EP0246956B1 - Procédé de désasphaltage d'une charge hydrocarbonée lourde. - Google Patents

Procédé de désasphaltage d'une charge hydrocarbonée lourde. Download PDF

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Publication number
EP0246956B1
EP0246956B1 EP87401091A EP87401091A EP0246956B1 EP 0246956 B1 EP0246956 B1 EP 0246956B1 EP 87401091 A EP87401091 A EP 87401091A EP 87401091 A EP87401091 A EP 87401091A EP 0246956 B1 EP0246956 B1 EP 0246956B1
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EP
European Patent Office
Prior art keywords
solvent
carbon atoms
hydrocarbon
fraction
volume
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.)
Expired - Lifetime
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EP87401091A
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German (de)
English (en)
French (fr)
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EP0246956A1 (fr
Inventor
Didier Chombart
François-Xavier Cormerais
Michel Laborde
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TotalEnergies Marketing Services SA
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Total France SA
Compagnie de Raffinage et de Distribution Total France SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics

Definitions

  • the present invention relates to a process for deasphalting a heavy hydrocarbon feed.
  • heavy hydrocarbon filler is meant, within the meaning of the present invention, a filler having a density at 15 ° C greater than about 930 kg / m 3 , composed essentially of hydrocarbons, but also containing other chemical compounds which, in addition to carbon and hydrogen atoms, have heteroatoms such as oxygen, nitrogen, sulfur and metals such as vanadium or nickel.
  • This charge can be constituted, in particular, by a crude oil or a heavy oil having the density indicated above.
  • the feedstock can also come from the fractionation or processing of crude oil, heavy oil, oil shale or even coal. It may thus be the residue from the distillation under reduced pressure or the residue from the distillation at atmospheric pressure of the starting materials mentioned above or, for example, the products obtained by the heat treatment of these starting materials or their distillation residues.
  • the heaviest part of the heavy hydrocarbon charges consists of a mixture of an oily phase and an asphaltic phase.
  • One way to obtain light products from the oily phase is to subject it to catalytic cracking.
  • the catalytic cracking charge must not, however, be excessively polluted by metals and must not have an excessively high "Conradson” residue. It may be recalled that the "Conradson” residue, which gives indications on the tendency of a product to form coke, is determined according to the AFNOR NFT 60-116 standard.
  • heavy hydrocarbon feedstocks contain compounds having, in addition to hydrogen and carbon atoms, heteroatoms such as oxygen, nitrogen, sulfur and metals. Some of these compounds, especially those having metals, are contained in particular in the asphalt phase.
  • Asphaltenes like resins have polycyclic aromatic structures. Next to the aromatic rings are thiophenic and pyridine rings. But resins have less condensed structures than asphaltenes and lower molecular weights.
  • the compounds which precipitate by addition to the charge of a saturated aliphatic hydrocarbon having from 5 to 7 carbon atoms are generally designated under the name of asphaltenes: pentane, hexane, heptane.
  • pentane, hexane, heptane pentane, hexane, heptane.
  • a hydrocarbon with a lower boiling point for example propane.
  • this distinction is conventional and it is obvious that, if a given solvent is used at a given temperature to treat a charge, it will be possible, if the solvent and the temperature are suitable, to obtain the precipitation of asphaltene-type compounds . If the charge freed from asphaltenes is then treated with the same solvent at a higher temperature, precipitation of the resins can be obtained.
  • the deasphalting can be carried out in a single step, obtaining, in this case, an oily phase and an asphaltic phase, the latter containing both the asphaltenes and the resins. It can also be carried out in two stages, with the use of two different solvents and / or different operating conditions in the two stages (see, for example, US Pat . Nos . 3,830,732 and 2,940,920).
  • the oily phase, the resins and the asphaltenes are obtained separately, in this two-step process.
  • Also known from FR-A 2 007 587 is a process for deasphalting a heavy hydrocarbon feed, which uses two solvents in two stages.
  • the residual oil is separated into asphaltenes and into deasphaltenized oil using as solvent a hydrocarbon comprising from 5 to 10 carbon atoms.
  • the deasphalted oil is separated into resins and into deasphaltened oil and freed from the resins using as solvent one or more hydrocarbons, comprising less than 5 carbon atoms, for example propane, and mixtures thereof with aliphatic hydrocarbons comprising from 5 to 10 carbon atoms.
  • the asphaltenes fraction does not require an additional expense of flux to be used liquid.
  • the object of the present invention is therefore the preparation, in particular from a heavy hydrocarbon feedstock, of a product suitable as feedstock for a catalytic cracking.
  • the process is therefore characterized by a search for selectivity, which leads to the combination of two solvents containing little or no hydrocarbons with 4 carbon atoms, so as to vary the selectivity according to the stage at which one takes place. .
  • Solvents can consist of a single hydrocarbon, or a mixture of hydrocarbons; thus, the heavy solvent can consist of a mixture of pentane and hexane for example.
  • hydrocarbon pentane for example
  • it may be either a well-defined hydrocarbon, such as normal pentane, or also, and this is practically always the case industrially, of a mixture of isomers of this hydrocarbon, such as, in the case of pentane, normal pentane and isopentane, essentially.
  • the light solvent contains a higher proportion than the heavy hydrocarbon solvent comprising 3 carbon atoms.
  • the method according to the invention can be implemented in two different ways.
  • the first step is the step of separation of the "asphaltenes" fraction using the heavy solvent.
  • the "resins" fraction is then precipitated using a light solvent.
  • the treatment of the solution of the oily phase in the light solvent can in particular consist of heating said solution, preferably vaporizing the hydrocarbon comprising 3 carbon atoms.
  • the heating can be replaced by an expansion under reduced pressure of said solution.
  • the heavy solvent may preferably contain from 10 to 40% by volume of hydrocarbon with 3 carbon atoms and from 60 to 90% by volume d '' at least one hydrocarbon with at least 5 carbon atoms, and, better still, from 15 to 35% by volume of hydrocarbon with 3 carbon atoms and from 65 to 85% by volume of at least one hydrocarbon with at least 5 carbon atoms.
  • the light solvent may preferably contain from 20 to 80% by volume of hydrocarbon with 3 carbon atoms and from 20 to 80% by volume. volume of at least one hydrocarbon with at least 5 carbon atoms and, better still, from 25 to 75% by volume of hydrocarbon with 3 carbon atoms and from 25 to 75% by volume of at least one hydrocarbon with at minus 5 carbon atoms.
  • the light solvent may preferably contain from 20 to 80% by volume of hydrocarbon with 3 carbon atoms and from 20 to 80% by volume. volume of at least one hydrocarbon with at least 5 carbon atoms and, better still, from 30 to 70% by volume of at least one hydrocarbon with 3 carbon atoms and from 30 to 70% by volume of at least one hydrocarbon with at least 5 carbon atoms.
  • the heavy solvent may preferably contain from 5 to 30% by volume of hydrocarbon with 3 carbon atoms and from 70 to 95% by volume d '' at least one hydrocarbon with at least 5 carbon atoms and, better still, from 10 to 25% by volume of hydrocarbon with 3 carbon atoms and 75 to 90% by volume of at least one hydrocarbon with at least 5 atoms of carbon.
  • the hydrocarbon charge is introduced via line 1, into the upper part of a first extraction tower 2 heavy to deasphalt.
  • a heavy solvent the source of which will be explained later, is also introduced into the bottom of tower 2, via line 3.
  • the same heavy solvent can also be added to the feed in line 1, by a line not shown.
  • the heavy solvent of line 3 and the operating conditions of tower 2 are chosen so that only the "asphaltenes" fraction of feed 1 whose softening point is greater than or equal to 150 ° C. precipitates in said tower.
  • the pressure inside tower 2 can be between 20.105 and 1.10 7 absolute pascals, the temperature between 100 and 200 ° C, and the mass rate can be between 1 and 10, without these values being considered as limits.
  • the pressure may be approximately 40.10 5 absolute pascals, the temperatures at the bottom and at the top of tower 2 being respectively approximately 100 and 140 ° C., the mass ratio of heavy solvent on charge being approximately 2/1.
  • the "asphaltenes" fraction containing a little heavy solvent is collected at the bottom of tower 2, by line 4.
  • the charge is collected at the top of tower 2, via line 5, freed from the "asphaltenes" fraction, in solution in most of the heavy solvent introduced into tower 2.
  • the fraction collected by line 4 is conducted, after passing through at least one heater 6, in an expansion tower 7 operating, in the case of a heavy solvent C 3 -20 / C 5 -80, at a temperature of approximately 300 ° C and a pressure of approximately 5.105 absolute pascals. Heavy solvent is collected at the top of the tower 7, by the line 8, which, after passage through a coolant 9, is led into a flask 10.
  • the balloon 10 serves as storage for the heavy solvent.
  • the temperature in the flask 10 is approximately 60 ° C and the pressure approximately 5.10 5 absolute pascals.
  • the “asphaltenes” fraction is collected in the bottom of tower 7, by line 11, which is conducted in a tower 12, operating, in the case of a heavy solvent C 3 -20 / C 5 -80, at a temperature of about 300 ° C and a pressure of about 0.5.10 5 pascals absolute.
  • the “asphaltenes” fraction freed from the heavy solvent, is collected at the bottom of tower 12, via line 13. This fraction can be used as solid fuel after grinding.
  • Solvent is collected at the top of tower 12, via line 19, which is led into a condenser 14.
  • the mixture of heavy solvent and filler freed from the "asphaltenes" fraction collected by line 5 is carried out in a second extraction tower 20.
  • a third solvent is introduced into this tower, via line 21, so that , in tower 20, the extraction is carried out in fact using a light solvent, resulting from the combination of the heavy solvent and the third solvent and whose proportion of hydrocarbon with 3 carbon atoms is higher than that of the heavy solvent.
  • the third solvent can be a solvent C 3 -40 / C 5 -60, that is to say containing 40% by volume of propane and 60% by volume of pentane, the light solvent then being a solvent C 3 -30 / C 5 -70, containing 30% by volume of propane and 70% by volume of pentane.
  • the operating conditions inside tower 20 are such that the "resin" fraction precipitates.
  • the pressure inside tower 20 can be between 20.10 5 and 1.107 absolute pascals, the temperature between 100 and 300 ° C, the mass rate being between 1 and 10, without these values being considered as limits.
  • the pressure can be approximately 40 ⁇ 10 5 absolute pascals, the temperatures at the bottom and at the top of tower 20 being approximately, respectively, 110 and 150 ° C, the mass rate being about 4/1.
  • the "resins" fraction containing a little light solvent is collected at the bottom of tower 20, through line 28.
  • the mixture of deasphalted oily phase and of light solvent collected by line 22 is led, after passage through a heater 23, in an expansion tower 24 operating, in the case of a light solvent C 3 -30 / C 5 -70 , at a pressure of about 25.105 absolute pascals and a temperature of about 150 ° C.
  • a heater 23 As a result of the passage through the heater 23, part of the solvent is vaporized.
  • the hydrocarbon with 3 carbon atoms is preferably so.
  • a third solvent enriched in hydrocarbon with 3 carbon atoms is therefore collected at the top of tower 24, via line 25.
  • a third solvent C 3 -40 / C 5 -60 is thus obtained.
  • the third solvent collected by line 25 is led, after passage through a cooler 26, into a storage flask 27.
  • the temperature inside the tank 27 is around 110 ° C and the pressure around 25 bar.
  • the third solvent is then recycled via line 21 to tower 20.
  • the major part of the heavy solvent is collected at the top of the tower 32, via the line 33, which, after passing through a condenser 34, is led to the flask 10.
  • the flask 10 is connected by line 35 to line 3 and the heavy solvent can therefore be recycled to tower 2.
  • the deasphalted oily phase containing a small amount of solvent is collected at the bottom of the tower 32, via line 36, which, after passing through a heater 37, is conducted in a steam tower 38, where water vapor is introduced via line 39.
  • this tower operates at a pressure of approximately 1.5 ⁇ 10 5 absolute pascals and a temperature of approximately 250 ° C.
  • the deasphalted oil is collected at the bottom of the tower 38, by the line 41, and, at the top of the said tower, by the line 40, water and solvent, which are led to the condenser 14.
  • the "resins" fraction containing a little light solvent, collected by line 28 at the bottom of tower 20, is conducted, after passing through a heater 50, in an expansion tower 51 operating, in the case of a light solvent C 3 -30 / C 5 -70, at a pressure of approximately 5,105 absolute pascals and at a temperature of approximately 280 ° C.
  • the hydrocarbon charge is introduced via line 101, into the upper part of a first extraction tower 102 heavy to deasphalt.
  • a light solvent is also introduced into the bottom of tower 102, via line 103, the source of which will be explained below.
  • the "resins” and “asphaltenes” fractions precipitate.
  • the light solvent can be, for example, a solvent C 3 -60 / C s -40, containing 60% by volume of propane and 40% by volume of pentane.
  • the pressure inside tower 102 can be between 20.105 and 1.107 absolute pascals, the temperature between 100 and 300 ° C, the mass rate can be between 1 and 10, without these values being considered as limits.
  • the pressure may be approximately 40 ⁇ 10 5 absolute pascals, the temperatures at the bottom and at the top of the tower 102 being approximately, respectively, of 100 and 130 ° C, the mass rate
  • the solvent and the operating conditions of tower 109 are chosen so that only the "asphaltenes" fraction of line 105 whose softening point is greater than or equal to 150 ° C. precipitates in said tower.
  • the heavy solvent can be a solvent C 3 -20 / C 5 -80, the solvent of line 106 being a solvent C 3 -10 / C 5 -90.
  • the pressure inside tower 109 can be between 20.105 and 1.105 absolute pascals, the temperature between 100 and 200 ° C, the mass rate can be between 1 and 10, without these values being considered as limits.
  • the pressure can be around 40 ⁇ 10 5 absolute pascals, the temperatures at the bottom and at the top of the tower 109 being respectively about 100 and 140 ° C, the heavy solvent mass ratio on charge of tower 102 being approximately 2/1.
  • the "asphaltenes" fraction containing a little heavy solvent is collected at the bottom of tower 109, via line 110.
  • the mixture of "resins" fraction and of heavy solvent collected by line 111 is led, after passage through a heater 112, in an expansion tower 113 operating, in the case of a heavy solvent C 3 -20 / Cs-80 , at a pressure of approximately 25.10 5 absolute pascals and at a temperature of approximately 150 ° C. Following the passage through the heater 112, part of the solvent is vaporized.
  • the hydrocarbon with 3 carbon atoms is preferably so. Therefore, at the top of tower 113, by line 114, light solvent C 3 -60 / C 5 -40 is collected, which is recycled to line 103, after passage through a condenser 115, to reconstitute the solvent. slight drag in line 105.
  • the major part of the solvent is collected at the top of the tower 119, via the line 120, which, after passing through a condenser 121, is led to the flask 122.
  • the flask 122 is connected by line 123 to line 106 and the solvent can therefore be recycled.
  • this tower operates at a pressure of approximately 1.5 ⁇ 10 5 absolute pascals and a temperature of approximately 280 ° C.
  • the "resins” are collected at the bottom of the tower 126, by the line 128, and at the top of the said tower, by the line 129, water and solvent, which are led to the condenser 14 '.
  • a mixture of deasphalted oil and light solvent is collected at the top of the tower 102, via the line 129, which, after passing through a heater 131, is led into an expansion tower 132 operating, in the case of a light solvent C 3 -60 / C 5 -40, at a pressure of about 25,105 absolute pascals and a temperature of about 140 ° C.
  • the major part of the light solvent is collected at the top of tower 132, via line 133, which is recycled to line 103 through line 114 and the refrigerant 115.
  • the deasphalted oily phase containing a little solvent is collected at the bottom of tower 132, via line 134, which, after passing through a heater 135, is carried out in a tower 136 for driving with steam, where water vapor is introduced via line 137.
  • this tower operates at a pressure of approximately 1.5 ⁇ 10 5 absolute pascals and a temperature of approximately 250 ° C.
  • the deasphalted oil is collected at the bottom of the tower 136, by the line 138, and, at the top of the said tower, by the line 139, water and solvent, which are led to the condenser 14 '.
  • FIG. 3 represents a variant of FIG. 1, in which the separation of the light solvent from the deasphalted oil is carried out in such a way that the light solvent contains even more hydrocarbon with 3 carbon atoms.
  • the separation of the resins from the oil is better and allows an even "cleaner” deasphalted oil to be obtained, that is to say having an even lower “Conradson” residue.
  • the mixture of heavy solvent C 3 20 / C 5 -80 and of filler no longer containing "asphaltenes" collected by line 5 is led into a second extraction tower 200.
  • line 210 is introduced.
  • a third solvent C 3 -50 / C 5 -50 the extraction being carried out in fact using a light solvent C 3 -35 / C 5 -65.
  • the pressure in the tower can be approximately 40.10 s absolute pascals, the temperatures at the bottom and at the top of the tower 200 being approximately, respectively, 115 and 145 ° C., the mass rate being about 4/1.
  • the mixture of deasphalted oily phase and of light solvent C 5 -35 / C 5 -65 is collected at the top of the tower 200, via line 220.
  • the “resins” fraction containing a little light solvent is collected at the bottom of tower 200, by line 28, which is treated in the same way as for FIG. 1.
  • the mixture of deasphalted oily phase and light solvent C 3 -35 / C 5 -65 is led, after passage through a heater 230, in an expansion tower 240, operating, in the case of the light solvent C 3 -35 / C 5 -65, at a pressure of 25.10 s pascals absolute and a temperature of 145 ° C.
  • this phase after passing through a heater 370, is carried out in a water vapor drive tower 380, where water vapor is introduced via line 390.
  • deasphalted oil is collected by line 410 and, at the top of said tower, by line 400, water and solvent, which are led to condenser 14.
  • the process according to the invention is particularly useful, as the following examples show, for the simultaneous preparation of a deasphalted oil, suitable as a catalytic cracking charge, having a "Conradson" residue less than or equal to 10, preferably less than or equal to 9 and, better still, less than or equal to 8, and of an "asphaltenes" fraction, having a softening point equal to or greater than 150 ° C, preferably equal to or greater than 160 ° C and, better still, 170 ° C or higher.
  • This example relates to the treatment of a hydrocarbon feedstock constituted by the residue from the distillation under reduced pressure of the residue from the distillation under atmospheric pressure of a crude oil of Safaniya origin.
  • This charge is treated in a unit implementing the method according to the invention of the type presented in FIG. 1.
  • Solvents C 3 -C 5 are used in the unit, the compositions of which are given in Table 1 below.
  • This example relates to the treatment of a hydrocarbon feedstock constituted by the residue from the distillation under atmospheric pressure of the visbreaking effluent from a residue from the distillation under reduced pressure of a SAFANIYA crude oil.
  • This load is treated in a unit implementing the method according to the invention of the type shown in FIG. 1.
  • Solvents C 3 -C 5 are used in the unit with compositions identical to those of the solvents of Example 1.
  • This example relates to the treatment of a hydrocarbon feedstock constituted by the residue of the distillation under reduced pressure of the residue of the distillation under atmospheric pressure of a crude oil of Iraq origin.
  • This load is treated in a unit implementing the method according to the invention of the type shown in FIG. 1.
  • Solvents C 3 -C 6 are used in the unit, the compositions of which are given in Table VIII below. The operating conditions are given in Table IX below.
  • This example concerns the treatment of a hydrocarbon feedstock constituted by the residue from the distillation under reduced pressure of the residue from the distillation under atmospheric pressure of a crude oil of SAFANIYA origin.
  • This charge is treated in a unit implementing the method according to the invention of the type presented in FIG. 2.
  • Solvents C 3 -C 5 are used in the unit, the compositions of which are given in Table XII below. The operating conditions are given in Table XIII below.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP87401091A 1986-05-15 1987-05-14 Procédé de désasphaltage d'une charge hydrocarbonée lourde. Expired - Lifetime EP0246956B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8606994 1986-05-15
FR8606994A FR2598716B1 (fr) 1986-05-15 1986-05-15 Procede de desasphaltage d'une charge hydrocarbonee lourde

Publications (2)

Publication Number Publication Date
EP0246956A1 EP0246956A1 (fr) 1987-11-25
EP0246956B1 true EP0246956B1 (fr) 1990-11-28

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EP87401091A Expired - Lifetime EP0246956B1 (fr) 1986-05-15 1987-05-14 Procédé de désasphaltage d'une charge hydrocarbonée lourde.

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US (1) US4810367A (ja)
EP (1) EP0246956B1 (ja)
JP (1) JP2525409B2 (ja)
CA (1) CA1330063C (ja)
DE (1) DE3766415D1 (ja)
FR (1) FR2598716B1 (ja)

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Also Published As

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FR2598716A1 (fr) 1987-11-20
JP2525409B2 (ja) 1996-08-21
JPS62273289A (ja) 1987-11-27
EP0246956A1 (fr) 1987-11-25
FR2598716B1 (fr) 1988-10-21
US4810367A (en) 1989-03-07
DE3766415D1 (de) 1991-01-10
CA1330063C (fr) 1994-06-07

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