EP0778331B1 - Verfahren und Einrichtung zur Visbreaking von schweren Kohlenwasserstoffeinsätzen - Google Patents

Verfahren und Einrichtung zur Visbreaking von schweren Kohlenwasserstoffeinsätzen Download PDF

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Publication number
EP0778331B1
EP0778331B1 EP96402450A EP96402450A EP0778331B1 EP 0778331 B1 EP0778331 B1 EP 0778331B1 EP 96402450 A EP96402450 A EP 96402450A EP 96402450 A EP96402450 A EP 96402450A EP 0778331 B1 EP0778331 B1 EP 0778331B1
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EP
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Prior art keywords
gas
feed
unit
maturation
maturation unit
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Expired - Lifetime
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EP96402450A
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English (en)
French (fr)
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EP0778331A1 (de
Inventor
Marc Fersing
Luc Gouzien
Elisabeth Mouchot
Geraud Bourely
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Total Marketing Services SA
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Total Raffinage Distribution SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/007—Visbreaking
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps

Definitions

  • the present invention relates to improvements brought to visbreaking processes and devices heavy loads of hydrocarbons.
  • the ripener is usually in the form of a cylindrical enclosure, which does not have any means of additional heating of the load and, the cracking being endothermic, the temperature of the load drops by a few tens of degrees between its entry into the ripener and its release.
  • the temperature there is generally of the order of 400 to 500 ° C and the pressure of about 2 to 30.10 5 Pascals.
  • the residence time of the charge in the ripener is approximately 10 to 30 minutes.
  • the severity, depending on the residence time and the temperature of the ripener is of the order of 20 minutes.
  • the treated charge is injected at the base of the ripener, while cracked products, including products gaseous possibly formed, are evacuated to the part upper towards a split assembly by atmospheric distillation, then by vacuum distillation.
  • the feedstock can be heavy crude oil, a residue from atmospheric distillation, which is little frequent, because there are other types of recovery, a vacuum distillation residue or a pitch of deasphalting.
  • the products resulting from visbreaking are, after fractionation, gaseous hydrocarbons and gas liquefied petroleum, petrol, diesel, distillate and the visbreaking vacuum residue.
  • the visbreaking vacuum residue is the last recoverable product and it must meet requirements severe stability and compatibility with others petroleum cuts to be able to be used as a base for fuel oil, which causes the operator to adjust the conditions of implementation of visbreaking, in particular the temperature, so as to comply with the imposed criteria.
  • a major problem encountered in the units of visbreaking resides in a non-homogeneous progression of the charge inside the ripener, effects of back mixing (in English, "back mixing") and vortices encountered in particular in the vicinity of the side walls of the ripener, in particular at the bottom thereof.
  • back mixing in English, "back mixing”
  • vortices encountered in particular in the vicinity of the side walls of the ripener, in particular at the bottom thereof.
  • Each tray thus produces, at the orifices that he understands and borrows the bubbles of the gases present, a charge mixing effect, and the patent application aforementioned European recommends the use of 1 to 20 trays of this type in the ripener.
  • Document FR-A-2 528 444 proposes a method of thermal cracking of hydrocarbon oils in which a fluid, such as water vapor, can be introduced tangentially in the lower part of the ripener (see page 6, lines 8 to 17) through nozzles. This introduction aims to rotate the load of hydrocarbons.
  • the present invention aims to avoid these drawbacks by proposing means suitable for ensuring a residence time more homogeneous charge in the ripener and a better stability of the visbreaker.
  • the invention also aims to limit the phenomena of retromix associated with the treatment of a load of heavy hydrocarbons in the ripener of a set of visbreaking.
  • the invention finally aims to reduce the formation of coke in visbreaking processes and devices.
  • the Applicant has in fact established that by injecting a gas such as water vapor or nitrogen in the ripener, co-current, at least near the bottom and side walls of it, we get simultaneously a better conversion of the load, and therefore a significant reduction in coke formed, and better stability of the residue under visbreaking.
  • a gas such as water vapor or nitrogen
  • the invention therefore relates to a method of visbreaking of a heavy load of hydrocarbons in the state liquid, in which this charge is brought to a temperature likely to cause cracking of at least one part of the hydrocarbons present, then is introduced to the lower part of a ripener in which it is moves from bottom to top, to be evacuated to the part superior of this ripener towards a unit of fractionation, and in which a gas, preferably inert, is injected inside the ripener into the charge of hydrocarbons, at least at the base of the ripener, at near its side walls.
  • This process is characterized in that the gas is injected upwards along the walls side of the soaker and flows from bottom to top along of said walls, co-current with the hydrocarbon charge.
  • the gas produces a stripping effect on the load products, which facilitates the separation of light products (liquefied petroleum gas, petrol, diesel, etc ...), obtained by conversion in the ripener.
  • injections may be provided, always in the vicinity of the side walls, different levels in the ripener, to further minimize more back mixes and coke production.
  • the flow rate of the injected gas will advantageously be between 0.2 and 3 t / h and preferably between 0.5 and 2 t / h.
  • the gas, superheated and at a pressure greater than that of the ripener will be injected annually at the different injection levels, but the gas can also be introduced into the supply line of the charge charge to crack, upstream of the charge.
  • the invention also relates to a device for visbreaking of a heavy load of hydrocarbons in the state liquid, of the type comprising a means for heating the charge up to a temperature suitable for causing cracking of at least part of the oil, and a ripener comprising, in its lower part, at least one preheated load supply line and part thereof upper, at least one load evacuation line processed to a fractionation unit for this charge,
  • this device being characterized in that it comprises a means injection of a gas, preferably inert, into the charge of hydrocarbons to be treated, the injection means being arranged in a location such that the injected gas moves co-current of the charge, inside the ripener, at less at the base of it, near the inner side of its side walls.
  • the gas injection means may include nozzles regularly distributed injection systems connected to a source gas under pressure and arranged annularly, either along the lower part of the internal face of the walls of the ripener, or according to the bottom thereof.
  • This injection means may also include a conduit substantially toroidal in shape, connected to a gas source under pressure and fitted with regularly distributed orifices gas evacuation, this duct being arranged in the vicinity from the bottom of the ripener, coaxial to it.
  • the injection means may also include a line for introducing this gas into the heavy load of hydrocarbons downstream of the load heating means and upstream of the ripener, in the direction of circulation of the charge.
  • the single figure in this drawing is a schematic view visbreaking equipment in accordance with this invention.
  • a means of injecting a preferably inert gas in the hydrocarbon feed is provided inside the ripener 3, in the vicinity of the bottom of it and near its side walls.
  • this injection means comprises a toroidal shape 5, arranged coaxially to the side walls of the ripener, at the bottom thereof, and supplied with gas under pressure through a line 6.
  • This conduit 5 includes regularly spaced orifices which let the gas escape under pressure to the upper part of the ripener 3, at co-current of the hydrocarbon charge. This limits the dead volumes of this ripener and the feedbacks from the charge, while avoiding the formation of coke and ensuring stripping of light cracking products present in the ripener.
  • conduit 5 is advantageous compared to using nozzles such as that described in document FR-A-2 528 444 in connection with FIGS. 3A and 3B, because it avoids a modification of the reactor and therefore greater complexity of implementation.
  • the process according to the invention makes it possible to obtain a vacuum residue visoreduction of greatly improved stability, such as it will emerge from the examples below.
  • a visbreaking unit is controlled using stability as a benchmark of the visbreaking residue, for its use as that fuel oil, because if the stability is not greater than one certain threshold, fuel oil can present problems of use, due to the formation of sediments by precipitation of asphaltenes.
  • the stripping of light products of cracking by the injected gas allows to increase the stability of the visbreaking residue. In retaining the same stability value, it is thus possible increase the charge conversion rate by increasing the temperature of the ripener.
  • This vacuum residue is heated to a temperature of around 440 ° C in an oven of a visbreaking unit, then is introduced into the visbreaking ripener not modified in accordance with the present invention.
  • This ripener has a diameter of 2.5 meters and an axial height of 14 meters.
  • the visbreaking effluent is fractionated in a distillation column atmospheric and then in a distillation column under empty.
  • Example 2 The same vacuum distillation residue as in Example 1 is again subjected to a visbreaking treatment under conditions of identical severity.
  • the charge is heated in the oven to a temperature of the order of 450 ° C and the ripener is operated at a temperature of 430 ° C under a pressure of 8.10 5 Pascals.
  • the ripener is equipped, in accordance with the invention, with a pressurized steam distributor, consisting of a toric duct with a diameter of 30 millimeters, having regularly distributed injection ports, facing upwards .
  • This distributor rests on the bottom of the ripener and is arranged coaxially to the side walls.
  • the superheated steam is injected at a pressure of 11.10 5 Pascals and at a flow rate of 0.5 t / h, while the flow rate of the charge is 100 t / h.
  • the charge residence time is around 15 minutes. We therefore operate under severity conditions roughly analogous to those of Example 1.
  • the viscosity of the visbreaking residue is unchanged, but its stability is improved and production decreased sediment.
  • Example 2 With the same vacuum distillation residue as in Example 1, a visbreaking treatment is carried out under conditions of increased severity compared to Examples 1 and 2.
  • the residue is heated in the oven to 455 ° C, then is introduced into the ripener equipped with an injection ring of water vapor identical to that of Example 2.
  • the ripener is operated at a temperature of 434 ° C.
  • the water vapor pressure and flow conditions in the ripener are the same as in Example 2.
  • the effluent from the ripener is fractionated in an atmospheric distillation column, then in a vacuum distillation column.

Claims (10)

  1. Verfahren zum Visbreaking eines schweren Kohlenwasserstoffeinsatzes in flüssigem Zustand, bei welchem dieser Einsatz bei einer entsprechenden Temperatur zum Herbeiführen der Spaltdestillation mindestens eines Teils der vorhandenen Kohlenwasserstoffe zugeführt wird, anschließend dieser Einsatz in den unteren Teil eines Ablagerbehälters (3) eingeleitet wird, in welchem er sich von unten nach oben verlagert und dann am oberen Teil dieses Ablagerbehälters zu einer Fraktioniereinheit hin ausgetragen wird, und bei welchem ein vorzugsweise inertes Gas innen im Ablagerbehälter (3) in den Kohlenwasserstoffeinsatz zumindest im Unterteil des Ablagerbehälters (3) in der Nähe von dessen Seitenwandungen eingespritzt wird, dadurch gekennzeichnet, daß das Gas entlang der Seitenwandungen des Ablagerbehälters (3) nach oben eingespritzt wird und von unten nach oben entlang der Wandungen im Gleichstrom mit dem Kohlenwasserstoffeinsatz umläuft.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gas in den Ablagerbehälter (3) in mehreren unterschiedlichen Höhen in der Nähe der Innenfläche der Seitenwandungen eingespritzt wird.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß das Gas in den Ablagerbehälter (3) mittels kranzförmig angeordneten Einspritzeinrichtungen eingespritzt wird.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gas in den Kohlenwasserstoffeinsatz nach Erwärmung dieses Einsatzes auf der Anströmseite des Ablagerbehälters (3) in Fließrichtung des Einsatzes eingespritzt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß für eine Durchsatzleistung des Einsatzes in dem Ablagerbehälter von 75 bis 200 t/Std. die Gasmenge zwischen 0,2 und 3 5/Std. und vorzugsweise zwischen 0,5 und 2 t/Std. liegt.
  6. Vorrichtung zum Visbreaking eines schweren Kohlenwasserstoffeinsatzes in flüssigem Zustand, von der Art, welche eine Einrichtung (2) zum Erwärmen des Einsatzes auf eine entsprechende Temperatur zum Herbeiführen der Spaltdestillation mindestens eines Teils der Kohlenwasserstoffe und einen Ablagerbehälter (3) umfaßt, der in seinem unteren Teil mindestens eine Leitung (1) zum Zuführen des vorgewärmten Einsatzes und in seinem oberen Teil mindestens eine Leitung (4) zum Austragen des verarbeiteten Einsatzes zu einer Fraktioniereinheit hin aufweist, sowie eine Einrichtung (5) zum Einspritzen eines vorzugsweise inerten Gases in den zu verarbeitenden Kohlenwasserstoffeinsatz, wobei die Einspritzeinrichtung (5) im Inneren des Ablagerbehälters (3) zumindest an dessen Unterteil in der Nähe der Innenfläche von dessen Seitenwandungen angeordnet ist, dadurch gekennzeichnet, daß diese Einspritzeinrichtung (5) derart nach oben gerichtete Einspritzöffnungen aufweist, daß das Gas zum oberen Teil des Ablagerbehälters (3) hin entweichen kann.
  7. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß die Gaseinspritzeinrichtung regelmäßig verteilte Einspritzdüsen aufweist, die an eine druckbeaufschlagte Gasquelle angeschlossen und ringförmig angeordnet sind, entweder entlang des unteren Teils der Innenfläche der Seitenwandungen des Ablagerbehälters (3) oder entlang des Bodens desselben.
  8. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß die Gaseinspritzeinrichtung eine im wesentlichen wulstförmige Leitung (5) aufweist, die an eine druckbeaufschlagte Inertgasquelle angeschlossen ist und Öffnungen zum Austragen des inerten Gases aufweist, wobei diese Leitung (5) in der Nähe des Bodens des Ablagerbehälters (3) koaxial zu diesem angeordnet ist.
  9. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß die Gaseinspritzeinrichtung eine Leitung (7) zum Einleiten dieses Gases in den schweren Kohlenwasserstoffeinsatz auf der Abströmseite der Erwärmungseinrichtung (2) und auf der Anströmseite des Ablagerbehälters (3) in Umlaufrichtung des Einsatzes aufweist.
  10. Vorrichtung nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, daß sie eine Vielzahl von Einrichtungen zum Einspritzen von Gas in den Ablagerbehälter (3) aufweist, die in unterschiedlichen Höhen desselben angeordnet sind.
EP96402450A 1995-12-04 1996-11-15 Verfahren und Einrichtung zur Visbreaking von schweren Kohlenwasserstoffeinsätzen Expired - Lifetime EP0778331B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9514314A FR2741889B1 (fr) 1995-12-04 1995-12-04 Perfectionnements apportes aux procedes et aux dispositifs de viscoreduction de charges lourdes d'hydrocarbures
FR9514314 1995-12-04

Publications (2)

Publication Number Publication Date
EP0778331A1 EP0778331A1 (de) 1997-06-11
EP0778331B1 true EP0778331B1 (de) 1999-10-06

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US (1) US5925236A (de)
EP (1) EP0778331B1 (de)
JP (1) JP3833318B2 (de)
CN (1) CN1083876C (de)
AT (1) ATE185372T1 (de)
CA (1) CA2191913C (de)
DE (1) DE69604557T2 (de)
DK (1) DK0778331T3 (de)
ES (1) ES2137645T3 (de)
FR (1) FR2741889B1 (de)
ZA (1) ZA9610150B (de)

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US6533925B1 (en) 2000-08-22 2003-03-18 Texaco Development Corporation Asphalt and resin production to integration of solvent deasphalting and gasification
US6964199B2 (en) 2001-11-02 2005-11-15 Cantocor, Inc. Methods and compositions for enhanced protein expression and/or growth of cultured cells using co-transcription of a Bcl2 encoding nucleic acid
EP1999235B1 (de) * 2006-03-29 2018-09-05 Shell International Research Maatschappij B.V. Verfahren zur herstellung niedrigerer olefine
WO2007117919A2 (en) * 2006-03-29 2007-10-18 Shell Oil Company Improved process for producing lower olefins from heavy hydrocarbon feedstock utilizing two vapor/liquid separators
JP5070205B2 (ja) 2006-04-27 2012-11-07 タピオカ コマーシオ エ サービコス ソシエダーデ ウニペッソアル エルディーエー 重質油軽質化装置及び該方法
EP2234710A2 (de) 2007-11-28 2010-10-06 Saudi Arabian Oil Company Verfahren zum katalytischen hydrotreating von sauren rohölen
MX351574B (es) * 2011-05-13 2017-10-18 Catalytic Distillation Tech Metodo para producir coque alto en vcm.
CN105921079B (zh) * 2016-05-09 2019-01-22 怀化学院 一种含长链氟烷基的聚硅氧烷低聚物裂解的方法
USD844091S1 (en) 2016-10-20 2019-03-26 Bravo Company Mfg, Inc. Firearm handguard
CN110699114B (zh) * 2019-10-23 2020-12-29 东营联合石化有限责任公司 一种改进除水方法的石油炼化常减压装置
US11149219B2 (en) * 2019-12-19 2021-10-19 Saudi Arabian Oil Company Enhanced visbreaking process

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Publication number Publication date
DE69604557T2 (de) 2000-03-02
JP3833318B2 (ja) 2006-10-11
FR2741889B1 (fr) 1999-01-29
ES2137645T3 (es) 1999-12-16
ZA9610150B (en) 1997-06-17
ATE185372T1 (de) 1999-10-15
DE69604557D1 (de) 1999-11-11
CN1083876C (zh) 2002-05-01
EP0778331A1 (de) 1997-06-11
FR2741889A1 (fr) 1997-06-06
DK0778331T3 (da) 2000-02-07
CA2191913A1 (fr) 1997-06-05
CN1159474A (zh) 1997-09-17
JPH09183983A (ja) 1997-07-15
CA2191913C (fr) 2007-08-21
US5925236A (en) 1999-07-20

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