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
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1074—Vacuum distillates
• • 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
  • C10G2300/1088—Olefins
  • C10G2300/1092—C2-C4 olefins
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range

Definitions

• the present invention relates to upgrading crude oil.
• One or more of the above or other objects can be achieved by providing a method of upgrading crude oil, the method at least comprising the steps of:
• Olefin metathesis is a well-known reaction and has been subject to a Nobel Prize in Chemistry in 2005 (in particular for the discovery of a variety of highly efficient and selective catalysts). Because of the relative simplicity of olefin metathesis it often creates fewer undesired by-products than alternative organic reactions.
• the olefin metathesis reaction typically provides for the redistribution of fragments of olefins by the scission and regeneration of carbon-carbon double bonds.
• the olefin metathesis reaction can be carried out at room and elevated temperatures using a wide variety of catalysts.
• the present inventors have now surprisingly found that the presence of contaminants commonly present in crude oil (such as nitrogen, oxygen and/or sulphur compounds, and/or metal contaminants such as nickel and vanadium compounds), in particular in heavy crude oils, do not hamper or detrimentally retard the olefin metathesis reaction. Also, the present inventors have surprisingly found that the metathesis catalysts used survive the presence of typical contaminants as present in crude oil, in particular heavy crude oil.
• contaminants commonly present in crude oil such as nitrogen, oxygen and/or sulphur compounds, and/or metal contaminants such as nickel and vanadium compounds
• an olefin-containing crude oil stream is provided.
• the olefin-containing crude oil stream is not particularly limited, it typically is from a mineral or fossil (hence non-vegetable and non-synthetic) origin.
• the olefin-containing crude oil stream may have been obtained as a fraction during processing and refining crude oil.
• at least 10 wt.%, more preferably, at least 20 wt.%, even more preferably at least 50 wt.% or even more than 80 wt.% or even 100 wt.% of the olefin-containing crude oil stream is from a mineral origin.
• the olefin-containing crude oil stream provided in step (a) has an aromatic content of at least 10 wt.%, preferably at least 20 wt.%, as determined by 1 H-NMR. Further, it is preferred that the olefin-containing crude oil stream provided in step (a) has a sulphur content of at least 0.1 wt.%, preferably at least 0.5 wt.%, more preferably at least 1.0 wt.%, even more preferably at least 2.0 wt.%, as determined by ASTM D2622. Also, it is preferred that the olefin-containing crude oil stream provided in step (a) has an API gravity of at most 19, as determined according to ASTM D 6822 at 15°C.
• the olefin-containing crude oil stream provided in step (a) has a total Ni/V/Fe content of at least 50 ppm, preferably at least 100 ppm, as determined by ASTM D5863. Also, it is preferred that the olefin-containing crude oil stream provided in step (a) has an asphaltene content of at least 0.04 gram per 100 gram, as determined by ASTM D2007. Further, it is preferred that the olefin-containing crude oil stream provided in step (a) has an Micro-Carbon Residue ('MCR') of at least 0.02 gram per 100 gram as determined by ASTM D4530.
• 'MCR' Micro-Carbon Residue
• At least 50 wt.%, preferably at least 90 wt.%, of the olefin-containing crude oil stream provided in step (a) has a boiling point of above 250°C at atmospheric pressure, preferably above 300°C, more preferably above 330°C, even more preferably above 360°C, yet even more preferably above 390°C.
• the olefin-containing crude oil stream provided in step (a) contains at least 2.0 wt.%, preferably at least 5.0 wt.%, more preferably at least 10.0 wt.%, even more preferably at least 20 wt.% olefins.
• the content of olefins can be determined by 1 H NMR or by bromine number according to ASTM D2710.
• step (b) an olefin-containing stream is added to the olefin-containing crude oil stream provided in step (a), thereby obtaining an olefin-enriched stream.
• the olefin-containing stream added in step (b) is not particularly limited, it typically contains lighter olefins than the olefins present in the olefin-containing crude oil stream provided in step (a).
• At least 50 wt.%, preferably at least 90 wt.%, of the olefin-containing stream added in step (b) has a boiling point of below 150°C at atmospheric pressure, preferably below 100°C, more preferably below 80°C, even more preferably below 50°C.
• the olefin-containing stream added in step (b) contains at least 2.0 wt.%, preferably at least 5.0 wt.%, more preferably at least 10.0 wt.%, even more preferably at least 20 wt.% olefins.
• At least 90 wt.% of the olefins of the olefin-containing stream added in step (b) are selected from the group consisting of ethylene, propylene, butenes and mixtures thereof.
• step (c) the olefin-enriched stream obtained in step (b) is subjected to an olefin metathesis reaction in the presence of one or more metathesis catalysts thereby obtaining a metathesis product, the metathesis product containing at least 20 wt.% of a fraction having a boiling point between 50-380°C at atmospheric pressure.
• Suitable metathesis catalysts include the so-called 'Schrock catalysts' (molybdenum(IV)- and tungsten(IV)-based) and 'Grubbs' catalysts' (ruthenium(II) carbenoid complexes). Suitable metathesis catalysts have been described in detail in paragraphs [0041]-[0091] of WO 2010/062958 , the teaching of which is hereby incorporated by specific reference.
• the one or more metathesis catalysts to be used according to the present invention are metal carbene catalysts based on the group consisting of ruthenium, molybdenum, osmium, chromium, rhenium and tungsten and a combination thereof; preferably metal carbene catalysts based on the group consisting of ruthenium, molybdenum, tungsten and a combination thereof; more preferably heterogeneous catalysts based on molybdenum.
• iron oxide catalysts there is also a preference for iron oxide catalysts.
• the olefin-enriched stream is subjected to the olefin metathesis reaction in step (c) at a temperature between 10°C and 400°C, more typically above 20°C, even more typically above 50°C, preferably above 70°C.
• the olefin-enriched stream is subjected to the olefin metathesis reaction in step (c) at a temperature below 300°C, preferably below 200°C, more preferably below 160°C.
• the olefin-enriched stream is typically subjected to the olefin metathesis reaction in step (c) at a pressure above 2.0 bar, more typically above 5 bar, more typically above 20 bar, preferably above 50 bar.
• the metathesis product contains at least 20 wt.% of a fraction having a boiling point between 50-380°C at atmospheric pressure.
• the metathesis product obtained in step (c) contains at least 25 wt.%, more preferably at least 30 wt.%, even more preferably at least 40 wt.%, yet even more preferably at least 50 wt.%, of a fraction having a boiling point between 50-380°C at atmospheric pressure.
• the metathesis product obtained in step (c) comprises at least 5.0 wt.% more of a fraction having a boiling point between 50-380°C at atmospheric pressure, when compared to the olefin-enriched stream as obtained in step (b), preferably at least 7.0 wt.% more, more preferably at least 10 wt.% more, or even at least 20 wt.% more.
• step (d) the fraction having a boiling point between 50-380°C is at least partly removed from the metathesis product as obtained in step (c), typically by distillation.
• the fraction having a boiling point between 50-380°C can be suitably used as a middle distillate.
• the fraction having a boiling point between 50-380°C as removed at least partly in step (d) contains at least 20 wt.%, preferably at least 50 wt.% olefins, more preferably at least 80 wt.% olefins.
• VGO dehydrogenated vacuum gas oil
• Table 1 Properties and composition of VGO Property / component Amount Measuring method Specific gravity 15/4C 0 . 898 Hydrogen [wt.%] 12.4 Carbon [wt.%] 3.3 H/C ratio 1.74 Oxygen [wt.%] 0.071 Total nitrogen [ppmw] 706 Sulfur content [wt.%] 2.121 ASTM D2622 Basic nitrogen [ppmw] 232 Mono aromatic nuclei [wt.%] 4.72 Di aromatic nuclei [wt.%] 3.77 Tri aromatic nuclei [wt.%] 3.13 Tetra+ aromatic nuclei [wt.%] 2.49 Total aromatic nuclei [wt.%] 14.1 Micro Carbon Residue (MCR) [wt.%] 0.33 ASTM D4530 Bromine number 6.9 Fraction of carbon atoms in naphthenic structure [wt.%] 25.4 Fraction of carbon atoms in aromatic structure
• a fraction having a boiling point between 50-380°C at atmospheric pressure was removed from the metathesis product.
• the removed fraction may be suitably used as a middle distillate.
• the present invention provides a method for upgrading crude oil.

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• 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)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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Citations (3)

• 2016
  • 2016-01-19 EP EP16151925.1A patent/EP3196276A1/de not_active Withdrawn

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