EP0778331A1 - 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
EP0778331A1
EP0778331A1 EP96402450A EP96402450A EP0778331A1 EP 0778331 A1 EP0778331 A1 EP 0778331A1 EP 96402450 A EP96402450 A EP 96402450A EP 96402450 A EP96402450 A EP 96402450A EP 0778331 A1 EP0778331 A1 EP 0778331A1
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EP
European Patent Office
Prior art keywords
gas
ripener
charge
injected
side walls
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.)
Granted
Application number
EP96402450A
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English (en)
French (fr)
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EP0778331B1 (de
Inventor
Marc Fersing
Luc Gouzien
Elisabeth Mouchot
Geraud Bourely
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.)
TotalEnergies Marketing Services SA
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Total Raffinage Distribution SA
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Publication of EP0778331A1 publication Critical patent/EP0778331A1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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 made to processes and devices for visbreaking 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 the cracked products, including the gaseous products that may be formed, are evacuated at the top towards a fractionation unit by atmospheric distillation, then by vacuum distillation.
  • the feedstock treated can be heavy crude oil, an atmospheric distillation residue, which is not very frequent because there are other types of recovery, a vacuum distillation residue or a deasphalting pitch.
  • the products resulting from visbreaking are, after fractionation, gaseous hydrocarbons and liquefied petroleum gas, gasoline, diesel, distillate and the residue under visbreaking vacuum.
  • the visbreaking vacuum residue is the last recoverable product and it must meet severe requirements of stability and compatibility with other petroleum fractions to be able to be used as fuel oil base, which leads the operator to adjust the conditions of implementation of visbreaking, including temperature, so as to meet the criteria imposed.
  • a major problem encountered in visbreaking units lies in an inhomogeneous progression of the charge inside the ripener, back-mixing effects and vortices encountered in particular in the vicinity of the side walls of the ripener, especially at the bottom of it. These disturbances are further increased by the gases which form during the cracking reactions, and the residence time of the charge in the ripener varies considerably, depending on the zones considered, in the same cross section. As a result, part of the treated charge may be overcracked, while another fraction will be insufficiently cracked.
  • Document FR-A-2 528 444 proposes a thermal cracking process for hydrocarbon oils in which a fluid, such as water vapor, can be introduced tangentially into the lower part of the ripener (cf. page 6 , lines 8 to 17) through nozzles. The purpose of this introduction is to drive the hydrocarbon charge in rotation.
  • the present invention aims to avoid these drawbacks by proposing means capable of ensuring a more homogeneous residence time of the charge in the ripener and better stability of the visbreaker.
  • the invention also aims to limit the backmixing phenomena associated with the treatment of a heavy hydrocarbon charge in the ripener of a visbreaking unit.
  • 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 into the maturer, co-current, at least near the bottom and the side walls thereof, a better conversion of the charge is obtained simultaneously, and consequently a significant reduction of the coke formed, and a better stability of the residue under vacuum visbreaking.
  • a gas such as water vapor or nitrogen
  • the subject of the invention is therefore a process for visbreaking a heavy charge of hydrocarbons in the liquid state, in which this charge is brought to a temperature capable of causing cracking of at least part of the hydrocarbons present, then it is introduced into the lower part of a ripener in which it moves from bottom to top, to be discharged in the upper part of this ripener in the direction of a fractionation unit, and in which a gas, preferably inert, is injected inside the ripener into the hydrocarbon charge, at least at the base of the ripener, in the vicinity of its side walls.
  • This process is characterized in that the gas is injected upwards along the side walls of the ripener and flows from bottom to top along said walls, co-current with the hydrocarbon charge.
  • the gas water vapor, nitrogen, hydrogen, refinery gas or other
  • moving from bottom to top in the vicinity of the walls of the ripener thus limits the formation of dead zones and back-mixes at the bottom and walls lateral, and the residence time of the various streams of hydrocarbon fluid inside the ripener will tend to homogenize and approach the average residence time of the charge.
  • the gas produces a stripping effect on the charge products, which facilitates the separation of the 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, at different levels in the ripener, to further minimize back-mixing and the production of coke. .
  • 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 higher than that of the regulator will be injected annually at the different injection levels, but the gas may also be introduced into the supply line of the regulator with the charge to be cracked, upstream of the ripener.
  • the invention also relates to a device for visbreaking a heavy load of hydrocarbons in the liquid state, of the type comprising a means for heating the load to a temperature capable of causing cracking of at least one part of the hydrocarbons, and a ripener comprising, at its lower part, at least one feed line for preheated charge and, at its upper part, at least one line for discharging the treated charge towards a fractionation unit for this charge ,
  • this device being characterized in that it comprises a means for injecting 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 is moves co-current of the charge, inside the ripener, at least at the base thereof, in the vicinity of the internal face of its side walls.
  • the gas injection means may comprise regularly distributed injection nozzles, connected to a source of pressurized gas and arranged annularly, either along the lower part of the internal face of the walls of the regulator, or along the bottom thereof. this.
  • This injection means may also include a substantially toroidal-shaped conduit, connected to a source of pressurized gas and equipped with regularly distributed orifices. gas evacuation, this conduit being arranged in the vicinity of the bottom of the maturator, coaxial with it.
  • the injection means may also include a line for introducing this gas into the heavy hydrocarbon charge downstream of the means for heating the charge and upstream of the ripener, in the direction of flow of the charge.
  • the single figure of this drawing is a schematic view of a visbreaking apparatus according to the present invention.
  • a means for injecting a gas, preferably inert, into the hydrocarbon feedstock is provided inside the ripener 3, in the vicinity of the bottom thereof and near its side walls.
  • this injection means comprises a toric-shaped duct 5, arranged coaxially with the side walls of the ripener, at the bottom of the latter, and supplied with gas under pressure by a line 6.
  • This conduit 5 has regularly spaced orifices, which allow the gas under pressure to escape towards the upper part of the regulator 3, co-current with the hydrocarbon charge. This limits the dead volumes of this ripener and the feed backward movements, while avoiding the formation of coke and ensuring stripping of the light cracking products present in the ripener.
  • conduit 5 is advantageous compared to the use of nozzles such as that described in document FR-A-2 528 444 in connection with FIGS. 3A and 3B, because it avoids modification of the reactor and therefore more great complexity of implementation.
  • gas preferably inert under pressure
  • the process according to the invention makes it possible to obtain a vacuum residue with visbreaking of greatly improved stability, as will emerge from the examples below.
  • a visbreaking unit is controlled by taking as a benchmark the stability of the visbreaking residue, for its use as than fuel oil, because, if the stability is not greater than a certain threshold, fuel oil can present problems of use, due to the formation of sediments by precipitation of asphaltenes.
  • the stripping of light cracking products by the injected gas makes it possible to increase the stability of the visbreaking residue. By retaining the same stability value, it is thus possible to increase the charge conversion rate by increasing the temperature of the ripener.
  • This vacuum residue is heated to a temperature of the order of 440 ° C. in an oven of a visbreaking unit, then is introduced into the visbreaking maturer unmodified 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 an atmospheric distillation column, then in a vacuum distillation column.
  • 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 maturator 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 vacuum residue is unchanged, but its stability is improved and the production of sediment is reduced.
  • 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 it is introduced into the ripener equipped with a water vapor injection ring identical to that of example 2.
  • the ripener is operated at a temperature of 434 ° vs.
  • the pressure and flow conditions of the water vapor 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.
  • the filtration temperature is adapted to the viscosity of the product and is greater than 100 ° C. Additional washing with a solvent suitable for the filtration temperature is carried out before that with dodecane.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Steroid Compounds (AREA)
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 true EP0778331A1 (de) 1997-06-11
EP0778331B1 EP0778331B1 (de) 1999-10-06

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Application Number Title Priority Date Filing Date
EP96402450A Expired - Lifetime EP0778331B1 (de) 1995-12-04 1996-11-15 Verfahren und Einrichtung zur Visbreaking von schweren Kohlenwasserstoffeinsätzen

Country Status (11)

Country Link
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)

Families Citing this family (16)

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RU2148609C1 (ru) * 1999-02-26 2000-05-10 Государственный научный центр Российской Федерации "Научно-исследовательский институт атомных реакторов" Способ разделения смеси углеводородов с различной температурой кипения
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
RU2215020C1 (ru) * 2002-06-21 2003-10-27 Общество с ограниченной ответственностью "Астраханьгазпром" Способ переработки тяжелого углеводородного сырья
EP1999234B1 (de) * 2006-03-29 2018-05-30 Shell International Research Maatschappij B.V. Verbessertes verfahren zur herstellung niedrigerer olefine aus einem schweren kohlenwasserstoff-rohmaterials mit zwei dampf- bzw. flüssigkeitstrennern
CN101400766B (zh) * 2006-03-29 2013-07-24 国际壳牌研究有限公司 利用两个气液分离器由重质烃原料生产低级烯烃的改进方法
WO2007125576A1 (ja) * 2006-04-27 2007-11-08 Sunfuu Co., Ltd. 重質油軽質化装置及び該方法
WO2009073436A2 (en) 2007-11-28 2009-06-11 Saudi Arabian Oil Company Process for catalytic hydrotreating of sour crude oils
PL2707459T3 (pl) * 2011-05-13 2019-07-31 Catalytic Distillation Technologies Sposób i aparatura do wytwarzania koksu o dużej zawartości 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
US11802245B1 (en) * 2022-11-16 2023-10-31 Saudi Arabian Oil Company Processes for viscosity breaking of plastics
FR3164472A1 (fr) 2024-07-15 2026-01-16 Totalenergies Onetech Procede de craquage thermique d’hydrocarbures d’origine fossile en presence d’huile de pneus
FR3164468A3 (fr) 2024-07-15 2026-01-16 Totalenergies Onetech Procede de conversion d’hydrocarbures d’origine fossile suivi d’un fractionnement en presence d’huile de pneus

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007656A1 (de) 1978-07-11 1980-02-06 Shell Internationale Researchmaatschappij B.V. Verfahren zum kontinuierlichen thermischen Kracken von Kohlenwasserstoffölen und damit gewonnene Kohlenwasserstoffgemische
FR2528444A1 (fr) 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
EP0138247A1 (de) 1983-09-02 1985-04-24 Shell Internationale Researchmaatschappij B.V. Verfahren und Vorrichtung für kontinuierliches thermisches Cracken von Kohlenwasserstoffölen und danch hergestellte Kohlenwasserstoffmischungen
EP0166604A2 (de) * 1984-06-27 1986-01-02 Fuji Standard Research Inc. Verfahren zur thermischen Spaltung von schweren Kohlenwasserstoffölen
EP0204410A2 (de) * 1985-05-28 1986-12-10 Mobil Oil Corporation Methode zur Erzeugung von Wärme zu Hochtemperatur-Verarbeitungsströmen
US4784744A (en) * 1987-09-10 1988-11-15 Mobil Oil Corporation Process for stabilizing intermediates and improving liquid yields and coke quality

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US1899889A (en) * 1929-04-25 1933-02-28 Standard Oil Dev Co Eliminating water hazard in treating oils
US2161247A (en) * 1936-06-12 1939-06-06 Texas Co Treating hydrocarbon oil
US2312719A (en) * 1938-11-01 1943-03-02 Standard Oil Dev Co Cracking process
US4836909A (en) * 1985-11-25 1989-06-06 Research Association For Residual Oil Processing Process of thermally cracking heavy petroleum oil
US4695367A (en) * 1986-03-24 1987-09-22 The M. W. Kellogg Company Diesel fuel production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007656A1 (de) 1978-07-11 1980-02-06 Shell Internationale Researchmaatschappij B.V. Verfahren zum kontinuierlichen thermischen Kracken von Kohlenwasserstoffölen und damit gewonnene Kohlenwasserstoffgemische
FR2528444A1 (fr) 1982-06-14 1983-12-16 Neste Oy Procede de craquage thermique d'huiles d'hydrocarbures
EP0138247A1 (de) 1983-09-02 1985-04-24 Shell Internationale Researchmaatschappij B.V. Verfahren und Vorrichtung für kontinuierliches thermisches Cracken von Kohlenwasserstoffölen und danch hergestellte Kohlenwasserstoffmischungen
EP0166604A2 (de) * 1984-06-27 1986-01-02 Fuji Standard Research Inc. Verfahren zur thermischen Spaltung von schweren Kohlenwasserstoffölen
EP0204410A2 (de) * 1985-05-28 1986-12-10 Mobil Oil Corporation Methode zur Erzeugung von Wärme zu Hochtemperatur-Verarbeitungsströmen
US4784744A (en) * 1987-09-10 1988-11-15 Mobil Oil Corporation Process for stabilizing intermediates and improving liquid yields and coke quality

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Title
"ASTM Standards", vol. 05.01, 1989, pages: 657 - 661

Also Published As

Publication number Publication date
CN1159474A (zh) 1997-09-17
DE69604557T2 (de) 2000-03-02
ZA9610150B (en) 1997-06-17
FR2741889B1 (fr) 1999-01-29
FR2741889A1 (fr) 1997-06-06
ES2137645T3 (es) 1999-12-16
EP0778331B1 (de) 1999-10-06
CN1083876C (zh) 2002-05-01
CA2191913A1 (fr) 1997-06-05
US5925236A (en) 1999-07-20
DK0778331T3 (da) 2000-02-07
DE69604557D1 (de) 1999-11-11
JP3833318B2 (ja) 2006-10-11
JPH09183983A (ja) 1997-07-15
CA2191913C (fr) 2007-08-21
ATE185372T1 (de) 1999-10-15

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