en queue un extrait (Q2) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,6 % en poids, un indice de cétane de 25, une teneur en poids de composés aromatiques soufrés et non soufrés de 77 % et une teneur en azote de 500 ppm.A product (P) containing 0.2% by weight of sulfur, 28% by weight of sulfur and non-sulfur aromatic compounds and a content of n- and iso-alkanes of 40% is recovered via line 2. This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 175 ppm by weight. The cetane number of the product (P) is 56. This product has a final distillation point of 400 ° C. It is sent to a steam stripping zone of water (SEP1) from which a product (P1) having a final distillation point of 220 ° C is recovered via line 3 and a product (P2) having an initial distillation point of 220 ° via line 4 C and a final distillation point of 400 ° C. This product (P2) after cooling to 70 ° C, that is to say at the temperature of the extraction zone, is sent to an extraction zone (EXT.) By line 4 into which we introduce also by line 5 an amount of furfural equal in volume to the amount of product (P2) introduced into this zone. This zone is an extraction column comprising a packing formed by Pall rings with an overall efficiency substantially equal to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C. A raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for possible recycling at extraction zone and at the bottom a raffinate (Q1) containing less than 5 ppm of furfural for example, having a sulfur content of 0.04% by weight, a cetane number of 67, a content by weight of sulfur-containing aromatic compounds and non-sulfur of 12%, an n- and iso-alkane content of 49%, a nitrogen content of 40 ppm and a Saybolt color of 30 and which can be introduced into the diesel tank (pool). From this extraction zone, an extract (E1) is also recovered which is sent to a distillation zone (D2) followed by a steam stripping zone in which the furfural which is recovered is separated at the head. via line 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.6% by weight, a cetane number of 25 , a content by weight of sulfur and non-sulfur aromatic compounds of 77% and a nitrogen content of 500 ppm.

Ce produit Q2 peut être envoyé par les conduites 11 et 11b dans une zone (HDS3) d'hydrodésulfuration distincte de celle dans laquelle on a introduit la charge initiale. Cette hydrodésulfuration est effectuée en présence du catalyseur HR 306C, sous une pression partielle d'hydrogène de 2,5 MPa, à une température de 330 °C avec un recyclage d'hydrogène de 200 litres par litre de charge et une vitesse spatiale horaire de 2,5 h⁻¹. A la sortie de cette hydrodésulfuration on obtient un produit ayant une teneur en soufre de 0,2 % en poids. Ses autres caractéristiques sont pratiquement inchangées. Ce produit peut être mélangé au fuel domestique, c'est à dire introduit dans ce que les hommes du métier appellent le pool fuel domestique.This product Q2 can be sent via lines 11 and 11b to a hydrodesulfurization zone (HDS3) distinct from that into which the initial charge has been introduced. This hydrodesulfurization is carried out in the presence of the HR 306C catalyst, under a partial hydrogen pressure of 2.5 MPa, at a temperature of 330 ° C. with a hydrogen recycling of 200 liters per liter of charge and an hourly space velocity of 2.5 h⁻¹. At the outlet of this hydrodesulfurization, a product is obtained having a sulfur content of 0.2% by weight. Its other characteristics are practically unchanged. This product can be mixed with domestic fuel, that is to say introduced into what those skilled in the art call the domestic fuel pool.

EXEMPLE 2EXAMPLE 2

La charge utilisée dans cet exemple est la même que celle utilisée dans l'exemple 1.The charge used in this example is the same as that used in Example 1.

Cette charge est introduite par la conduite 1 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 2,5 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 306C, la température est maintenue à 330 °C, la quantité d'hydrogène est égale à 200 litres par litre de charge et la vitesse spatiale horaire est de 1 h⁻¹. La quantité d'hydrogène consommé est de 0,4% poids par rapport à la charge.This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.5 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen is equal to 200 liters per liter of charge and the hourly space speed is 1 h⁻ ¹. The amount of hydrogen consumed is 0.4% by weight relative to the charge.

On récupère par la ligne 2 un produit (P) contenant 0,05 % en poids de soufre, 27 % en poids de composés aromatiques soufrés et non soufrés et une teneur en n- et iso-alcanes de 40% en poids. Ce produit a une couleur mesurée selon la méthode ASTM D-1500 inférieure à 1 et une teneur en azote de 130 ppm en poids. L'indice de cétane du produit (P) est de 57. Ce produit a un point final de distillation de 400 °C. Il est envoyé dans une zone de strippage à la vapeur d'eau (SEP1) à partir de laquelle on récupère par la ligne 3 un produit (P1) ayant un point final de distillation de 220 °C et par la ligne 4 un produit (P2) ayant un point initial de distillation de 220 °C et un point final de distillation de 400 °C. Ce produit (P2) après avoir été refroidi à 70°C, est envoyé dans une zone d'extraction (EXT.) par la ligne 4 dans laquelle on introduit également par la ligne 5 une quantité de furfural égale en volume à la quantité de produit (P2), introduite dans cette zone. Cette zone est une colonne d'extraction comportant un garnissage formé d'anneaux de Pall d'une efficacité sensiblement équivalente à trois étages théoriques. L'extraction s'effectue à contre-courant, sous pression atmosphérique et à la température de 70 °C. On obtient un raffinat (R1) que l'on envoie par la conduite 6 dans la zone de strippage à la vapeur (D1) dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 8 en vue de son recyclage éventuel à la zone d'extraction et en queue un raffinat (Q1) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,01 % en poids, un indice de cétane de 69, une teneur en poids de composés aromatiques soufrés et non soufrés de 10 %, une teneur en n- et iso-alcanes de 50% en poids, une teneur en azote de 20 ppm et une couleur Saybolt de 30. Ce raffinat est envoyé par la ligne 9 vers le pool gazole. A partir de cette zone d'extraction on récupère également un extrait (E1) que l'on envoie dans une zone de distillation suivie d'une zone de strippage à la vapeur D2 dans lesquelles on sépare en tête le furfural qui est récupéré par la conduite 10 en vue de son recyclage éventuel à la zone d'extraction et en queue un extrait (Q2) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,15 % en poids, un indice de cétane de 26, une teneur en poids de composés aromatiques soufrés et non soufrés de 77 % et une teneur en azote de 500 ppm.A product (P) containing 0.05% by weight of sulfur, 27% by weight of sulfur and non-sulfur aromatic compounds and a content of n- and iso-alkanes of 40% by weight is recovered via line 2. This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 130 ppm by weight. The cetane number of the product (P) is 57. This product has a final distillation point of 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P1) is recovered by line 3 having an end point of distillation of 220 ° C. and by line 4 a product ( P2) having an initial distillation point of 220 ° C and a final distillation point of 400 ° C. This product (P2) after having been cooled to 70 ° C., is sent to an extraction zone (EXT.) By line 4 into which is also introduced by line 5 an amount of furfural equal in volume to the amount of product (P2), introduced in this area. This zone is an extraction column comprising a packing formed by Pall rings of an efficiency substantially equivalent to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C. A raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for recycling possible at the extraction zone and at the bottom a raffinate (Q1) containing practically no more furfural, having a sulfur content of 0.01% by weight, a cetane number of 69, a content by weight of aromatic sulfur compounds and non-sulfur of 10%, an n- and iso-alkane content of 50% by weight, a nitrogen content of 20 ppm and a Saybolt color of 30. This raffinate is sent by line 9 to the diesel pool. From this extraction zone, an extract (E1) is also recovered which is sent to a distillation zone followed by a steam stripping zone D2 in which the furfural which is recovered by the head is separated. line 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.15% by weight, a cetane number of 26, a content by weight of sulfur and non-sulfur aromatic compounds of 77% and a nitrogen content of 500 ppm.

Ce produit Q2 peut être envoyé par les conduites 11 et 11a au pool fuel domestique.This product Q2 can be sent via lines 11 and 11a to the domestic fuel pool.

EXEMPLE 3EXAMPLE 3

La charge utilisée dans cet exemple est la même que celle utilisée dans l'exemple 1.The charge used in this example is the same as that used in Example 1.

Cette charge est introduite par la conduite 1 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 2,5 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 306C, la température est maintenue à 330 °C, la quantité d'hydrogène introduit est égale à 200 litres par litre de charge et la vitesse spatiale horaire est de 1 h⁻¹. La quantité d'hydrogène consommé est de 0,4% poids par rapport à la charge.This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.5 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 1 h ⁻¹. The amount of hydrogen consumed is 0.4% by weight relative to the charge.

On récupère par la ligne 2 un produit (P) contenant 0,05 % en poids de soufre, 27 % en poids de composés aromatiques soufrés et non soufrés. Ce produit a une couleur mesurée selon la méthode ASTM D-1500 inférieure à 1 et une teneur en azote de 130 ppm en poids. L'indice de cétane du produit (P) est de 57. Ce produit a un point final de distillation de 400 °C. Le produit P est strippé à la vapeur d'eau pour éliminer les fractions légères (< 150°C) et l'hydrogène sulfuré formés dans le réacteur d'hydrodésulfuration (moins de 2% de la charge initiale). Il est envoyé ensuite dans une zone de distillation à partir de laquelle on récupère par la ligne 3 un produit (P1) ayant un point final de distillation de 300 °C et par la ligne 4 un produit (P2) ayant un point initial de distillation de 300 °C. Le produit (P2) après avoir été refroidi à 70°C, est envoyé dans une zone d'extraction (EXT.) par la ligne 4 dans laquelle on introduit également par la ligne 5 une quantité de furfural égale en volume à la quantité de produit (P2) introduite dans cette zone. Cette zone est une colonne d'extraction comportant un garnissage formé d'anneaux de Pall d'une efficacité sensiblement équivalente à trois étages théoriques. L'extraction s'effectue à contre-courant, sous pression atmosphérique et à la température de 70 °C. On obtient un raffinat (R1) que l'on envoie par la conduite 6 dans la zone de distillation D1 dans laquelle on sépare en tête le furfural qui est récupérée par la conduite 8 en vue de son recyclage éventuel à la zone d'extraction et en queue, par la ligne 9, un raffinat (Q1) ne contenant pratiquement plus de furfural. Une partie au moins de ce produit (Q1) est mélangé à une partie au moins du produit (P1) débarrassé de sa fraction légère et on obtient alors une fraction (F) ayant une teneur en soufre de 0,01% en poids, un indice de cétane de 62, une teneur en poids de composés aromatiques soufrés et non soufrés de 15 %, sa teneur en n- et isoalcanes est 49 % en poids, une teneur en azote de 30 ppm et une couleur Saybolt de 20. Cette fraction 7 est mélangée au pool gazole. A partir de cette zone d'extraction, on récupère également un extrait (E1) que l'on envoie dans une zone de distillation D2 dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 10 en vue de son recyclage éventuel à la zone d'extraction et en queue un extrait (Q2) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,25 % en poids, un indice de cétane de 25, une teneur en poids de composés aromatiques soufrés et non soufrés de 82 % et une teneur en azote de 700 ppm.A product (P) containing 0.05% by weight of sulfur, 27% by weight of sulfur and non-sulfur aromatic compounds is recovered via line 2. This product has a color measured by the ASTM D-1500 method less than 1 and a nitrogen content of 130 ppm by weight. The cetane number of the product (P) is 57. This product has a final distillation point of 400 ° C. Product P is stripped with steam to remove the light fractions (<150 ° C) and the hydrogen sulfide formed in the hydrodesulfurization reactor (less than 2% of the initial charge). It is then sent to a distillation zone from which a product (P1) having a final distillation point of 300 ° C is recovered via line 3 and a product (P2) having an initial distillation point through line 4 300 ° C. The product (P2) after having been cooled to 70 ° C., is sent to an extraction zone (EXT.) By line 4 into which is also introduced by line 5 an amount of furfural equal in volume to the amount of product (P2) introduced into this area. This zone is an extraction column comprising a packing formed by Pall rings of an efficiency substantially equivalent to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C. A raffinate (R1) is obtained which is sent via line 6 to the distillation zone D1 in which the furfural which is recovered at the head is separated by line 8 for possible recycling to the extraction zone and at the tail, by line 9, a raffinate (Q1) containing practically no more furfural. At least part of this product (Q1) is mixed with at least part of the product (P1) stripped of its light fraction and one then obtains a fraction (F) having a sulfur content of 0.01% by weight, a cetane number of 62, a content by weight of sulfur and non-sulfur aromatic compounds of 15%, its content of n- and isoalkanes is 49% by weight, a nitrogen content of 30 ppm and a Saybolt color of 20. This fraction 7 is mixed with the diesel pool. From this extraction zone, an extract (E1) is also recovered which is sent to a distillation zone D2 in which the furfural which is recovered at the top is separated by line 10 for possible recycling at the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.25% by weight, a cetane number of 25, a content by weight of aromatic sulfur compounds and not 82% sulfur and a nitrogen content of 700 ppm.

Ce produit Q2 peut être traité comme décrit ci-devant dans l'exemple 1.This product Q2 can be treated as described above in Example 1.

EXEMPLE 4EXAMPLE 4

La charge utilisée dans cet exemple est la même que celle utilisée dans l'exemple 1. Elle est introduite par la ligne 100 dans une zone de distillation à partir de laquelle on récupère par la ligne 110 une fraction (F1) ayant un point d'ébullition initial de 150 °C et un point d'ébullition final de 300 °C. Cette fraction est introduite par la conduite 110 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 2,0 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 306C, la température est maintenue à 330 °C, la quantité d'hydrogène introduit est égale à 150 litres par litre de charge et la vitesse spatiale horaire est de 4 h⁻¹. La quantité d'hydrogène consommé est de 0,05% poids par rapport à la charge. On récupère par la ligne 120 un produit (P') contenant 0,005 % en poids de soufre, 20 % en poids de composés aromatiques soufrés et non soufrés. Ce produit a une couleur mesurée selon la méthode ASTM D-1500 inférieure à 1 et une teneur en azote de 20 ppm en poids. L'indice de cétane du produit (P') est de 57. Ce produit a un point final de distillation de 300 °C. Il est envoyé dans une zone de strippage à la vapeur d'eau (SEP2) à partir de laquelle on récupère par la ligne 130 un produit (P10) ayant un point final de distillation de 150 °C et par la ligne 140 un produit (P20) ayant un point initial de distillation de 150 °C et un point final de distillation de 300 °C. Ce produit (P20) est envoyé par la ligne 140 et la ligne 149 au pool carburant moteur.The charge used in this example is the same as that used in Example 1. It is introduced via line 100 into a distillation zone from which a fraction (F1) having a point of recovery is recovered via line 110. initial boiling point of 150 ° C and a final boiling point of 300 ° C. This fraction is introduced via line 110 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 150 liters per liter of charge and the hourly space speed is 4 h ⁻¹. The amount of hydrogen consumed is 0.05% by weight relative to the charge. A product (P ′) containing 0.005% by weight of sulfur, 20% by weight of sulfur and non-sulfur aromatic compounds is recovered via line 120. This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 20 ppm by weight. The cetane number of the product (P ') is 57. This product has a final distillation point of 300 ° C. It is sent to a stripping zone with water vapor (SEP2) from which a product (P10) is recovered by line 130 having an end point of distillation of 150 ° C. and by line 140 a product ( P20) having an initial distillation point of 150 ° C and a final distillation point of 300 ° C. This product (P20) is sent by line 140 and line 149 to the engine fuel pool.

A partir de la zone de distillation (TOP) on récupère par la ligne 1 une fraction (F2) ayant un point d'ébullition initial de 300 °C et un point d'ébullition final de 400 °C. Sa teneur en hydrocarbures aromatiques est de 37% en poids et sa teneur en n- et iso-alcanes est de 34% en poids. Cette charge est introduite par la conduite 1 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 3,0 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 316C, la température est maintenue à 350 °C, la quantité d'hydrogène introduit est égale à 200 litres par litre de charge et la vitesse spatiale horaire est de 1h⁻¹. La quantité d'hydrogène consommé est de 0,45 % par rapport à la charge.From the distillation zone (TOP), a fraction (F2) is recovered via line 1 having an initial boiling point of 300 ° C and a final boiling point of 400 ° C. Its aromatic hydrocarbon content is 37% by weight and its content of n- and iso-alkanes is 34% by weight. This charge is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 3.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 316C, the temperature is maintained at 350 ° C., the quantity of hydrogen introduced is equal to 200 liters per liter of charge and the hourly space speed is 1h⁻¹. The amount of hydrogen consumed is 0.45% relative to the feed.

On récupère par la ligne 2 un produit (P) contenant 0,15 % en poids de soufre, 34 % en poids de composés aromatiques soufrés et non soufrés et une teneur en n et iso-alcanes de 35%. Ce produit a une couleur mesurée selon la méthode ASTM D-1500 inférieure à 2 et une teneur en azote de 300 ppm en poids. L'indice de cétane du produit (P) est de 56. Ce produit a un point final de distillation de 400 °C. Il est envoyé dans une zone de strippage à la vapeur d'eau (SEP1) à partir de laquelle on récupère par la ligne 3 un produit (P1) ayant un point final de distillation de 300 °C et par la ligne 4 un produit (P2) ayant un point initial de distillation de 300 °C et un point final de distillation de 400 °C. Ce produit, après avoir été refroidi à 70°C, (P2) est envoyé dans une zone d'extraction (EXT.) par la ligne 4 dans laquelle on introduit également par la ligne 5 une quantité de furfural égale en volume à la quantité de produit (P2) introduite dans cette zone. Cette zone est une colonne d'extraction comportant un garnissage formé d'anneaux de Pall d'une efficacité sensiblement équivalente à trois étages théoriques. L'extraction s'effectue à contre-courant, sous pression atmosphérique et à la température de 70 °C. On obtient un raffinat (R1) que l'on envoie par la conduite 6 dans la zone de strippage à la vapeur D1 dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 8 en vue de son recyclage éventuel à la zone d'extraction et en queue un raffinat (Q1) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,04 % en poids, un indice de cétane de 67, une teneur en poids de composés aromatiques soufrés et non soufrés de 20 %, une teneur en n- et iso-alcanes de 48 % en poids, une teneur en azote de 30 ppm et une couleur Saybolt de 20. A partir de cette zone d'extraction on récupère également un extrait (E1) que l'on envoie dans une zone de distillation D2 dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 10 en vue de son recyclage éventuel à la zone d'extraction et en queue un extrait (Q2) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,5 % en poids, un indice de cétane de 25, une teneur en poids de composés aromatiques soufrés et non soufrés de 80 % et une teneur en azote de 1 000 ppm.A product (P) containing 0.15% by weight of sulfur, 34% by weight of sulfur and non-sulfur aromatic compounds and a content of n and iso-alkanes of 35% is recovered via line 2. This product has a color measured according to the ASTM D-1500 method less than 2 and a nitrogen content of 300 ppm by weight. The cetane number of the product (P) is 56. This product has a final distillation point of 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P1) is recovered by line 3 having an end point of distillation of 300 ° C. and by line 4 a product ( P2) having an initial distillation point of 300 ° C and a final distillation point of 400 ° C. This product, after having been cooled to 70 ° C., (P2) is sent to an extraction zone (EXT.) By line 4 into which is also introduced by line 5 an amount of furfural equal in volume to the amount of product (P2) introduced into this zone. This zone is an extraction column comprising a packing formed by Pall rings of an efficiency substantially equivalent to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C. A raffinate is obtained (R1) which is sent via line 6 to the steam stripping zone D1 in which the furfural which is recovered at the head is separated by line 8 with a view to its possible recycling to zone d extraction and tail a raffinate (Q1) containing practically no more furfural, having a sulfur content of 0.04% by weight, a cetane number of 67, a content by weight of aromatic sulfur and non-sulfur compounds of 20 %, an n- and iso-alkane content of 48% by weight, a nitrogen content of 30 ppm and a Saybolt color of 20. From this extraction zone an extract (E1) is also recovered that the we send to a distillation zone D2 in which the furfural which is recovered at the head is separated at the head 10 for possible recycling to the extraction zone and at the tail an extract (Q2) containing practically no more furfural, having a sulfur content of 0.5% by weight, a cetane number of 25, a e content by weight of aromatic sulfur and non-sulfur compounds of 80% and a nitrogen content of 1000 ppm.

Le produit (Q1) est envoyé par les lignes 9, 9b, et 149 au pool carburant moteur. Le mélange de P20 et Q1 est un produit ayant un indice de cétane de 61, une teneur en poids de composés aromatiques soufrés et non soufrés de 23 %, une teneur en soufre de 0,02 % en poids, une teneur en azote de 30 ppm et une couleur Saybolt de 25.
Ce mélange peut aussi être mélangé, en partie au moins, avec une partie au moins du produit P1, une fois strippé.The product (Q1) is sent via lines 9, 9b, and 149 to the engine fuel pool. The mixture of P20 and Q1 is a product having a cetane number of 61, a content by weight of sulfur and non-sulfur aromatic compounds of 23%, a sulfur content of 0.02% by weight, a nitrogen content of 30 ppm and a Saybolt color of 25.
This mixture can also be mixed, at least in part, with at least part of the product P1, once stripped.

EXEMPLE 5EXAMPLE 5

Une charge de gazole de distillation directe de point initial de distillation de 150°C et de point final de distillation de 400°C contenant 35% poids d'aromatiques et composés soufrés et 10% de di- et polyaromatiques, est traitée selon l'exemple 1 dans des conditions d'hydrotraitement définies ci-dessous. Pression partielle en hydrogène (MPa) Produit P Aromatiques + composés soufrés % poids Produit P Di- et polyaromatiques % poids Gain en cétane après extraction entre les produits Q₁ et P (à isorendement) 3,0 34 7 + 12 5,0 32 4 + 10 7,0 (comparatif) 23 1 + 6 A charge of direct distillation diesel fuel with an initial distillation point of 150 ° C. and a final distillation point of 400 ° C. containing 35% by weight of aromatics and sulfur compounds and 10% of di- and polyaromatics is treated according to the Example 1 under hydrotreatment conditions defined below. Hydrogen partial pressure (MPa) Product P Aromatics + sulfur compounds% by weight Product P Di- and polyaromatics% by weight Cetane gain after extraction between Q₁ and P products (isorefficient) 3.0 34 7 + 12 5.0 32 4 + 10 7.0 (comparison) 23 1 + 6

Sachant que l'on a observé un gain en indice de cétane de 14 points par extraction directe liquide-liquide, on montre par cet exemple que les performances de l'unité aval d'extraction dépendent de la sévérité de l'étape d'hydrotraitement.Knowing that a gain in cetane index of 14 points was observed by direct liquid-liquid extraction, it is shown by this example that the performance of the downstream extraction unit depends on the severity of the hydrotreatment step .

En particulier, elles sont d'autant plus importantes que la teneur en hydrocarbures aromatiques de l'effluent d'hydrotraitement est sensiblement identique à celle de la charge initiale et que l'étape d'hydrogénation des hydrocarbures di- et polyaromatiques est limitée.In particular, they are all the more important as the content of aromatic hydrocarbons in the hydrotreatment effluent is substantially identical to that of the initial charge and the step of hydrogenation of di- and polyaromatic hydrocarbons is limited.

On montre ainsi qu'une sélection des conditions de l'étape d'hydrotraitement du procédé selon l'invention conditionne les performances de l'étape d'extraction.It is thus shown that a selection of the conditions of the hydrotreatment step of the process according to the invention conditions the performance of the extraction step.

EXEMPLE 6EXAMPLE 6

La charge utilisée dans cet exemple est un mélange de coupe gazole de distillation directe et de coupe gazole issue du craquage catalytique, type LCO.The feed used in this example is a mixture of direct distillation diesel cut and diesel cut resulting from catalytic cracking, LCO type.

La coupe gazole de distillation directe a une densité à 15°C de 857, un indice de réfraction à 60°C de 1,4617, un indice de cétane de 55, une teneur totale en composés aromatiques, soufrés e non soufrés, de 35,4% en poids, une teneur en n- et iso-alcanes et en naphtènes de 64,6 % en poids, une teneur en soufre de 1,33% en poids et une teneur en azote exprimée en poids d'azote de 124 ppm.The direct distillation diesel cut has a density at 15 ° C of 857, a refractive index at 60 ° C of 1.4617, a cetane index of 55, a total content of aromatic compounds, sulfur and non-sulfur, of 35 , 4% by weight, a content of n- and iso-alkanes and naphthenes of 64.6% by weight, a sulfur content of 1.33% by weight and a nitrogen content expressed by weight of nitrogen of 124 ppm.

La coupe gazole LCO a une densité à 15°C de 944,1 un indice de réfraction à 60°C de 1,5245, un indice de cétane de 23, une teneur totale en composés aromatiques, soufrés et non soufrés de 67,4% en poids, une teneur en n- et iso-alcanes et naphtènes de 32,6% en poids, une teneur en soufre de 3,13% en poids et une teneur en azote exprimée en poids d'azote de 930 ppm.The LCO diesel cut has a density at 15 ° C of 944.1, a refractive index at 60 ° C of 1.5245, a cetane index of 23, a total content of aromatic, sulfur and non-sulfur compounds of 67.4 % by weight, a content of n- and iso-alkanes and naphthenes of 32.6% by weight, a sulfur content of 3.13% by weight and a nitrogen content expressed by weight of nitrogen of 930 ppm.

On note charge C₁, la charge contenant 80% de coupe gazole de distillation directe et 20% de coupe LCO, et charge C₂, la charge contenant 50% de coupe gazole de distillation directe et 50% de coupe LCO. Les coupes C₁ et C₂ ont un point initial de distillation de 200°C et un point final de distillation de 400°C. La charge C₁ est introduite par la conduite 1 dans une zone d'hydrodésulfuration dans laquelle elle est soumise à un traitement d'hydrodésulfuration sous une pression partielle d'hydrogène de 2,0 MPa en présence d'un catalyseur industriel contenant du cobalt et du molybdène sur un support d'alumine vendu par la société PROCATALYSE sous la référence HR 306C, la température est maintenue à 330°C, la quantité d'hydrogène introduit est égale à 200 litre de charge et la vitesse spatiale horaire est de 2,5 h⁻¹. La quantité d'hydrogène consommé est de 0,25% poids par rapport à la charge.Note load C₁, the load containing 80% of direct distillation diesel cut and 20% of LCO cut, and load C₂, the load containing 50% of direct distillation diesel cut and 50% of LCO cut. The sections C₁ and C₂ have an initial distillation point of 200 ° C and a final distillation point of 400 ° C. The charge C₁ is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial hydrogen pressure of 2.0 MPa in the presence of an industrial catalyst containing cobalt and molybdenum on an alumina support sold by the company PROCATALYSE under the reference HR 306C, the temperature is maintained at 330 ° C, the quantity of hydrogen introduced is equal to 200 liters of charge and the hourly space speed is 2.5 h⁻¹. The amount of hydrogen consumed is 0.25% by weight relative to the charge.

On récupère par la ligne 2 un produit (P') d'une densité à 15°C de 862,2 et contenant 0,051% de soufre, 31% en poids de composés aromatiques soufrés et non soufrés, 61% en poids de n- et iso-alcanes et 285 ppm d'azote.A product (P ′) with a density at 15 ° C. of 862.2 and containing 0.051% of sulfur, 31% by weight of sulfur and non-sulfur aromatic compounds, 61% by weight of n- is recovered via line 2 and iso-alkanes and 285 ppm nitrogen.

L'indice de cétane du produit (P') est de 53 et son point final de distillation est de 400°C. Il est envoyé dans une zone de strippage à la vapeur d'eau (SEP1) à partir de laquelle on récupère par la ligne 3 un produit (P'1) ayant un point final de distillation de 230°C, et par la ligne 4 un produit (P'2) ayant un point initial de distillation de 230°C et un point final de distillation de 400°C. Ce produit (P'2) après avoir refroidi à 70°C, c'est-à-dire à la température de la zone d'extraction, est envoyé dans un zone d'extraction (EXT.) par la ligne 4 dans laquelle on introduit également par la ligne 5 une quantité de furfural égale en volume à la quantité de produit( P'2) introduite dans cette zone. Cette zone est une colonne d'extraction comportant un garnissage formé d'anneaux de Pall d'une efficacité globale sensiblement égale à trois étapes théoriques. L'extraction s'effectue à contre-courant, sous pression atmosphérique et à la température de 70°C. On obtient un raffinat (R'1) que l'on envoie par la conduite 6 dans la zone de strippage à la vapeur (D1) dans laquelle on sépare en tête le furfural qui est récupéré par la conduite 8 en vue de son recyclage éventuel à la zone d'extraction et en queue un raffinat (Q'1) contenant moins de 5 ppm de furfural par exemple, ayant une teneur en soufre de 0,02% en poids, un indice de cétane de 67,3, une teneur en poids de composés aromatiques soufrés et non soufrés de 19,1, une teneur en n- et iso-alcanes et naphtènes de 80,9% en poids, une teneur en azote de 54 ppm et une densité à 15°C de 826,5 et qui peut être introduit dans le réservoir (pool) gazole. A partir de cette zone d'extraction on récupère également un extrait (E'1) que l'on envoie dans une zone de distillation (D2) suivie d'une zone de strippage à la vapeur dans lesquelles on sépare en tête le furfural qui est récupéré par la conduite 10 en vue de son recyclage éventuel à la zone d'extraction et en queue un extrait (Q'2) ne contenant pratiquement plus de furfural, ayant une teneur en soufre de 0,14% en poids, une teneur en poids de composé aromatiques soufrés et non soufrés de 87,2%, une teneur en azote de 800ppm, une teneur en n- et iso-alcanes et naphtènes de 12,8% en poids et une densité à 15°C de 1002,8.The cetane number of the product (P ') is 53 and its final point of distillation is 400 ° C. It is sent to a stripping zone with water vapor (SEP1) from which a product (P'1) having a final distillation point of 230 ° C. is recovered via line 3, and through line 4 a product (P'2) having an initial distillation point of 230 ° C and a final distillation point of 400 ° C. This product (P'2) after cooling to 70 ° C, that is to say at the temperature of the extraction zone, is sent to an extraction zone (EXT.) By line 4 in which line 5 is also introduced with an amount of furfural equal in volume to the amount of product (P'2) introduced into this zone. This zone is an extraction column comprising a packing formed of Pall rings with an overall efficiency substantially equal to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at a temperature of 70 ° C. A raffinate is obtained (R'1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered at the head is separated by line 8 for possible recycling. at the extraction zone and at the tail a raffinate (Q'1) containing less than 5 ppm of furfural for example, having a sulfur content of 0.02% by weight, a cetane number of 67.3, a content by weight of sulfur and non-sulfur aromatic compounds of 19.1, a content of n- and iso-alkanes and naphthenes of 80.9% by weight, a nitrogen content of 54 ppm and a density at 15 ° C. of 826, 5 and which can be introduced into the diesel tank. From this extraction zone, an extract (E'1) is also recovered which is sent to a distillation zone (D2) followed by a steam stripping zone in which the furfural which is separated at the head is separated. is recovered via line 10 for possible recycling to the extraction zone and at the tail an extract (Q'2) containing practically no more furfural, having a sulfur content of 0.14% by weight, a content by weight of sulfur and non-sulfur aromatic compound of 87.2%, a nitrogen content of 800 ppm, a content of n- and iso-alkanes and naphthenes of 12.8% by weight and a density at 15 ° C. of 1002, 8.

La charge C₂ subit le même traitement que la charge C1.The load C₂ undergoes the same treatment as the load C1.

On récupère par la ligne 2 un produit (P'') d'une densité à 15°C de 888,1 et contenant 0,067% en poids du soufre, 44,6% en poids de composés aromatiques soufrés et non soufrés, 47,4% en poids de n- et iso-alcanes et de naphtènes et 527 ppm d'azote.
L'indice de cétane du produit (P'') est de 43 et son point final de distillation et de 400°C.Line 2 is used to recover a product (P '') with a density at 15 ° C of 888.1 and containing 0.067% by weight of sulfur, 44.6% by weight of aromatic sulfur and non-sulfur compounds, 47, 4% by weight of n- and iso-alkanes and naphthenes and 527 ppm of nitrogen.
The cetane number of the product (P '') is 43 and its final point of distillation is 400 ° C.

Le produit (P''1) récupéré par la ligne 3 a un point final de distillation de 230°C, et le produit (P''2) récupéré par la ligne 4 a un point initial de distillation de 230°C et un point final de distillation de 400°C.The product (P''1) recovered by line 3 has a final distillation point of 230 ° C, and the product (P''2) recovered by line 4 has an initial distillation point of 230 ° C and a 400 ° C final distillation point.

Le raffinat (R''1) obtenu après extraction est envoyé par la conduite 6 dans la zone de strippage à la vapeur (D1) de la même manière que le raffinat (R'1). Le raffinat (Q''1) obtenu en queue contient moins de 5 ppm de furfural par exemple, 0,02% en poids de soufre, un indice de cétane de 66,1, 17% en poids de composés aromatiques soufrés et non soufrés, 83% en poids de n- et isoalcanes et de naphtènes, 150 ppm d'azote et une densité à 15°C de 883,9.The raffinate (R''1) obtained after extraction is sent via line 6 to the steam stripping zone (D1) in the same way as the raffinate (R'1). The raffinate (Q''1) obtained at the tail contains less than 5 ppm of furfural, for example, 0.02% by weight of sulfur, a cetane number of 66.1, 17% by weight of aromatic sulfur and non-sulfur compounds , 83% by weight of n- and isoalkanes and naphthenes, 150 ppm of nitrogen and a density at 15 ° C of 883.9.

L'extrait (E''1) obtenu après extraction est envoyé dans la zone de distillation (D2) suivie de strippage à la vapeur. L'extrait (Q''2) obtenu en queue ne contient pratiquement plus de furfural, 0,12% en poids de soufre, 87,9% en poids de composés aromatiques soufrés et non soufrés, 900 ppm d'azote, 12,1% en poids de n- et iso-alcanes et de naphtènes, et une densité à 15°C de 985,3.The extract (E''1) obtained after extraction is sent to the distillation zone (D2) followed by steam stripping. The extract (Q''2) obtained at the tail contains practically no more furfural, 0.12% by weight of sulfur, 87.9% by weight of sulfur and non-sulfur aromatic compounds, 900 ppm of nitrogen, 12, 1% by weight of n- and iso-alkanes and naphthenes, and a density at 15 ° C of 985.3.

Les produits Q'2 et Q''2 peuvent être envoyés par les conduites 11 et 11 b dans une zone (HDS3) d'hydrodésulfuration distincte de celle dans laquelle on a introduit la charge initiale. Cette hydrodésulfuration est effectuée en présence du catalyseur HR 306C, sous pression partielle d'hydrogène de 2,5 MPa, à une température de 330°C avec un recyclage d'hydrogène de 200 litres par litre de charge et une vitesse spatiale horaire de 2,5 h⁻¹. A la sortie de cette hydrodésulfuration on obtient un produit ayant une teneur en soufre de 0,2% en poids. Ses autres caractéristiques sont pratiquement inchangées. Ce produit peut être mélangé au fuel domestique, c'est-à-dire introduit dans ce que les hommes du métier appellent le pool fuel domestique.The products Q'2 and Q''2 can be sent via lines 11 and 11b to a hydrodesulfurization zone (HDS3) distinct from that into which the initial charge has been introduced. This hydrodesulfurization is carried out in the presence of the HR 306C catalyst, under partial hydrogen pressure of 2.5 MPa, at a temperature of 330 ° C. with a hydrogen recycling of 200 liters per liter of charge and an hourly space speed of 2 , 5 h⁻¹. At the outlet of this hydrodesulfurization, a product is obtained having a sulfur content of 0.2% by weight. Its other characteristics are practically unchanged. This product can be mixed with domestic fuel, that is to say introduced into what those skilled in the art call the domestic fuel pool.

Claims (15)

1 - Procédé d'obtention d'un produit pétrolier pouvant servir de base dans la composition d'un carburant pour moteur à combustion interne à allumage par compression présentant un indice de cétane et une teneur en soufre améliorés, à partir d'une charge hydrocarbonée ayant un point initial d'ébullition d'au moins 150 °C et de point final d'ébullition d'au plus 500 °C, contenant environ 0,05 % à environ 5 % en poids de soufre, environ 10 à environ 60 % en poids de n- et iso-alcanes, environ 10 % à environ 85 % en poids d'hydrocarbures aromatiques au moins en partie sous forme de composés polyaromatiques soufrés ou non, ayant un indice de cétane d'environ 20 à environ 60 et ayant une teneur en azote d'environ 50 à environ 5 000 ppm en poids, ledit procédé étant caractérisé en ce qu'il comprend les étapes suivantes : - une étape a) d'hydrotraitement dans laquelle on effectue l'hydrotraitement de ladite charge dans des conditions permettant d'obtenir un produit (P) contenant une quantité de soufre de 2 à 50 fois moindre que celle de la charge initiale, ledit hydrotraitement étant effectué sous une pression partielle d'hydrogène en sortie de réacteur d'environ 0,5 MPa (mégapascal) à environ 6 MPa, telle que le taux de désaromatisation de la charge est au plus égale à 30%, - une étape b) de séparation du produit (P) en un produit (P2) ayant un point d'ébullition initial supérieur à la température d'ébullition du solvant d'extraction de l'étape suivante c) et de préférence au moins supérieur de 20°C, et en un produit (P1) ayant un point d'ébullition final inférieur au point d'ébullition initial du produit P2, - une étape c) d'extraction liquide/liquide dans laquelle on met en contact, à une température d'extraction au plus égale à 140°C, dans des conditions d'extraction des composés polyaromatiques, le produit (P2) obtenu à l'étape b) avec un solvant ou un mélange de solvant (S1) permettant d'extraire au moins en partie les composé polyaromatiques qu'il contient, ledit solvant ayant un point initial d'ébullition inférieur au point initial d'ébullition du produit (P2) obtenu à l'étape b), et au cours de laquelle on récupère un extrait (E1) enrichi en composés polyaromatiques, soufrés ou non et un raffinat (R1) et, - une étape d) de récupération du solvant (S1) employé à l'étape c) à partir du raffinat (R1) obtenu à l'étape c) dans laquelle on récupère un produit enrichi en solvant (S1) et un produit (Q1) appauvri en solvant (S1) ayant des qualités améliorées et contenant moins de 500 ppm en poids de soufre. 1 - Process for obtaining a petroleum product which can serve as a base in the composition of a fuel for an internal combustion engine with compression ignition having an improved cetane number and a sulfur content, from a hydrocarbon feedstock having an initial boiling point of at least 150 ° C and an end boiling point of at most 500 ° C, containing from about 0.05% to about 5% by weight of sulfur, from about 10 to about 60% by weight of n- and iso-alkanes, about 10% to about 85% by weight of aromatic hydrocarbons at least partly in the form of polyaromatic compounds, sulfur or not, having a cetane number of about 20 to about 60 and having a nitrogen content of about 50 to about 5,000 ppm by weight, said process being characterized in that it comprises the following steps: a hydrotreatment stage a) in which the hydrotreatment of said charge is carried out under conditions allowing a product (P) containing a quantity of sulfur from 2 to 50 times less than that of the initial charge to be obtained, said hydrotreatment being carried out under a partial pressure of hydrogen at the outlet of the reactor from approximately 0.5 MPa (megapascal) to approximately 6 MPa, such that the charge dearomatization rate is at most equal to 30%, a step b) of separation of the product (P) into a product (P2) having an initial boiling point higher than the boiling point of the extraction solvent of the following step c) and preferably at least higher 20 ° C, and a product (P1) having a final boiling point lower than the initial boiling point of product P2, a step c) of liquid / liquid extraction in which the product (P2) obtained at 1 is at contact, at an extraction temperature at most equal to 140 ° C., under conditions of extraction of the polyaromatic compounds step b) with a solvent or a mixture of solvent (S1) making it possible to extract at least partially the polyaromatic compounds which it contains, said solvent having an initial boiling point lower than the initial boiling point of the product ( P2) obtained in step b), and during which a extract (E1) enriched in polyaromatic compounds, sulfur or not and a raffinate (R1) and, a step d) of recovery of the solvent (S1) used in step c) from the raffinate (R1) obtained in step c) in which a product enriched in solvent (S1) and a product (Q1) is recovered ) depleted in solvent (S1) having improved qualities and containing less than 500 ppm by weight of sulfur. 2 - Procédé selon la revendication 1, dans lequel la pression en hydrogène en sortie du réacteur est de 1 à 5 MPa, de telle façon que le taux de désaromatisation de la charge est au plus égal à 15% environ. 2 - Process according to claim 1, wherein the hydrogen pressure at the outlet of the reactor is from 1 to 5 MPa, so that the rate of dearomatization of the charge is at most equal to approximately 15%. 3 - Procédé selon l'une des revendications 1 à 2 dans lequel l'étape c) est effectuée dans des conditions permettant d'obtenir un raffinat (R1) contenant en poids au plus 90 % et de préférence au plus 70 % en poids du poids total des hydrocarbures aromatiques, ne contenant pas d'atome de soufre dans leur molécule, présents dans le produit (P2) obtenu à l'étape b). 3 - Method according to one of claims 1 to 2 wherein step c) is carried out under conditions allowing to obtain a raffinate (R1) containing by weight at most 90% and preferably at most 70% by weight of the total weight of aromatic hydrocarbons, not containing a sulfur atom in their molecule, present in the product (P2) obtained in step b). 4 - Procédé selon l'une des revendications 1 à 3 dans lequel l'extrait (El) obtenu à l'étape c) est envoyé dans une zone de récupération du solvant (S1) employé à l'étape c) dans laquelle on récupère un produit enrichi en solvant (S1) et un produit (Q2) appauvri en solvant (S1). 4 - Method according to one of claims 1 to 3 wherein the extract (El) obtained in step c) is sent to a solvent recovery zone (S1) used in step c) in which one recovers a product enriched in solvent (S1) and a product (Q2) depleted in solvent (S1). 5 - Procédé selon la revendication 4 dans lequel le produit de queue (Q2) est envoyé dans une zone d'hydrotraitement distincte de la zone d'hydrotraitement de l'étape a), dans laquelle il est soumis à un hydrotraitement dans des conditions permettant d'obtenir un produit (P3) ayant une teneur en soufre inférieure ou égale à 0,3 % en poids et de préférence inférieure ou égale à 0,2 % en poids. 5 - Process according to claim 4 in which the bottoms product (Q2) is sent to a hydrotreatment zone distinct from the hydrotreatment zone of step a), in which it is subjected to hydrotreatment under conditions allowing to obtain a product (P3) having a sulfur content less than or equal to 0.3% by weight and preferably less than or equal to 0.2% by weight. 6 - Procédé selon l'une des revendications 1 à 5 dans lequel le ou les produits de tête, obtenus par séparation du raffinat (R1) et éventuellement de l'extrait (E1), enrichi(s) en solvant (S1), sont recyclés à l'étape c) d'extraction liquide/liquide. 6 - Method according to one of claims 1 to 5 wherein the top product or products, obtained by separation of the raffinate (R1) and optionally the extract (E1), enriched (s) in solvent (S1), are recycled in step c) of liquid / liquid extraction. 7 - Procédé selon l'une des revendications 1 à 6 dans lequel le solvant est choisi dans le groupe formé par le méthanol, I'acétonitrile, la monométhylformamide, la diméthylformamide, la diméthylacétamide, le furfural, la N-méthylpyrolidone et le diméthylsulfoxyde. 7 - Method according to one of claims 1 to 6 wherein the solvent is selected from the group formed by methanol, acetonitrile, monomethylformamide, dimethylformamide, dimethylacetamide, furfural, N-methylpyrolidone and dimethylsulfoxide. 8- Procédé selon l'une des revendications 1 à 7 dans lequel le solvant utilisé est un solvant non azoté oxygéné, de préférence le furfural. 8- Method according to one of claims 1 to 7 wherein the solvent used is a non-nitrogenous oxygenated solvent, preferably furfural. 9 - Procédé selon l'une des revendications 1 à 8 dans lequel à l'étape a) d'hydrotraitement on introduit dans le réacteur d'hydrotraitement, outre la charge hydrocarbonée à traiter, au moins une partie du produit de queue (Q2) obtenu à partir de l'extrait (E1) de l'étape c) après séparation du solvant (S1). 9 - Method according to one of claims 1 to 8 wherein in step a) of hydrotreatment is introduced into the hydrotreatment reactor, in addition to the hydrocarbon feed to be treated, at least part of the bottom product (Q2) obtained from the extract (E1) of step c) after separation of the solvent (S1). 10 - Procédé selon l'une des revendications 1 à 9 dans lequel au moins une partie du produit (P1) résultant de l'étape b) est débarrassée de sa fraction légère et est mélangée à une partie au moins du produit (Q1) résultant de l'étape d). 10 - Method according to one of claims 1 to 9 wherein at least part of the product (P1) resulting from step b) is freed of its light fraction and is mixed with at least part of the product (Q1) resulting from step d). 11 - Procédé dans lequel la charge hydrocarbonée ayant un point initial d'ébullition d'au moins 150 °C et un point final d'ébullition d'au plus 500 °C est envoyée dans une zone de distillation dans laquelle on sépare en tête une fraction (F1) ayant un point final d'ébullition d'au moins 250 °C et en queue une fraction (F2) ayant un point initial d'ébullition d'au moins 250 °C, ledit procédé étant caractérisé en ce que la fraction (F2) est traitée selon le procédé de l'une des revendications 1 à 11 et en ce que la fraction (F1) est envoyée dans une zone d'hydrotraitement distincte de celle de l'étape a) à partir de laquelle on récupère un produit (P') hydrotraité que l'on envoie dans une zone de séparation à partir de laquelle on récupère une fraction (P10) ayant un point d'ébullition final inférieur à 150 °C, et une fraction (P20) ayant un point d'ébullition initial supérieur au point d'ébullition final de la fraction (P10). 11 - Process in which the hydrocarbon feedstock having an initial boiling point of at least 150 ° C and a final boiling point of at most 500 ° C is sent to a distillation zone in which a head is separated fraction (F1) having a final boiling point of at least 250 ° C and at the tail a fraction (F2) having an initial boiling point of at least 250 ° C, said process being characterized in that the fraction (F2) is treated according to the method of one of claims 1 to 11 and in that the fraction (F1) is sent to a hydrotreating zone separate from that of step a) from which a hydrotreated product (P ') which is sent to a separation zone from which a fraction (P10) having a final boiling point below 150 ° C is recovered, and a fraction (P20) having a d point 'initial boiling above the final boiling point of the fraction (P10). 12 - Procédé selon les revendications 10 et 11 dans lequel la fraction (P20) est au moins en partie mélangée au produit (Q1) obtenu à l'étape d) ou au mélange des produits (P1) et (Q1). 12 - Process according to claims 10 and 11 wherein the fraction (P20) is at least partly mixed with the product (Q1) obtained in step d) or with the mixture of products (P1) and (Q1). 13 - Produit pétrolier caractérisé en ce qu'il est obtenu par le procédé selon l'une des revendications 1 à 12. 13 - Petroleum product characterized in that it is obtained by the process according to one of claims 1 to 12. 14 - Produit pétrolier selon la revendication 13 utilisable notamment comme base entrant dans la composition d'un carburant pour moteur à combustion interne à allumage par compression présentant un indice de cétane supérieur d'au moins 3 points à celui de la charge dont il provient, une teneur en n- et iso-alcanes supérieure d'au moins 4 points à celle de la charge et une teneur en soufre par rapport à la charge inférieure ou égale à 5 % poids. 14 - Petroleum product according to claim 13 usable in particular as a base used in the composition of a fuel for an internal combustion engine with compression ignition having a cetane number higher by at least 3 points than that of the charge from which it comes, a content of n- and iso-alkanes greater by at least 4 points than that of the filler and a sulfur content relative to the filler less than or equal to 5% by weight. 15 - Produit pétrolier selon l'une des revendications 13 à 14 caractérisé en ce que la coupe de distillation correspond à 95% distillés entre 320° C et 460° C, son indice de cétane est supérieur à 60, sa teneur en n- et iso-alcanes est au moins égale à 48 % poids, et sa teneur en soufre inférieure ou égale à 500 ppm (poids). 15 - Petroleum product according to one of claims 13 to 14 characterized in that the distillation cut corresponds to 95% distilled between 320 ° C and 460 ° C, its cetane number is greater than 60, its content of n- and iso-alkanes is at least equal to 48% by weight, and its sulfur content less than or equal to 500 ppm (weight).
EP94403024A 1993-12-28 1994-12-26 Process for the production of an internal combustion engine fuel by hydrotreatment and extraction Expired - Lifetime EP0661371B1 (en)

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FR9315857 1993-12-28

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US6110358A (en) * 1999-05-21 2000-08-29 Exxon Research And Engineering Company Process for manufacturing improved process oils using extraction of hydrotreated distillates
EP1451269B1 (en) * 2001-11-22 2007-08-15 Institut Francais Du Petrole Two-step method for middle distillate hydrotreatment comprising two hydrogen recycling loops
FR2900157B1 (en) * 2006-04-24 2010-09-24 Inst Francais Du Petrole PROCESS FOR THE DESULFURATION OF OLEFINIC ESSENCES COMPRISING AT LEAST TWO DISTINCT HYDRODESULFURATION STAGES
US8424181B2 (en) * 2009-04-17 2013-04-23 Exxonmobil Research And Engineering Company High pressure revamp of low pressure distillate hydrotreating process units
CA2880341A1 (en) * 2012-07-31 2014-03-20 Cetamax Ventures Ltd. Methods and systems for combined oxidative and hydrotreatment of hydrocarbon fuel
FR3015514B1 (en) 2013-12-23 2016-10-28 Total Marketing Services IMPROVED PROCESS FOR DESAROMATIZATION OF PETROLEUM CUTTERS
CN109196078B (en) * 2016-05-25 2021-07-09 埃克森美孚研究工程公司 Producing upgraded extract and raffinate
EP3515882B1 (en) * 2016-09-19 2023-03-08 B.G. Negev Technologies & Applications Ltd., at Ben-Gurion University Novel, highly efficient eco-friendly processes for converting co2 or co-rich streams to liquid fuels and chemicals
US10711208B2 (en) * 2017-06-20 2020-07-14 Saudi Arabian Oil Company Process scheme for the production of optimal quality distillate for olefin production

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WO1999058625A1 (en) * 1998-05-08 1999-11-18 Sasol Technology (Proprietary) Limited Removal of impurities from a hydrocarbon component or fraction
US6483003B1 (en) 1998-05-08 2002-11-19 Sasol Technology (Proprietary) Limited Removal of impurities from a hydrocarbon component or fraction
WO2017200640A1 (en) * 2016-05-17 2017-11-23 Exxonmobil Research And Engineering Company Jet and diesel selective hydrocracking

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DE69433053T2 (en) 2004-04-01
US5925234A (en) 1999-07-20
ATE247703T1 (en) 2003-09-15
FR2714387A1 (en) 1995-06-30
FR2714387B1 (en) 1996-02-02
US6165348A (en) 2000-12-26
DE69433053D1 (en) 2003-09-25
NO313420B1 (en) 2002-09-30
NO945004L (en) 1995-06-29
ES2206464T3 (en) 2004-05-16
EP0661371B1 (en) 2003-08-20

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