EP0229458A1 - Procédé d'extraction au solvant pour hydrocarbure - Google Patents

Procédé d'extraction au solvant pour hydrocarbure Download PDF

Info

Publication number
EP0229458A1
EP0229458A1 EP86308408A EP86308408A EP0229458A1 EP 0229458 A1 EP0229458 A1 EP 0229458A1 EP 86308408 A EP86308408 A EP 86308408A EP 86308408 A EP86308408 A EP 86308408A EP 0229458 A1 EP0229458 A1 EP 0229458A1
Authority
EP
European Patent Office
Prior art keywords
aromatic
solvent
extract
pseudo
extraction
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.)
Withdrawn
Application number
EP86308408A
Other languages
German (de)
English (en)
Inventor
Byung Chang Choi
Grant George Karsner
Chang-Kuei Lee
Madhava Malladi
Donald Milstein
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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 Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0229458A1 publication Critical patent/EP0229458A1/fr
Withdrawn legal-status Critical Current

Links

Images

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
    • 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
    • C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
    • C10G47/34—Organic compounds, e.g. hydrogenated 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

Definitions

  • This invention relates to a process for the selective solvent extraction of hydrocarbon mixtures, and in particular to a process for the solvent extraction of lubricating oils using furfural.
  • the invention related also to the processing of residual petroleum stocks by visbreaking in the presence of certain highly aromatic hydrogen-donor materials obtained from the solvent extraction process.
  • Solvent extraction is a well known procedure for the separation of aromatic hydrocarbons from mixtures with nonaromatic hydrocarbons of similar boiling range. Furfural has been found to be an excellent selective solvent in the separation of hydrocarbons of relatively high boiling point, for example hydrocarbons useful in the manufacture of lubricating oils and catalytic cracking feed stocks. Furfural extraction has also been found useful in the manufacture of kerosine and low boiling gas oil products where a raffinate of low aromatic content is produced.
  • a liquid hydrocarbon mixture containing aromatic and non-aromatic hydrocarbons is contacted with liquid furfural in an extraction column effecting formation of a raffinate phase, which is withdrawn from the top of the column and which contains a major portion of the non-aromatic hydrocarbons, and an extract phase which is withdrawn from the bottom of the column and which contains most of the furfural containing dissolved hydrocarbons including a major portion of the aromatic hydrocarbons and the remaining non-aromatic hydrocarbons.
  • the two phases can then be separated into their constituents by distillation.
  • Patent 3,205,167 proposes to treat the extract phase by cooling thus separating it into one phase comprising a naphthenic oil known as a pseudo-raffinate and containing a little solvent and the other phase comprising the so-called "extract proper" containing the more aromatic and sulfurized components of the oil and a large quantity of solvent.
  • U.S. Patent 3,205,167 is silent regarding the specific temperature range within which this cooling operation is to be carried out and says nothing of the composition or properties of the "extract proper".
  • Visbreaking or viscosity breaking, is a well known petroleum refining process in which reduced crudes are pyrolyzed, or cracked, under comparatively mild conditions to provide products having lower viscosities and pour points, thus reducing the amounts of less viscous and more valuable blending oils, so-called "cutter stock", required to make the residual stocks useful as fuel oils.
  • the visbreaker feed stock usually consists of a mixture of two or more refinery streams derived from sources such as atmospheric residuum, vacuum residuum, furfural-extract, propane-deasphalted tar and catalytic cracker bottoms. Most of these feed stock components, except the heavy aromatic oils, behave independently in the visbreaking operation.
  • the severity of the operation for a mixed feed is limited greatly by the least desirable (highest coke-forming) components.
  • the crude or resid feed is passed through a heater and heated to 425 to 525°C at 450 to 7000 kPa.
  • Light gas-oil may be recycled to lower the temperature of the effluent.
  • Cracked products from the reaction are flash distilled with the vapor overhead being fractionated into a light distillate overhead product, for example gasoline and light gas-oil bottoms, and the liquid bottoms are vacuum fractionated into heavy gas-oil distillate and residual tar.
  • European Patent Application 133,774 describes a process for visbreaking a heavy petroleum residual oil which comprises subjecting the oil to an elevated temperature for a period of time corresponding to an equivalent reaction time of 250 to 1500 ERT seconds at 427°C in the presence of from 0.1 to 50 weight percent, based on the residual oil, of a hydro-aromatic solvent having a content of H Ar hydrogen (protons which are attached directly to aromatic rings and which constitute a measure of aromaticity of a material) and H alpha hydrogen (protons which are attached to non-aromatic carbon atoms themselves attached directly to an aromatic ring, for example alkyl groups and naphthenic ring structures) each of at least 20 percent of the total hydrogen content, and recovering a fuel oil product having a viscosity lower than that of the starting residual oil.
  • H Ar hydrogen protons which are attached directly to aromatic rings and which constitute a measure of aromaticity of a material
  • H alpha hydrogen protons which are attached to non-aromatic carbon atoms themselves attached directly to an aromatic ring, for
  • the hydro-aromatic solvent used in this process is a thermally stable, polycyclic, aromatic/hydroaromatic distillate hydrogen donor material, preferably one which results from one or more petroleum refining operations.
  • the hydrogen-donor solvent nominally has an average boiling point of 200 to 500°C, and a density of 0.85 to 1.1 g/cc.
  • suitable hydrogen donor materials are highly aromatic petroleum refinery streams, such as fluidized catalytic cracker "main column” bottoms which are highly preferred, fluidized catalytic cracker “light cycle oil,” and thermofor catalytic cracker “syntower” bottoms, all of which contain a substantial proportion of polycyclic aromatic hydrocarbon constituents such as naphthalene, dimethylnaphthalene, anthracene, phenanthrene, fluorene, chrysene, pyrene, perylene, diphenyl, benzothiophene, tetralin and dihydronaphthalene, for example.
  • Such refractory petroleum materials are resistant to conversion to lighter (lower molecular weight) products by conventional non-hydrogenative procedures.
  • these petroleum refinery residual and recycle fractions are hydrocarbonaceous mixtures having an average carbon to hydrogen ratio above 1:1, and an average boiling point above 230°C.
  • the pseudo-extract resulting from the process referred to herein as a "double decantation" process, is well-suited for use in processes employing a hydrogen-donor, for example in the visbreaking process described in European Patent Application 133,774.
  • the pseudo-raffinate is advantageously used as feedstock in an otherwise conventional catalytic cracking processes, the operational parameters of which are well known in the art.
  • the pseudo-raffinate can also be recycled to the first extraction step of the process to produce additional lube stock.
  • a liquid hydrocarbon charge stock containing both aromatic and non-aromatic hydrocarbon components for example Arab medium crude
  • a suitable extraction solvent in this case the preferred solvent, furfural.
  • the amount of extraction solvent can vary widely and will frequently range from 100 to 300 volume percent of the charge stock.
  • the extraction process of the invention contemplates the use of a conventional solvent extraction unit operated under conventional conditions. For example, in a typical lube oil facility, the extraction column is operated within a predetermined temperature profile so as to provide a raffinate phase which, following dewaxing, will provide a lube oil product meeting specifications taking into account the properties of the charge stock.
  • the extraction column is commonly operated at 65 to 150°C, and preferably 80 to 120°C, at the bottom, the temperature at the top of the column being some 10 to 35°C, and preferably from 15 to 30°C, higher than this.
  • a temperature profile is entirely suitable for practicing the extraction process of the invention.
  • the extract phase will usually contain a relatively minor amount of non-aromatic components, for example from 10 to 25 weight percent of the non-aromatic content of the original feed. Although more of these non-aromatics can be shifted to the raffinate phase by lowering the bottom temperature of the extraction unit, this may be achieved only at the expense of lube stock quality.
  • the extraction column can be operated within a different temperature profile.
  • the extract phase is passed through a heat exchanger where it is cooled to a temperature resulting in the separation of the stream into a pseudo-raffinate containing most of the non-aromatic components and a pseudo-extract containing most of the aromatic components.
  • Such cooling must, at a minimum, be sufficient to provide a pseudo extract possessing a hydro-aromatic content of H alpha hydrogen of at least 20 percent, and preferably up to 50 percent, based on total hydrogen content.
  • the cooled two-phase stream is then separated in a decanter to provide the pseudo-extract which, after removal of furfural (or other extraction solvent as the case might be), for example by distillation, is ready to be employed as a hydrogen-donor.
  • the pseudo-raffinate resulting from the double decantation process is advantageously employed as co-feed in a catalytic cracking operation, for example an FCC or TCC process.
  • the pseudo-raffinate can be recycled to the initial extraction unit to produce more lube oil.
  • the use of the pseudo-extract as a hydrogen-donor in visbreaking is advantageously carried out in a facility of the type shown schematically in Fig. 2 in which a viscous hydrocarbon oil feed, typified by a 496°C+ Arab Heavy resid, is supplied by line 22 to visbreaking heater 25.
  • the feed is blended with the pseudo-extract as the hydrogen-donor material supplied through line 50 in an amount of 0.1 to 50 weight percent, preferably 0.1 to 20 weight percent, based on the resid charge, (a weight ratio of hydrogen-donor to resid of 0.001 to 0.5, preferably 0.001 to 0.2).
  • Mild thermal cracking of the resid under visbreaking conditions occurs in visbreaker 25 and produces a visbreaker effluent stream carried by line 28.
  • Visbreaking process conditions can vary widely based on the nature of the heavy oil material, the hydrogen-donor pseudo-extract and other factors.
  • the process is carried out at temperatures ranging from 350 to 485°C, preferably 425 to 455°C, at residence times ranging from 1 to 60 minutes, preferably 7 to 20 minutes.
  • Equivalent Reaction Time also referred to as "ERT” refers to the severity of the visbreaking operation expressed as seconds of residence time in a reactor operating at 427°C.
  • the reaction rate doubles for every 12 to 13°C increase in temperature.
  • 50 seconds of residence at 427°C is equivalent to 50 ERT, and increasing the temperature to 456°C would make the operation five times as severe, that is 300 ERT.
  • the visbreaking process operates at an Equivalent Reaction Time of 250 to 1500 ERT seconds, and preferably 400 to 1200 ERT seconds and more preferably 500 to 800 ERT seconds, at 427°C.
  • the pressure employed in the visbreaker will usually be sufficient to maintain most of the material in the reactor coil and/or soaker drum in the liquid phase. Normally the pressure is not considered as a control variable, although attempts should be made to keep the pressure high enough to maintain most of the material in the visbreaker in the liquid phase.
  • Some vapor formation in the visbreaker is not harmful, and is frequently inevitable because of the production of some light ends in the visbreaking process.
  • Some visbreaker units operate with 20-40 percent vaporization material at the visbreaker coil outlet.
  • the visbreaker effluent stream carried by line 28 is cooled by admixture with a quench stream from line 31, and the visbreaker effluent continued through line 29 to distillation column 30 where it is fractionated to obtain C5- gases (C3, C4 and lower) and a C5 - 135°C naptha fraction from the top through line 34.
  • a 220 to 370°C gas oil fraction is taken off as a bottoms stream through line 33 where portions may be recycled as a quench stream through line 31, recovered as heavy fuel oil 32 or, via line 33, blended with cutter stock to meet fuel oil product specifications.
  • the overhead fraction removed from the distillation column in line 34 is passed through a cooler separator 36 which is operated under conditions effective to separate the incoming liquid into a C5- off-gas stream 38, mainly C3 or C4 and lower, and a C5 - 135°C naptha fraction which is taken off via line 40. Because of the boiling range and quality of the hydrogen-donor, it can simply be allowed to remain with the bottom fraction and used directly as heavy fuel oil, this avoiding the need for separation.
  • the use of the pseudo-extract as hydrogen-donor in visbreaking is not limited to the visbreaker/distillation arrangement described above.
  • Any visbreaker scheme can be used, ranging from a tubular reactor which is entirely in the heater, to a soaking drum reactor wherein most of the visbreaking reaction occurs in the soaking drum. Any combination of the two processes can also be used, for example much of the visbreaking reaction can be accomplished in a coil while the remainder of the visbreaking can be made to occur in a soaking drum down-stream of the coil.
  • any distillation scheme known in the art can be used to process the visbreaker reactor effluent.
  • Example 5 The following Examples illustrate the double decantation process of this invention (Examples 1 to 3), the use of pseudo-extract as hydrogen donor in visbreaking (Example 4) and the use of pseudo-raffinate in a thermofor catalytic cracking operation (Example 5).
  • Visbreaking was carried out upon an Arab Heavy Resid base stock (580°C+) both with and without the pseudo-extract of Example 1 as hydrogen donor. Use of the pseudo-extract permitted the visbreaking unit to be operated under more severe conditions as expressed in terms of "equivalent reaction time” (ERT), as explained above.
  • ERT equivalent reaction time
  • Thermofor catalytic cracking was carried out upon a virgin gas oil (VGO) both with and without the addition of the pseudo-raffinate of Example 2.
  • VGO virgin gas oil

Landscapes

  • 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)
EP86308408A 1985-11-01 1986-10-29 Procédé d'extraction au solvant pour hydrocarbure Withdrawn EP0229458A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79393885A 1985-11-01 1985-11-01
US793938 1991-11-19

Publications (1)

Publication Number Publication Date
EP0229458A1 true EP0229458A1 (fr) 1987-07-22

Family

ID=25161217

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86308408A Withdrawn EP0229458A1 (fr) 1985-11-01 1986-10-29 Procédé d'extraction au solvant pour hydrocarbure

Country Status (4)

Country Link
EP (1) EP0229458A1 (fr)
JP (1) JPS62119294A (fr)
AU (1) AU6394886A (fr)
ZA (1) ZA868328B (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB993927A (en) * 1962-07-11 1965-06-02 British Petroleum Co Improvements relating to the treatment of aromatic extracts
EP0128047A1 (fr) * 1983-06-06 1984-12-12 Exxon Research And Engineering Company Séparation sélective d'huile lourde en utilisant un mélange de solvants polaires et non-polaires
US4498980A (en) * 1983-02-14 1985-02-12 Union Carbide Corporation Separation of aromatic and nonaromatic components in mixed hydrocarbon feeds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB993927A (en) * 1962-07-11 1965-06-02 British Petroleum Co Improvements relating to the treatment of aromatic extracts
US4498980A (en) * 1983-02-14 1985-02-12 Union Carbide Corporation Separation of aromatic and nonaromatic components in mixed hydrocarbon feeds
EP0128047A1 (fr) * 1983-06-06 1984-12-12 Exxon Research And Engineering Company Séparation sélective d'huile lourde en utilisant un mélange de solvants polaires et non-polaires

Also Published As

Publication number Publication date
JPS62119294A (ja) 1987-05-30
ZA868328B (en) 1988-06-29
AU6394886A (en) 1987-05-07

Similar Documents

Publication Publication Date Title
EP0133774B1 (fr) Procédé de viscoréduction
US2953513A (en) Hydrogen donor diluent cracking process
EP0121376B1 (fr) Procédé pour la valorisation d'hydrocarbures lourds visqueux
US9327260B2 (en) Integrated process for steam cracking
EP0175511B1 (fr) Procédé de diminution de la viscosité
US4428824A (en) Process for visbreaking resid deasphaltenes
WO2014123807A1 (fr) Procédé de production d'aromatiques
US4013549A (en) Lube extraction with NMP/phenol/water mixtures
US10767122B2 (en) Method for producing high-quality feedstock for a steam cracking process
US4389302A (en) Process for vis-breaking asphaltenes
KR0148566B1 (ko) 중 탄화수소성 공급 원료의 전환 방법
US4587007A (en) Process for visbreaking resids in the presence of hydrogen-donor materials and organic sulfur compounds
US4673485A (en) Process for increasing deasphalted oil production from upgraded residua
US4892644A (en) Upgrading solvent extracts by double decantation and use of pseudo extract as hydrogen donor
US3796768A (en) Combined wulff process and coking process
US20040173504A1 (en) Coker operation without recycle
SG186124A1 (en) Integrated process for steam cracking
EP0229458A1 (fr) Procédé d'extraction au solvant pour hydrocarbure
US3247096A (en) Hydrocarbon conversion process to produce lubricating oils and waxes
US2748061A (en) Thermal treatment and separation process
US2067869A (en) Process for the treatment of hydrocarbon oils
US2952613A (en) Processing petroleum oils
US2272297A (en) Conversion of hydrocarbon oils
US2160875A (en) Cracking hydrocarbon oils
US2132129A (en) Treatment of hydrocarbon oils

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19871217

17Q First examination report despatched

Effective date: 19890329

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19890826

R18W Application withdrawn (corrected)

Effective date: 19890826

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KARSNER, GRANT GEORGE

Inventor name: MILSTEIN, DONALD

Inventor name: CHOI, BYUNG CHANG

Inventor name: MALLADI, MADHAVA

Inventor name: LEE, CHANG-KUEI