EP0125709B1 - Verfahren zur Herstellung von Kohlenwasserstoffgemischen mit niedrigem Asphaltgehalt - Google Patents

Verfahren zur Herstellung von Kohlenwasserstoffgemischen mit niedrigem Asphaltgehalt Download PDF

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Publication number
EP0125709B1
EP0125709B1 EP19840200457 EP84200457A EP0125709B1 EP 0125709 B1 EP0125709 B1 EP 0125709B1 EP 19840200457 EP19840200457 EP 19840200457 EP 84200457 A EP84200457 A EP 84200457A EP 0125709 B1 EP0125709 B1 EP 0125709B1
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Prior art keywords
deasphalted oil
deasphalting
separated
asphalt
product
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English (en)
French (fr)
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EP0125709A2 (de
EP0125709A3 (en
Inventor
Lucas Maria Andreas De Bont
John Robert Newsome
Petrus Matthias Marie Blauwhoff
Gerrit Jan Barend Assink
Karl Heinz Röbschläger
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority claimed from NL8301353A external-priority patent/NL8301353A/nl
Priority claimed from NL8301354A external-priority patent/NL8301354A/nl
Priority claimed from NL8301352A external-priority patent/NL8301352A/nl
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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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • the invention relates to a process for the production of deasphalted oils and hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures.
  • a drawback of the conventional solvent-deasphalting in which an asphaltenes-containing feed is separated in one step into a deasphalted oil as desired main product and an asphalt as by-product, is that for realizing a sufficiently high yield of de-asphalted oil, one usually has to accept a deasphalted oil of insufficient quality.
  • the quality of the de-asphalted oil is meant to be its suitability for conversion into hydrocarbon oil distillates by catalytic cracking optionally in the presence of hydrogen. Said suitability is higher according as the deasphalted oil has, inter alia, a lower asphaltenes, metal and sulphur content.
  • Deasphalted oil 1 differs from deasphalted oil 2 mainly by a substantially lower asphaltenes, metal and sulphur content.
  • solvent-deasphalting has in practice been found to be suitable for the production of deasphalted oils from various asphaltenes-containing hydrocarbon mixtures and a two-step solvent-deasphalting process has moreover been found to yield better results than a one-step process, it was ascertained to what extent it would be possible to obtain a better result by combining the two-step solvent-deasphalting process with after treatment(s) of the deasphalted oil 2 and/or the asphalt and application of a residual fraction of the aftertreated product(s) as a feed component for the two-step solvent-deasphalting, than when using just a two-step solvent-deasphalting process.
  • Said suitability is higher according as the asphalt has a lower metal and sulphur content and a lower viscosity and density.
  • the combinations tested Compared with a mode of operation in which just a two-step solvent-deasphalting is used, the combinations tested generally resulted in a higher yield of deasphalted oil 1 and a considerable yield of hydrocarbon oil distillate. Some combinations have been found to yield deasphalted oils and/or asphalt of a better quality.
  • the present invention therefore relates to a process for the production of deasphalted oils and hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures, characterized in that an asphaltenes-containing hydrocarbon mixture is separted by two-step solvent-deasphalting into a deasphalted oil 1 of high quality, a deasphalted oil 2 of lower quality and an asphalt, that the deasphalted oil 2 or the asphalt is converted by a catalytic hydrotreatment into a product having a reduced RCT which is separated by distillation into one or more distillate fractions and a residual fraction, that the residual fraction is subjected to thermal or catalytic cracking or used as a feed component for solvent-deasphalting and the cracked product obtained is separated by distillation into one or more distillate fractions and a residual fraction, which latter fraction is used as a feed component for solvent-deasphalting, or that the deasphalted oil 2 is subjected to thermal or catalytic cracking and/or that the asphalt is subjecte
  • the asphaltenes-containing hydrocarbon mixture used as feed is first separated by a two-step solvent-deasphalting treatment into a deasphalted oil 1, a deasphalted oil 2 and an asphalt and that at least one of the residual fractions obtained in the aftertreatment is used as feed component for solvent-deasphalting, in particular the two-step solvent-deasphalting treatment referred to hereinabove.
  • a preferred embodiment of the process according to the present invention relates to a process for the production of a deasphalted oil and hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures, in which an asphaltenes-containing hydrocarbon mixture is separated by two-step solvent-deasphalting into a deasphalted oil 1 of high quality, a deasphalted oil 2 of lower quality and an asphalt, in which deasphalted oil 2 is converted by catalytic hydrotreatment into a product having a reduced RCT which is separted by distillation into one or more distillate fractions and a residual fraction, in which said residual fraction is converted by thermal or catalytic cracking into a cracked product which is separated by distillation into one or more distillate fractions and a residual fraction, the latter residual fraction being used as a feed component for the two-step solvent-deasphalting.
  • class I the deasphalted oil 2 is subjected to a catalytic hydrotreatment.
  • Class I can be further subdivided depending on whether the distillation residue of the hydrotreated product is subjected to thermal cracking (class IA) or to catalytic cracking (class IB).
  • a preferred embodiment of class I comprises a process wherein the residual fraction separated from the product of the catalytic hydrotreatment is subjected to thermal cracking and that the asphalt is used as a feed component for thermal cracking.
  • a further preferred embodiment of the process according to the present invention 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 is separated by two-step solvent-deasphalting into a deasphalted oil 1 of high quality, a deasphalted oil 2 of lower quality and an asphalt, in which the asphalt is converted by catalytic hydrotreatment into a product having a reduced RCT which is separated by distillation into one or more distillate fractions and a residual fraction and in which the residual fraction is used as a feed component for the solvent-deasphalting or is converted by thermal or catalytic cracking into a cracked product which is separated by distillation into one or more distillate fractions and a residual fraction, the latter residual fraction being used as a feed component for solvent-deasphalting.
  • class II the asphalt is subjected to a catalytic hydrotreatment.
  • Class II can be further subdivided depending on whether the distillation residue of the hydrotreated product is used as a feed component for solvent-deasphalting, in particular two-step solvent-deasphalting (class IIA) or is subjected to thermal cracking (class IIB) or to catalytic cracking (class IIC).
  • a preferred embodiment of class II comprises a process wherein the residual fraction separated from the product of the catalytic hydrotreatment is used as a feed component for solvent-deasphalting and that the deasphalted oil 2 is converted by thermal or catalytic cracking into a cracked product which is separated by distillation into one or more distillate fractions and a residual fraction that is used as a feed component for solvent-deasphalting.
  • a further preferred embodiment of class II comprises a process wherein the residual fraction separated from the product of the catalytic hydrotreatment is converted by thermal or catalytic cracking into a cracked product and that the deasphalted oil 2 is used as a feed component for thermal or catalytic cracking and that a distillation residue of the thermally or catalytically cracked product is used as a feed component for solvent-deasphalting.
  • a third preferred embodiment of the process according to the present invention 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 is separated by two-step solvent-deasphalting into a deasphalted oil 1 of high quality, a deasphalted oil 2 of lower quality and an asphalt, in which the deasphalted oil 2 is subjected to thermal or catalytic cracking and/or in which the asphalt is subjected to thermal cracking, in which a distillation residue of the cracked product is converted by catalytic hydrotreatment into a product with a reduced RCT that is separated by distillation into one or more distillate fractions and a residual fraction and in which the residual fraction is used as a feed component for solvent-deasphalting, in particular two-step solvent-deasphalting.
  • class III the deasphalted oil 2 is subjected to thermal or catalytic cracking and/or the asphalt is subjected to thermal cracking.
  • Class III can be further subdivided depending on whether the apparatus in which the process is carried out contains in addition to a two-step solvent-deasphalting section and a catalytic hydrotreatment section, either a thermal cracking section (class IIIA) or a catalytic cracking section (class IIIB), or both a thermal and a catalytic cracking section (class IIIC), in which the deasphalted oil 2 and/or the asphalt separated in the two-step solvent-deasphalting section is/are further processed.
  • a thermal cracking section class IIIA
  • a catalytic cracking section class IIIB
  • Class IIIC thermal and a catalytic cracking section
  • a preferred embodiment of class III comprises a process wherein the deasphalted oil 2 is thermally or catalytically cracked and that the asphalt is used as a feed component for the catalytic hydrotreatment.
  • a further preferred embodiment of class III comprises a process wherein the deasphalted oil 2 is catalytically cracked and that the asphalt is thermally cracked and that the mixture of the distillation residues of the cracked products is subjected to catalytic hydrotreatment.
  • the feed used is an asphaltenes-containing hydrocarbon mixture.
  • the process is preferably applied to hydrocarbon mixturres mainly boiling above 350°C and more than 35% by weight boiling above 520°C and having an RCT above 7.5% by weight.
  • hydrocarbon mixtures are residues obtained in the'distillation of crude mineral oils as well as heavy hydrocarbon mixtures obtained from shale and tar sand.
  • the process can also be used for heavy crude mineral oils and for residues obtained in the distillation of products formed in the thermal cracking of hydrocarbon mixtures.
  • the process according to the invention is very suitable to be applied to residues obtained in the vacuum distillation of atmospheric distillation residues of crude mineral oils.
  • the process according to the invention is further very suitable to be applied to residues obtained in the vacuum distillation of atmospheric distillation residues of products formed in the thermal cracking of asphaltenes-containing hydrocarbon mixtures. If an atmospheric distillation residue is available as feed for the process according to the invention, it is preferred to separate therefrom a vacuum distillate by vacuum distillation and subject the resultant vacuum residue to the process according to the invention.
  • the separated vacuum distillate can be converted into light hydrocarbon oil distillates by subjecting it to thermal cracking or catalytic cracking optionally in the presence of hydrogen.
  • Suitable solvents for carrying out the deasphalting treatment are paraffinic hydrocarbons with 3-7 carbon atoms per molecule, such as propane, n-butane, iso-butane, n-pentane, iso-pentane and mixtures thereof, such as mixtures of propane with n-butane and mixtures of n-butane with iso-butane.
  • Suitable solvent/oil weight ratios lie between 7:1 and 1:1.
  • the solvent-deasphalting is preferably carried out at elevated temperature and pressure.
  • the two-step solvent-deasphalting can in principle be carried out in two manners.
  • the feed may be subjected to an extraction under mild conditions in which the feed is separated into a deasphalted oil 1 and a "light" asphalt and in the second step the light asphalt is subsequently subjected to a second extraction in which it is separated into a deasphalted oil 2 and the final asphalt as by-product.
  • the same solvent can be used, the degree of extraction being controlled by means of the temperature (temperature in the first step higher than in the second step). It is also possible to use different solvents, for example propane in the first step and n-butane in the second step.
  • the feed may be subjected to an extraction under heavier conditions in which the feed is separated into a de-asphalted oil and the final asphalt as by-product and in the second step the deasphalted oil is subsequently separated into a deasphalted oil 1 and a deasphalted oil 2.
  • the mixture of deasphalted oil and solvent from the extractor should only be supplied to a settler in which the temperature is higher than that applied in the first step.
  • the asphaltenes-containing hydrocarbon mixtures used as feed in the process according to the invention usually contain a substantial quantity of metals, especially vanadium and nickel. In the two-step solvent-deasphalting treatment some of these metals find their way into the deasphalted oil 2 or the asphalt. In the catalytic hydrotreatment of the deasphalted oil 2, the asphalt or the distillation products obtained therefrom by thermal or catalytic cracking at least part of said metals deposits on the catalyst and consequently shortens its life.
  • a deasphalted oil 2 an asphalt or a cracking residue or a mixture of a cracking residue and an asphalt having a vanadium+nickel content above 50 parts per million by weight (ppmw)
  • Said demetallization can very suitably be carried out by contacting the product(s) to be demetallized in the presence of hydrogen with a catalyst consisting more than 80% by weight of silica.
  • catalysts completely consisting of silica and catalysts containing one or more metals having hydrogenation activity, in particular a combination of nickel and vanadium, present on a carrier support substantially consisting of silica are suitable for said purpose.
  • a catalytic demetallization in the presence of hydrogen is applied said demetallization can be carried out in a separate reactor. Since the catalytic demetallization and the catalytic hydrotreatment to reduce the RCT can be carried out under the same conditions, the two processes can also very suitably be carried out in the same reactor, consecutively containing a bed of the demetallization catalyst and a bed of the catalyst used in the catalytic hydrotreatment.
  • Suitable catalysts for carrying out the catalytic hydrotreatment are those containing at least one metal chosen from the group formed by nickel and cobalt and at least one metal chosen from the group formed by molybdenum and tungsten on a carrier consisting more than 40% by weight of alumina.
  • Very suitable catalysts for carrying out the catalytic hydrotreatment are those containing the metal combination nickel/molybdenum or cobalt/molybdenum on alumina.
  • the catalytic hydrotreatment 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 an H 2 /feed ratio of from 100-5000 NI - kg- 1 and in particular of from 500-2000 NI ⁇ kg- 1 .
  • the same preference holds as stated above for the catalytic hydrotreatment to reduce the RCT.
  • the catalytic hydrotreatment is preferably carried out in such a manner that a product is obtained the C 5 + fraction of which fulfils the following requirements:
  • a product with a reduced RCT is obtained from which one or more distillate fractions and a residual fraction 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. Said vacuum distillate can be converted into light hydrocarbon oil distillates in the manners stated hereinbefore.
  • a distillation residue of the hydrotreated product is subjected to thermal or catalytic cracking.
  • One or more distillate fractions are then separated from the cracked product.
  • Said distillate fraction(s) may be atmospheric distillate(s) only, but it is preferred to separate a vacuum distillate from the cracked product(s).
  • Said vacuum distillate can be converted into light hydrocarbon oil distillates in the manners stated hereinbefore.
  • IA-1, IA-2, IB, IIA-1 to IIA-3 inclusive, IIB-1, IIB-2, IIC-1, IIC-2, IIIA-1 to IIIA-4 inclusive, IIIB-1, IIIB-2 and IIIC are discussed in some detail hereinafter.
  • the embodiments IA-1 and IA-2 are characterized in that the apparatus in which they are carried out contains in addition to a two-step solvent-deasphalting section and a catalytic hydrotreatment section, a thermal cracking section.
  • a distillation residue of the hydrotreated product is used as feed for the thermal cracking section and asphalt is separated off as final product.
  • both a distillation residue of the hydrotreated product and the asphalt are used as feed components for the thermal cracking section.
  • Embodiment IB is characterized in that the apparatus in which it is carried out contains a catalytic cracking section in addition to a two-step solvent-deasphalting section and a catalytic hydrotreatment section.
  • the embodiments IIA-1 to IIA-3 inclusive are characterized in that the distillation residue of the hydrotreated product is used as a feed component for the two-step solvent-deasphalting.
  • the deasphalted oil 2 is separated off as final product.
  • the deasphalted oil 2 is subjected to thermal and catalytic cracking respectively and a distillation residue of the cracked product is used as a feed component for the two-step solvent-deasphalting.
  • the embodiments IIB-1, IIB-2, IIC-1 and IIC-2 are characterized in that the distillation residue of the hydrotreated product is subjected to thermal (IIB-1 and IIB-2) or catalytic (IIC-1 and IIC-2) cracking.
  • a distillation residue of the cracked product is used as a feed component for the two-step solvent-deasphalting.
  • the deasphalted oil 2 is separated off as final product.
  • the deasphalted oil 2 is used as a feed component for the thermal and catalytic cracking section respectively.
  • the embodiments IIIA-1 to IIIA-4 inclusive are characterized in that the apparatus in which they are carried out consecutively consists of a two-step solvent-deasphalting section, a thermal cracking section and a catalytic hydrotreatment section.
  • the deasphalted oil 2 is subjected to thermal cracking and the asphalt is separated off as final product.
  • Embodiment IIIA-2 is a variant of the embodiment IIIA-1 in which the asphalt is mixed with the distillation residue of the thermally cracked product and the mixture is subjected to catalytic hydrotreatment.
  • the asphalt is subjected to thermal cracking and the deasphalted oil 2 is separated off as final product.
  • both the deasphalted oil 2 and the asphalt are thermally cracked.
  • the embodiments IIIB-1 and IIIB-2 are characterized in that the apparatus in which they are carried out consecutively consists of a two-step solvent-deasphalting section, a catalytic cracking section and a catalytic hydrotreatment section.
  • the deasphalted oil 2 is subjected to catalytic cracking and the asphalt is separated off as final product.
  • Embodiment IIIB-2 is a variant of the embodiment IIIB-1 in which the asphalt is mixed with the distillation residue of the catalytically cracked product and the mixture is subjected to catalytic hydrotreatment.
  • Embodiment IIIC is characterized in that the apparatus in which it is carried out consecutively consists of a two-step solvent-deasphalting section, a thermal cracking section, a catalytic cracking section and a catalytic hydrotreatment section.
  • the asphalt is thermally cracked
  • the deasphalted oil 2 is catalytically cracked and a mixture of the two cracking residues is subjected to catalytic hydrotreatment.
  • the embodiments IA-1, IA-2 and IB are diagrammatically shown in Figures 1, 2 and 3 respectively.
  • the embodiments IIA-1 to IIA-3 inclusive, IIB-1, IIB-2, IIC-1 and IIC-2 are diagrammatically shown in Figures 6-12 respctively.
  • the embodiments IIIA-1 to IIIA-4 inclusive, IIIB-1, IIIB-2 and IIIC are diagrammatically shown in Figures 15-21 respectively. The following streams and sections are designated throughout the Figures 1-3, 6-12 and 15 ⁇ 21 respectively with the following numerals.
  • a heavy fraction of the cracked product from the cracking unit in which stream 6 is treated is preferably recycled to said cracking unit.
  • a thermal cracking section containing two cracking units it is possible, if desired, to separate a relatively low-asphaltenes fraction from the product obtained in the cracking unit in which stream 4 is cracked, and said relatively low-asphaltenes fraction can be used as feed component for the cracking unit in which stream 6 is treated.
  • a heavy fraction of the cracked product from the cracking unit in which stream 3 is treated is preferably recycled to said cracking unit.
  • a thermal cracking section containing two cracking units it is possible, if desired, to separate a relatively low-asphaltenes fraction from the product obtained in the cracking unit in which stream 4 is cracked, and said relatively low-asphaltenes fraction can be used as a feed component for the cracking unit in which stream 3 is treated.
  • the process is carried out in an apparatus consecutively consisting of a two-step solvent-deasphalting section 111, a catalytic hydrotreatment section built up of a catalytic hydrotreatment unit 115, a first atmospheric distillation unit 116 and a first vacuum distillation unit 117 and a thermal cracking section built up of a thermal cracking unit 118, a second atmospheric distillation unit 119 and a second vacuum distillation unit 120.
  • An asphaltenes-containing hydrocarbon mixture 101 is mixed with a recycled stream 108 and the mixture 122 is separated by two-step solvent-deasphalting into a deasphalted oil 1 (stream 102), a deasphalted oil 2 (stream 103) and an asphalt (104).
  • the deasphalted oil 2 (stream 103) together with hydrogen 123 is subjected to catalytic hydrotreatment.
  • the hydrotreated product 124 is separated by atmospheric distillation into a gas fraction 125, at atmospheric distillate 105A and an atmospheric residue 126.
  • the atmospheric residue 126 is separated by vacuum distillation into a vacuum distillate 105B and a vacuum residue 106.
  • the vacuum residue 106 is thermally cracked and the cracked product 127 is separated by atmospheric distillation into a gas fraction 128, an atmospheric distillate 107A and an atmospheric residue 129.
  • the atmospheric residue 129 is separated by vacuum distillation into a vacuum distillate 107B and a vacuum residue 108.
  • the process is mainly carried out in the same manner as that described under flow diagram 1, except that the thermal cracking unit 118 present in flow diagram 1 has been replaced by a catalytic cracking unit 221 in flow diagram 2.
  • the process is carried out in an apparatus consecutively consisting of a two-step solvent-deasphalting section 311, a catalytic hydrotreatment section built up of a catalytic hydrotreatment unit 315, a first atmospheric distillation unit 316, a first vacuum distillation unit 317 and a catalytic cracking section built up of a catalytic cracking unit 321, a second atmospheric distillation unit 319 and a second vacuum distillation unit 320.
  • An asphaltenes-containing hydrocarbon mixture 301 is mixed with a recycle stream 306 and a recycle stream 310 and the mixture 322 is separated by two-step solvent-deasphalting into a deasphalted oil 1 (stream 302), a deasphalted oil 2 (stream 303) and an asphalt 304.
  • the asphalt 304 is separated into two portions 304A and 304B. Portion 304B is subjected to catalytic hydrotreatment together with hydrogen 323.
  • the hydrotreated product 324 is separated by atmospheric distillation into a gas fraction 325, an atmospheric distillation 305A and an atmospheric residue 326.
  • the atmospheric residue 326 is separated by vacuum distillation into a vacuum distillate 305B and a vacuum residue 306.
  • the deasphalted oil 2 (stream 303) is catalytically cracked and the cracked product 327 is separated by atmospheric distillation into a gas fraction 328, an atmospheric distillate 309A and an atmospheric residue 329.
  • the atmospheric residue 329 is separated by vacuum distillation into a vacuum distillate 309B and a vacuum residue 310.
  • the process is carried out in an apparatus consecutively consisting of a two-step solvent-deasphalting section 511, a thermal cracking section built up of a thermal cracking unit 518, a first atmospheric distillation unit 519 and a first vacuum distillation unit 520 and a catalytic hydrotreatment section built up of a catalytic hydrotreatment unit 515, a second atmospheric distillation unit 516 and a second vacuum distillation unit 517.
  • An asphaltenes-containing hydrocarbon mixture 501 is mixed with a recycle stream 506 and the mixture 522 is separated by two-step solvent-deasphalting into a deasphalted oil 1 (stream *
  • the various streams and apparatuses in the flow diagrams are referred to by three-digit numbers, .
  • the first digit corresponds with the diagram concerned. 502), a deasphalted oil 2 (stream 503) and an asphalt 504.
  • the asphalt 504 is separated into two portions (504A and 504B).
  • Portion 504B and deasphalted oil 2 (stream 503) are thermally cracked and the cracked product 527 is separated by atmospheric distillation into a gas fraction 528, an atmospheric distillate 507A and an atmospheric residue 529.
  • the atmospheric residue 529 is separated by vacuum distillation into a vacuum distillate 507B and a vacuum residue 508.
  • the vacuum residue 508 is subjected to catalytic hydrotreatment together with hydrogen 523.
  • the hydrotreated product 524 is separated by atmospheric distillation into a gas fraction 525, an atmospheric distillate 505A and an atmospheric residue 526.
  • the atmospheric residue 526 is separated by vacuum distillation into a vacuum distillate 505B and a vacuum residue 506.
  • the present application also relates to apparatuses for carrying out the process according to the invention, substantially corresponding with those diagrammatically shown in Figures 1-23.
  • the starting material was an asphaltenes-containing hydrocarbon mixture obtained as residue in the vacuum distillation of an atmospheric distillation residue of a crude mineral oil.
  • the vacuum residue mainly boiled above 520°C and had an RCT of 18.8% by weight, a total vanadium and nickel content of 167 ppmw and a sulphur content of 5.4% by weight.
  • the process was carried out according to the flow diagrams 1-6 respectively. The following conditions were applied in the various sections.
  • the two-step solvent-deasphalting was carried out by contacting the feed to be deasphalted in the first step in an extractor with an n-butane/isobutane mixture (weight ratio 65:35) at a temperature 110°C, a pressure of 40 bar and a solvent/oil weight ratio of 2:1 and, after separation of the asphalt, separating the deasphalted oil into a deasphalted oil 1 and a deasphalted oil 2 in the second- step in a settler at a temperature of 140°C and a pressure of 40 bar.
  • an n-butane/isobutane mixture weight ratio 65:35
  • the catalytic hydrotreatment unit consisted of two reactors the first of which was filled with an NiN/Si0 2 catalyst containing 0.5 parts by weight (pbw) of nickel and 2.0 pbw of vanadium per 100 pbw of silica and the second of which was filled with an Ni/Mo/AI 2 0 3 catalyst containing 4 pbw of nickel and 12 pbw of molybdenum per 100 pbw of alumina.
  • the catalysts were used in a volume ratio of 1:4.
  • the catalytic hydrotreatment was carried out at a hydrogen pressure of 150 bar, a space velocity (measured over both reactors) of 0.5 kg feed/catalyst/h, an H 2 /feed ratio of 1000 NI per kg and an average temperature of 410°C in the first reactor and of 390°C in the second reactor.
  • the catalytic cracking was carried out at a temperature of 510°C, a pressure of 2.2 bar, a space velocity of 2 kg - kg-' - h- 1 and a catalyst regeneration rate of 1.0 part by weight of catalyst per 1000 pbw of oil and using a zeolitic cracking catalyst.
  • the thermal cracking was carried out as described for flow diagram 1, but at a space velocity of 0.4 kg of fresh feed per cracking coil volume per minute and in the process described in flow diagram 5, the thermal cracking was carried out in two cracking coils under conditions as described for flow diagram 1, but at space velocities of 0.4 and 2.5 kg of fresh feed per cracking coil volume per minute for asphalt and deasphalted oil 2 respectively.
  • Example 7 the two-step solvent-deasphalting was mainly carried out in the same manner as described in the Examples 1-6, with the exception that the temperature in the settler described in Example 7 was 144°C.
  • the one-step solvent-deasphalting described in Example 8 was carried out in the same manner as the first step of the two-step solvent-deasphalting described in the Examples 1-6.
  • asphaltenes-containing hydrocarbon mixture (1) used as starting material was 100 parts by weight of vacuum residue.
  • Table II gives a survey of the yield of final products obtained in Examples 1-8.
  • Table III gives a survey of the properites of the final products obtained in the Examples 1-8.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (19)

1. Verfahren zur Herstellung von entasphaltierten Ölen und Kohlenwasserstofföldestillaten aus asphaltenhaltigen Kohlenwasserstoffmischungen, in welchem eine asphaltenhaltige Kohlenwasserstoffmischung durch Lösungsmittelentasphaltierung in ein entasphaltiertes Öl und Bitumen aufgetrennt wird und in welchem mindestens eines, nämlich das entasphaltierte Öl oder das Bitumen einer Nachbehandlung unterzogen wird, dadurch gekennzeichnet, daß die asphaltenhaltige Kohlenwasserstoffmischung durch zweistufiges Lösungsmittelentasphaltieren in ein entasphaltiertes ÖI von hoher Qualität, in ein entasphaltieres Ö1 2 von geringer Qualität und ein Bitumen aufgetrennt wird, daß das entasphaltierte Öl 2 oder das Bitumen durch katalytische Hydrobehandlung in ein Produkt mit reduziertem RCT-Wert umgewandelt wird, welches durch Destillation in eine oder mehrere Destillatfraktion und in eine Rückstandsfraktion aufgetrennt wird, daß die Rückstandsfraktion einer Wärmecrackbehandlung oder einer katalytischen Crackbehandlung unterworfen wird oder als Zuspeisungskomponente für das Lösungsmittelentasphaltieren verwendet wird und das gecrackte Produkt, das dabei erhalten wird, durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, welchletztere als Zuspeisungskomponente für das Lösungsmittelentasphaltieren benutzt wird, oder daß das entasphaltierte Öl 2 einer Wärmecrackbehandlung oder einer katalytischen Crackbehandlung unterworfen wird und/oder daß das Bitumen einer Wärmecrackbehandlung unterworfen wird und daß ein Destillationsrückstand des gecrackten Produktes (der gecrackten Produkte) durch katalytische Hydrobehandlung in ein Produkt mit einem reduzierten RCT-Wert umgewandelt wird, das durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, welche als Zuspeisungskomponente für das Lösungsmittelentasphaltieren eingesetzt wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine asphaltenhaltige Kohlenwasserstoffmischung durch zweistufiges Lösungsmittelentasphaltieren in ein entasphaltiertes 01 hoher Qualität, ein entasphaltiertes Öl 2 geringer Qualität und ein Bitumen aufgetrennt wird, daß das entasphaltierte Öl 2 durch katalytische Hydrobehandlung in ein Produkt mit einem reduzierten RCT-Wert umgewandelt wird, welches durch Destillation in einer oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, daß die genannte Rückstandsfraktion durch Wärmecrackbehandlung oder katalytische Crackbehandlung in ein gecracktes Produkt umgewandelt wird, das durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird und daß die Rückstandsfraktion als Zuspeisungskomponente für das Lösungsmittel entasphaltieren eingesetzt wird.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Rückstandsfraktion, die aus dem Produkt aus der katalytischen Hydrobehandlung abgetrennt worden ist, einer Wärmecrackbehandlung unterworfen wird und daß das Bitumen als Zuspeisungskomponente für die Wärmecrackbehandlung verwendet wird.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine asphaltenhaltige Kohlenwasserstoffmischung durch zweistufiges Lösungsmittelentasphaltieren in ein entaspaltieres Öl 1 hoher Qualität, ein entasphaltiertes Öl 2 geringer Qualität und ein Bitumen aufgretrennt wird, daß das Bitumen durch katalytische Hydrobehandlung in ein Produkt mit einem reduzierten RCT-Wert umgewandelt wird, welches durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird und daß die Rückstandsfraktion als Zuspeisungskomponente für das Lösungsmittelentasphaltieren eingesetzt wird oder durch Wärmecrackbehandlung oder katalytische Crackbehandlung in ein gecracktes Produkt umgewandelt wird, welches durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, wobei die letztere als Zuspeisungskomponente für das Lösungsmittelentasphaltieren verwendet wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Rückstandsfraktion, die von dem Produkt aus der katalytischen Hydrobehandlung abgetrennt worden ist, als Zuspeisungskomponente für das Lösungsmittelentasphaltieren eingesetzt wird und daß das entasphaltierte Öl 2 durch Wärmecrackbehandlung oder katalytische Crackbehandlung in ein gecracktes Produkt umgewandelt wird, welches durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, die als Zuspeisungskomponente für das Lösungsmittelentasphaltieren eingesetzt wird.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Rückstandsfraktion, die aus dem Produkt auf der katalytischen Hydrobehandlung abgetrennt worden ist, durch Wärmecrackbehandlung oder katalytische Crackbehandlung in ein gecracktes Produkt umgewandelt wird, daß das entasphaltierte Öl 2 als Zuspeisungskomponente für die Wärmecrackbehandlung oder katalytische Crackbehandlung eingesetzt wird und daß ein Destillationsrückstand des durch Wärmecrackbehandlung oder durch katalytische Crackbehandlung gecrackten Produkts als Zuspeisungskomponente für das Lösungsmittelentasphaltieren verwendet wird.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine asphaltenhaltige Kohlenwasserstoffmischung durch zweistufiges Lösungsmittelentasphaltieren in ein entasphaltiertes Öl 1 von hoher Qualität und ein entasphaltiertes Öl 2 von geginger Qualität und ein Bitumen auf getrennt wird, das das entasphaltierte ÖI 2 einer Wärmecrackbehandlung oder einer katalytischen Crackbehandlung unterworfen wird und/oder daß das Bitumen einer Wärmecrackbehandlung unterworfen wird, daß ein Distillationsrückstand des gecrackten Produkts (der gecrackten Produkte) durch katalytische Hydrobehandlung in ein Produkt mit reduziertem RCT-Wert umgewandelt wird, das durch Destillation in eine oder mehrere Destillatfraktionen und eine Rückstandsfraktion aufgetrennt wird, und daß die Rückstandsfraktion als eine Zuspeisungskomponente für das Lösungsmittelentasphaltieren verwendet wird.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das entasphaltierte Öl 2 einer Wärmecrackbehandlung oder einer katalytischen Crackbehandlung unterworfen wird und daß das Bitumen als Zuspeisungskomponente für die katalytische Hydrobehandlung eingesetzt wird.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das entasphaltierte Öl 2 katalytisch gecrackt wird, daß das Bitumen durch Wärmecrackbehandlung gecrackt wird und daß die Mischung der Destillationsrückstände des gecrackten Produktes einer katalytischen Hydrobehandlung unterworfen wird.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die verwendete Zuspeisung eine Kohlenwasserstoffmischung ist, die hauptsächlich über 350°C siedet und von der mehr als 35 Gewichtsprozent einen Siedepunkt von über 520°C aufweist und einen RCT-Wert von mehr als 7,5 Gewichtsprozent hat.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die eingesetzte Zuspeisung ein Rückstand ist, der beu der Vakuumdestillation eines Rückstands aus der atmosphärischen Destillation eines Rohmineralöls erhalten wird.
12. Verfahren nach den Ansprüchen 1 bis 11, dadurch gekennzeichnet, daß die zweistufige Lösungsmittelentasphaltierung durchgeführt wird, indem man die Zuspeisung in der ersten Stufe einer Extraktion unter strengeren Bedingungen durchführt, in welcher sie in ein entasphaltiertes Öl 1 und in ein "leichtes" Bitumen aufgetrennt wird, und indem man das leichte Bitumen in der zweiten Stufe einer zweiten Extraktion unterwirft, in welcher er in ein entasphaltiertes Öl 2 und das endgültige Bitumen als Nebenprodukt des Verfahrens aufgetrennt wird.
13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das Zweistufen-Lösungsmittelentasphaltieren derart durchgeführt wird, daß man in der esten Stufe die Zuspeisung einer Extraktion unter strengeren Bedingungen unterwirft, in welcher sie in ein entasphaltiertes Öl und ein endgültiges Bitumen als Nebenprodukt der Verfahrens aufgetrennt wird und indem man in der zweiten Stufe das entasphaltierte Öl in ein entasphaltiertes Öl 1 und ein entasphaltiertes Öl 2 auftrennt.
14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß bei der katalytischen Hydrobehandlung für die Reduktion des RCT-Wertes ein Katalysator eingesetzt wird, der mindestens ein Metall ausgewählt aus der Gruppe, bestehend aus Nickel und Kobalt, und mindestens ein Metall ausgewählt aus der Gruppe, bestehend aus Molybdän und Wolfram, auf einem Träger enthält, der zu mehr als 40 Gewichtsprozent aus Aluminiumoxid besteht.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß bei der katalytischen Hydrobehandlung für die Reduktion des RCT-Wertes ein Katalysator verwendet wird, der die Metallkombination Nickel/ Molybdän oder Kobalt/Molybdän auf Aluminiumoxid als Träger enthält.
16. Verfahren nach Anspruch 14 oder 15, dadurch gekennzeichnet, daß die Zuspeisung für die katalytische Hydrobehandlung einen Vanadium/Nickel-Gehalt über 50 Gewichtsteile pro Million hat und daß bei der katalytischen Hydrobehandlung die Zuspeisung nacheinander mit zwei Katalysatoren kontaktiert wird, wovon der erste ein Entmetallisierungskatalysator ist, der zu mehr als 80 Gewichtsprozent aus Siliciumdioxid besteht, und der zweite ein RCT-Reduktionskatalysator ist, wie in Anspruch 14 bzw. 15 beschrieben.
17. Verfahren wie in Anspruch 16 beansprucht, dadurch gekennzeichnet, daß der Entmetallisierungskatalysator die Metallkombination Nickel/Vanadium auf Siliciumdioxid als Träger enthält.
18. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß die katalytische Hydrobehandlung bei einer Temperatur im Bereich von 350 bis 450°C, einem Druck von 75 bis 200 bar, einer Raumgeschwindigkeit von 0,1 bis 2 g - g-1 · h-1 und einem H2/Zuspeisung-Verhältnis von 500 bis 2000 Nt - kg-1 durchgeführt wird.
19. Verfahren nach einem der Ansprüche 1 bis 18, dadurch gekennzeichnet, daß die katalytische Hydrobehandlung derart durchgeführt wird, daß ein Produkt erhalten wird, dessen C5 +-Fraktion die folgenden Bedingungen erfüllt:
a) der RCT-Wert der C5 +-Fraktion liegt um 50% niedriger als der RCT-Wert des der katalytischen Hydrobehandlung unterworfenen Stroms, und
b) die Menge der unter 350°C siedenden Kohlenwasserstoffe in der C5 +-Fraktion beträgt weniger als 40 Gewichtsprozent.
EP19840200457 1983-04-18 1984-03-28 Verfahren zur Herstellung von Kohlenwasserstoffgemischen mit niedrigem Asphaltgehalt Expired EP0125709B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
NL8301353A NL8301353A (nl) 1983-04-18 1983-04-18 Werkwijze voor de bereiding van asfaltenenarme koolwaterstofmengsels.
NL8301352 1983-04-18
NL8301354A NL8301354A (nl) 1983-04-18 1983-04-18 Werkwijze voor de bereiding van asfaltenenarme koolwaterstofmengsels.
NL8301353 1983-04-18
NL8301352A NL8301352A (nl) 1983-04-18 1983-04-18 Werkwijze voor de bereiding van asfaltenenarme koolwaterstofmengsels.
NL8301354 1983-04-18

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EP0125709A2 EP0125709A2 (de) 1984-11-21
EP0125709A3 EP0125709A3 (en) 1987-03-25
EP0125709B1 true EP0125709B1 (de) 1989-08-02

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US8062504B2 (en) 2007-08-06 2011-11-22 Exxonmobil Research & Engineering Company Method for reducing oil fouling in heat transfer equipment
US8425761B2 (en) 2008-12-11 2013-04-23 Exxonmobil Research And Engineering Company Non-high solvency dispersive power (non-HSDP) crude oil with increased fouling mitigation and on-line cleaning effects
US8440069B2 (en) 2007-08-06 2013-05-14 Exxonmobil Research And Engineering Company Methods of isolating and using components from a high solvency dispersive power (HSDP) crude oil

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* Cited by examiner, † Cited by third party
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GB8828206D0 (en) * 1988-12-02 1989-01-05 Shell Int Research Process for conversion of hydrocarbonaceous feedstock
DE69506565T2 (de) * 1994-09-05 1999-06-17 Shell Int Research Verfahren zum thermischen spalten von rückstandskohlenwasserstofföl

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NL7512090A (nl) * 1975-10-15 1977-04-19 Shell Int Research Werkwijze voor het omzetten van koolwaterstof- fen.
US4354922A (en) * 1981-03-31 1982-10-19 Mobil Oil Corporation Processing of heavy hydrocarbon oils
NL8105660A (nl) * 1981-12-16 1983-07-18 Shell Int Research Werkwijze voor de bereiding van koolwaterstofoliedestillaten.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8062504B2 (en) 2007-08-06 2011-11-22 Exxonmobil Research & Engineering Company Method for reducing oil fouling in heat transfer equipment
US8440069B2 (en) 2007-08-06 2013-05-14 Exxonmobil Research And Engineering Company Methods of isolating and using components from a high solvency dispersive power (HSDP) crude oil
US8425761B2 (en) 2008-12-11 2013-04-23 Exxonmobil Research And Engineering Company Non-high solvency dispersive power (non-HSDP) crude oil with increased fouling mitigation and on-line cleaning effects

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EP0125709A2 (de) 1984-11-21
MX170899B (es) 1993-09-21
AU573739B2 (en) 1988-06-23
EP0125709A3 (en) 1987-03-25
ES531652A0 (es) 1985-05-16
DE3479225D1 (en) 1989-09-07
ES8505400A1 (es) 1985-05-16
AU2687284A (en) 1984-10-25

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