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WO2008124043A1 - Valorisation des résidus du pétrole, du bitume, de l'huile de schiste et autres huiles lourdes par la séparation des asphaltènes et/ou résines à partir de ceux-ci par substitution aromatique électrophile - Google Patents

Valorisation des résidus du pétrole, du bitume, de l'huile de schiste et autres huiles lourdes par la séparation des asphaltènes et/ou résines à partir de ceux-ci par substitution aromatique électrophile Download PDF

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Publication number
WO2008124043A1
WO2008124043A1 PCT/US2008/004359 US2008004359W WO2008124043A1 WO 2008124043 A1 WO2008124043 A1 WO 2008124043A1 US 2008004359 W US2008004359 W US 2008004359W WO 2008124043 A1 WO2008124043 A1 WO 2008124043A1
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Prior art keywords
asphaltenes
feed stream
heavy
resid
aromatic substitution
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Inventor
Manuel A. Francisco
Michael Siskin
Alan R. Katritzky
Simon R. Kelemen
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • 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

Definitions

  • the present invention relates to the upgrading of petroleum residium (petroleum resid), bitumen, shale oil and/or other heavy oils by the removal therefrom of heavy, high molecular weight multi-ring aromatics and metals present in such petroleum resid, bitumen and/or heavy oils in the form of asphaltenes and/or heavy resins and/or polycyclic hetero (N 5 S 3 O) aromatics.
  • Heavy, high molecular weight multi-ring aromatics, polycyclic hetero (N 5 S, O) aromatics and metals-containing molecules, e.g., porphyrins, are present in petroleum resid, bitumen and/or heavy oils largely in the form of a solubility class called asphaltenes or, depending on the feed, as individually identifiable molecular types, e.g., the asphaltene can comprise a mixture of such materials, or materials such as polycyclic hetero (N,S,O) aromatics and be present per se, in such feeds.
  • the asphaltene fraction present in such feeds contains the most polar molecules.
  • a process known as solvent deasphalting is practiced.
  • an excess of non-polar solvent is added to the petroleum resid, bitumen and/or heavy oils (hereinafter collectively referred to as heavy hydrocarbon feed stream) to force the polar asphaltene material out of the heavy hydrocarbon feed stream.
  • Current commercial deasphalting processes use liquid propane or liquid butane as the non-polar precipitation inducing solvent. Such processes are energy intensive requiring the refrigeration and compression/pressurization of the propane or butane to condense them into a liquid.
  • the propane or butane is recovered by evaporation from the heavy hydrocarbon feed stream, necessitating the re-refrigeration and re-pressurization of the now gaseous propane or butane for re-condensation into liquid form for reuse.
  • Another drawback of solvent deasphalting is the lack of selectivity in the solvent deasphalting process. The lack of selectivity of the solvents is evidenced by the co-precipitation of non- asphaltenic molecules along with the asphaltenes and the presence of residual asphaltene molecules in the deasphalted oil (DAO) fraction.
  • petroleum resid can be visbroken, coked or used as residual sulfur fuel oil (RSFO) or as asphalt without removal of the asphaltene fraction.
  • RSFO residual sulfur fuel oil
  • Such processes are also either energy intensive, expensive or wasteful of high value hydrocarbons present in the petroleum resid feed stream.
  • DAO deasphalted oil
  • RSFO residual sulfur fuel oil
  • FCC fluid catalytic cracking
  • Figure 1 is a Thermogravimetric Analysis (TGA) comparing heavy
  • Figure 2 is a TGA comparing heavy Canadian Vacuum Resid per se against heavy Canadian Vacuum Resid Heptane Deasphalted Oil and Sulfonated heavy Canadian Vacuum Resid Toluene Solubles.
  • Figure 3 is a TGA comparing European Vacuum Resid Heptane Asphaltenes against the Toluene Insolubles recovered from Sulfonated European Vacuum Resid.
  • Figure 4 is a TGA comparing European Vacuum Resid Heptane Deasphalted Oil against the Toluene Solubles recovered from 165°C Sulfonation of European Vacuum Resid.
  • Figure 5 is a TGA comparing European Vacuum resid per se against Sulfonated European Vacuum Resid.
  • Figure 6 is a plot of the Flash Pyrolysis GCMS comparing untreated asphaltenes against asphaltenes subjected to sulfonation under four different sets of conditions as well as against the Toluene Insolubles recovered from Sulfonated heavy Canadian Vacuum Resid.
  • Figure 7 is a plot of the Pyrolysis GCMS at 250 0 C for 1 hour comparing heavy Canadian Vacuum Resid Heptane Asphaltenes against the Toluene Insolubles recovered from large scale Sulfonation of heavy Canadian Vacuum Resid Heptane Asphaltenes.
  • Figure 8 is a plot of the Pyrolysis GCMS at 250 0 C for 1 hour comparing European Vacuum Resid against European Vacuum Resid sulfonated in methylene chloride at 25°C for 1 hour.
  • Heavy, high molecular weight multi-ring aromatics, and/or resins, and/or polycyclic hetero (N 5 S 5 O) aromatics are separated from petroleum resid, bitumen, shale oil and/or other heavy oils (heavy hydrocarbon feed stream) by the process of selectively substituting polar substituents onto the aromatic rings of the heavy, high molecular weight multi-ring aromatics, and/or resins, and/or polycyclic hetero (N,S,O) aromatics (hereinafter collectively referred to for heavy feeds as asphaltenes) present in the heavy hydrocarbon feed stream via electrophilic aromatic substitution.
  • Such a process utilizes little, if any, solvent, any solvent used being aromatic-containing diluent to control viscosity rather than liquid propane or butane, the aromatic diluent being easily recovered by one skilled in the art.
  • the heavy hydrocarbon feed stream in liquid form, is contacted with a reagent suitable for selectively substituting polar group(s) onto the aromatic rings of the asphaltene material via electrophilic aromatic substitution.
  • Electrophilic aromatics substitution reactions are exemplified by halogenation, nitration, sulfonation, Friedel-Crafts acylation and hydroxy alkylation.
  • the heavy hydrocarbon feed stream needs to be in the liquid form. If not already liquid at ambient condition, the heavy hydrocarbon feed stream can be heated to make it liquid, i.e., to a temperature of between about 50 to 200 0 C, preferably between about 100 to 175°C, more preferably between about 100 to 165 0 C.
  • a light aromatic diluent such as toluene can be added to solvate the heavy hydrocarbon feed stream to reduce viscosity (i.e., make it liquid) and/or facilitate reaction.
  • both heating and an aromatic or aromatic-containing diluent can be employed.
  • sufficient electrophilic aromatic substitution reagent is used to result in the addition of from about 1 to 8, preferably about 2 to 6, more preferable about 2 to 4 polar groups per asphaltene molecule.
  • the asphaltene content of the subject feed can be determined by the application of ASTM method D3279. XPS and/or wt% C, H, N and S analysis was used; the XPS analysis identifies the functional groups while elemental analysis confirms the amount of the elements, e.g., sulfur, added.
  • electrophilic aromatic substitution reagent such as oleum or SO 3
  • the use of sufficient electrophilic aromatic substitution reagent to add 2 to 4 polar groups to the asphaltene structure is desirable to achieve the selective reaction of the asphaltenes versus reaction with the smaller, lighter polycyclic aromatic molecules present in the heavy hydrocarbon feed stream.
  • larger polycyclic aromatics and heterocyclic aromatics react preferentially in comparison to the smaller ring systems.
  • the heating step to dimerize/oligomerize the polar functionalized asphaltene is effective only when the polar functionalizing group is sulfonic acid (-SO 3 H) or hydroxy alkyl (-R-OH). While the dimerization/oligomerization will not increase the polar species content on a polar species per 100 carbon atom basis, it will result in an at least doubling of the molecular weight of the molecule which increases solubility parameter and will help precipitation. [0022] Practicing the electrophilic aromatic substitution reaction process on asphaltenes to deposit -SO 3 H or -ROH groups at temperatures of 120-165 0 C could lead to the production of the above described dimers or oligomers without additional heating.
  • Sulfonation of aromatic compounds by concentrated or fuming sulfuric acid, or pure sulfur trioxide or its pyridine complex are of known industrial importance due to the availability and low cost of the reagents.
  • Using sulfuric acid has some disadvantages: higher reaction temperature, longer reaction time, formation of waste acid due to the production of water, and pollution to the environment.
  • the use of sulfur trioxide (SO 3 ) i.e., pure reagent, or oleum reagent, preferably SO 3 pure reagent as the sulfonating agent is more efficient because only direct addition of the SO 3 group is involved and there is no formation of water during the reaction.
  • SO 3 include faster reaction, obviation of waste acid disposal and minimal environmental impact.
  • using SO 3 -nitrobenzene has advantage in that a significant body of kinetics under these conditions exists for model compounds in the literature.
  • Aromatic sulfonation by sulfuric acid has been known to be complicated by temperature dependent isomerization, reversibility, further sulfonation, as well as by water produced by the reaction, but all of these are reported in the literature and known to those skilled in the art and can be taken into consideration and compensated for by the practitioner.
  • the heavy hydrocarbon feed stream is, as previously indicated, a petroleum resid, shale oil, bitumen or heavy oil.
  • Petroleum resid is a high boiling fraction recovered from crude distillation at 900-1050 0 F, preferably 900-1030 0 F, more preferably 980-1030 0 F at atmospheric pressure or at the vacuum distillation temperature equivalent thereof.
  • Petroleum resid is commonly made-up of asphaltenes, which are heavy, high molecular weight ( ⁇ 1500 Mn) polar aromatic molecules which also contain metals; other polar molecules such as resins contain minimal metals but which do contain sulfur and nitrogen are smaller than asphaltenes; other poly cyclic aromatics; naphthalene aromatics; naphthalenes; and paraffins.
  • Resins are lower molecular weight versions of asphaltenes with their polar functionality located at one end of the molecule rather than being distributed homogenously throughout the molecule.
  • the resins act as surfactant "like" molecules, stabilizing and dispersing the polar asphaltenes in the relatively less polar hydrocarbon matrix which is the bulk of petroleum crude oil, resids and bitumens.
  • bitumen means the heavy oil recovered from tar sands while “heavy oils” include resids, heavy Venezuelan, Russian, Brazilian, arctic etc. oils not necessarily associated with sands, but which have greater than about 20% boiling above 1000 0 F.
  • materials such as pyrrolic N-containing N heterocyclic and polycyclic aromatic analogues which contain at least one unsubstituted available aromatic carbon such as the carbazole and indole moiety-containing aromatic molecules and polycyclic aromatic analogues thereof can be removed from lighter oil feed streams, which do not contain asphaltenes, other than just from the aforesaid heavy hydrocarbon feed streams, which similarly contain pyrollic-N ⁇ containing nitrogen compounds; e.g., other lighter oil feed streams such as from a VGO or shale oil derived feeds, by functionalization with polar substituents via electrophilic aromatic substitution because of the high selectivity of the electrophilic aromatics substitution reaction for these pyrrolic nitrogen containing heterocyclic aromatics in preference over non-heterocyclic aromatics, the sulfur containing heterocyclic aromatic and even non-pyrrolic nitrogen containing heterocyclic aromatics
  • the amount of electrophilic aromatic substitution reagent employed to remove pyrrolic N-containing nitrogen heterocyclic compounds and/or polycyclic aromatic analogue thereof can be less than that needed to remove asphaltenes from petroleum resid, bitumen and/or heavy oils, the amount of electrophilic aromatic substitution reagent employed in such cases being as little as just sufficient to add one functionalizing polar substituent group to the pyrrolic-N-containing nitrogen heterocycle compounds and/or polycyclic. aromatic analogue thereof.
  • the electriphilic aromatic substitution reagent can be used in amounts just sufficient to preferentially and selectively remove the pyrrolic-N-containing nitrogen compounds from such feeds.
  • the value of the electrophilic aromatic substitution of polar group(s) onto the asphaltenes in petroleum resid, and/or bitumen, and/or heavy oil is because in the petroleum resid, and/or bitumen and/or heavy oil the electrophilic aromatic substitution is selective with respect to the asphaltene molecules present in the heavy hydrocarbon feed stream.
  • the asphaltenes in the heavy hydrocarbon feed stream react much more readily and completely than do the lighter, smaller, polycyclic aromatics in the heavy hydrocarbon feed stream. This selectivity in a mixed polycyclic aromatics-containing stream is crucial for the process to be viable.
  • the filtered precipitate (Toluene Insoluble asphaltenes) was air dried and then dried to constant weight in a vacuum oven at 12O 0 C. Unfunctionalized asphaltenes are toluene soluble but heptane insoluble. Here, adding polar functionality makes them also toluene insoluble (TI). Because the H/C atomic ratio of the asphaltenes has not been significantly changed by functionalization, they are still asphaltenes, as opposed to "coke” which is traditionally defined as toluene insoluble material but with a much lower H/C ratio. The yield of sulfonated asphaltenes is shown in Table 1. The filtrate was washed with water three times in a separatory funnel. The filtrate (Tolene Solubles) was dried over anhydrous sodium sulfate overnight, suction filtered and evaporated to dryness. The yield is shown in Table 1.
  • the filtered precipitate (Toluene Insoluble asphaltenes) was air dried and then dried to constant weight in a vacuum oven at 120 0 C.
  • the yield of sulfonated asphaltenes is shown in Table 1.
  • the filtrate (Toluene Solubles) was washed with water three times in a separatory funnel. The filtrate was dried over anhydrous _ -
  • the filtered precipitate (Toluene Insolubles) was washed with distilled water (900 mL), air dried and then dried to constant weight in a vacuum oven at 120 degrees centigrade. The water layer was submitted for acid titration. The yield of sulfonated asphaltenes is shown in Table 1.
  • the filtrate (Toluene Solubles) was washed in a separatory funnel with water (3000 mL) three times. The filtrate was dried over anhydrous sodium sulfate overnight, suction filtered and evaporated to dryness. The yield is shown in Table 1.
  • Each of the Toluene Solubles and Toluene Insolubles products were subjected to a series of tests and analyses outlined in detail below. The TIs did not melt in either the Penetration (D5-25) or Softening (D36) Point tests and therefore was deemed unfit for asphalt use.
  • a European vacuum resid (96.13 g, FST-4262) was heated to 160 0 C in a 500 mL three necked flask under a nitrogen atmosphere. The flask was equipped with a mechanical stirrer. The resid was fluid enough to stir at 165 0 C. Sulfur trioxide (5.76 g, 0.072 moles, 3 mL) was slowly added to the hot, stirring resid under nitrogen. When addition of the sulfur trioxide was complete, the reaction mixture was allowed to stir at 160 0 C for 1 hour under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and toluene (700 mL) was added and the mixture was allowed to sit overnight.
  • the reaction mixture was suction filtered and the filtered solids were washed with toluene.
  • the solids were dried in a vacuum oven at 110 0 C overnight to yield (4.43 g) of toluene insolubles (TIs).
  • the toluene filtrates were evaporated to dryness, using a rotary evaporator and dried in a vacuum oven to constant weight to yield (97.02 g) of toluene solubles (TSs). Total yield was 101.45 g (106% based on starting resid).
  • the TIs did not melt in either the Penetration (D5-25) or Softening (D36) Point tests and therefore was deemed unfit for asphalt use.
  • the European vacuum resid (99.79 g, FST-4262) was dissolved in dry methylene chloride (100 mL) and poured into a 500 mL three necked flask under a nitrogen atomosphere in a dry box at room temperature. The flask was equipped with a mechanical stirrer. Sulfur trioxide (1.92 g, 0.024 moles, 1 mL) was slowly added to the stirring resid at room temperature. When addition of the sulfur trioxide was complete, the reaction mixture was allowed to stir at room temperature for 1 hour under a nitrogen atmosphere.
  • reaction mixture was evaporated to dryness, using a rotary evaporator and dried in a vacuum oven to constant weight to yield 100.65 g of product (101% yield based on starting resid).
  • the product had a Penetration and Softening (98 MM/10 and 46.4 0 C) Point different than the starting resid (92 MM/ 10 and 38 0 C).
  • TGA Coke analysis was done on a Perkin Elmer Pyris 1 TGA. Temperature was increased from 30 0 C to 800 0 C at 10 degrees per minute with a flow (20 mL/min.) of nitrogen. The temperature was then held for 20 minutes at 800 0C and then the nitrogen was switched to air at a flow rate of 50 mL/min.
  • the components are eluted directly to the MS source where they undergo 70 eV electron impact which fragments the molecules into characteristic spectra. These spectra are compared to a library where the best fit is determined.
  • Thermal desorption The sample is heated at a constant rate (10-50 °C/min) to the desired temperature of 250 0 C, using a Pyran system (made by Ruska Labs, -1995, Ruska Pyran Thermal Desorption/Pyrolysis unit HP GC 5890 Series II, HP MS Engine 5989B). Sample size can be as much as 50 mg. Helium flows through the sample from below as it is being heated at 30 cc/min.
  • the volatiles are carried via a heated transfer line (325 0 C) to the head of a GC column (60 m DB-I, 0.25 mm, lum) maintained at -60 0 C for the entire desorption time.
  • a GC oven is heated at a constant rate (10 °C/min) to elute the components to the mass spectrometer for detection.
  • the GC carrier gas is helium (constant flow; 2 cc/min).
  • the weight loss of the sample is also measured, similar to a ThermoGravimetric Analysis (TGA).
  • a small scale mini reactor is hooked up to a GC with a sulfur detector that mimics a Fluid Catalytic Cracker (FCC) fairly well (in terms of conversion and products produced).
  • FCC Fluid Catalytic Cracker
  • a very small sample (—0.15 mg) is injected and allowed to come in contact with an FCC catalyst at 600 ° C (in a pyrolysis chamber).
  • the product(s) is/are introduced into the GC and Flame Ionization Detector (FID) and sulfur signals are collected.
  • FCC Fluid Catalytic Cracker
  • the unreacted asphaltenes differ from the other samples in two ways. One is the evolution of volatiles occurs at a much lower temperature for the sulfonated asphaltenes, and the coke @ 525 0 C is higher.
  • the sulfonic acid groups in the sulfonated asphaltenes are thermally labile and may be responsible for some of the lower temperature weight loss. Other options include oleum salt formation, occlusion of oleum, reaction and incorporation of residual toluene into the sulfonated asphaltenes. Sulfonation may also be causing reactions other than the addition of sulfonic acid groups to the asphaltenes. It is possible that sulfonation causes some condensation and dehydrogenation thereby increasing the size and number of coke forming polycyclic aromatics.
  • Examples IA to ID in Table 1 indicate that about 10% of the sulfonated asphaltenes are still soluble in toluene. This suggests the possibility that some of the asphaltenes may have fewer sulfonic acid functions added which would be an indication of selectivity. The other possibility is that the toluene soluble asphaltenes are sulfonated to the same degree as the insoluble product, but this is not adequate to make them insoluble in toluene.
  • asphaltene molecule (average molecular weight 1500 amu and presuming about 40% of the asphaltene carbons are aromatic ring carbons) ranged from about seven tenths (0.7 -SOaH/average asphaltene molecule) to thirty-five (35 - SO 3 H/average asphaltene molecule), depending on the amount of oleum used and the reaction time.
  • the values were corrected for the fact that resid only contains about 25 wt% asphaltenes and the -SO 3 H groups per average asphaltene molecule are calculated from yield (in grams) on the whole resid. It was presumed that all the -SO 3 H groups have gone only to asphaltene molecules.
  • the data indicates that it is likely that the increased SO 3 H group content in the yield (in grams) analysis is due to the occlusion of unreacted oleum with the product and/or the formation of salts carried over into the recovered product and included in the yield (in grams) data and not exclusively due to the addition of -sulfonic acid groups to the asphaltene molecule.
  • TIs toluene insolubles
  • X-ray photoelectron spectroscopy indicates that the number of sulfonic acid groups added per asphaltene molecule in Examples IA to ID, 2 and 3 ranges from 0.1 to 4.8 which is directionally more consistent with the wt% C, H, N and S data than it is with the yield data.
  • Quarternary ammonium salts of the nitrogen species were also observed. The range of salt formation goes from 17 to 63% of the total nitrogen species. These would be quaternary ammonium salts formed by the reaction of sulfuric acid (H 2 SO 4 ) from the oleum with basic nitrogen species.
  • the toluene solubles (TSs) from the sulfonation of Heavy Canadian vacuum resid were compared to the DAO recovered by heptane deasphalting of the unreacted Heavy Canadian vacuum resid.
  • the TSs are very similar in quality to the conventional heptane DAO.
  • the number of atoms per 100 carbon atoms (lOOC) were calculated from the wt% C, H, N and S analysis of a heptane DAO from an unreacted Heavy Canadian vacuum resid and the TSs from the sulfonation of Heavy Canadian vacuum resid (Table 3). Oxygen content was calculated by differene.
  • a small scale Fluid Catalytic Cracking (FCC) unit was used to evaluate the catalytic cracking behavior of the TSs and the DAO.
  • Table 4 shows that the overall conversion and gasoline yield is higher for the DAO than it is for the TS.
  • the metals content of the TSs are compared to those of the DAO from the heptane deasphalting of Heavy Canadian vacuum resid in Table 5.
  • the TSs from the sulfonation reaction have somewhat higher concentrations of metals than the DAO from heptane deasphalting of Heavy Canadian vacuum resid.
  • the TSs from selectivie sulfonation are still reasonable feedstocks for FCC.
  • Figure 8 illustrates the results. Again the sulfonated product evolved more SO 2 than the unreacted EVR.
  • the sulfonated product is the EVR that was sulfonated with liquid SO 3 and without separation of the TIs.
  • the results indicate that the product would need to be stabilized as for example by heat soaking at a minimum of 250 0 C for a time sufficient, e.g., one hour, to prevent evolution of SO 2 during subsequent asphalt processing and use.
  • the sulfonation reaction described above yielded three products: the TIs (sulfonated Heavy Canadian vacuum resid heptane asphaltenes), Toluene Solubles (TSs) and first water wash.
  • the first water wash was titrated for acid : content.
  • the TIs were submitted for a second water wash.
  • the second water wash involved stirring the TIs with distilled water overnight, suction filtering and sending the second water wash for acid titration.
  • the base line pure, distilled water requires 0.10031 mg KOH/g to
  • asphaltenes required 6.49 mg KOH/g to neutralize the acid content.
  • heptane asphaltenes requires 156.8 mg KOH/g to neutralize the
  • heptane asphaltenes requires 6.49 mg KOH/g to neutralize the
  • the first water wash indicates the presence of residual or occluded
  • Penetration Point and Softening Point The TIs from the sulfonation of Heavy Canadian vacuum resid heptane asphaltenes with oleum at room temperature in toluene would not melt or soften at the temperatures needed to conduct these two tests. The same was true of the TIs from the sulfonation of EVR at 165 0 C with no toluene. Therefore it can be concluded that these sulfonated products are not suitable feedstocks to make asphalt. The last experiment was to test the sulfonation product of EVR without removing the TIs.
  • the reaction mixture was filtered and the filtrate was analyzed using a gas chromatograph-mass spectrometer (Hewlett-Packard Model 5972 Series).
  • the filtrate (1 ⁇ L) was injected at an injection port temperature of 250 0 C and an oven temperature of 100 0 C; after an initial hold time of 3 min at 100 0 C, the oven temperature was programmed at 10°C/min until 250 0 C.
  • Table 9 Competitive Rates of Sulfonation (more reactive compound is in bold)
  • Dibenzothiophene considered as 1. Pyrene was not detected; Phenanthrene was not detected.
  • pyrrolic N containing N-heterocyclic aromatic compounds are much more susceptible to sulfonation than are ordinary polycyclic aromatics and even sulfur containing heterocyclic aromatics.

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Abstract

L'invention concerne des aromatiques à multiples cycles, de masse moléculaire élevée, lourds, présents dans des résidus du pétrole, le bitume et des huiles lourdes sous la forme d'asphaltènes, de résidus lourds et de molécules hétéro(N)aromatiques polycycliques qui sont séparés des résidus du pétrole, du bitume et/ou des huiles lourdes, par le procédé comprenant une substitution aromatique électrophile de groupes polaires sur les aromatiques à multiples cycles de masse moléculaire élevée, lourds, les rendant de cette façon insolubles dans les, et facilitant leur séparation et leur récupération à partir des, résidus du pétrole, bitume et/ou huile lourde.
PCT/US2008/004359 2007-04-06 2008-04-03 Valorisation des résidus du pétrole, du bitume, de l'huile de schiste et autres huiles lourdes par la séparation des asphaltènes et/ou résines à partir de ceux-ci par substitution aromatique électrophile Ceased WO2008124043A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US92220607P 2007-04-06 2007-04-06
US60/922,206 2007-04-06
US12/079,189 US20080251418A1 (en) 2007-04-06 2008-03-25 Upgrading of petroleum resid, bitumen, shale oil, and other heavy oils by the separation of asphaltenes and/or resins therefrom by electrophilic aromatic substitution
US12/079,189 2008-03-25

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WO2008124043A1 true WO2008124043A1 (fr) 2008-10-16

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