EP0090441A1 - Verfahren zur Herstellung von entasphaltierten Ölen und Kohlenwasserstofföldestillaten - Google Patents

Verfahren zur Herstellung von entasphaltierten Ölen und Kohlenwasserstofföldestillaten Download PDF

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Publication number
EP0090441A1
EP0090441A1 EP83200317A EP83200317A EP0090441A1 EP 0090441 A1 EP0090441 A1 EP 0090441A1 EP 83200317 A EP83200317 A EP 83200317A EP 83200317 A EP83200317 A EP 83200317A EP 0090441 A1 EP0090441 A1 EP 0090441A1
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Prior art keywords
feed
stream
treatment
asphaltenes
fraction
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EP83200317A
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French (fr)
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EP0090441B1 (de
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Jacobus Mathias Hendrikus Dirkx
John Robert Newsome
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen

Definitions

  • the invention relates to a process for the production of deasphalted oils and hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures.
  • Another option is to separate an atmospheric residue into a vacuum distillate and a vacuum residue by vacuum distillation, to separate a deasphalted oil from the vacuum residue by solvent deasphalting and to subject both the vacuum distillate and the deasphalted oil to catalytic cracking in the presence or absence of hydrogen.
  • Solvent deasphalting a process in which an asphaltenes-containing feedstock is converted into a product from which a deasphalted oil can be separated as the desired main product and an asphaltic bitumen as a by-product, has proven in actual practice to be a suitable treatment for the production of deasphalted oils from a variety of asphaltenes-containing hydrocarbon mixtures.
  • This suitability is greater according as the deasphalted oil has, among other things, lower asphaltenes, metal and sulphur contents.
  • the quality of the light product is taken to be its suitability for processing into a valuable light fuel.
  • This suitability is greater according as the light product has, among other things, lower sulphur and olefins contents.
  • the quality of the heavy product is taken to be its suitability for serving as a fuel oil component.
  • This suitability is greater according as the heavy product has, among other things, lower metal and sulphur contents and lower viscosity and density.
  • thermal cracking in which a heavy feed is converted into a product which contains less than 20 %w C. hydrocarbons and from which one or more distillate fractions and a heavy fraction are separated
  • HT catalytic hydrotreatment
  • the embodiments belonging to class II constitute the subject matter of the present patent application.
  • the embodiments belonging to class I constitute the subject matter of Netherlands Patent Application 8201233.
  • the embodiments to which the present patent application relates may be subdivided further depending on whether the heavy fraction separated from the product of the TC treatment is used as feed or feed component for the HT (class IIA) or as feed or feed component for the DA treatment (class IIB).
  • the heavy fraction separated from the product of the HT is used as the feed for the DA treatment.
  • the asphaltic bitumen fraction is used as the feed for the HT and the heavy fraction separated from the product of the HT is used as a feed component for the TC treatment and/or as a feed component for the DA treatment.
  • the present patent application therefore relates to a process for the production of deasphalted oils and hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures, in which an asphaltenes-containing hydrocarbon mixture (stream 1) is subjected to a thermal cracking treatment (TC) in which a feed is converted into a product which contains less than 20 %w c 4 hydrocarbons and from which one or more distillate fractions and a heavy fraction (stream 4) are separated, in which stream 4 is subjected to a combination of the following two treatments: a catalytic hydro-treatment (HT) in which an asphaltenes-containing feed is converted into a product which has a reduced asphaltenes content and from which one or more distillate fractions and a heavy fraction (stream 2) are separated and a solvent deasphalting treatment (DA) in which an asphaltenes-containing feed is converted into a product from which a deasphalted oil fraction and an asphaltic bitumen fraction (stream 3) are separated, and in which stream 4 is used either
  • the feed used is an asphaltenes-containing hydrocarbon mixture.
  • a suitable parameter for the assessment of the asphaltenes content of a hydrocarbon mixture as well as of the reduction of the asphaltenes content which appears when an asphaltenes-containing hydrocarbon mixture is subjected to a HT, is the Ramsbottom Carbon Test value (RCT).
  • RCT Ramsbottom Carbon Test value
  • the process is applied to hydrocarbon mixtures which boil substantially above 350°C and more than 35 %w of which boils above 520°C and which have an RCT higher than 7.5 %w.
  • hydrocarbon mixtures are residues obtained in the distillation of crude mineral oils and also heavy hydrocarbon mixtures obtained from shale and tar sands. If required, the process may also be applied to heavy crude mineral oils, residues obtained in the distillation of products formed in the thermal cracking of hydrocarbon mixtures and asphaltic bitumen obtained in the solvent deasphalting of asphaltenes-containing hydrocarbon mixtures.
  • the process according to the invention can very suitably be applied to residues obtained in the vacuum distillation of atmospheric distillation residues from crude mineral oils. If an atmospheric distillation residue from a crude mineral oil is available as feed for the process according to the invention, it is preferred to separate a vacuum distillate therefrom by vacuum distillation and to subject the resulting vacuum residue to the TC treatment.
  • the separated vacuum distillate may be subjected to thermal cracking or to catalytic cracking in the presence or in the absence of hydrogen to convert it into light hydrocarbon oil distillates.
  • the process according to the invention is a three-step process in which in the first step an asphaltenes-containing feed (stream 1) is subjected to a TC treatment for the production of a product which contains less than 20 %w C 4 - hydrocarbons and from which one or more distillate fractions and a heavy fraction (stream 4) are separated.
  • a DA treatment a combination of a DA treatment and a HT.
  • the distillate fractions separated from the product of the TC treatment may be atmospheric distillates only, but preferably a vacuum distillate should be separated from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways indicated hereinbefore.
  • the TC treatment is preferably carried out at a temperature of from 400-525°C and a space velocity of from 0.01-5 kg fresh feed per litre cracking reactor volume per minute.
  • the second or third step used is a HT in which an asphaltenes-containing feed is converted into a product which has a reduced asphaltenes content and from which one or more distillate fractions and a heavy fraction (stream 2) are separated.
  • Asphaltenes-containing hydrocarbon mixtures usually include a considerable percentage of metals, particularly vanadium and nickel.
  • a catalytic treatment for instance a HT for the reduction of the asphaltenes content as is the case in the process according to the invention, these metals are deposited on the catalyst used in the HT and thus shorten its effective life.
  • asphaltenes-containing hydrocarbon mixtures having a vanadium + nickel content of more than 50 parts per million by weight (pprw) should preferably be subjected to a demetallization treatment before they are contacted with the catalyst used in the HT.
  • This demetallization may very suitably be carried out by contacting the asphaltenes-containing hydrocarbon mixture, in the presence of hydrogen, with a catalyst consisting more than 80 %w of silica.
  • a catalyst consisting more than 80 %w of silica.
  • Both catalysts consisting entirely of silica and catalysts containing one or more metals having hydrogenating activity - in particular a combination of nickel and vanadium - emplaced on a carrier substantially consisting of silica are suitable for the purpose.
  • an asphaltenes-containing feed is subjected to a catalytic dematal- lization treatment in the presence of hydrogen, this demetallization may be carried out in a separate reactor.
  • the two processes may very suitably be carried out in the same reactor containing a bed of the demetallization catalyst and a bed of the catalyst used in the HT, successively.
  • Suitable catalysts for carrying out the HT are those containing at least one metal chosen from the group formed by nickel and cobalt and in addition at least one metal chosen from the group formed by molybdenum and tungsten on a carrier, which carrier consists more than 40 %w of alumina.
  • Catalysts very suitable for use in the HT are those comprising the metal combinations nickel/molybdenum or cobalt/molybdenum on alumina as the carrier.
  • the HT is preferably carried out at a temperature of from 300-500°C and in particular of from 350-450°C, a pressure of from 50-300 bar and in particular of from 75-200 bar, a space velocity of from 0.02-10 g.g -1 .h -1 and in particular of from 0.1-2 g.g -1. h -1 and a H 2 /feed ratio of from 100-5000 Nl.kg -1 and in particular of from 500-2000 Nl.kg -1 .
  • the conditions used in a catalytic demetallization treatment in the presence of hydrogen, to be carried out if required, are subject to the same preference as those for the HT for the reduction of the asphaltenes content stated hereinbefore.
  • the HT is preferably carried out in such a way that it yields a product, the C 5 + fraction of which meets the following requirements:
  • the HT yields a product having a reduced asphaltenes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated.
  • the distillate fractions separated from the product may be atmospheric distillates only, but it is preferred to separate a vacuum distillate from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways stated hereinbefore.
  • the second or third step used is a DA treatment in which an asphaltenes-containing feed is converted into a product from which a deasphalted oil and an asphaltic bitumen (stream 3) are separated.
  • Suitable solvents for carrying out the DA treatment are paraffinic hydrocarbons having 3-6 carbon atoms per molecule, such as n-butane and mixtures thereof, such as mixtures of propane and n-butane and mixtures of n-butane and n-pentane. Suitable solvent/oil weight ratios lie between 7:1 and 1:1 and in particular between 4:1 and 1:1.
  • the DA treatment is preferably carried out-at a pressure in the range of between 20 and 100 bar. When n-butane is used as the solvent, the deasphalting is preferably carried out at a pressure of from 35-45 bar and a temperature of from 100-150°C.
  • a subdivision of the embodiments belonging to class II, to which the present patent application relates, may be made depending on whether stream 4 is used as feed or feed component for the HT (class IIA) or as feed or feed component for the DA treatment (class IIB).
  • stream 4 is used as feed or feed component for the HT (class IIA) or as feed or feed component for the DA treatment (class IIB).
  • stream 2 is used as the feed for the DA treatment.
  • stream 3 is used as the feed for the HT and stream 2 is used as a feed component for the TC treatment and/or as a feed component for the DA treatment.
  • the various embodiments belonging to class IIA are represented schematically in Figure I.
  • the various streams, fractions and reaction zones are indicated by three digit numbers, the first of which refers to the Figure concerned.
  • the vacuum residue (302) for instance, refers to vacuum residue 2 in the context of Figure III.
  • the process is carried out in an apparatus comprising a TC zone (105), a HT zone (106) and a DA zone (107), successively.
  • An asphaltenes-containing hydrocarbon mixture (101) is subjected to a TC treatment and the cracked product is separated into one or more distillate fractions (108) and a residual fraction (104).
  • Stream 4 is subjected to a HT and the hydrotreated product is separated into one or more distillate fractions (109) and a residual fraction (102).
  • Figure I includes the following three embodiments:
  • FIG. II The various embodiments belonging to class IIB are represented schematically in Figure II. According to this Figure the process is carried out in an apparatus comprising a TC zone (205), a DA zone (206) and a HT zone (207), successively.
  • An asphaltenes-containing hydrocarbon mixture (201) is subjected to a TC treatment and the cracked product is separated into one or more distillate fractions (208) and a residual fraction (204).
  • Stream 204 is subjected to a DA treatment and the product is separated into a deasphalted oil (209) and an asphaltic bitumen (203).
  • Stream 203 is subjected to a HT and the hydrotreated product is separated into one or more distillate fractions (210) and a residual fraction (202).
  • Stream 202 is used either as a feed component for the TC treatment (embodiment IIB1) or as a feed component for the DA treatment (embodiment IIB2) or as a feed component both for the TC treatment and for the DA treatment (embodiment IIB3).
  • bleed stream should preferably be separated from one of the heavy streams of the process. In that way the build-up during the process of undesirably heavy conpo- nents can be obviated.
  • the process is carried out in an apparatus comprising a TC zone composed of a thermal cracking unit (305), an atmospheric distillation unit (306) and a vacuum distillation unit (307), successively, a HT zone composed of a unit for catalytic hydro- treatment (308), a second atmospheric distillation unit (309) and a second vacuum distillation unit (310) and a DA zone (311).
  • An asphaltenes-containing hydrocarbon mixture (301) is mixed with an asphaltic bitumen stream (312) and the mixture (313) is subjected to thermal cracking.
  • the cracked product (314) is separated by atmospheric distillation into a gas fraction (315), an atmospheric distillate (316) and an atmospheric residue (317).
  • the atmospheric residue (317) is separated by vacuum distillation into a vacuum distillate (318) and a vacuum residue (304).
  • the vacuum residue (304) is subjected together with hydrogen (319) to catalytic hydrotreatment.
  • the hydrotreated product (320) is separated by atmospheric distillation into a gas fraction (321), an atmospheric distillate (322) and an atmospheric residue (323).
  • the atmospheric residue (323) is separated by vacuum distillation into a vacuum distillate (324) and a vacuum residue (302).
  • the vacuum residue (302) is separated by solvent deasphalting into a deasphalted oil (325) and an asphaltic bitumen (303).
  • the asphaltic bitumen (303) is divided into two portions (312) and (326).
  • the process is carried out in an apparatus comprising a TC zone composed of a thermal cracking unit (405), an atmospheric distillation unit (406) and a vacuum distillation unit (407), successively, a DA zone (408) and a HT zone composed of a unit for catalytic hydrotreatment (409), a second atmospheric distillation unit (410) and a second vacuum distillation unit (411).
  • An asphaltenes-containing hydrocarbon mixture (401) is mixed with a vacuum residue (402) and the mixture (412) is subjected to thermal cracking.
  • the cracked product (413) is separated by atmospheric distillation into a gas fraction (414), an atmospheric distillate (415) and an atmospheric residue (416).
  • the atmospheric residue (416) is separated by vacuum distillation into a vacuum distillate (417) and a vacuum residue (418).
  • the vacuum residue (418) is separated by solvent deasphalting into a deasphalted oil (419) and an asphaltic bitumen (403).
  • the asphaltic bitumen (403) is divided into two portions (420) and (421). Portion (421) is subjected together with hydrogen (422) to catalytic hydrotreatment.
  • the hydrotreated product (423) is separated by atmospheric distillation into a gas fraction (424), an atmospheric distillate (425) and an atmospheric residue (426).
  • the atmospheric residue (426) is separated by vacuum distillation into a vacuum distillate (427) and a vacuum residue (402).
  • the present patent application also includes apparatuses for carrying out the process according to the invention, which correspond substantially with those represented schematically by Figures I- IV.
  • the units for catalytic hydrotreatment consisted of two reactors, the first of which was filled with a Ni/V/Si0 2 catalyst containing 0.5 parts by weight (pbw) nickel and 2.0 pbw vanadium per 100 pbw silica and the second of which was filled with a Co/Mo/Al 2 O 3 catalyst containing 4 pbw cobalt and 12 pbw molybdenum per 100 pbw alumina.
  • the catalysts were used in a 1:4 volume ratio.
  • the catalytic hydrotreatment was carried out at a hydrogen pressure of 150 bar, a space velocity (measured over the two reactors) of 0.5 kg feed per litre catalyst per hour, a H 2 /feed ratio of 1000 N1 per kg and an average temperature of 410°C in the first reactor and of 385°C in the second reactor.
  • the DA treatment was carried out using n-butane as the solvent, at a temperature of 115°C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1.
  • the TC treatment was carried out in a cracking coil at a pressure of 10 bar, a space velocity of 0.4 kg fresh feed per litre cracking coil volume per minute and a temperature of 485°C (temperature measured at the outlet of the cracking coil).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
EP83200317A 1982-03-25 1983-03-04 Verfahren zur Herstellung von entasphaltierten Ölen und Kohlenwasserstofföldestillaten Expired EP0090441B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8201243 1982-03-25
NL8201243A NL8201243A (nl) 1982-03-25 1982-03-25 Werkwijze voor de bereiding van asfaltanenarme koolwaterstofmengsel.

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EP0090441A1 true EP0090441A1 (de) 1983-10-05
EP0090441B1 EP0090441B1 (de) 1985-10-09

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EP83200317A Expired EP0090441B1 (de) 1982-03-25 1983-03-04 Verfahren zur Herstellung von entasphaltierten Ölen und Kohlenwasserstofföldestillaten

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EP (1) EP0090441B1 (de)
JP (1) JPS58173191A (de)
AU (1) AU552694B2 (de)
CA (1) CA1206906A (de)
DE (1) DE3360953D1 (de)
ES (1) ES520830A0 (de)
MX (1) MX162479A (de)
NL (1) NL8201243A (de)
ZA (1) ZA831990B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216448A1 (de) * 1985-06-28 1987-04-01 Gulf Canada Resources Limited Verfahren zur Ausbeuteverbesserung von Destillaten beim Kracken mit Wasserstoff liefernden Verdünnungsmitteln
WO1996007716A1 (en) * 1994-09-05 1996-03-14 Shell Internationale Research Maatschappij B.V. Process for the thermal cracking of a residual hydrocarbon oil
US6511937B1 (en) 1999-10-12 2003-01-28 Exxonmobil Research And Engineering Company Combination slurry hydroconversion plus solvent deasphalting process for heavy oil upgrading wherein slurry catalyst is derived from solvent deasphalted rock
US6524469B1 (en) * 2000-05-16 2003-02-25 Trans Ionics Corporation Heavy oil upgrading process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2328033A1 (fr) * 1975-10-15 1977-05-13 Shell Int Research Procede pour la transformation par hydrocraquage de residus atmospheriques d'huiles d'hydrocarbures en distillats atmospheriques
GB2024850A (en) * 1978-07-07 1980-01-16 Shell Int Research Preparation of gas oil from heavy oils
GB2093477A (en) * 1981-01-25 1982-09-02 Chiyoda Chem Eng Construct Co Process for the conversion of heavy hydrocarbon oils into light hydrocarbon oils

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS559426U (de) * 1978-07-04 1980-01-22
NL8201119A (nl) * 1982-03-18 1983-10-17 Shell Int Research Werkwijze voor de bereiding van koolwaterstofoliedestillaten.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2328033A1 (fr) * 1975-10-15 1977-05-13 Shell Int Research Procede pour la transformation par hydrocraquage de residus atmospheriques d'huiles d'hydrocarbures en distillats atmospheriques
GB2024850A (en) * 1978-07-07 1980-01-16 Shell Int Research Preparation of gas oil from heavy oils
GB2093477A (en) * 1981-01-25 1982-09-02 Chiyoda Chem Eng Construct Co Process for the conversion of heavy hydrocarbon oils into light hydrocarbon oils

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216448A1 (de) * 1985-06-28 1987-04-01 Gulf Canada Resources Limited Verfahren zur Ausbeuteverbesserung von Destillaten beim Kracken mit Wasserstoff liefernden Verdünnungsmitteln
WO1996007716A1 (en) * 1994-09-05 1996-03-14 Shell Internationale Research Maatschappij B.V. Process for the thermal cracking of a residual hydrocarbon oil
US6511937B1 (en) 1999-10-12 2003-01-28 Exxonmobil Research And Engineering Company Combination slurry hydroconversion plus solvent deasphalting process for heavy oil upgrading wherein slurry catalyst is derived from solvent deasphalted rock
US6524469B1 (en) * 2000-05-16 2003-02-25 Trans Ionics Corporation Heavy oil upgrading process

Also Published As

Publication number Publication date
AU1268483A (en) 1983-09-29
DE3360953D1 (en) 1985-11-14
EP0090441B1 (de) 1985-10-09
AU552694B2 (en) 1986-06-12
CA1206906A (en) 1986-07-02
ZA831990B (en) 1983-11-30
ES8401516A1 (es) 1983-12-16
ES520830A0 (es) 1983-12-16
MX162479A (es) 1991-05-13
NL8201243A (nl) 1983-10-17
JPS58173191A (ja) 1983-10-12

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