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EP1699905A1 - Method for treating a hydrocarbon feedstock including resin removal - Google Patents

Method for treating a hydrocarbon feedstock including resin removal

Info

Publication number
EP1699905A1
EP1699905A1 EP04805695A EP04805695A EP1699905A1 EP 1699905 A1 EP1699905 A1 EP 1699905A1 EP 04805695 A EP04805695 A EP 04805695A EP 04805695 A EP04805695 A EP 04805695A EP 1699905 A1 EP1699905 A1 EP 1699905A1
Authority
EP
European Patent Office
Prior art keywords
fraction
extraction
residue
heavy fraction
resins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP04805695A
Other languages
German (de)
French (fr)
Inventor
Christophe Gueret
Raphaël HUYGHE
Hugues Dulot
Patrick Euzen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1699905A1 publication Critical patent/EP1699905A1/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/14—Hydrocarbons
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G67/0454—Solvent desasphalting
    • C10G67/049—The hydrotreatment being a hydrocracking
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents

Definitions

  • the present invention relates to the technical field of the cracking of hydrocarbon charges.
  • the invention relates to a process in which the resins are removed from a charge comprising hydrocarbons before the cracking of this charge.
  • the elimination of pollutants is generally carried out on the entire load of hydrocarbons which must undergo a catalytic treatment. This implies a suitable dimensioning of the means for extracting these pollutants as a function of the flow rate of the charge.
  • the extraction means used must be sized according to the concentration and the nature of these pollutants.
  • the subject of the present invention is therefore a process for the treatment of a hydrocarbon feedstock of which at least 80% of the compounds have a boiling point greater than or equal to 340 ° C., process in which: a) the feedstock is sent to a fractionation step during which we recover:
  • At least part of the heavy fraction is sent in an extraction step during which at least part of the resins are extracted contained in said heavy fraction and a purified fraction is recovered, c) a mixture is produced comprising at least part of the purified fraction obtained in the extraction stage and at least a light fraction obtained in the fractionation stage, and d) the mixture thus obtained is sent in a cracking step.
  • the hydrocarbon charge of the invention is such that at least 80% of the compounds have a boiling point greater than or equal to 340 ° C, preferably greater than 350 ° C.
  • the hydrocarbon charge generally contains more than 30% by weight, preferably more than 50% by weight, of boiling compounds 340 ° C and 700 ° C.
  • the hydrocarbon feedstock can be a residue from direct (atmospheric) distillation, a conversion process such as coking, a fixed bed hydroconversion process such as the HYVAHL process or a process in a bubbling bed such as the H-Oil process.
  • the hydrocarbon charge can be formed by mixing the charges mentioned above, and this in any proportion.
  • the invention proves to be particularly advantageous for fillers of hydrocarbons rich in impurities such as nitrogen, polyaromatics or having a Conradson Carbon or a high asphaltene content. This is for example the case of heavy crude residue, or West African residue.
  • an extraction step is carried out on at least part of a heavy fraction of the hydrocarbon feedstock.
  • All the heavy fractions are generally obtained with a yield of at least 15% by weight relative to the 340-700 ° C fraction of the hydrocarbon feed.
  • the heavy fraction is obtained with a yield of at least 20% by weight, or even at least 30% by weight relative to the distillate under vacuum.
  • the heavy fraction may contain at least 90% by weight of compounds boiling below 700 ° C and above 480 ° C, or even above 500 ° C.
  • At least one light fraction is obtained during the fractionation step which, unlike said heavy fraction, is not extracted. At least one light fraction is obtained with a yield of at least 5% by weight relative to the 340-700 ° C fraction of the filler, preferably at least 20% or at least 50%.
  • this light fraction comprises at least 90% by weight of compounds boiling below 450 ° C, preferably below 480 ° C, more preferably below 500 ° C.
  • a single heavy fraction is obtained, and preferably all of this fraction is treated in the extraction step.
  • the extraction step is implemented to selectively extract resins.
  • These resins are generally present in the 340 ° C-700 ° C fraction of the hydrocarbon feedstock used in the process of the invention.
  • the resin content in the 340 ° C-700 ° C fraction of the filler can range from 3 to 15% by weight.
  • the heavy fraction resulting from the first fractionation stage may, for its part, have a resin content of more than 5% by weight, or even more than 10% by weight, or even even more than 15% by weight.
  • resin In the petroleum field, the term resin generally designates constituents which have been eluted on solid adsorbents by polar solvents. Thus, resins are generally characterized by their polarity rather than their chemical nature; hence the implementation of separation methods to isolate them.
  • These separation methods making it possible to isolate the resins can be methods of liquid chromatography on petroleum fractions of the distillate type under vacuum or residue, in which: - firstly, these sections with a solvent such as n-heptane to precipitate asphaltenes and recover a soluble portion comprising the maltenes, and - in a second step, the resins are isolated by elution of said soluble portion in a chromatographic column containing, for example, activated alumina and silica gel using a very polar solvent, such as a mixture of methylene chloride, toluene and methanol.
  • the resins isolated by these characterization methods mainly consist of a mixture comprising condensed naphtheno-aromatic compounds, compounds containing sulfur, nitrogen, oxygen, and possibly metals such as nickel and vanadium. .
  • an extraction step in which the aim is to selectively extract the resins, makes it possible to improve the activity and / or the selectivity of the catalysts used in the subsequent steps of the process of the invention.
  • the selective extraction of the resins defined above makes it possible to significantly improve the performance of the subsequent cracking step of the process of the invention.
  • At least 10% by weight of the resins contained in said heavy fraction are extracted from the heavy fraction (quantitative determination by a separation method of the ASTM-D-4124 type).
  • At least 20% by weight, preferably at least 40% by weight, or even at least 50% by weight, are extracted from the resins contained in the heavy fraction.
  • the resins extracted from the heavy fraction are generally polar compounds.
  • the polarity of these resins can be determined from the relationship that exists between, on the one hand said polarity and, on the other hand, the naphtheno-aromatic structure and the nitrogen content of these resins. In fact, at least 90% by weight, or even at least 95% by weight of the nitrogen of a vacuum distillate is generally contained in the resins of said vacuum distillate.
  • the naphtheno-aromatic structure can be determined by nuclear magnetic resonance (NMR 13 C and 1 H, cf. ASTM D5292).
  • the nitrogen content can, for its part, be measured by chemiluminescence (cf. ASTM D4629).
  • C 13 NMR Analysis by nuclear magnetic resonance (C 13 NMR) shows that the average structure of the resins in the heavy fraction can be characterized by: an aromatic carbon content (CA) greater than 50% by weight, or even greater than 60% by weight, - a quaternary aromatic carbon content greater than 30% by weight, or even greater than 35% by weight, an aromatic carbon content quaternary condensed greater than 10% by weight, or even greater than 15% by weight, and a condensation index greater than 2.3, or even greater than 2.6.
  • CA aromatic carbon content
  • the polarity of the resins of this heavy fraction of the vacuum distillate is therefore generally greater than that of the resins of the filler.
  • Extraction of the resins from the heavy fraction generally makes it possible to obtain a purified fraction having a content of polyaromatic compounds comprising up to 5 cycles of less than 2% by weight, preferably less than 1% by weight.
  • This polyaromatic content comprising up to 5 cycles of the purified fraction can be measured by Fischer mass spectrometry (cf. Fischer IP, Fischer P., Talanta, 21, 867-875 (1974) and Bouquet M., Brument J. , Fuel Science and Technology INTL, 8 (9), 961-986 (1990)).
  • Extraction of the resins from the heavy fraction can also make it possible to obtain a purified fraction having a nitrogen content which is reduced by at least 20% by weight, preferably 30% by weight, more preferably 40% by weight relative to the heavy fraction introduced in the extraction step.
  • This nitrogen content of the purified fraction can be measured by chemiluminescence (cf. ASTM D4629).
  • the extraction step can be carried out by any means known to those skilled in the art.
  • this extraction step can be carried out by adsorption / desorption or, preferably by solvent extraction.
  • this extraction step generally comprises bringing the heavy fraction into contact with a solvent based on light hydrocarbons.
  • This contacting can be carried out in an extraction zone or by simple mixing.
  • the quantity of solvent, the temperature, the pressure are chosen so as to allow the formation of two distinct phases constituted on the one hand by a liquid mixture essentially comprising solvent and de-resinated oil and, on the other hand, a mixture fluid essentially comprising solvent and resin oil.
  • the phases thus formed can then be separated from one another, for example by decantation.
  • the solvent of each phase can finally be removed by vaporization so that it can be recycled.
  • This extraction step thus makes it possible to extract a large part of the resin compounds from the treated filler, these compounds generally having naphtheno-aromatic structures.
  • the solvent used during the extraction step is preferably a paraffinic solvent.
  • This solvent can essentially comprise (or consist of) compounds having from 3 to 7 carbon atoms, preferably from 3 to 5 carbon atoms.
  • the yield of oil extracted and the quality of the oil depend on the nature of the solvent used.
  • the yield of the de-resinated oil generally increases with the carbon number of the solvent to the detriment of the quality of the oil extracted.
  • the extraction step is generally carried out in a settling mixer or, preferably in an extraction column.
  • the operating conditions of the extraction step can be comparable to those of a deasphalting process.
  • the volume ratio between the solvent based on light hydrocarbons on the heavy fraction to be extracted is usually between 2 and 12, preferably between 3 and 5.
  • a preformed mixture comprising the heavy fraction and a first fraction of solvent is introduced into an extraction column in order to carry out the precipitation of a resin phase by decantation at the bottom. of the column.
  • a second fraction of solvent is introduced into the decantation zone.
  • the settling of the resin part is then obtained by washing with pure solvent against the current of the emulsion of the resin fraction in a mixture essentially comprising solvent and oil. It is favored by an increase in the solvent content, that is to say by replacing the environment comprising the solvent and the oil with a pure solvent environment, and this at a low temperature.
  • the existence of a temperature gradient between the head and the bottom of the extraction column generally makes it possible to create an internal reflux, which has the effect of improving the separation between the oily medium and the resins.
  • the mixture essentially comprising solvent and oil which is heated at the top of the extraction column makes it possible to precipitate a resin fraction which descends into the extraction column. The rising counter-current of this mixture therefore tends to dissolve, at a lower temperature, the lighter resin fractions.
  • the temperature depends on the nature of the solvent used and is generally between 70 and 220 ° C.
  • advantageous operating conditions for the extraction are: - a solvent content between 2/1 and 12/1, preferably between 4/1 and 10/1, - a temperature of the extractor head between 55 and 95 ° C, - a temperature of the extractor bottom between 30 and 80 ° C, - an extractor pressure between 300 and 400 MPa, to be adjusted so that all the products remain in the liquid state, and - a number of theoretical stages between 2 and 5.
  • the cracking step is carried out on a mixture comprising the purified fraction obtained during the extraction step with at least one light fraction obtained during the splitting.
  • a mixture is produced which comprises, in addition, other fractions which can be obtained during the fractionation step, or even from all of these others. fractions.
  • the cracking step of the process of the invention can comprise a catalytic cracking and / or a hydrocracking.
  • the specific conditions of the extraction step of the process of the invention are such that the mixture at the inlet of the cracking step has a high level of purity allowing efficient catalytic cracking.
  • the cracking step comprises a catalytic cracking
  • at least part of the mixture is cracked by a catalytic cracking to obtain an effluent comprising gasoline, diesel and a residue.
  • This catalytic cracking can be a cracking in a fluidized bed, known under the Anglo-Saxon name of "fluid catalytic cracking" or abbreviated as FCC.
  • the process of the invention makes it possible to obtain, at the entry to the cracking step, an effluent having a reduced content of Conradson Carbon and of nitrogen suitable for obtaining a high conversion of the mixture associated with obtaining high gasoline and diesel yields.
  • a catalytic cracking In the case of a catalytic cracking, at least part of the mixture can be catalytically cracked under conditions well known to those skilled in the art to produce a fuel fraction, which can itself comprise a petrol fraction and a diesel fraction, as well as a fraction of type "slurry".
  • This fuel fraction is usually sent, at least in part, to fuel pools.
  • the fraction of the "slurry" type can be sent, at least in part, to the heavy fuel pool or recycled, at least in part at the inlet of the catalytic cracking.
  • conventional catalytic cracking includes cracking processes comprising at least one regeneration step by partial combustion and those comprising at least one regeneration step by total combustion and / or those comprising both at least a partial combustion step and at least one total combustion step.
  • Catalytic cracking is generally described in Ullmans Encyclopedia Of Industrial Chemistry Volume A 18, 1991, pages 61 to 64.
  • the catalytic cracking step can advantageously be preceded by a hydrotreatment.
  • a pretreatment of the mixture by a catalytic process in the presence of hydrogen may be necessary in order, by for example, to protect the cracking catalysts or to improve the quality of the cracking products.
  • This step can be done, for example, with a catalyst of NiMo type on alumina under conditions well known to those skilled in the art.
  • the cracking step is a hydrocracking.
  • At least part of the mixture is cracked on the catalyst in the presence of hydrogen, under conditions well known to those skilled in the art, in order to produce, after distillation, at least one fuel fraction (petrol fraction , a kerosene fraction, a diesel fraction).
  • This fuel fraction (s) is generally sent, at least in part, to the fuel pools.
  • the residue fraction obtained can be treated in different ways.
  • this residue fraction can be sent, at least in part, to a dewaxing and hydrofinishing section to produce oil bases.
  • this residue fraction can be recycled, at least in part, at the entrance to the hydrocracking step.
  • this residue fraction can be sent, at least in part, to an FCC unit.
  • the operating conditions used according to this mode make it possible to achieve conversion by pass into products having boiling points below 340 ° C, or even below 370 ° C, which is greater than 10% by weight, preferably between 15 and 95% by weight.
  • Hydrocracking can be carried out at a temperature ranging from 340 to 450 ° C., preferably ranging from 340 to 420 ° C.
  • the pressure can be significantly reduced compared to the hydrocracking stages of vacuum distillates of the prior art which generally require a high hydrogen partial pressure.
  • the hydrocracking pressure can advantageously range from 4 to 20 MPa, preferably from 4 to 16 MPa. We can distinguish low or moderate pressures (4 to 10 MPa) from higher pressures (more than 10 MPa to 16MPa).
  • hydrocracking includes mild hydrocracking, the objective of which is a pretreatment converting a charge originating from an FCC, hydrorefining, the objective of which is the production of a residue for making lubricating oils and middle distillates, and conventional hydrocracking whose flexibility allows either to produce middle distillates, or jointly middle distillates and a residue to make lubricating oils.
  • An advantage of the process of the invention is to reduce the loss of activity of the catalyst (s) used during the cracking step and / or the catalytic pretreatment step by reducing the impurities which tend to strongly adsorb on the catalyst, which reduce its cracking acid function and / or which are coke precursors. This results, in the case of a catalytic cracking step, by a reduced consumption of fresh catalyst for a given conversion level and, in the case of a hydrocracking step, by a longer cycle time.
  • Another advantage of the process of the invention is, in the case where the cracking step comprises (or is) hydrocracking, to allow a significant reduction in the pressure at which the hydrocracking step is carried out.
  • Selective extraction of the resins makes it possible, in fact, to eliminate the unsaturated compounds which usually consume a large amount of hydrogen from hydrocracking.
  • the implementation of the process of the invention thus makes it possible to reduce the operating cost of the hydrocracker.
  • Another advantage of the invention is to limit the negative effects of resins and nitrogen, in particular on the cracking catalyst.
  • Another advantage of the invention is to limit the negative effects of polyaromatics on the stability of the catalysts and the quality of the products.
  • Another advantage of the process of the invention is, in the case where the cracking step comprises (or is) hydrocracking, of reducing the size of the equipment used during this hydrocracking.
  • Another advantage of the method of the invention is to allow a reduction in the size of the equipment used during the extraction step, the extraction being carried out only on a heavy fraction of the distillate under vacuum.
  • Figure 1 For a better understanding, a preferred embodiment of the method of the invention is illustrated in Figure 1. This embodiment is given by way of example and has no limiting character. This illustration of the process of the invention does not include all of the components necessary for its implementation. Only the elements necessary for understanding the invention are represented, the skilled person being able to complete this representation to implement the invention.
  • the hydrocarbon feedstock is sent via line 1 to a vacuum distillation column 2. From this distillation column, a light fraction is drawn off through line 3, a heavy fraction through line 4 and a vacuum residue through line 5.
  • the heavy fraction withdrawn from column 2 is sent via line 4 to liquid extraction means 10 with a solvent.
  • the solvent is sent to the extraction means via a pipe 11.
  • Solvent can optionally be added via a pipe 12.
  • an external charge can be added through the pipe 13.
  • This charge is for example a vacuum distillate, such as a straight-run vacuum distillate (crude), a vacuum distillate from a heavy load conversion process (coking, H-oil or T-Star bubbling bed, Hyvahl fixed bed). It can also be an aromatic extract from an aromatic extraction unit.
  • the purified fraction and of the solvent coming from the extraction means 10 are drawn off through line 15 and sent to a device for recovering and regenerating the solvent 16.
  • the solvent thus regenerated is sent to the extraction zone through line 11.
  • the residue comprising the resins extracted and the solvent are drawn off through a line 19 and sent to a recovery and regeneration system for the solvent 20.
  • the solvent thus regenerated is sent to the extraction zone via a line 21 and the line 11.
  • the residue comprising the extracted resins which has been freed from the solvent is withdrawn through line 22.
  • the purified fraction freed from the solvent is withdrawn, via a conduit 30.
  • This purified fraction is mixed with the light fraction of the vacuum distillate supplied by the conduit 3.
  • the purified fraction and the light fraction of the vacuum distillate are sent as a mixture, with hydrogen supplied by a line 31, in hydrocracking means 32.
  • the effluent from the hydrocracking means is discharged through line 33 and sent to means 34 for separating the gas and the liquid.
  • the gas is evacuated through a pipe 35.
  • the liquid from the separation means 34 is discharged through a pipe 40 to an atmospheric distillation column 41. From this column are drawn off a gaseous fraction by a pipe 42, a gasoline cut by a pipe 43, a kerosene cut by a pipe 44 , a diesel cut through a pipe 45 and a residue cut through a pipe 46.
  • Example 1 A vacuum distillate was distilled from an atmospheric residue with a yield of 40% by weight. This vacuum distillate has the following properties:
  • This vacuum distillate is introduced into a pilot comprising two reactors in series.
  • the first reactor R1 is filled with catalyst known under the reference HR448 from the company AXENS, a pre-treatment catalyst for vacuum distillate of the NiMo type on alumina, the objective of which is to de-nitrogen the vacuum distillate at very low contents.
  • the second reactor R2 is filled with the catalyst known under the reference HYC642 from the company AXENS, a zeolitic hydrocracking catalyst (zeolite Y on alumina) allowing a conversion of the order of 70% by weight of the 370 ° C + fraction of the vacuum distillate.
  • the operating conditions and yields are given in the following table:
  • Example 1 The vacuum distillate of Example 1 is distilled under vacuum to obtain a light fraction and a heavy fraction corresponding to a cutting point of 500 ° C.
  • the yields and properties of the vacuum distillate and of the two fractions are as follows:
  • the heavy fraction is de-resinated by liquid-liquid extraction with a non-polar paraffinic solvent, propane.
  • the technology used is that commonly used to perform deasphalting of residues under vacuum.
  • 40 kilograms of the heavy fraction were mixed with propane in a stirred reactor with a solvent / heavy fraction volume ratio of 8/1.
  • the mixture is brought to 90 ° C. and stirred for 60 minutes. After this period, the stirring is stopped and the mixture settles for 90 minutes to cause the separation of two phases.
  • the purified phase of the resins at the top of the capacity and the phase rich in resins at the bottom of the capacity are drawn off separately and treated to evaporate the propane.
  • the purified phase of the resins and the phase rich in resins after evaporation of the propane have the following properties, compared to that of the heavy fraction:
  • the mixture thus reconstituted has the following properties compared to the vacuum distillate of Example 1:
  • the mixture has resin and nitrogen contents reduced by about 30% compared to the vacuum distill t of Example 1. This partial purification of the feed may seem low, nevertheless it has the advantage of requiring equipment for 'reduced extraction and have a significant impact on the hydrocracking operating conditions.
  • the mixture thus reconstituted is introduced into the same pilot as in Example 1 with the same catalytic system. To carry out the same overall conversion of the order of 70% by weight of the 370 ° C. + fraction of the mixture as in Example 1, the following operating conditions must be established:
  • Example 2 The operating conditions of Example 2 are characterized with respect to Example 1 by a lower partial pressure of hydrogen of 30 bars, all other things being equal.
  • the yield structure is identical to Example 1 as well as the quality of the products but associated with a hydrogen consumption reduced by 13%.

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Abstract

The invention relates to a method for treating a hydrocarbon feedstock whose at least 80 % of compounds have a boiling point equal or higher than 340 °C. Said method also involves resin removal and consists in transferring said feedstock for a fractionating stage for recovering at least one heavy fraction and at least one light fraction, in transferring at least one part of the heavy fraction for extracting stage for extracting resins contained in said heavy fraction and recovering a purified fraction, in producing a mixture containing at least one part of the purified fraction obtainable at the extracting stage and at least one light fraction obtainable at the fractionating stage and in transferring the thus obtained mixture for to a cracking stage.

Description

PROCEDE DE TRAITEMENT D'UNE CHARGE HYDROCARBONEE INCLUANT UN ENLEVEMENT DES RESINES La présente invention se rapporte au domaine technique du craquage des charges d'hydrocarbures. En particulier, l'invention concerne un procédé dans lequel on élimine les résines d'une charge comportant des hydrocarbures préalablement au craquage de cette charge.The present invention relates to the technical field of the cracking of hydrocarbon charges. In particular, the invention relates to a process in which the resins are removed from a charge comprising hydrocarbons before the cracking of this charge.

La demande de brevet internationale WO 99/67345 décrit une méthode pour produire des carburants plus propres dans laquelle des composés polaires naturels sont préalablement éliminés d'une fraction pétrolière d'hydrocarbures ayant un point d'ébullition compris entre 110 et 560 °C, ce qui permet d'améliorer l'efficacité des traitements catalytiques destinés à produire lesdits carburants. Cette demande de brevet décrit, plus particulièrement, que cette élimination des composés polaires naturels est réalisée par adsorption/désorption ou par extraction au solvant.International patent application WO 99/67345 describes a method for producing cleaner fuels in which natural polar compounds are previously eliminated from a petroleum fraction of hydrocarbons having a boiling point of between 110 and 560 ° C. which improves the efficiency of catalytic treatments intended to produce said fuels. This patent application describes, more particularly, that this elimination of the natural polar compounds is carried out by adsorption / desorption or by solvent extraction.

Dans ce type de méthode, l'élimination des polluants est généralement réalisée sur l'ensemble de la charge d'hydrocarbures devant subir un traitement catalytique. Ceci implique un dimensionnement adaptée des moyens d'extraction de ces polluants en fonction du débit de la charge. De plus, les moyens d'extraction mis en œuvre doivent être dimensionnés en fonction de la concentration et de la nature de ces polluants.In this type of method, the elimination of pollutants is generally carried out on the entire load of hydrocarbons which must undergo a catalytic treatment. This implies a suitable dimensioning of the means for extracting these pollutants as a function of the flow rate of the charge. In addition, the extraction means used must be sized according to the concentration and the nature of these pollutants.

Le brevet américain US 4,454,023 décrit un procédé pour améliorer la fluidité d'un hydrocarbure lourd et visqueux incluant une viscoréduction, une distillation et une extraction au solvant. Ce brevet ne fait pas référence à une quelconque étape de craquage. De plus, la fraction envoyée à l'étape d'extraction au solvant correspond à la fraction la plus lourde de la distillation.US patent US 4,454,023 describes a process for improving the fluidity of a heavy and viscous hydrocarbon including visbreaking, distillation and solvent extraction. This patent does not refer to any cracking step. In addition, the fraction sent to the solvent extraction step corresponds to the heaviest fraction of the distillation.

Il a été trouvé que la mise en œuvre d'une étape d'extraction dans laquelle on extrait sélectivement les résines, et ceci sur une fraction spécifique d'une charge comportant un distillât sous vide, conduit à une réduction significative du montant des investissements et des coûts opératoires du procédé d'élimination des résines et de craquage de ladite charge tout en permettant de maintenir un bon niveau de performances du craquage de ladite charge. Ce niveau de performance du craquage peut s'apprécier en termes d'allongement de la durée de cycle du catalyseur mise en œuvre ou de conditions opératoires plus économiques, par exemple une réduction de pression.It has been found that the implementation of an extraction step in which the resins are selectively extracted, and this on a specific fraction of a feed comprising a vacuum distillate, leads to a significant reduction in the amount of investment and operating costs of the resin removal process and cracking said load while maintaining a good level of cracking performance of said load. This level of cracking performance can be assessed in terms of lengthening the cycle time of the catalyst used or more economical operating conditions, for example a reduction in pressure.

La présente invention a donc pour objet un procédé de traitement d'une charge hyd rocarbonee dont au moins 80% des composés ont un point d'ébullition supérieur ou égal à 340°C, procédé dans lequel : a) on envoie la charge dans une étape de fractionnement lors de laquelle on récupère :The subject of the present invention is therefore a process for the treatment of a hydrocarbon feedstock of which at least 80% of the compounds have a boiling point greater than or equal to 340 ° C., process in which: a) the feedstock is sent to a fractionation step during which we recover:

- au moins une fraction lourde comportant au moins 90% en poids de composés bouillant au-dessus de 450°C et au-dessous de 700°C,- at least one heavy fraction comprising at least 90% by weight of compounds boiling above 450 ° C and below 700 ° C,

- et au moins une fraction légère bouillant en-dessous de la (les) fraction(s) lourde(s),- and at least one light fraction boiling below the heavy fraction (s),

- un résidu bouillant en-dessus de la (les) fraction(s) Iourde(s), b) on envoie au moins une partie de la fraction lourde dans une étape d'extraction lors de laquelle on extrait au moins une partie des résines contenues dans ladite fraction lourde et on récupère une fraction purifiée, c) on réalise un mélange comportant au moins une partie de la fraction purifiée obtenu à l'étape d'extraction et au moins une fraction légère obtenue à l'étape de fractionnement, et d) on envoie le mélange ainsi obtenu dans une étape de craquage..- a boiling residue above the yeast fraction (s), b) at least part of the heavy fraction is sent in an extraction step during which at least part of the resins are extracted contained in said heavy fraction and a purified fraction is recovered, c) a mixture is produced comprising at least part of the purified fraction obtained in the extraction stage and at least a light fraction obtained in the fractionation stage, and d) the mixture thus obtained is sent in a cracking step.

La charge d'hydrocarbures de l'invention est telle que au moins 80 % des composés ont un point d'ébullition supérieur ou égal à 340°C, de préférence supérieur à 350°C.The hydrocarbon charge of the invention is such that at least 80% of the compounds have a boiling point greater than or equal to 340 ° C, preferably greater than 350 ° C.

La charge d'hydrocarbures contient généralement plus de 30 % en poids, de préférence plus de 50 % en poids, de composés bouillant 340°C et 700°C. La charge d'hydrocarbures peut être un résidu provenant d'une distillation directe (atmosphérique), d'un procédé de conversion tel que la cokéfaction, d'un procédé d'hydroconversion en lit fixe tel que le procédé HYVAHL ou d'un procédé en lit bouillonnant tel que le procédé H-Oil. La charge d'hydrocarbures peut être formée par mélange des charges évoquées ci-dessus, et ceci dans n'importe quelle proportion.The hydrocarbon charge generally contains more than 30% by weight, preferably more than 50% by weight, of boiling compounds 340 ° C and 700 ° C. The hydrocarbon feedstock can be a residue from direct (atmospheric) distillation, a conversion process such as coking, a fixed bed hydroconversion process such as the HYVAHL process or a process in a bubbling bed such as the H-Oil process. The hydrocarbon charge can be formed by mixing the charges mentioned above, and this in any proportion.

L'invention se révèle particulièrement intéressante pour des charges d'hydrocarbures riches en impuretés telles que l'azote, les polyaromatiques ou présentant un Carbone Conradson ou une teneur en asphaltenes élevée. C'est par exemple le cas de résidu de brut lourd, ou de résidu ouest africain.The invention proves to be particularly advantageous for fillers of hydrocarbons rich in impurities such as nitrogen, polyaromatics or having a Conradson Carbon or a high asphaltene content. This is for example the case of heavy crude residue, or West African residue.

Selon un aspect de l'invention, une étape d'extraction est mise en œuvre sur au moins une partie d'une fraction lourde de la charge d'hydrocarbure.L'ensemble des fractions lourdes est généralement obtenu avec un rendement d'au moins 15 % en poids par rapport à la fraction 340-700°C de la charge d'hydrocarbures. De préférence, la fraction lourde est obtenue avec un rendement d'au moins 20 % en poids, voire d'au moins 30 % en poids par rapport au distillât sous vide.According to one aspect of the invention, an extraction step is carried out on at least part of a heavy fraction of the hydrocarbon feedstock. All the heavy fractions are generally obtained with a yield of at least 15% by weight relative to the 340-700 ° C fraction of the hydrocarbon feed. Preferably, the heavy fraction is obtained with a yield of at least 20% by weight, or even at least 30% by weight relative to the distillate under vacuum.

La fraction lourde peut comporter au moins 90 % en poids de composés bouillant au-dessous de 700°C et au-dessus de 480 °C, voire au-dessus de 500 °C.The heavy fraction may contain at least 90% by weight of compounds boiling below 700 ° C and above 480 ° C, or even above 500 ° C.

Parallèlement à cette fraction lourde, on obtient, lors de l'étape de fractionnement, au moins une fraction légère qui, contrairement à ladite fraction lourde, ne fait pas l'objet d'une extraction. Au moins une fraction légère est obtenue avec un rendement d'au moins 5 % en poids par rapport à la fraction 340-700°C de la charge, de préférence au moins 20% ou au moins 50%.At the same time as this heavy fraction, at least one light fraction is obtained during the fractionation step which, unlike said heavy fraction, is not extracted. At least one light fraction is obtained with a yield of at least 5% by weight relative to the 340-700 ° C fraction of the filler, preferably at least 20% or at least 50%.

De préférence, cette fraction légère comporte au moins 90 % en poids de composés bouillant au-dessous de 450°C, de préférence au-dessous de 480°C, de manière plus préférée au-dessous de 500°C. De manière préférée, une seule fraction lourde est obtenue, et de manière préférée la totalité de cette fraction est traitée dans l'étape d'extraction.Preferably, this light fraction comprises at least 90% by weight of compounds boiling below 450 ° C, preferably below 480 ° C, more preferably below 500 ° C. Preferably, a single heavy fraction is obtained, and preferably all of this fraction is treated in the extraction step.

Selon un autre aspect de l'invention, l'étape d'extraction est mise en œuvre pour extraire sélectivement des résines.According to another aspect of the invention, the extraction step is implemented to selectively extract resins.

Ces résines sont généralement présentes dans la fraction 340°C-700°C de la charge d'hydrocarbures mis en œuvre dans le procédé de l'invention.These resins are generally present in the 340 ° C-700 ° C fraction of the hydrocarbon feedstock used in the process of the invention.

La teneur en résines dans la fraction 340°C-700°C de la charge peut aller de 3 à 15 % en poids.The resin content in the 340 ° C-700 ° C fraction of the filler can range from 3 to 15% by weight.

La fraction lourde issue de la première étape de fractionnement peut, quant à elle, comporter une teneur en résines supérieure à 5 % en poids, voire supérieure à 10 % en poids, voire même supérieure à 15% en poids.The heavy fraction resulting from the first fractionation stage may, for its part, have a resin content of more than 5% by weight, or even more than 10% by weight, or even even more than 15% by weight.

Dans le domaine du pétrole, le terme résine désigne généralement des constituants qui ont été élues sur des adsorbants solides par des solvants polaires. Ainsi, les résines sont généralement caractérisées par leur polarité plutôt que par leur nature chimique; d'où la mise en œuvre de méthodes de séparation pour les isoler.In the petroleum field, the term resin generally designates constituents which have been eluted on solid adsorbents by polar solvents. Thus, resins are generally characterized by their polarity rather than their chemical nature; hence the implementation of separation methods to isolate them.

Ces méthodes de séparation (telle que ASTM- D-4124) permettant d'isoler les résines peuvent être des méthodes de chromatographie liquide sur des coupes pétrolières de type distillât sous vide ou résidu, dans lesquelles : - dans un premier temps, on mélange ces coupes avec un solvant tel que du n-heptane pour précipiter des asphaltenes et récupérer une portion soluble comportant les maltènes, et - dans un deuxième temps, on isole les résines par élution de ladite portion soluble dans une colonne chromatographique contenant, par exemple, de l'alumine activée et du gel de silice à l'aide d'un solvant très polaire, tel qu'un mélange de méthylène chloride de toluène et de méthanol. Les résines isolées par ces méthodes de caractérisation sont principalement constituées d'un mélange comportant des composés naphténo-aromatiques condensés, des composés contenant du soufre, de l'azote, de l'oxygène, et éventuellement des métaux tels que du nickel et du vanadium.These separation methods (such as ASTM-D-4124) making it possible to isolate the resins can be methods of liquid chromatography on petroleum fractions of the distillate type under vacuum or residue, in which: - firstly, these sections with a solvent such as n-heptane to precipitate asphaltenes and recover a soluble portion comprising the maltenes, and - in a second step, the resins are isolated by elution of said soluble portion in a chromatographic column containing, for example, activated alumina and silica gel using a very polar solvent, such as a mixture of methylene chloride, toluene and methanol. The resins isolated by these characterization methods mainly consist of a mixture comprising condensed naphtheno-aromatic compounds, compounds containing sulfur, nitrogen, oxygen, and possibly metals such as nickel and vanadium. .

Il a été constaté qu'une étape d'extraction, dans laquelle on vise à extraire sélectivement les résines, permet d'améliorer l'activité et/ou la sélectivité des catalyseurs mis en œuvre dans les étapes ultérieures du procédé de l'invention. Ainsi, l'extraction sélective des résines définies ci-dessus permet d'améliorer singulièrement les performances de l'étape de craquage ultérieure du procédé de l'invention.It has been found that an extraction step, in which the aim is to selectively extract the resins, makes it possible to improve the activity and / or the selectivity of the catalysts used in the subsequent steps of the process of the invention. Thus, the selective extraction of the resins defined above makes it possible to significantly improve the performance of the subsequent cracking step of the process of the invention.

Lors de l'étape d'extraction, on extrait de la fraction lourde au moins 10 % en poids des résines contenues dans ladite fraction lourde (détermination quantitative par une méthode de séparation de type ASTM- D-4124).During the extraction step, at least 10% by weight of the resins contained in said heavy fraction are extracted from the heavy fraction (quantitative determination by a separation method of the ASTM-D-4124 type).

De préférence, on extrait au moins 20 % en poids, de préférence au moins 40 % en poids, voire au moins 50 % en poids des résines contenues dans la fraction lourde.Preferably, at least 20% by weight, preferably at least 40% by weight, or even at least 50% by weight, are extracted from the resins contained in the heavy fraction.

Les résines extraites de la fraction lourde sont généralement des composés polaires. La polarité de ces résines peut être déterminée à partir de la relation qu'il existe entre, d'une part ladite polarité et, d'autre part, la structure naphténo- aromatique et la teneur en azote de ces résines. En effet, au moins 90% en poids, voire au moins 95% en poids de l'azote d'un distillât sous vide est généralement contenu dans les résines dudit distillât sous vide.The resins extracted from the heavy fraction are generally polar compounds. The polarity of these resins can be determined from the relationship that exists between, on the one hand said polarity and, on the other hand, the naphtheno-aromatic structure and the nitrogen content of these resins. In fact, at least 90% by weight, or even at least 95% by weight of the nitrogen of a vacuum distillate is generally contained in the resins of said vacuum distillate.

La structure naphténo-aromatique peut être déterminée par résonance magnétique nucléaire (RMN du C13 et 1H, cf. ASTM D5292) . La teneur en azote peut, quant à elle, être mesurée par chimiluminescense (cf. ASTM D4629).The naphtheno-aromatic structure can be determined by nuclear magnetic resonance (NMR 13 C and 1 H, cf. ASTM D5292). The nitrogen content can, for its part, be measured by chemiluminescence (cf. ASTM D4629).

Une analyse par résonance magnétique nucléaire (RMN du C13) montre que la structure moyenne des résines dans la fraction lourde peut être caractérisée par : un taux de carbone aromatique (CA) supérieur à 50 % en poids, voire supérieur à 60 % en poids, - un taux de carbone aromatique quaternaire supérieur à 30 % en poids, voire supérieur à 35 % en poids, un taux de carbone aromatique quaternaire condensé supérieur à 10 % en poids, voire supérieur à 15 % en poids, et un indice de condensation supérieur à 2,3, voire supérieur à 2,6.Analysis by nuclear magnetic resonance (C 13 NMR) shows that the average structure of the resins in the heavy fraction can be characterized by: an aromatic carbon content (CA) greater than 50% by weight, or even greater than 60% by weight, - a quaternary aromatic carbon content greater than 30% by weight, or even greater than 35% by weight, an aromatic carbon content quaternary condensed greater than 10% by weight, or even greater than 15% by weight, and a condensation index greater than 2.3, or even greater than 2.6.

L'analyse par RMN du C13 des résines de la fraction 340°C-700°C de la charge montre que la structure moyenne de ces résines peut être caractérisée par : un taux de carbone aromatique (CA) inférieur à 50 % en poids, un taux de carbone aromatique quaternaire inférieur à 30 % en poids, un taux de carbone aromatique quaternaire condensé inférieur à 10 % en poids, et un indice de condensation inférieur à 2,3.Analysis by C 13 NMR of the resins of the 340 ° C-700 ° C fraction of the filler shows that the average structure of these resins can be characterized by: an aromatic carbon (CA) level of less than 50% by weight , a quaternary aromatic carbon content of less than 30% by weight, a condensed quaternary aromatic carbon content of less than 10% by weight, and a condensation index of less than 2.3.

Une analyse par chimiluminescense de la teneur en azote montre que la teneur en azote des résines de la fraction lourde peut être 1 ,5 fois supérieure, voire 2 fois supérieure, voire même 2,5 fois supérieure à celle des résines de la charge.An analysis by chemiluminescence of the nitrogen content shows that the nitrogen content of the resins of the heavy fraction can be 1, 5 times greater, or even 2 times greater, or even 2.5 times greater than that of the resins of the filler.

La polarité des résines de cette fraction lourde du distillât sous vide est donc généralement supérieure à celle des résines de la charge.The polarity of the resins of this heavy fraction of the vacuum distillate is therefore generally greater than that of the resins of the filler.

L'extraction des résines de la fraction lourde permet généralement d'obtenir une fraction purifiée ayant une teneur en composés polyaromatiques comportant jusqu'à 5 cycles inférieure à 2 % en poids, de préférence inférieure à 1 % en poids. Cette teneur en polyaromatiques comportant jusqu'à 5 cycles de la fraction purifiée peut être mesurée par spectrométrie de masse Fischer (cf. Fischer I.P, Fischer P., Talanta, 21 , 867-875(1974) et Bouquet M., Brument J., Fuel Science and Technology INTL, 8(9), 961-986 (1990)).Extraction of the resins from the heavy fraction generally makes it possible to obtain a purified fraction having a content of polyaromatic compounds comprising up to 5 cycles of less than 2% by weight, preferably less than 1% by weight. This polyaromatic content comprising up to 5 cycles of the purified fraction can be measured by Fischer mass spectrometry (cf. Fischer IP, Fischer P., Talanta, 21, 867-875 (1974) and Bouquet M., Brument J. , Fuel Science and Technology INTL, 8 (9), 961-986 (1990)).

L'extraction des résines de la fraction lourde peut permettre également d'obtenir une fraction purifiée ayant une teneur en azote qui est réduite d'au moins 20 % en poids, de préférence de 30 % en poids, de manière plus préférée de 40 % en poids par rapport à la fraction lourde introduite dans l'étape d'extraction. Cette teneur en azote de la fraction purifiée peut être mesurée par chimiluminescence (cf. ASTM D4629).Extraction of the resins from the heavy fraction can also make it possible to obtain a purified fraction having a nitrogen content which is reduced by at least 20% by weight, preferably 30% by weight, more preferably 40% by weight relative to the heavy fraction introduced in the extraction step. This nitrogen content of the purified fraction can be measured by chemiluminescence (cf. ASTM D4629).

L'étape d'extraction peut être réalisée par tout moyen connu de l'homme du métier. En particulier, cette étape d'extraction peut être réalisée par adsorption/désorption ou, de préférence par extraction au solvant.The extraction step can be carried out by any means known to those skilled in the art. In particular, this extraction step can be carried out by adsorption / desorption or, preferably by solvent extraction.

Dans le cas préféré où l'étape d'extraction est réalisée par extraction au solvant, cette étape d'extraction comprend généralement une mise en contact de la fraction lourde avec un solvant à base d'hydrocarbures légers. Cette mise en contact peut être réalisée dans une zone d'extraction ou par simple mélange. La quantité de solvant, la température, la pression sont choisies de manière à permettre la formation de deux phases distinctes constituées d'une part par un mélange liquide comportant essentiellement du solvant et de l'huile dérésinée et, d'autre part, un mélange fluide comportant essentiellement du solvant et de l'huile résinique. Les phases ainsi formées peuvent être ensuite séparées l'une de l'autre, par exemple par décantation. Le solvant de chaque phase peut être finalement éliminé par vaporisation afin de pouvoir être recyclé.In the preferred case where the extraction step is carried out by solvent extraction, this extraction step generally comprises bringing the heavy fraction into contact with a solvent based on light hydrocarbons. This contacting can be carried out in an extraction zone or by simple mixing. The quantity of solvent, the temperature, the pressure are chosen so as to allow the formation of two distinct phases constituted on the one hand by a liquid mixture essentially comprising solvent and de-resinated oil and, on the other hand, a mixture fluid essentially comprising solvent and resin oil. The phases thus formed can then be separated from one another, for example by decantation. The solvent of each phase can finally be removed by vaporization so that it can be recycled.

Cette étape d'extraction permet ainsi d'extraire une grande partie des composés résiniques de la charge traitée, ces composés ayant généralement des structures naphténo-aromatiques.This extraction step thus makes it possible to extract a large part of the resin compounds from the treated filler, these compounds generally having naphtheno-aromatic structures.

Le solvant utilisé lors de l'étape d'extraction est préférentiellement un solvant paraffinique. Ce solvant peut comporter essentiellement (ou être constitué de) des composés ayant de 3 à 7 atomes de carbone, préférentiellement de 3 à 5 atomes de carbone.The solvent used during the extraction step is preferably a paraffinic solvent. This solvent can essentially comprise (or consist of) compounds having from 3 to 7 carbon atoms, preferably from 3 to 5 carbon atoms.

Le rendement en huile extraite et la qualité de l'huile dépendent de la nature du solvant mis en œuvre. Le rendement de l'huile dérésinée augmente généralement avec le nombre de carbone du solvant au détriment de la qualité de l'huile extraite. L'étape d'extraction est généralement réalisée dans un mélangeur décanteur ou, de préférence dans une colonne d'extraction.The yield of oil extracted and the quality of the oil depend on the nature of the solvent used. The yield of the de-resinated oil generally increases with the carbon number of the solvent to the detriment of the quality of the oil extracted. The extraction step is generally carried out in a settling mixer or, preferably in an extraction column.

Les conditions opératoires de l'étape d'extraction peuvent être comparables à celles d'un procédé de désasphaltage. Le rapport volumique entre le solvant à base d'hydrocarbures légers sur la fraction lourde à extraire est habituellement compris entre 2 et 12, de préférence compris entre 3 et 5.The operating conditions of the extraction step can be comparable to those of a deasphalting process. The volume ratio between the solvent based on light hydrocarbons on the heavy fraction to be extracted is usually between 2 and 12, preferably between 3 and 5.

A titre d'exemple, lors de l'étape d'extraction, on introduit dans une colonne d'extraction un mélange préformé comportant la fraction lourde et une première fraction de solvant afin de réaliser la précipitation d'une phase résinique par décantation au fond de la colonne. Dans la zone de décantation, on introduit une seconde fraction de solvant. La décantation de la partie résinique est ensuite obtenue par lavage par du solvant pur à contre-courant de l'émulsion de la fraction résinique dans un mélange comportant essentiellement du solvant et de l'huile. Elle est favorisée par une augmentation du taux de solvant, c'est à dire par le remplacement de l'environnement comportant le solvant et l'huile par un environnement de solvant pur, et ceci à une température basse.For example, during the extraction step, a preformed mixture comprising the heavy fraction and a first fraction of solvent is introduced into an extraction column in order to carry out the precipitation of a resin phase by decantation at the bottom. of the column. A second fraction of solvent is introduced into the decantation zone. The settling of the resin part is then obtained by washing with pure solvent against the current of the emulsion of the resin fraction in a mixture essentially comprising solvent and oil. It is favored by an increase in the solvent content, that is to say by replacing the environment comprising the solvent and the oil with a pure solvent environment, and this at a low temperature.

Par ailleurs, l'existence d'un gradient de température entre la tête et le fond de la colonne d'extraction permet généralement de créer un reflux interne ce qui a pour effet d'améliorer la séparation entre le milieu huileux et les résines. En effet, le mélange comportant essentiellement du solvant et de l'huile qui est chauffé en tête de la colonne d'extraction permet de précipiter une fraction résinique qui descend dans la colonne extraction. Le contre-courant ascendant de ce mélange a donc tendance à dissoudre, à plus faible température, les fractions résiniques les plus légères. La température dépend de la nature du solvant utilisé et se situe généralement entre 70 et 220°C.Furthermore, the existence of a temperature gradient between the head and the bottom of the extraction column generally makes it possible to create an internal reflux, which has the effect of improving the separation between the oily medium and the resins. Indeed, the mixture essentially comprising solvent and oil which is heated at the top of the extraction column makes it possible to precipitate a resin fraction which descends into the extraction column. The rising counter-current of this mixture therefore tends to dissolve, at a lower temperature, the lighter resin fractions. The temperature depends on the nature of the solvent used and is generally between 70 and 220 ° C.

Dans le cas d'une extraction au solvant dans une colonne d'extraction à l'aide d'un solvant qui est le propane, des conditions opératoires avantageuses pour l'extraction sont : - un taux de solvant compris entre 2/1 et 12/1 , préférentiellement entre 4/1 et 10/1 , - une température de la tête d'extracteur comprise entre 55 et 95 °C, - une température du fond d'extracteur comprise entre 30 et 80 °C, - une pression de l'extracteur comprise entre 300 et 400 MPa, à ajuster pour que tous les produits demeurent à l'état liquide, et - un nombre d'étages théoriques compris entre 2 et 5.In the case of a solvent extraction in an extraction column using a solvent which is propane, advantageous operating conditions for the extraction are: - a solvent content between 2/1 and 12/1, preferably between 4/1 and 10/1, - a temperature of the extractor head between 55 and 95 ° C, - a temperature of the extractor bottom between 30 and 80 ° C, - an extractor pressure between 300 and 400 MPa, to be adjusted so that all the products remain in the liquid state, and - a number of theoretical stages between 2 and 5.

Selon encore un autre aspect du procédé de l'invention, l'étape de craquage est mise en œuvre sur un mélange comportant la fraction purifiée obtenue lors de l'étape d'extraction avec au moins une fraction légère obtenue lors de l'étape de fractionnement.According to yet another aspect of the process of the invention, the cracking step is carried out on a mixture comprising the purified fraction obtained during the extraction step with at least one light fraction obtained during the splitting.

De préférence, lors de l'étape de mélange du procédé de l'invention, on réalise un mélange qui comporte, en outre, des autres fractions qui peuvent être obtenues lors de l'étape de fractionnement, voire de l'ensemble de ces autres fractions.Preferably, during the mixing step of the process of the invention, a mixture is produced which comprises, in addition, other fractions which can be obtained during the fractionation step, or even from all of these others. fractions.

Il a été constaté que la mise en œuvre de l'étape de craquage d'hydrocarbures sur un mélange pour lequel, d'une part seulement une fraction bien définie dudit mélange a été préalablement soumise à une étape d'extraction, et d'autre part pour lequel l'extraction de ladite fraction vise à extraire des composés bien précis, en l'occurrence des résines, ne pénalise en rien les performances de ce craquage, et au contraire permet de travailler à des températures plus basses en craquage.It has been observed that the implementation of the step of cracking hydrocarbons on a mixture for which, on the one hand only a well-defined fraction of said mixture has been previously subjected to an extraction step, and on the other hand part for which the extraction of said fraction aims to extract very precise compounds, in this case resins, does not penalize in any way the performance of this cracking, and on the contrary makes it possible to work at lower temperatures in cracking.

En effet, on a constaté que l'extraction des résines sur la totalité de la charge, résidu excepté (c'est-à-dire l'ensemble des fractions lourdes et légères) produit un effluent qui se montre plus réfractaire au craquage que l'effluent selon l'invention, pour une teneur équivalente en résine dans la fraction 340°C-700°C de la charge.In fact, it has been found that the extraction of the resins on the entire load, except for the residue (that is to say all the heavy and light fractions) produces an effluent which is more refractory to cracking than l effluent according to the invention, for an equivalent resin content in the 340 ° C-700 ° C fraction of the feed.

A cet avantage technique, s'ajoute le fait que les équipements nécessaires à l'étape d'extraction des résines présente une taille réduite. L'étape de craquage du procédé de l'invention peut comporter un craquage catalytique ou/et un hydrocraquage.In addition to this technical advantage, the fact that the equipment required for the resin extraction stage has a reduced size. The cracking step of the process of the invention can comprise a catalytic cracking and / or a hydrocracking.

Les conditions spécifiques de l'étape d'extraction du procédé de l'invention sont telles que le mélange à l'entrée de l'étape de craquage présente un haut niveau de pureté autorisant un craquage catalytique performant.The specific conditions of the extraction step of the process of the invention are such that the mixture at the inlet of the cracking step has a high level of purity allowing efficient catalytic cracking.

Dans le cas où l'étape de craquage comporte un craquage catalytique, on craque au moins une partie du mélange par un craquage catalytique pour obtenir un effluent comprenant de l'essence, du gazole et un résidu. Ce craquage catalytique peut être un craquage en lit fluidisé, connu sous l'appellation anglo-saxonne de "fluid catalytic cracking" ou en abrégé FCC.In the case where the cracking step comprises a catalytic cracking, at least part of the mixture is cracked by a catalytic cracking to obtain an effluent comprising gasoline, diesel and a residue. This catalytic cracking can be a cracking in a fluidized bed, known under the Anglo-Saxon name of "fluid catalytic cracking" or abbreviated as FCC.

Dans le cas d'un craquage de type FCC, le procédé de l'invention permet d'obtenir à l'entrée de l'étape de craquage un effluent ayant une teneur réduite en Carbone Conradson et en azote propice à l'obtention d'une conversion élevée du mélange associé à l'obtention de rendement en essence et gazole élevés.In the case of an FCC type cracking, the process of the invention makes it possible to obtain, at the entry to the cracking step, an effluent having a reduced content of Conradson Carbon and of nitrogen suitable for obtaining a high conversion of the mixture associated with obtaining high gasoline and diesel yields.

Dans le cas d'un craquage catalytique, au moins une partie du mélange peut être craquée catalytiquement dans des conditions bien connues des hommes du métier pour produire une fraction carburant, pouvant elle même comprendre une fraction essence et une fraction gazole, ainsi qu'une fraction de type "slurry". Cette fraction carburant est habituellement envoyée, au moins en partie, aux pools carburants. La fraction de type "slurry" peut être, quant à elle, envoyée, au moins en partie, au pool fuel lourd ou recyclée, au moins en partie à l'entrée du craquage catalytique.In the case of a catalytic cracking, at least part of the mixture can be catalytically cracked under conditions well known to those skilled in the art to produce a fuel fraction, which can itself comprise a petrol fraction and a diesel fraction, as well as a fraction of type "slurry". This fuel fraction is usually sent, at least in part, to fuel pools. The fraction of the "slurry" type can be sent, at least in part, to the heavy fuel pool or recycled, at least in part at the inlet of the catalytic cracking.

Dans le cadre de la présente invention l'expression craquage catalytique classique englobe les procédés de craquage comprenant au moins une étape de régénération par combustion partielle et ceux comprenant au moins une étape de régénération par combustion totale et/ou ceux comprenant à la fois au moins une étape de combustion partielle et au moins une étape de combustion totale. Le craquage catalytique est décrit de manière générale dans Ullmans Encyclopedia Of Industrial Chemistry Volume A 18, 1991 , pages 61 à 64.In the context of the present invention, the expression conventional catalytic cracking includes cracking processes comprising at least one regeneration step by partial combustion and those comprising at least one regeneration step by total combustion and / or those comprising both at least a partial combustion step and at least one total combustion step. Catalytic cracking is generally described in Ullmans Encyclopedia Of Industrial Chemistry Volume A 18, 1991, pages 61 to 64.

L'étape de craquage catalytique peut avantageusement être précédée par un hydrotraitement. Pour purifier le mélange des impuretés, comme le soufre et l'azote qui n'auraient pas été totalement éliminées lors de l'étape d'extraction, un prétraitement du mélange par un procédé catalytique en présence d'hydrogène peut être nécessaire afin, par exemple, de protéger les catalyseurs de craquage ou d'améliorer la qualité des produits de craquage. Cette étape peut se faire, par exemple, avec un catalyseur de type NiMo sur alumine dans des conditions bien connues de l'homme du métier.The catalytic cracking step can advantageously be preceded by a hydrotreatment. To purify the mixture of impurities, such as sulfur and nitrogen which were not completely removed during the extraction step, a pretreatment of the mixture by a catalytic process in the presence of hydrogen may be necessary in order, by for example, to protect the cracking catalysts or to improve the quality of the cracking products. This step can be done, for example, with a catalyst of NiMo type on alumina under conditions well known to those skilled in the art.

De préférence, l'étape de craquage est un hydrocraquage.Preferably, the cracking step is a hydrocracking.

Dans cette étape d'hydrocraquage au moins une partie du mélange est craquée sur du catalyseur en présence d'hydrogène, dans des conditions bien connues par l'homme du métier, afin de produire après une distillation, au moins une fraction carburant (fraction essence, une fraction kérosène, une fraction gazole). On envoie généralement, au moins en partie, cette (ces) fractions carburant aux pools carburants.In this hydrocracking step at least part of the mixture is cracked on the catalyst in the presence of hydrogen, under conditions well known to those skilled in the art, in order to produce, after distillation, at least one fuel fraction (petrol fraction , a kerosene fraction, a diesel fraction). This fuel fraction (s) is generally sent, at least in part, to the fuel pools.

Dans le cas d'un hydrocraquage, la fraction résidu obtenue peut être traitée de différente manières. Dans un mode de réalisation, cette fraction résidu peut être envoyée, au moins en partie, dans une section de déparaffinage et d'hydrofinition pour produire des bases huiles. Dans un autre mode de réalisation avec un objectif carburant , cette fraction résidu peut être recyclée, au moins en partie, à l'entrée de l'étape d'hydrocraquage. Dans encore un autre mode de réalisation, cette fraction résidu peut être envoyée, au moins en partie, dans une unité de FCC.In the case of hydrocracking, the residue fraction obtained can be treated in different ways. In one embodiment, this residue fraction can be sent, at least in part, to a dewaxing and hydrofinishing section to produce oil bases. In another embodiment with a fuel objective, this residue fraction can be recycled, at least in part, at the entrance to the hydrocracking step. In yet another embodiment, this residue fraction can be sent, at least in part, to an FCC unit.

Les conditions opératoires utilisées selon ce mode permettent d'atteindre une conversion par passe en produits ayant des points d'ébullition inférieurs à 340°C, voire inférieurs à 370°C, qui est supérieure à 10 % en poids, de manière préférée comprise entre 15 et 95 % en poids. L'hydrocraquage peut être réalisé à une température allant de 340 à 450 °C, de préférence allant de 340 à 420 °C. La pression peut être, quant à elle, significativement réduite par rapport aux étapes d'hydrocraquage de distillats sous vide de l'art antérieur qui requièrent généralement une pression partielle d'hydrogène élevée.The operating conditions used according to this mode make it possible to achieve conversion by pass into products having boiling points below 340 ° C, or even below 370 ° C, which is greater than 10% by weight, preferably between 15 and 95% by weight. Hydrocracking can be carried out at a temperature ranging from 340 to 450 ° C., preferably ranging from 340 to 420 ° C. The pressure can be significantly reduced compared to the hydrocracking stages of vacuum distillates of the prior art which generally require a high hydrogen partial pressure.

La pression de l'hydrocraquage peut avantageusement aller de 4 à 20 MPa, de préférence de 4 à 16 MPa. On peut distinguer les pressions faibles ou modérées (4 à 10 MPa) des pressions plus fortes (plus de 10 MPa à 16MPa).The hydrocracking pressure can advantageously range from 4 to 20 MPa, preferably from 4 to 16 MPa. We can distinguish low or moderate pressures (4 to 10 MPa) from higher pressures (more than 10 MPa to 16MPa).

L'expression hydrocraquage englobe l'hydrocraquage doux dont l'objectif est un prétraitement convertissant une charge provenant d'un FCC, l'hydroraffinage dont l'objectif est la production d'un résidu pour faire des huiles lubrifiantes et des distillats moyens, et l'hydrocraquage classique dont la flexibilité permet soit de produire des distillats moyens, soit conjointement des distillats moyens et un résidu pour faire des huiles lubrifiantes.The term hydrocracking includes mild hydrocracking, the objective of which is a pretreatment converting a charge originating from an FCC, hydrorefining, the objective of which is the production of a residue for making lubricating oils and middle distillates, and conventional hydrocracking whose flexibility allows either to produce middle distillates, or jointly middle distillates and a residue to make lubricating oils.

Un avantage du procédé de l'invention est de réduire la perte d'activité du ou des catalyseurs utilisés lors de l'étape de craquage et/ou de l'étape de pré-traitement catalytique en réduisant les impuretés qui ont tendance à s'adsorber fortement sur le catalyseur, qui réduisent sa fonction acide craquante et/ou qui sont des précurseurs de coke. Ceci se traduit, dans le cas d'une étape de craquage catalytique, par une consommation en catalyseur frais réduite pour un niveau conversion donnée et, dans le cas d'une étape d'hydrocraquage, par une durée de cycle plus longue.An advantage of the process of the invention is to reduce the loss of activity of the catalyst (s) used during the cracking step and / or the catalytic pretreatment step by reducing the impurities which tend to strongly adsorb on the catalyst, which reduce its cracking acid function and / or which are coke precursors. This results, in the case of a catalytic cracking step, by a reduced consumption of fresh catalyst for a given conversion level and, in the case of a hydrocracking step, by a longer cycle time.

Un autre avantage du procédé de l'invention est, dans le cas où l'étape de craquage comporte (ou est) un hydrocraquage, de permettre une réduction significative de la pression à laquelle est réalisée l'étape d'hydrocraquage. L'extraction sélective des résines permet, en effet, d'éliminer les composés insaturés qui consomment habituellement une quantité importante de l'hydrogène de l'hydrocraquage. La mise en oeuvre du procédé de l'invention permet ainsi de réduire le coût opératoire de l'hydrocraqueur. Un autre avantage de l'invention est de limiter les effets négatifs des résines et de l'azote, en particulier sur le catalyseur de craquage.Another advantage of the process of the invention is, in the case where the cracking step comprises (or is) hydrocracking, to allow a significant reduction in the pressure at which the hydrocracking step is carried out. Selective extraction of the resins makes it possible, in fact, to eliminate the unsaturated compounds which usually consume a large amount of hydrogen from hydrocracking. The implementation of the process of the invention thus makes it possible to reduce the operating cost of the hydrocracker. Another advantage of the invention is to limit the negative effects of resins and nitrogen, in particular on the cracking catalyst.

Un autre avantage de l'invention est de limiter les effets négatifs des polyaromatiques sur la stabilité des catalyseurs et la qualité des produits.Another advantage of the invention is to limit the negative effects of polyaromatics on the stability of the catalysts and the quality of the products.

Un autre avantage du procédé de l'invention est, dans le cas où l'étape de craquage comporte (ou est) un hydrocraquage, de réduire la taille des équipements utilisés lors de cette hydrocraquage.Another advantage of the process of the invention is, in the case where the cracking step comprises (or is) hydrocracking, of reducing the size of the equipment used during this hydrocracking.

Un autre avantage du procédé de l'invention est de permettre une réduction de la taille des équipements utilisés lors de l'étape d'extraction, l'extraction n'étant réalisée que sur une fraction lourde du distillât sous vide.Another advantage of the method of the invention is to allow a reduction in the size of the equipment used during the extraction step, the extraction being carried out only on a heavy fraction of the distillate under vacuum.

Pour une meilleure compréhension, un mode de réalisation préféré du procédé de l'invention est illustré à la Figure 1. Ce mode de réalisation est donné à titre d'exemple et ne présente aucun caractère limitatif. Cette illustration du procédé de l'invention ne comporte pas l'ensemble des composantes nécessaires à sa mise en œuvre. Seuls les éléments nécessaires à la compréhension de l'invention y sont représentés, l'homme du métier étant capable de compléter cette représentation pour mettre en œuvre l'invention.For a better understanding, a preferred embodiment of the method of the invention is illustrated in Figure 1. This embodiment is given by way of example and has no limiting character. This illustration of the process of the invention does not include all of the components necessary for its implementation. Only the elements necessary for understanding the invention are represented, the skilled person being able to complete this representation to implement the invention.

La charge hydrocarbonée est envoyé par le conduit 1 dans une colonne de distillation sous vide 2. De cette colonne de distillation on soutire une fraction légère par le conduit 3, une fraction lourde par le conduit 4 et un résidu sous vide par le conduit 5.The hydrocarbon feedstock is sent via line 1 to a vacuum distillation column 2. From this distillation column, a light fraction is drawn off through line 3, a heavy fraction through line 4 and a vacuum residue through line 5.

La fraction lourde soutirée de la colonne 2 est envoyé par le conduit 4 vers des moyens d'extraction liquide 10 avec un solvant. Le solvant est envoyé dans les moyens d'extraction par l'intermédiaire d'un conduit 11. Du solvant peut éventuellement être ajouté par un conduit 12. A la fraction lourde du distillât sous vide une charge extérieure peut être ajoutée par le conduit 13. Cette charge est par exemple un distillât sous vide, tel qu'un distillât sous vide straight-run (de brut), un distillât sous vide issu d'un procédé de conversion de charges lourdes (cokéfaction, lit bouillonnant H-oil ou T-Star, lit fixe Hyvahl). Ce peut être aussi un extrait aromatique provenant d'une unité d'extraction d'aromatiques.The heavy fraction withdrawn from column 2 is sent via line 4 to liquid extraction means 10 with a solvent. The solvent is sent to the extraction means via a pipe 11. Solvent can optionally be added via a pipe 12. To the heavy fraction of the vacuum distillate an external charge can be added through the pipe 13. This charge is for example a vacuum distillate, such as a straight-run vacuum distillate (crude), a vacuum distillate from a heavy load conversion process (coking, H-oil or T-Star bubbling bed, Hyvahl fixed bed). It can also be an aromatic extract from an aromatic extraction unit.

La fraction purifiée et du solvant issus des moyens d'extraction 10 sont soutirés par le conduit 15 et envoyés vers un dispositif de récupération et de régénération du solvant 16. Le solvant ainsi régénéré est envoyé dans la zone d'extraction par le conduit 11.The purified fraction and of the solvent coming from the extraction means 10 are drawn off through line 15 and sent to a device for recovering and regenerating the solvent 16. The solvent thus regenerated is sent to the extraction zone through line 11.

Le résidu comportant les résines extraites et du solvant sont soutirés par un conduit 19 et envoyés vers un système de récupération et de régénération du solvant 20. Le solvant ainsi régénéré est envoyé dans la zone d'extraction par un conduit 21 et le conduit 11. Le résidu comportant les résines extraites qui a été débarrassé du solvant est soutiré par le conduit 22.The residue comprising the resins extracted and the solvent are drawn off through a line 19 and sent to a recovery and regeneration system for the solvent 20. The solvent thus regenerated is sent to the extraction zone via a line 21 and the line 11. The residue comprising the extracted resins which has been freed from the solvent is withdrawn through line 22.

La fraction purifiée débarrassée du solvant est soutiré, par l'intermédiaire d'un conduit 30. Cette fraction purifiée est mélangée avec la fraction légère du distillât sous vide amenée par le conduit 3. La fraction purifiée et la fraction légère du distillât sous vide sont envoyé en mélange, avec de l'hydrogène alimenté par un conduit 31 , dans des moyens d'hydrocraquage 32. L'effluent issu des moyens d'hydrocraquage est évacué par le conduit 33 et envoyé vers des moyens de séparation 34 du gaz et du liquide. Le gaz est évacué par un conduit 35.The purified fraction freed from the solvent is withdrawn, via a conduit 30. This purified fraction is mixed with the light fraction of the vacuum distillate supplied by the conduit 3. The purified fraction and the light fraction of the vacuum distillate are sent as a mixture, with hydrogen supplied by a line 31, in hydrocracking means 32. The effluent from the hydrocracking means is discharged through line 33 and sent to means 34 for separating the gas and the liquid. The gas is evacuated through a pipe 35.

Le liquide issu des moyens de séparation 34 est évacué par un conduit 40 vers une colonne de distillation atmosphérique 41. De cette colonne sont soutirés une fraction gazeuse par un conduit 42, une coupe essence par un conduit 43, une coupe kérosène par un conduit 44, une coupe gazole par un conduit 45 et une coupe résidu par un conduit 46.The liquid from the separation means 34 is discharged through a pipe 40 to an atmospheric distillation column 41. From this column are drawn off a gaseous fraction by a pipe 42, a gasoline cut by a pipe 43, a kerosene cut by a pipe 44 , a diesel cut through a pipe 45 and a residue cut through a pipe 46.

Ainsi que mentionné précédemment, le résidu peut êtreAs mentioned earlier, the residue can be

1) au moins en partie recyclé en hydrocraquage (à la purge près),1) at least partly recycled in hydrocracking (except for the purge),

2) au moins en partie envoyé dans une unité de craquage catalytique en lit fluide , ou 3) au moins en partie envoyé dans une unité de dewaxing (déparaffinage de préférence catalytique) puis dans une unité d'hydrofinition; un recyclage partiel du résidu vers l'étape d'hydrocraquage étant également envisageable avec les options 2) ou 3).2) at least partly sent to a catalytic cracking unit in a fluid bed, or 3) at least partly sent to a dewaxing unit (preferably catalytic dewaxing) and then to a hydrofinishing unit; partial recycling of the residue to the hydrocracking stage also being possible with options 2) or 3).

Exemple 1 Un distillât sous vide a été distillé d'un résidu atmosphérique avec un rendement de 40% en poids. Ce distillât sous vide a les propriétés suivantes:Example 1 A vacuum distillate was distilled from an atmospheric residue with a yield of 40% by weight. This vacuum distillate has the following properties:

Ce distillât sous vide est introduit dans un pilote comportant deux réacteurs en séries. Le premier réacteur R1 est rempli avec du catalyseur connu sous la référence HR448 de la société AXENS, catalyseur de pré-traitement de distillât sous vide de type NiMo sur alumine dont l'objectif est de desazoter à de très faibles teneurs le distillât sous vide. Le second réacteur R2 est rempli du catalyseur connu sous la référence HYC642 de la société AXENS, catalyseur zéolithique d'hydrocraquage (zéolite Y sur alumine) permettant de réaliser une conversion de l'ordre de 70% en poids de la fraction 370°C+ du distillât sous vide. Les conditions opératoires et rendements sont données dans le tableau suivant:This vacuum distillate is introduced into a pilot comprising two reactors in series. The first reactor R1 is filled with catalyst known under the reference HR448 from the company AXENS, a pre-treatment catalyst for vacuum distillate of the NiMo type on alumina, the objective of which is to de-nitrogen the vacuum distillate at very low contents. The second reactor R2 is filled with the catalyst known under the reference HYC642 from the company AXENS, a zeolitic hydrocracking catalyst (zeolite Y on alumina) allowing a conversion of the order of 70% by weight of the 370 ° C + fraction of the vacuum distillate. The operating conditions and yields are given in the following table:

Exemple 2 (selon l'invention)Example 2 (according to the invention)

Le distillât sous vide de l'exemple 1 est distillé sous vide pour obtenir une fraction légère et une fraction lourde correspondant à un point de coupe de 500°C. Les rendements et propriétés du distillât sous vide et des deux fractions sont les suivantes:The vacuum distillate of Example 1 is distilled under vacuum to obtain a light fraction and a heavy fraction corresponding to a cutting point of 500 ° C. The yields and properties of the vacuum distillate and of the two fractions are as follows:

La fraction lourde est dérésinée par extraction liquide-liquide avec un solvant non polaire paraffinique, le propane. La technologie utilisée est celle couramment utilisée pour réaliser le désasphaltage des résidus sous vide. 40 kilogrammes de la fraction lourde ont été mélangés avec du propane dans un réacteur agité avec un rapport volumique solvant/fraction lourde de 8/1. Le mélange est porté à 90°C et agité pendant 60 minutes. Après cette période, l'agitation est stoppée et le mélange décante pendant 90 minutes pour entraîner la séparation de deux phases. La phase purifiée des résines en haut de la capacité et la phase riche en résines en fond de capacité sont soutirées séparemment et traitées pour évaporer le propane. La phase purifiée des résines et la phase riche en résines après évaporation du propane ont les propriétés suivantes, comparées à celle de la fraction lourde:The heavy fraction is de-resinated by liquid-liquid extraction with a non-polar paraffinic solvent, propane. The technology used is that commonly used to perform deasphalting of residues under vacuum. 40 kilograms of the heavy fraction were mixed with propane in a stirred reactor with a solvent / heavy fraction volume ratio of 8/1. The mixture is brought to 90 ° C. and stirred for 60 minutes. After this period, the stirring is stopped and the mixture settles for 90 minutes to cause the separation of two phases. The purified phase of the resins at the top of the capacity and the phase rich in resins at the bottom of the capacity are drawn off separately and treated to evaporate the propane. The purified phase of the resins and the phase rich in resins after evaporation of the propane have the following properties, compared to that of the heavy fraction:

On a extrait de la fraction lourde du distillât sous vide 40% en poids des résines contenues dans cette fraction. La fraction purifiée des résines est ensuite mélangée à la fraction légère du distillât sous vide afin de reconstituer un distillât sous vide large qui sera hydrocraqué.40% by weight of the heavy fraction of the distillate was removed under vacuum from the resins contained in this fraction. The purified fraction of the resins is then mixed with the light fraction of the vacuum distillate in order to reconstitute a wide vacuum distillate which will be hydrocracked.

Le mélange ainsi reconstitué a les propriétés suivantes comparées au distillât sous vide de l'exemple 1 :The mixture thus reconstituted has the following properties compared to the vacuum distillate of Example 1:

Le mélange possède des teneurs en résines et en azote réduites d'environ 30% par rapport au distill t sous vide de l'exemple 1. Cette purification partielle de la charge peut paraître faible, néanmoins elle a l'avantage de nécessiter des équipements d'extraction réduits et d'avoir un impact important sur les conditions opératoires de l'hydrocraquage. Le mélange ainsi reconstitué est introduit dans le même pilote que dans l'exemple 1 avec le même système catalytique. Pour réaliser la même conversion globale de l'ordre de 70% poids de la fraction 370°C+ du mélange que dans l'exemple 1 il faut établir les conditions opératoires suivantes:The mixture has resin and nitrogen contents reduced by about 30% compared to the vacuum distill t of Example 1. This partial purification of the feed may seem low, nevertheless it has the advantage of requiring equipment for 'reduced extraction and have a significant impact on the hydrocracking operating conditions. The mixture thus reconstituted is introduced into the same pilot as in Example 1 with the same catalytic system. To carry out the same overall conversion of the order of 70% by weight of the 370 ° C. + fraction of the mixture as in Example 1, the following operating conditions must be established:

Les conditions opératoires de l'exemple 2 sont caractérisées par rapport à l'exemple 1 par une pression partielle d'hydrogène plus faible de 30 bars, toutes choses égales par ailleurs. La structure de rendement est identique à l'exemple 1 ainsi que la qualité des produits mais associés à une consommation en hydrogène réduite de 13%. The operating conditions of Example 2 are characterized with respect to Example 1 by a lower partial pressure of hydrogen of 30 bars, all other things being equal. The yield structure is identical to Example 1 as well as the quality of the products but associated with a hydrogen consumption reduced by 13%.

Claims

REVENDICATIONS 1. Procédé de traitement d'une charge hydrocarbonée dont au moins 80% des composés ont un point d'ébullition supérieur ou égal à 340°C, procédé dans lequel : a) on envoie la charge dans une étape de fractionnement lors de laquelle on récupère :1. Process for treating a hydrocarbon feedstock of which at least 80% of the compounds have a boiling point greater than or equal to 340 ° C., process in which: a) the feedstock is sent in a fractionation step during which recovers: - au moins une fraction lourde comportant au moins 90% en poids de composés bouillant au-dessus de 450°C et au-dessous de 700°C,- at least one heavy fraction comprising at least 90% by weight of compounds boiling above 450 ° C and below 700 ° C, - et au moins une fraction légère bouillant en-dessous de la (les) fraction(s) lourde(s),- and at least one light fraction boiling below the heavy fraction (s), - un résidu bouillant en-dessus de la (les) fraction(s) lourde(s), b) on envoie au moins une partie de la fraction lourde dans une étape d'extraction lors de laquelle on extrait au moins une partie des résines contenues dans ladite fraction lourde et on récupère une fraction purifiée, c) on réalise un mélange comportant au moins une partie de la fraction purifiée obtenu à l'étape d'extraction et au moins une fraction légère obtenue à l'étape de fractionnement, et d) on envoie le mélange ainsi obtenu dans une étape de craquage.- a boiling residue above the heavy fraction (s), b) at least part of the heavy fraction is sent in an extraction stage during which at least part of the resins are extracted contained in said heavy fraction and a purified fraction is recovered, c) a mixture is produced comprising at least part of the purified fraction obtained in the extraction stage and at least a light fraction obtained in the fractionation stage, and d) the mixture thus obtained is sent in a cracking step. 2. Procédé selon la revendication 1 , dans lequel la teneur en résines dans la fraction 340°C-700°C de la charge est compris entre 3 et 15 % en poids.2. Method according to claim 1, in which the content of resins in the 340 ° C-700 ° C fraction of the filler is between 3 and 15% by weight. 3. Procédé selon l'une des revendications 1 à 2, dans lequel la fraction lourde issue de la première étape de fractionnement comporte une teneur en résines supérieure à 5 % en poids.3. Method according to one of claims 1 to 2, wherein the heavy fraction from the first fractionation step has a resin content greater than 5% by weight. 4. Procédé selon l'une des revendications 1 à 3, dans lequel on extrait au moins 20 % en poids des résines contenues dans la fraction lourde. 4. Method according to one of claims 1 to 3, wherein at least 20% by weight of the resins contained in the heavy fraction are extracted. 5. Procédé selon l'une des revendications 1 à 4, dans lequel l'extraction des résines de la fraction lourde permet d'obtenir une fraction purifiée ayant une teneur en composés polyaromatiques comportant jusqu'à 5 cycles inférieure à 2 % en poids.5. Method according to one of claims 1 to 4, in which the extraction of the resins from the heavy fraction makes it possible to obtain a purified fraction having a content of polyaromatic compounds comprising up to 5 cycles of less than 2% by weight. 6. Procédé selon l'une des revendications 1 à 5, dans lequel l'extraction des résines de la fraction lourde permet d'obtenir une fraction purifiée ayant une teneur en azote qui est réduite d'au moins 20 % en poids par rapport à la fraction lourde introduite dans l'étape d'extraction.6. Method according to one of claims 1 to 5, in which the extraction of the resins from the heavy fraction makes it possible to obtain a purified fraction having a nitrogen content which is reduced by at least 20% by weight relative to the heavy fraction introduced into the extraction step. 7. Procédé selon l'une des revendications 1 à 6, dans lequel l'étape d'extraction est réalisée dans une colonne d'extraction, à l'aide de propane, sous les conditions opératoires suivantes : - un taux de solvant compris entre 2/1 et 12/1 , - une température de la tête d'extracteur comprise entre 55 et 95 °C, - une température du fond d'extracteur comprise entre 30 et 80 °C, - une pression de l'extracteur comprise entre 300 et 400 MPa, et - un nombre d'étages théoriques compris entre 2 et 5.7. Method according to one of claims 1 to 6, in which the extraction step is carried out in an extraction column, using propane, under the following operating conditions: - a solvent content of between 2/1 and 12/1, - a temperature of the extractor head between 55 and 95 ° C, - a temperature of the extractor bottom between 30 and 80 ° C, - a pressure of the extractor between 300 and 400 MPa, and - a number of theoretical stages between 2 and 5. 8. Procédé selon l'une des revendications 1 à 7, dans lequel l'étape de craquage est un hydrocraquage.8. Method according to one of claims 1 to 7, wherein the cracking step is a hydrocracking. 9. Procédé selon la revendication 8 dans lequel une fraction résidu est obtenue de l'étape d'hydrocraquage et est envoyée, au moins en partie, dans une section de déparaffinage et d'hydrofinition pour faire des bases huiles.9. The method of claim 8 wherein a residue fraction is obtained from the hydrocracking step and is sent, at least in part, to a dewaxing and hydrofinishing section to make oil bases. 10. Procédé selon les revendications 1 à 8, dans lequel une fraction résidu est obtenue de l'étape d'hydrocraquage et est envoyée, au moins en partie, dans une unité de FCC.10. The method of claims 1 to 8, wherein a residue fraction is obtained from the hydrocracking step and is sent, at least in part, to an FCC unit. 11. Procédé selon l'une des revendications 8 à 10, dans lequel une fraction résidu est obtenue de l'étape d'hydrocraquage et est recyclée, au moins en partie, vers l'étape d'hydrocraquage. 11. Method according to one of claims 8 to 10, in which a residue fraction is obtained from the hydrocracking step and is recycled, at least in part, to the hydrocracking step. 12. Procédé selon l'une des revendications 1 à 7, dans lequel l'étape de craquage est un craquage catalytique en lit fluidisé (FCC).12. Method according to one of claims 1 to 7, in which the cracking step is a catalytic cracking in a fluidized bed (FCC). 13. Procédé selon la revendication 12, dans lequel l'étape FCC est précédée d'une étape d'hydrotraitement.13. The method of claim 12, wherein the FCC step is preceded by a hydrotreatment step. 14. Procédé selon l'une des revendications précédentes, dans lequel la charge est choisi parmi un résidu de distillation directe, un résidu d'un procédé de conversion, un résidu de cokéfaction, un résidu d'un procédé d'hydroconversion en lit fixe, un résidu d'un procédé de conversion en lit bouillonnant, ou l'un quelconque de leur mélange.14. Method according to one of the preceding claims, in which the feedstock is chosen from a direct distillation residue, a residue from a conversion process, a coking residue, a residue from a fixed bed hydroconversion process. , a residue from a bubbling bed conversion process, or any mixture thereof. 15. Procédé selon l'une des revendications précédentes, dans lequel une charge externe est ajoutée à la fraction lourde entrant dans l'étape d'extraction, ladite charge étant un distillât sous vide ou un extrait aromatique. 15. Method according to one of the preceding claims, in which an external charge is added to the heavy fraction entering the extraction step, said charge being a vacuum distillate or an aromatic extract.
EP04805695A 2003-12-23 2004-12-13 Method for treating a hydrocarbon feedstock including resin removal Ceased EP1699905A1 (en)

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FR0315212A FR2864103B1 (en) 2003-12-23 2003-12-23 PROCESS FOR TREATING A HYDROCARBONATED LOAD INCLUDING RESIN REMOVAL
PCT/FR2004/003210 WO2005071047A1 (en) 2003-12-23 2004-12-13 Method for treating a hydrocarbon feedstock including resin removal

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CA2548455A1 (en) 2005-08-04
KR20060130133A (en) 2006-12-18
WO2005071047A1 (en) 2005-08-04
FR2864103B1 (en) 2006-03-17
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RU2358005C2 (en) 2009-06-10
US7582204B2 (en) 2009-09-01

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