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EP0661371B1 - Verfahren zur Erzeugung eines Brennstoffes für innere Verbrennungsmotoren durch Wasserstoffbehandlung und Extraktion - Google Patents

Verfahren zur Erzeugung eines Brennstoffes für innere Verbrennungsmotoren durch Wasserstoffbehandlung und Extraktion Download PDF

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Publication number
EP0661371B1
EP0661371B1 EP94403024A EP94403024A EP0661371B1 EP 0661371 B1 EP0661371 B1 EP 0661371B1 EP 94403024 A EP94403024 A EP 94403024A EP 94403024 A EP94403024 A EP 94403024A EP 0661371 B1 EP0661371 B1 EP 0661371B1
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EP
European Patent Office
Prior art keywords
product
solvent
weight
boiling point
sulfur
Prior art date
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EP94403024A
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English (en)
French (fr)
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EP0661371A1 (de
Inventor
Frédéric Morel
Massimo Zuliani
Paul Mikitenko
Marc Boulet
Roben Loutaty
Jean Claude Company
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IFP Energies Nouvelles IFPEN
TotalEnergies Marketing Services SA
Original Assignee
IFP Energies Nouvelles IFPEN
TotalFinaElf France SA
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Publication of EP0661371A1 publication Critical patent/EP0661371A1/de
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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 method for obtaining of a petroleum product which can possibly be used for the formulation of a fuel for internal combustion engine and the product obtained by the process.
  • gas oils that are currently on the market are most often products from refining which contain sulfur in an amount (expressed by weight of sulfur) about 0.3%. They are usually obtained after treatment hydrodesulfurization from a feed which can come from the direct distillation of crude oil or special treatment of a crude oil (e.g. pyrolysis or distillation followed by pyrolysis of the fraction recovered during distillation, or cracking thermal or catalytic) generally containing at least 0.8% by weight sulfur.
  • sulfur content standards and cetane are in place or are going to be in place in a very close to come up. These standards are becoming more and more stringent, particularly for diesel fuels intended to be used as fuel for engines. It is as well as in France, in particular from 1995, the sulfur content of these gas oils must not be more than 0.05% by weight (500 ppm) while diesel in accordance with current standards have a sulfur content that can reach 0.3%.
  • diesel oils used in France as fuel for engines internal combustion must currently have a cetane number at less than 48 and the gas oils used as fuel an index of cetane at least 40. We can expect in the near future a tightening of these standards and in particular those concerning diesel used as fuel in engines.
  • the present invention therefore relates to a simple implementation method, consuming little hydrogen.
  • This process uses industrial units hydrotreating (hydrodesulfurization in particular). It improves qualities of the diesel produced and meet future standards and in particular that concerning the sulfur content.
  • the method of the invention allows in in addition, to improve the cetane engine index of diesel, to reduce its content aromatic compounds not containing a sulfur heteroatom in their molecule, reduce its content of nitrogen compounds, improve its color and its smell and finally to decrease the formation of solid particles during its use in an internal combustion engine.
  • the present invention provides a solution to the specific problem of obtaining, in the most quantity significant possible compared to the starting product, of a petroleum product used in the composition of engine grade 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 further relates to the process for obtaining a petroleum product. used in the composition of a fuel oil.
  • hydrodesulfurization instead of hydrotreatment.
  • polyaromatic compounds compounds having at least two aromatic cycles, sulfur or not.
  • the initial and final boiling point temperatures are TBP cut.
  • the hydrocarbon feedstock which is treated according to the process of the invention is most often referred to as a diesel cutter and it preferably has a point initial boiling point of approximately 150 ° C and a final boiling point of approximately 400 ° C, its sulfur content is usually more than 0.1% and the most often greater than 0.5% by weight, its content of n- and iso-alkanes is about 30 to 45% by weight, its content of aromatic compounds is usually from about 15% to about 65% by weight.
  • This charge is the more often a direct distillation diesel, a pyrolysis diesel or a mixture of the two. This charge can advantageously be mixed with a L.C.O.
  • the color of this load measured according to the ASTM D 1500 method is usually greater than or equal to 2.
  • the cetane number according to ISO 5165 standard of this charge is most often less than about 60 and it is for example from about 50 to about 55.
  • the nitrogen content of this feed is very often from about 100 to about 1000 ppm expressed by weight of nitrogen relative to the load weight.
  • the product Q1 obtained is a particularly interesting product taking into account all of its characteristics (cut point, cetane, paraffin content and sulfur) to obtain by formulation with other diesel cuts of quality fuels.
  • the product (Q1) obtained by the process of the present invention has usually 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) has most often a color measured according to the ASTM 1500 standard less than 1 and the cetane number of this product is generally at least 3 higher points and often at least 5 points at the cetane number of the initial charge (for example from 3 to 14 points).
  • Its sulfur content compared to that of the load is usually less than or equal to 5% by weight.
  • Its net content iso-alkanes generally increases by at least 4 points, advantageously by 5 to 20 points and most often 6 to 11 points, compared to that of the charge.
  • the content of aromatic compounds containing no atom sulfur in their molecule in this product (Q1) is usually reduced by at least at least 10% by weight compared to that of the initial charge and often at least minus 30% by weight.
  • the odor of this product is less strong than that of initial charge.
  • the invention advantageously relates to a petroleum product characterized in that 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 1 to 5
  • the pressure from 1 to 5 MPa the volume ratio H2 on load from 50 to 350 m 3 / m 3 measured under conditions normal.
  • 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.
  • one operates in the presence of a selective catalyst for the hydrodesulfurization of sulfur molecules compared to the hydrogenation of aromatics, adapted to limit hydrogenation, for example one of those marketed by PROCATALYSE, under pressure partial hydrogen at the outlet of the hydrodesulfurization reactor advantageously between approximately 1.0 MPa and approximately 3.0 MPa and recovers 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 3 to 10 times less than that of the initial charge.
  • the charge deflavor rate is then significantly less than 10%.
  • the other conditions for implementing this hydrodesulfurization step are conventional conditions of a hydrodesulfurization qualified by those skilled in the art of hydrodesulfurization simple and sweet.
  • one operates in the presence of a conventional catalyst suitable for limiting hydrogenation, for example one of those sold by the company PROCATALYSE, under partial pressure of hydrogen in hydrodesulfurization reactor outlet advantageously between about 2 MPa and about 5 MPa and recover a product (P) containing 5 to 60 times less sulfur, less than 0.1% by weight, per example between 0.02 and 0.05%, and most often 10 to 40 times less than that of the initial charge.
  • P product
  • the rate of disaromatization of the load is at most equal to approximately 15%.
  • the other conditions of implementation work of this hydrodesulfurization step are conventional conditions 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 more important, as well as a higher hydrogen pressure, calculated for perform further hydrodesulfurization.
  • 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 it is desired to send to the extraction 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 conditions classics. This extraction could for example be carried out against the current in a conventional device, for example a filling column, with plates or with mechanical agitation (R.D.C.: rotating dise contactor) having in general an efficiency from 3 to 20 theoretical stages and preferably from 5 to 10 theoretical stages, at a temperature generally between 0 ° C and 140 ° C, advantageously between 30 ° C and 80 ° C and under pressure allowing operation in the liquid phase and therefore between 0.1 and 1 MPa, preferably between 0.1 and 0.6 MPa.
  • R.D.C. rotating dise contactor
  • the volume ratio of the solvent (S1) to volume of the product (P2), obtained in step b), is preferably about 0.2: 1 to about 5: 1, preferably 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 to also extract at least part of the compounds aromatic, not containing a sulfur atom in their molecule, present in the product (P2) obtained in step b). 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 aromatic compounds, not containing a sulfur atom in their molecule, present in the product (P2) obtained in step b).
  • the extract (E1) in 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 in step b), thus that 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 dibenzothiophenics and naphthobenzothiophenics initially contained in the product (P2).
  • the product (Q1) thus obtained usually contains 2 to 10 times less sulfur than the product (P2) from step b) and the most often 4 to 10 times less.
  • the extraction solvent is most often a single solvent, but it is possible to also use solvent mixtures.
  • This solvent contains generally less than 20% and often less than 10% by weight of water.
  • This solvent may be an anhydrous solvent. He is often chosen from the group formed by methanol, acetonitrile, monomethylformamide, dimethylformamide, dimethylacetamide, furfural, N-methylpyrrolidone and dimethyl sulfoxide. We very often use a solvent containing no nitrogen and most often a non-nitrogenous solvent oxygen. The preferred solvent is furfural.
  • At least one cosolvent which may be an alcohol of 1 to 6 carbon atoms, for example an alcohol linear or branched, or furfuryl alcohol.
  • the feed to be treated has a high final boiling point and is particularly rich in nitrogen compounds, especially basic, it can be advantageous to introduce with the extraction solvent alone or as a mixture, a minor amount of acids, especially carboxylic acids (less than 1% by weight per solvent, for example).
  • carboxylic acids from 1 to 6 carbon atoms and more especially acids with 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, acid benzoic, and 2-furoic acid.
  • the solvent can be recovered from the raffinate by a stripping or distillation, preferably by steam stripping whose conditions have been described above.
  • the raffinate (R1) obtained in step c) is then sent to step d) by 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).
  • conditions for this separation are chosen so as to obtain a overhead fraction containing almost all of the solvent, that is to say by example, more than 95% by weight of the amount of solvent contained in the raffinate (R1) and introduced into this stripping zone.
  • the extract (E1) obtained at step c) is then sent to a solvent recovery zone (S1) used in step c) in which a product enriched in solvent is recovered (S1) and a product (Q2) depleted in solvent (S1).
  • S1 solvent recovery zone
  • the separation of the solvent from the extract is generally produced by distillation and / or stripping with steam and preferably by distillation followed by steam stripping under the conditions set out above.
  • This extract is therefore separated in conditions for recovering a fraction of enriched head, and preferably highly enriched, in solvent (S1) and a bottoms product (Q2) depleted in solvent (S1).
  • this separation Most often the conditions of this separation are chosen so as to obtain a fraction of head containing the quasi 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 zone of separation. At least about 99% by weight is thus preferably recovered. the quantity of solvent contained in the extract (E1).
  • step a) When operating in step a) under hydrodesulfurization conditions significantly more severe, that is to say in particular in the presence of a very significant amount of catalyst, the product (Q2) which is obtained by distillation of the extract (E1) will most often have a sulfur content less than or equal to about 0.3% by weight.
  • This product (Q2) will be fine heard not usable as fuel for engines, since it contains most often a quantity of sulfur higher than the future standard; through however we can probably use it as fuel.
  • the top product (s), obtained by separation of the raffinate (R1) and optionally extract (E1), enriched in solvent, are recycled in step c) liquid / liquid extraction.
  • At least part of the product (Q2) obtained from the extract (E1) after solvent separation (S1) can be sent to an area hydrodesulfurization separate from the feed hydrodesulfurization zone initial or even be returned to the hydrodesulfurization zone of the stage at).
  • the part of the product (Q2) is subjected to hydrodesulfurization in conditions for obtaining 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.
  • the charge hydrocarbon having an initial boiling point of at least 150 ° C and a boiling point of at most 500 ° C
  • the charge hydrocarbon is sent to a zone of distillation in which a fraction (F1) having a point is separated at the head boiling point of at least 250 ° C and at the bottom a fraction (F2) having a initial boiling point of at least 250 ° C.
  • the fraction (F2) is treated according to the process described above for the charge hydrocarbon 150-500 ° C steps a) to d).
  • the fraction (F1) is sent to a hydrodesulfurization zone distinct from that of step a) in which it is hydrodesulfurized under conventional conditions and for example in the simple conditions described above, then the hydrodesulfurized product (P ') obtained is sent to a separation zone, for example by stripping or by distillation of the product (P ') into a fraction (P10) having a point final boiling point below 150 ° C, and in a fraction (P20) having a point initial boiling point above the final boiling point of the fraction (P10).
  • This product (P20) can, at least in part, be mixed with the product (Q1) obtained from 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: a higher n- and iso-alkane content is obtained in the raffinate (table) than according to the hydrocracking or hydrodesaromatization processes, a higher cetane number, 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.
  • hydrocracking hydrodesaromatisation HDS and extraction density 0.815 to 0.825 0.820 to 0.850 0.815 to 0.840 cetane 53-63 45-60 62-71 n- and iso-alkanes 42-47 35-45 49-56 naphthenes 49-55 25-55 30-41 aromatic 3-7 10.20 10-20 Consumption in hydrogen% > 2 0.6-1.1 ⁇ 0.5
  • 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 letters reference.
  • the hydrocarbon charge to be treated is sent by the line (1) in the hydrodesulfurization zone (HDS1) at the outlet of which retrieve by line 2 a product (P) which is sent to an area of separation (SEP. 1) from which a product is recovered via line 3 (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.) in which also introduces an extraction solvent (S1) via line 5 and from which we recover an extract (E1) by line 7 and a raffinate (R1) by the line 6.
  • This raffinate (R1) is sent by line 6 to an area (D1) of recovery of the solvent (S1) via line 8 and of a petroleum product (Q1) possibly being used as a base in the composition of a diesel engine of improved qualities, by line 9.
  • the extract (E1) is sent by the line 7 in a zone (D2) for recovering the solvent (S1) via line 10 and of a product (Q2) by line 11.
  • This product (Q2) can be, at least in part, recovered by line 11a when valve V4 is open, or be, at less in part, sent by line 11b when the valve V1 is open either in a hydrodesulfurization zone (HDS3) not shown diagrammatically, either in the zone hydrodesulfurization (HDS1).
  • HDS3 hydrodesulfurization zone
  • the hydrocarbon charge to be treated is sent by the line (100) in a zone (TOP) from which a fraction (F2) is recovered heavy with initial boiling point above about 250 ° C which is treated as the hydrocarbon feed according to the description above made in link with figure 1.
  • TOP zone
  • the product (Q1) can be. at less partially recovered by line 9 and line 9a when valve V2 is open, or be, at least in part sent by line 9b in line 140 when valve V3 is open.
  • this petroleum product partially forms a base used in the composition of improved quality diesel fuel.
  • From the (TOP) area we recover on line 110 a slight fraction (F1) of final boiling point greater than about 250 ° C.
  • This fraction (F1) is sent by line 110 in a hydrodesulfurization zone (HDS2) at the outlet of which recovers via line 120 a hydrodesulfurized product (P ') which is sent in a separation zone (SEP. 2) from which we recover by line 130 a product (P10) and by line 140 a product (P20) whose point initial boiling point is higher than the product's final boiling point (P10).
  • This product (P20) is optionally mixed with the product (Q1) arriving via the driving 9b.
  • This mixture or the product (P20) forms a base entering the composition of an improved quality diesel fuel which is recovered by the line 149.
  • the feed used in this example is a diesel distillation cut direct (straight-run) with a cetane number of 55, a total content of aromatic compounds, sulfur and non-sulfur, 30% by weight, one content in n and iso-alkanes of 39% by weight, a naphthene content of 31%, a sulfur content of 1.22% by weight, a nitrogen content expressed by weight 255 ppm nitrogen and a color measured according to ASTM D 1500 equal à 2.
  • This diesel cut has an initial distillation point of 150 ° C and a point final distillation 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 is recovered via line 2, 28% by weight of sulfur and non-sulfur aromatics and a content in n- and iso-alkanes of 40%.
  • This product has a color measured according to the ASTM D-1500 method less than 1 and a nitrogen content of 175 ppm in weight.
  • the cetane number of the product (P) is 56.
  • This product has an end point distillation of 400 ° C. It is sent to a steam stripping zone of water (SEP1) from which a product (P1) is recovered via line 3 having a final distillation point of 220 ° C and through line 4 a product (P2) having an initial distillation point of 220 ° C and an end distillation point 400 ° C.
  • SEP1 steam stripping zone of water
  • This zone is an extraction column comprising a padding formed of Pall rings with an overall efficiency appreciably equal to three theoretical stages. The extraction is carried out against the current, under atmospheric pressure and at a temperature of 70 ° C.
  • a raffinate (R1) which is sent via line 6 to the steam stripping zone (D1) in which the furfural which is recovered by the line 8 for possible recycling to the extraction zone and in tail 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 aromatic sulfur and non-sulfur compounds of 12%, a 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 tank (pool) diesel.
  • 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 recycling of hydrogen 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.
  • 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. He is sent to an area of steam steam stripping (SEP1) from which it is recovered by line 3 a product (P1) having a final distillation point of 220 ° C and by the line 4 a product (P2) having an initial distillation point of 220 ° C and a 400 ° C final distillation point.
  • SEP1 steam steam stripping
  • This area is an extraction column comprising a packing formed by Pall rings with an efficiency roughly equivalent to three theoretical stages. The extraction is carried out against the current, at atmospheric pressure and at temperature of 70 ° C.
  • raffinate (R1) which we send by line 6 in the steam stripping zone (D1) in which we separate at the head the furfural which is recovered by line 8 with a view to its recycling possible at the extraction zone and at the back a raffinate (Q1) containing practically more furfural, having a sulfur content of 0.01% by weight, a cetane number of 69, a content by weight of compounds aromatic sulfur and non-sulfur of 10%, a content of n- and iso-alkanes 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.
  • This product Q2 can be sent via lines 11 and 11a to the fuel pool domesticated.
  • 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.
  • This product has a color measured by ASTM D-1500 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.
  • the product P is steam stripped to remove light fractions ( ⁇ 150 ° C) and hydrogen sulfide formed in the hydrodesulfurization reactor (less than 2% of the initial charge). It is then sent to a distillation zone at from which we recover by line 3 a product (P1) having a point final distillation of 300 ° C and through line 4 a product (P2) having a point initial distillation of 300 ° C.
  • the product (P2) after being cooled to 70 ° C, is sent to an extraction zone (EXT.) by line 4 in which we also introduces by line 5 an amount of furfural equal in volume the quantity of product (P2) introduced into this zone.
  • This area is a extraction column comprising a packing formed by Pall rings with an efficiency roughly equivalent to three theoretical stages.
  • the extraction is carried out against the current, at atmospheric pressure and at temperature of 70 ° C.
  • a raffinate (R1) which we send by line 6 in the distillation zone D1 in which the head is separated furfural which is recovered by line 8 for recycling possible at the extraction zone and at the tail, by line 9, a raffinate (Q1) does not containing practically more furfural.
  • At least part of this product (Q1) is mixed with at least part of the product (P1) free of its light fraction and a fraction (F) having a content of sulfur of 0.01% by weight, a cetane number of 62, a content by weight of 15% sulfur and non-sulfur aromatic compounds, its content of n- and iso-alkanes is 49% by weight, a nitrogen content of 30 ppm and a color Saybolt of 20.
  • This fraction (F) is mixed with the diesel pool.
  • 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 product 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 n- and iso-alkane content 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 1 hour - 1 . The amount of hydrogen consumed is 0.45% compared to the load.
  • This product has a color measured according to the ASTM D-1500 method less than 2 and a nitrogen content of 300 ppm in weight.
  • the cetane number of the product (P) is 56.
  • This product has an end point distillation of 400 ° C. It is sent to a steam stripping zone of water (SEP1) from which a product (P1) is recovered via line 3 having a final distillation point of 300 ° C and through line 4 a product (P2) having an initial distillation point of 300 ° C and an end distillation point 400 ° C.
  • SEP1 steam stripping zone of water
  • This product after being cooled to 70 ° C, (P2) 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 quantity of product (P2) introduced into this zone.
  • This area is a column extraction comprising a packing formed of Pall rings of a efficiency substantially equivalent to three theoretical stages. extraction is carried out against the current, at atmospheric pressure and at temperature 70 ° C.
  • raffinate (R1) which we send via line 6 in the steam stripping zone D1 in which the furfural is separated at the head which is recovered by line 8 for possible recycling to the area extraction and at the end a raffinate (Q1) containing practically no more furfural, having a sulfur content of 0.04% by weight, a cetane number 67, a content by weight of sulfur and non-sulfur aromatics of 20%, an n- and iso-alkane content of 48% by weight, a nitrogen content of 30 ppm and a Saybolt color of 20.
  • the product (Q1) is sent by lines 9, 9b, and 149 to the fuel pool engine.
  • the mixture of P20 and Q1 is a product with 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 a part at less of 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
  • Product P Di- and polyaromatics% by weight Cetane gain after extraction between products Q 1 and P (at isorientation) 3.0 34 7 + 12 5.0 32 4 + 10 7.0 (comparison) 23 1 + 6
  • the feed used in this example is a diesel cut mixture of direct distillation and diesel cut from catalytic cracking, LCO type.
  • the direct distillation diesel cut has a density at 15 ° C of 857, an index of refraction at 60 ° C. of 1.4617, a cetane number of 55, a total content of aromatic, sulfur and non-sulfur compounds, 35.4% by weight, one content in n- and iso-alkanes and naphthenes of 64.6% by weight, a sulfur content 1.33% by weight and a nitrogen content expressed by weight of nitrogen of 124 ppm.
  • the LCO diesel cutter has a density at 15 ° C of 944.1 a refractive index at 60 ° C 1.5245, cetane number 23, total content of compounds aromatic, sulfur and non-sulfur 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 C 1 the load containing 80% of diesel fraction for direct distillation and 20% of LCO cut
  • load C 2 the load containing 50% of diesel fraction for direct distillation and 50% of LCO cut.
  • the cuts C 1 and C 2 have an initial distillation point of 200 ° C and a final distillation point of 400 ° C.
  • the feed C 1 is introduced via line 1 into a hydrodesulfurization zone in which it is subjected to a hydrodesulfurization treatment under a partial pressure of hydrogen 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 is recovered via line 2 and containing 0.051% sulfur, 31% by weight of sulfur aromatic compounds and non-sulfur, 61% by weight of n- and iso-alkanes and 285 ppm of nitrogen.
  • the cetane number of the product (P ') is 53 and its final point of distillation is 400 ° C. It is sent to a steam stripping zone (SEP1) at from which we recover by line 3 a product (P'1) having a point final distillation of 230 ° C, and by line 4 a product (P'2) having a point initial distillation of 230 ° C and a final distillation point of 400 ° C.
  • SEP1 steam stripping zone
  • P'2 having a point initial distillation 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 we also introduce through line 5 a quantity of furfural equal in volume to the quantity of product (P'2) introduced into this zone.
  • This zone is an extraction column comprising a formed packing of Pall rings with an overall efficiency substantially equal to three stages theoretical. Extraction is carried out against the current, under pressure atmospheric and at a temperature of 70 ° C.
  • a raffinate (R'1) that it is sent via line 6 to the steam stripping zone (D1) in which separates at the head the furfural which is recovered by line 8 in view of its possible recycling to the extraction area and at the end a raffinate (Q'1) containing less than 5 ppm of furfural for example, having a content in sulfur of 0.02% by weight, a cetane number of 67.3, a content by weight of sulfur-containing and non-sulfur-containing 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 tank (pool) diesel.
  • the load C 2 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 an end point of distillation of 230 ° C
  • the product (P "2) recovered by line 4 has an initial point of 230 ° C distillation 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 per example, 0.02% by weight of sulfur, a cetane number of 66.1, 17% by weight of sulfur and non-sulfur aromatic compounds, 83% by weight of n- and iso-alkanes and naphthenes, 150 ppm 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 does not contains practically more furfural, 0.12% by weight of sulfur, 87.9% by weight of sulfur and non-sulfur aromatics, 900 ppm nitrogen, 12.1% by weight of n- and iso-alkanes and naphthenes, and a density at 15 ° C of 985.3.
  • 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 pressure of hydrogen of 2.5 MPa, at a temperature of 330 ° C. with a recycling of hydrogen of 200 liters per liter of charge and an hourly space speed of 2.5 h -1 .
  • This hydrodesulfurization produces a product having a sulfur content of 0.2% by weight. Its other characteristics are practically unchanged.
  • This product can be mixed with household fuel, that is to say introduced into what those skilled in the art call the domestic fuel pool.

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Claims (11)

  1. Verfahren zur Herstellung eines Erdölerzeugnisses, welches als Grundbestandteil in der Zusammensetzung eines Brennstoffs für Verbrennungsmotoren mit Zündung durch Verdichtung dienen kann, welches einen Zetanwert und einen Gehalt an veredeltem Schwefel aufweist, ausgehend von einer bituminösen Beschickung, die einen unteren Siedepunkt von mindestens 150°C hat und einen oberen Siedepunkt von über 500°C hat, enthaltend 0,05 Gewichts-% bis 5 Gewichts-% Schwefel, 10 bis 60 Gewichts-% n- und iso-Alkan, 10 Gewichts-% bis 85 Gewichts-% aromatische Kohlenwasserstoffe zumindest teilweise in Form von polyaromatischen, schwefelhaltigen oder nicht Bestandteilen, einen Zetanwert von 20 bis 60 habend und einen Stickstoffgehalt von 50 bis 5 000 ppm nach Gewicht habend, wobei das besagte Verfahren dadurch gekennzeichnet ist, dass es die folgenden Schritte umfaßt:
    einen Wasserstoffbehandlungs-Schritt a), in welchem man die Wasserstoffbehandlung der besagten Beschickung unter Bedingungen, die es zulassen, ein Produkt (P) zu erhalten, welches eine 2- bis 50-fach geringere Menge Schwefels als die AusgangsBeschickung enthält, durchführt, wobei die besagte Wasserstoffbehandlung unter einem Wasserstoffpartialdruck am Ausgang des Reaktors von 0,5MPa (Megapascal) bis 6 MPa durchgeführt wird, so dass das Entaromatisierungsverhältnis der Beschickung höchstens gleich 30% ist,
    einen Separations-Schritt b) des Produktes (P) in ein Produkt (P2), das einen unteren Siedepunkt oberhalb der Siedetemperatur des Extraktionslösungsmittels des folgenden Schrittes c) und vorzugsweise mindestens oberhalb von 20°C hat, und ein Produkt (P1), das einen oberen Siedepunkt unterhalb des unteren Siedepunktes des Produktes P2 hat,
    einen Schritt c) der flüssig/flüssig Extraktion, in welchem man bei einer Extraktionstemperatur von mindestens gleich 140°C unter Extraktionsbedingungen der polyaromatischen Bestandteile das in Schritt b) erzeugte Produkt (P2) mit einem Lösungsmittel oder einem Gemisch von Lösungsmitteln (S1), das es zuläßt, die polyaromatischen Bestandteile, die es enthält, zumindest teilweise zu extrahieren, zusammenbringt, wobei das besagte Lösungsmittel einen unteren Siedepunkt unterhalb des unteren Siedepunktes des in Schritt b) erzeugten Produktes (P2) hat, und im Verlaufe dessen man ein mit polyaromatischen, schwefelhaltigen oder nicht Bestandteilen angereichertes Extrakt (E1) und ein Raffinat (R1) zurückgewinnt und,
    einen Schritt d) der Rückgewinnung des im Schritt c) eingesetzten Lösungsmittels (S1) ausgehend von dem im Schritt c) erzeugten Raffinat (R1), in welchem man ein mit Lösungsmittel (S1) angereichertes Produkt und ein mit Lösungsmittel (S1) abgereichertes Produkt (Q1), das einen verbesserten Zetanwert hat und weniger als 500ppm nach Gewicht Schwefels enthält, zurückgewinnt;
    wobei das Verfahren außerdem dadurch gekennzeichnet ist, dass mindestens ein Teil des sich aus Schritt b) ergebenden Produktes (P1) seiner leichten Fraktion entledigt und mindestens mit einem Teil des sich aus Schritt d) ergebenden Produktes (Q1) vermischt wird.
  2. Verfahren nach dem Anspruch 1, in welchem der Wasserstoffdruck am Ausgang des Reaktors zwischen 1 und 5MPa liegt, so dass das Entaromatisierungsverhältnis der Beschickung höchstens gleich 15% ist.
  3. Verfahren nach einem der Ansprüche 1 bis 2, in welchem der Schritt c) unter Bedingungen durchgeführt wird, die die Erzeugung eines Raffinates (R1) zulassen, das höchstens 90 Gewichts-% des Gesamtgewichtes der in dem in Schritt b) erzeugten Produkt (P2) vorhandenen, in ihren Molekülen keine Schwefelatome enthaltenen aromatischen Kohlenwasserstoffe enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, in welchem das in Schritt c) erzeugte Extrakt (E1) in einen Rückgewinnungsbereich für das in dem Schritt c) eingesetzte Lösungsmittel (S1) geleitet wird, in welchem man ein mit Lösungsmittel (S1) angereichertes Produkt und ein mit Lösungsmittel (S1) abgereichertes Produkt (Q2) zurückgewinnt.
  5. Verfahren nach dem Anspruch 4, in welchem das Bodenprodukt (Q2) in einen von dem Wasserstoffbehandlungsbereich des Schrittes a) verschiedenen Wasserstoffbehandlungsbereich eingeleitet wird, wo es einer Wasserstoffbehandlung unter Bedingungen, die es zulassen, ein Produkt (P3) mit einem Schwefelgehalt unterhalb oder gleich 0,3 Gewichts-% zu erzeugen, unterzogen wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in welchem das oder die durch Separation des Raffinats (R1) und eventuell des Extrakts (E1) erhaltenen, mit Lösungsmittel (S1) angereicherten Kopfprodukte zu dem Schritt c) der flüssig/flüssig Extraktion zurückgeführt werden.
  7. Verfahren nach einem der Ansprüche 1 bis 6, in welchem das Lösungsmittel aus der aus Methanol, Acetonitril, Monomethylformamid, Dimethylformamid, Dimethylacetamid, Furfural, N-Methylpyrrolidon und Dimethylsulfoxid gebildeten Gruppe ausgewählt wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, in welchem das verwendete Lösungsmittel ein nicht stickstoffhaltiges, nicht sauerstoffhaltiges Lösungsmittel ist.
  9. Verfahren nach einem der Ansprüche 1 bis 8, in welchem man im Wasserstoffbehandlungs-Schritt a) zusätzlich zu der zu behandelnden bituminösen Beschickung mindestens einen Teil des ausgehend von dem Extrakt (E1) des Schrittes c) nach der Separation des Lösungsmittels (S1) erhaltenen Bodenprodukts in den Wasserbehandlungsreaktor einleitet.
  10. Verfahren nach einem der Ansprüche 1 bis 9, in welchem die bituminöse Beschickung, die einen unteren Siedepunkt von mindestens 150°C und einen oberen Siedepunkt von höchstens 500°C hat, in eine Destillationszone geleitet wird, in welcher man am Kopfende eine Fraktion (F1), die einen oberen Siedepunkt von mindestens 250°C hat, und am Fußende eine Fraktion, die einen unteren Siedepunkt von mindestens 250°C hat, separiert, wobei das besagte Verfahren dadurch gekennzeichnet ist, dass die Fraktion (F2) gemäß dem Verfahren nach einem der Ansprüche 1 bis 9 behandelt wird, und dadurch gekennzeichnet, dass die Fraktion (F1) in einen von dem des Schrittes a) verschiedenen Wasserstoffbehandlungsbereich eingeleitet wird, von dem aus man ein wasserstoffbehandeltes Produkt (P') zurückgewinnt, welches man in einen Separationsbereich leitet, von dem aus man eine Fraktion (P10), die einen oberen Siedepunkt unterhalb von 150°C hat, und eine Fraktion (P20), die einen unteren Siedepunkt oberhalb des oberen Siedepunktes der Fraktion (P10) hat, zurückgewinnt.
  11. Verfahren nach den Ansprüchen 9 und 10, in welchem die Fraktion (P20) zumindest teilweise mit dem im Schritt d) erzeugten Produkt (Q1) oder mit dem Gemisch aus dem Produkt (Q1) und dem seiner leichten Fraktion entledigten Produkt (P1) vermischt wird.
EP94403024A 1993-12-28 1994-12-26 Verfahren zur Erzeugung eines Brennstoffes für innere Verbrennungsmotoren durch Wasserstoffbehandlung und Extraktion Expired - Lifetime EP0661371B1 (de)

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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
WO2003044132A1 (fr) * 2001-11-22 2003-05-30 Institut Francais Du Petrole Procede d'hydrotraitement de distillats moyens en deux etapes comprenant deux boucles de recyclage d'hydrogene
FR2900157B1 (fr) * 2006-04-24 2010-09-24 Inst Francais Du Petrole Procede de desulfuration d'essences olefiniques comprenant au moins deux etapes distinctes d'hydrodesulfuration
US8424181B2 (en) * 2009-04-17 2013-04-23 Exxonmobil Research And Engineering Company High pressure revamp of low pressure distillate hydrotreating process units
EA201590289A1 (ru) * 2012-07-31 2015-10-30 Сетамакс Венчерз Лтд. Способы и системы для комбинированной окислительной обработки и гидрообработки углеводородного топлива
FR3015514B1 (fr) 2013-12-23 2016-10-28 Total Marketing Services Procede ameliore de desaromatisation de coupes petrolieres
WO2017200640A1 (en) * 2016-05-17 2017-11-23 Exxonmobil Research And Engineering Company Jet and diesel selective hydrocracking
EP3464517A1 (de) * 2016-05-25 2019-04-10 ExxonMobil Research and Engineering Company Herstellung von aufgewertetem extrakt und raffinat
AU2017328489B2 (en) * 2016-09-19 2021-09-23 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Novel, highly efficient eco-friendly processes for converting CO2 or CO-rich streams to liquid fuels and chemicals
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DE69433053D1 (de) 2003-09-25
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US5925234A (en) 1999-07-20
FR2714387B1 (fr) 1996-02-02

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