WO2018122274A1 - Procédé de production de distillats moyens - Google Patents

Procédé de production de distillats moyens Download PDF

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Publication number
WO2018122274A1
WO2018122274A1 PCT/EP2017/084668 EP2017084668W WO2018122274A1 WO 2018122274 A1 WO2018122274 A1 WO 2018122274A1 EP 2017084668 W EP2017084668 W EP 2017084668W WO 2018122274 A1 WO2018122274 A1 WO 2018122274A1
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WO
WIPO (PCT)
Prior art keywords
thermally cracked
product
range
thermally
fuel oil
Prior art date
Application number
PCT/EP2017/084668
Other languages
English (en)
Inventor
Ariel Bru
Nicolaas Van Dijk
Bastiaan Willem Van Hasselt
Eduardus Theodorus Cornelis BINNEVELD
Eduard Meijer
Hendrik Stichter
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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 Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP17821941.6A priority Critical patent/EP3562916A1/fr
Priority to CN201780078935.3A priority patent/CN110114445A/zh
Publication of WO2018122274A1 publication Critical patent/WO2018122274A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G21/003—Solvent de-asphalting
    • 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
    • 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
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454—Solvent desasphalting
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • 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
    • 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
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to process for producing middle distillates.
  • the present invention further relates to a process for producing a fuel oil that meets the maximum sulphur specification in force as of 1 st January 2020, as set by the International Maritime Organisation.
  • the present invention further relates to a low sulphur fuel oil or fuel oil blending component .
  • WO2015/097199 describes a process for producing ultra-low sulphur middle distillates in high yield using a hydrodemetallisation unit. Not many refineries have substantial hydrodemetallisation units and, in the absence of very substantial capital investment, not a practical solution for those refineries.
  • EP0372652 describes a process for the conversion of a heavy hydrocarbonaceous feedstock in a two-step process of thermal cracking of a short residue and solvent deasphalting of the thermally cracked residue to prepare a deasphalted oil.
  • EP0372652 is silent about sulphur content or metal content and does not describe a process for producing ultra-low sulphur middle distillates or ultra-low sulphur fuel oil.
  • Page 4, lines 25-26 describe that the deasphalted oil can be used as feed for a hydrotreatment or a hydrocracking process, for a
  • the present invention provides a process for producing middle distillates from a residual hydrocarbonaceous feedstock, comprising the steps of: (a) thermally cracking the residual hydrocarbonaceous feedstock in a first thermal cracking unit to obtain a thermally cracked product comprising a thermally cracked residue ; (b) deasphalting at least the thermally cracked residue to obtain a thermally cracked deasphalted oil and an asphaltic product;
  • step (d) hydrocracking at least part of the twice thermally cracked deasphalted oil as obtained in step (c) to obtain a hydrocracked product;
  • step (e) subjecting at least part of the hydrocracked product as obtained in step (d) to a separation treatment to obtain at least a middle distillate fraction.
  • hydrocarbonaceous feedstocks hydrocarbonaceous feedstocks .
  • the present invention provides a process for producing ultra-low sulphur fuel oil and middle distillates from a residual hydrocarbonaceous feedstock, comprising the steps of:
  • step (c) thermally cracking at least part of the thermally cracked deasphalted oil in a second thermal cracking unit to obtain a twice thermally cracked deasphalted oil;
  • step (d) hydrocracking at least part of the twice thermally cracked deasphalted oil as obtained in step (c) to obtain a hydrocracked product;
  • step (e) subjecting at least part of the hydrocracked product as obtained in step (d) to a separation treatment to obtain at least a middle distillate fraction, and a fraction boiling in the fuel oil range;
  • step (g) subjecting at least part of the hydrocracked product as obtained in step (f) to a separation treatment to obtain at least a middle distillate fraction and a fraction boiling in the fuel oil range.
  • the present invention provides a low-sulphur fuel oil or fuel oil blending component having a sulphur content in the range of from 0.03%wt. to less than 0.5%wt., comprising 50-95% wt . of a fraction boiling in the fuel oil range obtainable from step (e) or (g) of the process as described above and 5-
  • the drawing figure depicts one or more
  • Figure 1 depicts a preferred embodiment of the process for producing middle distillates according to the present invention.
  • the residual hydrocarbonaceous feedstocks to be used in accordance with the present invention may be residual hydrocarbon oils, such as those obtained as residue in the distillation of crude oils at atmospheric or reduced pressure, commonly referred to as atmospheric (or long) residue and vacuum (or short) residue respectively.
  • the residual hydrocarbonaceous feedstock is a vacuum residue.
  • hydrocarbonaceous feedstock has a boiling point at atmospheric pressure of above 550 °C.
  • Step (a) comprises thermally cracking the residual hydrocarbonaceous feedstock in a first thermal cracking unit to obtain a thermally cracked product comprising a thermally cracked residue.
  • the residual hydrocarbonaceous feedstock is preheated, usually in one or more furnaces or furnace sections provided with heat exchange tubes or coils through which the feedstock is passed.
  • the feedstock is preferably pre-heated to a temperature in the range of from 350 - 600 °C and fed to a thermal cracking zone.
  • the feedstock may be passed in an upward or a downward direction through the cracking zone.
  • the flow is upward.
  • the feedstock may be passed through a cracking zone that is constituted as an empty vessel, e.g. as described in US-A 1,899,889.
  • the thermal cracking zone is situated in a soaking vessel containing internals.
  • the internals are preferably in the form of perforated plates.
  • the internals provide compartments by means of which the occurrence of back-mixing is decreased.
  • An example of a soaking vessel is described in EP-A 7656.
  • the effluent is flashed or fractionated to yield a thermally cracked distillate fraction, or fractions, and a
  • the thermally cracked product in the thermal cracking step (a) is separated into a thermally cracked residue and one or more thermally cracked distillates.
  • the thermal cracking step (a) is operated at a conversion in the range of from 25 to 55%wt, more preferably in the range of from 30 to 50 %wt .
  • the thermal cracking is generally carried out in the absence of reducing gases, such as hydrogen.
  • the cracking can be carried out in the presence of steam.
  • Suitable cracking conditions include a temperature of 350 to 600 °C, a pressure of 1 to 100 bar abs .
  • step (b) at least the thermally cracked residue is deasphalted to obtain a thermally cracked deasphalted oil of which at least 45 wt% , preferably at least 65 wt%, more preferably at least 80 wt%, and even more preferably at least 85 wt% has a boiling point above 550
  • the deasphalting in step (b) may be carried out in any conventional manner.
  • a well-known and suitable deasphalting method is solvent deasphalting.
  • step (b) is preferably carried out by means of a solvent deasphalting treatment. More preferably, step (b) is carried out by means of a solvent deasphalting treatment and is operated at an extraction depth in the range of from 25 to 65%wt.
  • thermally cracked product of step (a) is passed without separate
  • step (b) distillation or (vacuum) flash step to step (b) .
  • the thermally cracked product of step (a) is flashed or fractionated such that only gases, or gases and a naphtha fraction (i.e. 95%wt. boiling up to 160°C) or gases, a naphtha fraction and a gasoil fraction (i.e. 95%wt. boiling up to 350 °C) are removed from the thermally cracked product and a thermally cracked residue is formed containing a relatively high amount of lighter oil components.
  • thermally cracked product or a thermally cracked residue having a relatively high amount of lighter oil components is passed to a solvent deasphalting step.
  • the amount of the thermally cracked residue having a boiling point at or below 520 °C is 10%wt. or less, more preferably less than 9%wt . even more preferably less than 5%wt.
  • the extraction depth is preferably from 30 to 60%wt, even more preferably from 35 to 55%wt.
  • paraffinic compounds include C3-8 paraffinic
  • hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane or mixtures of two or more of these.
  • C3-C5 paraffinic hydrocarbons most preferably butane, pentane or a mixture thereof, are used as the extracting solvent.
  • the extraction depth increases at increasing number of carbon atoms of the extracting solvent. In this connection it is noted that the higher the extraction depth, the larger the amount of hydrocarbons being extracted from the
  • step (b) the smaller and more viscous the asphaltic product will be, the heavier the asphaltenes will be in the asphaltic product to be obtained in step (b) .
  • a rotating disc contactor, empty column or a plate column may be used with the feedstock entering at the top and the extracting solvent entering at the bottom.
  • the lighter and/or paraffinic hydrocarbons which are present in the feedstock typically dissolve in the extracting solvent and are withdrawn as the thermally cracked deasphalted oil at the top of the apparatus .
  • deasphalting is carried out at a total extracting solvent to residual hydrocarbon oil ratio of 1.5 to 8 wt/wt, a pressure of from 1 to 60 bara and a temperature of from 40 to 200 ° C.
  • deasphalting step can be used for any use known in the art, such as for fuel oil, bitumen, gasifier feed or power station feed. It will be appreciated that the asphaltic product will not meet the recently adopted stringent maximum sulphur specifications for fuel oil but will have a sulphur content of more than 0.5%wt., typically at least 2%wt., such as from 2.5 %wt . to 7% wt .
  • At least part of the asphaltic product can be used as a fraction boiling in the fuel oil range having a sulphur content of more than 0.5%wt in the low- sulphur fuel oil or fuel oil blending component of the present invention.
  • a fraction boiling in the fuel oil range is typically a residual fraction boiling above 370 °C (5%wt point, i.e. 95%wt. boiling above 370 °C) .
  • step (b) At least part of the asphaltic product as obtained in step (b) is
  • deasphalting step may be limited by the maximum viscosity that the subsequent process unit as installed in the refinery can handle.
  • a deasphalting treatment generally causes a
  • the deasphalting step is preceded by a first thermal cracking step and followed by a second thermal cracking step, the metals content in at least part of the twice thermally cracked deasphalted oil is sufficiently low so as to allow hydrocracking of the twice thermally cracked deasphalted oil without unduly poisoning the hydrocracking catalyst.
  • the hydrocracking unit comprises a guard bed or catalyst bed having activity for further hydrodemetallisation, but in general no separate hydrodemetallisation step in a separate unit is needed.
  • step (c) at least part of the thermally cracked deasphalted oil as obtained in step (b) is thermally cracked in a second thermal cracking unit to obtain a twice thermally cracked deasphalted oil.
  • step (c) the entire thermally cracked deasphalted oil as obtained in step (b) is thermally cracked .
  • the second thermal cracking step (c) is operated at a conversion in - li the range of from 25 to 80%wt, more preferably a
  • the second thermal cracking is generally carried out in the absence of reducing gases, such as hydrogen.
  • the cracking can be carried out in the presence of steam.
  • the conditions at which the thermal cracking may be carried out can be varied. One might adjust the temperature, pressure and residence time at will in such a way that the desired conversion occurs. It will be evident to a person skilled in the art that the same conversion can be obtained at a high temperature and a short residence time on the one hand and at a lower temperature but at a longer residence time at the other hand. Further, the cracking reactions are endothermic and therefore the temperature tends to decrease over the cracking zone in the case of soaker cracking. Hence, the person skilled in the art will be able to select the conditions in the cracking zone such that the desired conversion level will be obtained. Suitable cracking conditions include a temperature of 350 to 600 °C, a pressure of 1 to 100 bar abs . and a residence time of 0.5 to 60 min. The residence time relates to the cold feedstock.
  • the conditions required to reach a desired conversion level in the second thermal cracking step are typically more severe than the conditions required to reach the same conversion in the first thermal cracking step.
  • the second thermal cracking step may typically be carried out at a temperature that is 10°C to 80 °C higher than the temperature used in the first thermal cracking step to reach the same level of conversion.
  • the thermally cracked deasphalted product which is thermally cracked again in step (c) is a pure and heavy deasphalted product.
  • hydroconversion processes such as for instance disclosed in EP 1731588
  • step (b) the entire undiluted deasphalted product as obtained in step (b) can now be processed in step (c) , and there is no need to dilute the deasphalted product before it can be further processed.
  • One of the advantages of the present invention is the fact that such an undiluted heavy deasphalted product can be further processed, resulting in such a high yield of low sulphur middle distillates .
  • the twice thermally cracked deasphalted oil will typically comprise light and middle distillates (Naphtha,
  • Kerosene, Gasoil and residual fraction (s), boiling above 370 °C (5%wt point, i.e. 95%wt. boiling above 370 °C) .
  • the thermal cracking step will produce products that are gaseous at ambient temperature and atmospheric pressure.
  • the twice thermally cracked deasphalted oil is separated into one or more fractions boiling below 370 °C (95%wt. point, i.e. maximum 5%wt. boiling above 370 °C) ; one or more fractions boiling in the vacuum gasoil range and a residue (at most 5%wt. boiling below 550 °C) .
  • the residue (i.e at most 5%wt . boiling below 550 °C) produced in this embodiment can be used for any use known in the art, such as for fuel oil, bitumen, gasifier feed, including a gasification step to obtain hydrogen and carbon monoxide, or power station feed. It will be appreciated that the residue will not meet the recently adopted stringent maximum sulphur specifications for fuel oil but will have a sulphur content of more than 0.5%wt., typically at least 2%wt., such as from 2.5 %wt . to 7% wt .
  • At least part of the residue can be used as a fraction boiling in the fuel oil range having a sulphur content of more than 0.5%wt in the low-sulphur fuel oil or fuel oil blending component of the present invention .
  • step (d) at least part of the twice thermally cracked deasphalted oil as obtained in step (c) is hydrocracked to obtain a hydrocracked product.
  • step (d) the entire twice thermally cracked deasphalted oil product as obtained in step (c) is hydrocracked. It is however not critical to the invention that the entire twice thermally cracked deasphalted oil product is hydrocracked.
  • the fraction of the twice thermally cracked deasphalted oil boiling in the vacuum gasoil range and higher (at most 5%wt. boiling below 320°C, preferably at most 5%wt.
  • step (d) is hydrocracked in step (d) .
  • the metals content in the twice thermally cracked deasphalted oil boiling in the vacuum gasoil range and higher may be sufficiently low so as to allow
  • the level of metals content that is acceptable depends on the hydrocracking catalyst being employed and the metals content in the feed to the process of the invention, which in turn is dependent on the crude diet of the refinery.
  • the hydrocracking unit comprises a guard bed or catalyst bed having activity for further hydrodemetallisation, but, preferably, no separate hydrodemetallisation step in a separate unit is needed.
  • the twice thermally cracked deasphalted oil fraction boiling in the vacuum gasoil range is used as feed to hydrocracking step (d) .
  • step (c) preferably at least 20%wt., more preferably at least 40%wt., even more preferably at least 60%wt., even more preferably at least 80%wt., even more preferably at least 90%wt., even more preferably at least 95%wt., even more preferably the entire twice thermally cracked deasphalted oil fraction boiling in the vacuum gasoil range as obtained in step (c) is hydrocracked.
  • the residual fraction of the twice thermally cracked deasphalted oil boiling above the vacuum gasoil range may be used as fuel oil, bitumen, gasifier feed, including a gasification step to obtain hydrogen and carbon monoxide, or power station feed.
  • the residual fraction will normally not meet the recently adopted stringent maximum sulphur specifications for fuel oil but will have a sulphur content of more than 0.5%wt.
  • At least part of the residual fraction can be used as a fraction boiling in the fuel oil range having a sulphur content of more than 0.5%wt in the low- sulphur fuel oil or fuel oil blending component of the present invention.
  • the residual fraction is used as feed to a hydrodemetallisation unit as described in
  • the hydrocracking in step (d) is preferably carried out in the presence of hydrogen at a temperature in the range of from 300-500 °C and at a pressure in the range of from 80-250 bara.
  • step (d) of the process according to the present invention may be conducted in any way known in the art .
  • the hydrocracking step (d) of the process according to the present invention may be conducted in any way known in the art .
  • hydrocracking catalyst typically uses a hydrocracking catalyst.
  • at least one of the catalysts used in the hydrocracking zone is acidic.
  • the hydrocracking is carried out in the presence of hydrogen and a hydrocracking catalyst at elevated temperature and pressure.
  • hydrocracking catalysts consist of one or more metals from nickel, tungsten, cobalt and molybdenum in
  • a carrier such as alumina, silica, silica-alumina or a zeolite.
  • alumina silica
  • silica-alumina silica-alumina
  • zeolite a carrier
  • hydrocracking catalysts which can be applied in the process of the present invention.
  • at least one of the catalysts used in the hydrocracking zone is acidic, i.e. contains a silica- alumina and/or zeolitic component as part of the carrier.
  • the hydrocracking in step (d) may be carried out in a single- or multiple-stage mode of operation.
  • a single-stage mode of operation a stacked bed of a hydrodenitrification/first-stage hydrocracking catalyst on top of a conversion catalyst may preferably be used.
  • hydrodenitrification/first-stage hydrocracking catalysts are NiMo/A1203 and CoMo/A1203, optionally promoted with phosphorus and/or fluor.
  • Preferred conversion catalysts are those based on NiW/zeolite or NiW/zeolite/silica- alumina.
  • Preferred hydrocracking conditions in step (d) are an operating pressure of 80-250 bara, preferably 90-
  • step (e) at least part of the hydrocracked product as obtained in step (d) is subjected to a separation treatment to obtain at least a middle
  • step (e) the entire hydrocracked product as obtained in step (d) is subjected to the separation treatment.
  • step (e) Typically, in the separation treatment in step (e) also a residual fraction is obtained.
  • At least part of the residual fraction is recycled to step (d) .
  • step (e) in the separation treatment which is carried out in step (e) also a residual fraction is obtained of which at least part is subjected to a further hydrocracking step (f), and at least part of the hydrocracked product as obtained in step (f) is recycled to step (e) .
  • At least part of the hydrocracked product as obtained in step (d) is subjected to a separation treatment to obtain at least a middle distillate fraction and a fraction boiling in the fuel oil range.
  • the separation treatment in step (e) may typically be a fractionating treatment which is preferably carried out at a temperature in the range from 50 to 400 °C, more preferably at a temperature in the range of from 70 to
  • At least 80%wt. of the residual fraction as obtained in the separation treatment in step (e) according to one embodiment of the invention has a boiling point above 370 °C.
  • at least 90%wt. of the residual fraction also obtained in the separation treatment in step (e) has a boiling point above 370 °C.
  • At least part of a residual fraction also obtained in step (e) may be recycled to step (a) .
  • the residual fraction may also be used as a feed for a fluidised bed catalytic cracking (FCC) unit or as a feedstock for lubricating oil manufacture.
  • FCC fluidised bed catalytic cracking
  • step (e) In order to achieve an optimum middle distillates yield, it is preferred that at least a part of the residual fraction obtained in step (e) is again subjected to hydrocracking to improve the yield of middle distillates. Hence, in a preferred embodiment at least part, more preferably 5 to 30 %wt, of a residual fraction which is also obtained in step (e) is recycled to step (d) .
  • step (e) At least part of a residual fraction also obtained in step (e) is subjected to a further hydrocracking step (f), and at least part of the hydrocracked product as obtained in such a step (f) is recycled to step (e) .
  • the hydrocracking in step (d) and/or step (f) is carried out in two or more reaction zones.
  • the two or more reaction zones are arranged in a stacked bed configuration.
  • At least part of the residual fraction is subjected to a further hydrocracking step to produce a hydrocracked product (f) ; and at least part of the hydrocracked product as obtained in step (f) is preferably subjected to a separation treatment.
  • the separation may be carried out separately or in the same unit as used for step (e) of the process of the invention.
  • the separation step is carried out so as to obtain at least a middle distillate fraction and a fraction boiling in the fuel oil range.
  • the asphaltic product as obtained in step (b) may be used in several ways. It can for instance be combusted for cogeneration of power and steam. Alternatively, it can be partially combusted for clean fuel gas production, cogeneration of power and steam, hydrogen manufacture or hydrocarbon synthesis. Still another option is
  • step (b) Preferably, at least part of the asphaltic product as obtained in step (b) is subjected to a gasification step (h) to obtain hydrogen and carbon monoxide.
  • such a gasification step (h) is a partial combustion step.
  • step (h) At least part of the hydrogen as obtained in step (h) is recycled to at least one of steps (d) and (f ) .
  • the middle distillates as obtained in step (e) typically contain less than 10 ppmwt of sulphur.
  • the middle distillates contain less than 8 ppmwt of sulphur, more preferably less than 6 ppmwt of sulphur, and most preferably less than 5 ppmwt of sulphur .
  • the process of the invention may in one embodiment produce ultra-low sulphur fuel oil and middle distillates from a residual hydrocarbonaceous feedstock, which process comprises the steps of:
  • step (d) hydrocracking at least part of the twice thermally cracked deasphalted oil as obtained in step (c) to obtain a hydrocracked product;
  • step (d) hydrocracked product as obtained in step (d) to a separation treatment to obtain at least a middle distillate fraction and a fraction boiling in the fuel oil range;
  • step (g) subjecting at least part of the hydrocracked product as obtained in step (f) to a separation treatment to obtain at least a middle distillate fraction and a fraction boiling in the fuel oil range.
  • ultra-low sulphur middle distillates are disadvantages that engines, in particular engines of ships that have been designed to run on fuel oil may need to be adapted to be able to handle ultra-low sulphur middle distillates such as diesel.
  • a low-sulphur fuel oil or fuel oil blending component having a sulphur content in the range of from 0.03%wt. to less than 0.5%wt., comprising 50-95% wt . of a fraction boiling in the fuel oil range
  • step (e) or (g) of the process as claimed in claim 10 obtainable from step (e) or (g) of the process as claimed in claim 10 and 5-50%wt. of a fraction boiling in the fuel oil range having a sulphur content of more than
  • crude oil or crude oil mix 1 is fractionated in atmospheric distillation unit 20 into multiple distillate products 14 (typically LPG, naphtha and gasoil) and atmospheric residue 2.
  • Atmospheric residue 2 is fractionated in vacuum distillation unit 30 into one or more vacuum distillation products 15
  • vacuum residue (typically vacuum gasoil) and vacuum residue 3.
  • Vacuum residue 3 is fed into thermal cracking unit 40 to produce multiple thermally cracked products 16 (typically thermally cracked vacuum gasoil and thermally cracked gasoil and lighter products) and thermally cracked residue 4.
  • At least a portion of thermally cracked residue 4 is passed via line 6 to solvent deasphalting unit 50.
  • thermally cracked residue 4 is passed via line 5 to storage and use as fuel oil, bitumen, gasifier feed, including a gasification step to obtain hydrogen and carbon monoxide, or power station feed (not shown) .
  • solvent deasphalting unit 50 thermally cracked residue is contacted with propane, iso-butane, butane, pentane, iso-pentane or a mixture thereof as a solvent.
  • the solvent is fed into solvent deasphalting unit 50 via line 19.
  • Thermally cracked deasphalted oil leaves the unit 50 via line 8 and asphaltic product via line 7.
  • solvent is mixed with thermally cracked residue and thermally cracked deasphalted oil is extracted from the residue using the solvent.
  • solvent is removed from the extract via means not shown and via line 21 and further means not shown recycled to line 19 for re-injection into unit 50.
  • deasphalted oil in line 8 is passed to a second thermal cracking unit 60 via line 9 to produce one or more fractions of twice thermally cracked deasphalted oil.
  • the residual fraction (95%wt. boiling above 550 °C) is passed via line 11 to storage and use as fuel oil, bitumen, gasifier feed, including a gasification step to obtain hydrogen and carbon monoxide, or power station feed (not shown)
  • deasphalted oil is recycled via line 10 to vacuum distillation unit 30.
  • optionally part of the thermally cracked deasphalted oil is recycled to thermal cracking unit 40 (not shown) .
  • At least 90% by weight, more preferably at least 95%wt of the thermally cracked deasphalted oil is passed to second thermal cracking unit 60.
  • the recycle of thermally cracked deasphalted oil via line 10 is not employed.
  • Twice thermally cracked deasphalted oil is typically fractionated into a vacuum gasoil product, a residual fraction and one or more lighter product. At least the twice thermally cracked deasphalted oil boiling in the vacuum gasoil range is fed via line 12 into hydrocracking unit 70 to produce hydrocracked products 17.
  • part of the lighter product from unit 60 may be fed with line 12 and lighter product via line 13 to hydrotreating unit 80, producing hydrotreating products 18.
  • Conversion is defined as the net "520 °C minus" conversion per pass, calculated as 100% * ⁇ [ (wt% boiling at or above 520 °C in feed) - (wt% boiling at or above 520 °C in product)]/ (wt% boiling at or above 520 °C in feed) ⁇ .
  • the wt% boiling at or above 520 °C in the feed or the product is determined according to ASTM D2887.
  • Extraction depth is defined as the yield of extracted "520 °C plus” material calculated as 100% * (wt% boiling at or above 520 °C in extracted product * extracted flow rate [in kg per second])/ (wt% boiling at or above 520 °C in feed * feed flow [in kg per second] ) and is determined according to ASTM D2887.
  • Vacuum gasoil range is defined as at most 5%wt boiling below 320 °C and at least 90%wt boiling below 550 °C and is determined according to ASTM D2887.
  • Fuel oil range is defined as a fraction boiling above 370 °C (5%wt point, i.e. 95%wt. boiling above 370 °C) and is determined according to ASTM D2887.
  • a fuel oil range therefore typically comprises a fraction boiling in the vacuum gasoil range and/or a fraction boiling above the vacuum gasoil range .

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé de production de distillats moyens à partir d'une charge d'alimentation hydrocarbonée résiduelle, comprenant les étapes suivantes : (a) craquage thermique de la charge d'alimentation hydrocarbonée résiduelle dans une première unité de craquage thermique pour obtenir un produit craqué thermiquement comprenant un résidu craqué thermiquement ; (b) désasphaltage d'au moins le résidu craqué thermiquement pour obtenir une huile désasphaltée craquée thermiquement et un produit asphaltique ; (c) craquage thermique d'au moins une partie de l'huile désasphaltée craquée thermiquement dans une seconde unité de craquage thermique pour obtenir une huile désasphaltée à craquage thermique double ; (d) hydrocraquage d'au moins une partie de l'huile désasphaltée à craquage thermique double telle qu'obtenue à l'étape (c) pour obtenir un produit hydrocraqué ; et (e) soumission d'au moins une partie du produit hydrocraqué tel qu'obtenu à l'étape (d) à un traitement de séparation pour obtenir au moins une fraction de distillat moyen. L'invention concerne en outre un procédé de production d'huile combustible à très faible teneur en soufre et de distillats moyens et un composant de mélange d'huile combustible à faible teneur en soufre ou d'huile combustible ayant une teneur en soufre dans la plage allant de 0,03 % en poids à moins de 0,5 % en poids.
PCT/EP2017/084668 2016-12-28 2017-12-27 Procédé de production de distillats moyens WO2018122274A1 (fr)

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WO2020161017A1 (fr) * 2019-02-05 2020-08-13 Shell Internationale Research Maatschappij B.V. Conversion de résidus
US11124714B2 (en) 2020-02-19 2021-09-21 Marathon Petroleum Company Lp Low sulfur fuel oil blends for stability enhancement and associated methods
US11319498B2 (en) 2018-12-04 2022-05-03 Sabic Global Technologies B.V. Optimizing the simultaneous production of high-value chemicals and fuels from heavy hydrocarbons
US11802257B2 (en) 2022-01-31 2023-10-31 Marathon Petroleum Company Lp Systems and methods for reducing rendered fats pour point
US11860069B2 (en) 2021-02-25 2024-01-02 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11891581B2 (en) 2017-09-29 2024-02-06 Marathon Petroleum Company Lp Tower bottoms coke catching device
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US11975316B2 (en) 2019-05-09 2024-05-07 Marathon Petroleum Company Lp Methods and reforming systems for re-dispersing platinum on reforming catalyst
US12000720B2 (en) 2018-09-10 2024-06-04 Marathon Petroleum Company Lp Product inventory monitoring
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US12031094B2 (en) 2021-02-25 2024-07-09 Marathon Petroleum Company Lp Assemblies and methods for enhancing fluid catalytic cracking (FCC) processes during the FCC process using spectroscopic analyzers

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US11352578B2 (en) 2020-02-19 2022-06-07 Marathon Petroleum Company Lp Low sulfur fuel oil blends for stabtility enhancement and associated methods
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US11906423B2 (en) 2021-02-25 2024-02-20 Marathon Petroleum Company Lp Methods, assemblies, and controllers for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11921035B2 (en) 2021-02-25 2024-03-05 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11905468B2 (en) 2021-02-25 2024-02-20 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US11898109B2 (en) 2021-02-25 2024-02-13 Marathon Petroleum Company Lp Assemblies and methods for enhancing control of hydrotreating and fluid catalytic cracking (FCC) processes using spectroscopic analyzers
US11885739B2 (en) 2021-02-25 2024-01-30 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US11860069B2 (en) 2021-02-25 2024-01-02 Marathon Petroleum Company Lp Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers
US12031094B2 (en) 2021-02-25 2024-07-09 Marathon Petroleum Company Lp Assemblies and methods for enhancing fluid catalytic cracking (FCC) processes during the FCC process using spectroscopic analyzers
US11970664B2 (en) 2021-10-10 2024-04-30 Marathon Petroleum Company Lp Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive
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