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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
• • 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
  • C10G21/30—Controlling or regulating
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/12—Recovery of used adsorbent
• • 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
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content
  • C10G2300/206—Asphaltenes
• • 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
  • C10G2300/302—Viscosity
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4043—Limiting CO2 emissions
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/44—Solvents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
  • C10G2300/802—Diluents

Definitions

• This invention relates generally to the field of processing hydrocarbons for pipeline transportation, and more particularly to treating hydrocarbons to reduce viscosity to meet pipeline requirements.
• Alberta oil sands bitumen shipped to U.S. refineries will be near 1.44 million barrels per day (Edmonton Journal 2008). This is an energy security issue since U.S. relations with Canada are cordial. Additional heavy oils will come from U.S. enhanced oil recovery production and other imports.
• the petroleum industry is currently undergoing a major paradigm shift in converting refineries to be able to process the heavier feeds.
• Alberta bitumens are solids or very viscous materials. To ship these materials in pipelines, a significant decrease in viscosity is required. About 25% by volume light oil diluent or 50% by volume light synthetic crude oil is added to the bitumen to lower the viscosity to meet pipeline specifications (Fan et al. 2009).
• the mixture of the diluent and heavy bitumen is then shipped to the U.S. to refineries that are capable of processing the Canadian material.
• the solvent is removed by distillation at the refinery, which is energy intensive.
• diluent is pipelined back to Canada for re- use since there is a limited supply, and the amount of diluent available will limit Canadian bitumen availability (Perry 2002).
• Enbridge is constructing a pipeline from Chicago to Edmonton to return 180,000 barrels per day of diluent solvent back to Canada (Reuters 2009).
• the pericondensed asphaltene component molecules cause association effects in oil since they can be modeled as being surrounded by other molecules of intermediate aromaticity and polarity that act as peptizing agents. This results in associated complexes which act as dispersed particles in the oil, resulting in significant viscosity increases above the viscosity of the base solvent oil.
• the associated complexes can be broken apart in a reversible manner by heating the oil to temperatures below the point where cracking reactions begin (Storm et al. 1995, 1996). If the asphaltenic components such as highly pericondensed aromatic core material can be freed from peptizing molecules which act as solubilizing agents, they can be selectively adsorbed using sorbents. Selective removal of the most pericondensed aromatic molecules in heavy oil could significantly lower the oil viscosity so that much less, if any diluent would be required for pipeline shipment.
• Asphaltene Component Adsorption and Deposition Asphaltenes are defined as a solubility class of associated chemical complexes which precipitate when petroleum is dissolved in a low polarity solvent such as heptane.
• a low polarity solvent such as heptane.
• Asphaltenes act as the major viscosity builders in oil. In catalytic upgrading processes such as hydrotreating, the presence of these materials can shorten catalyst life.
• the resulting asphaltenic material enriched in Ni and V was observed to deposit as dark spots on stainless steel and aluminum surfaces, but not on a non-polar Teflon ® surface. This phenomenon appears to be due to the partitioning of the intermediate polarity material surrounding the aromatic asphaltene component molecules into the oil matrix solution, exposing the highly pericondensed aromatic or polar material.
• the pericondensed aromatic or polar material can flocculate and adhere to the polar metal surface. This is a cause of heat-induced fouling of pipes and heat exchangers in refineries. The concept of using this approach to reduce the viscosity of the original oil was not considered at that time.
• Asphaltene DeterminatorTM A new analytical method called the Asphaltene DeterminatorTM has been developed and is now in routine use at WRI (Schabron and Rovani 2008, Schabron et al. 2010, U.S. Patent 7,875,464).
• the Asphaltene Determinator method involves analytical scale precipitation of asphaltene components from a portion of oil on a column packed with ground inert polytetrafluoroethylene (PTFE) using a heptane mobile phase. The precipitated material is re- dissolved in three steps using solvents of increasing solubility parameter: cyclohexane, toluene, and methylene chloride: methanol (98:2 v:v).
• the amount of asphaltenes (heptane insolubles) and the Total Pericondensed Aromatic (TPA) content can be determined in less than an hour. It was observed in the development work for the method that glass wool or glass beads strongly adsorbed asphaltene component molecules once they are separated from other peptizing molecules in the oil. This observation of an undesired effect in the analytical method reinforced the concept of the possibility of asphaltene component molecule removal by adsorption onto a sorbent. In addition, the Asphaltene Determinator method was ideally suited to evaluate the efficiency of removal of pericondensed aromatic molecules in solventless deasphaltening experiments conducted for this patent application.
• the resulting oil would be deficient in the most refractory viscosity-building pericondensed aromatic structures and the product oil would be much less viscous than the original oil.
• the pericondensed material adsorbed to the sorbent possibly could later be desorbed by solvent rinsing, or the whole material could be combusted as a fuel to provide heat for the process.
• Relatively inexpensive yet highly aromatic materials which might be utilized as sorbent include ground petroleum coke or coal based sorbents.
• Asphaltenes and Viscosity Asphaltenes can be modeled mathematically to be related to the dispersed phase of suspended particles in a base oil, or solvent phase.
• the effective size of the suspended particles is due to the presence of peptizing molecules that surround the more aromatic or refractory asphaltene "core" molecules.
• the effective size of these peptized complexes can be decreased by heating the oil.
• the relative viscosity of a residuum is affected significantly by the effective volume fraction of suspended particles (Schabron et al. 2001).
• the heat of interaction of the peptizing molecules with the asphaltene core materials was observed to range from 470- 1,600 cal/mol for five residua.
• Partial removal of asphaltenes can result in a significant decrease in viscosity. For example, up to 98% viscosity reduction of Canadian heavy oils has been observed when different asphaltene components were selectively removed in stages in laboratory asphaltene precipitation experiments using a series of solvent with decreasing solvent strength (Kharrat 2009). Decreasing the effective relative volume of the dispersed phase results in significant viscosity reduction (Storm et al. 1995, 1996).
• part of the invention includes sorbent-based asphaltene removal from oil that has been subjected to mild pyrolysis. Even if only a portion of the asphaltenes can be removed, if these represent the most pericondensed, aromatic and refractory components, both the viscosity of the oil can be decreased dramatically and the quality of the oil can be increased significantly. If the pyrolysis conditions are kept at a mild level, the formation of double bonds and unstable liquids requiring subsequent hydrogen addition can be minimized.
• Viscosity can be reduced by removing relatively small portions of the asphaltenes.
• This invention describes as novel method for viscosity reduction by selective removal of portions of the most refractory pericondensed aromatic or other types of asphaltene components that act as viscosity builders in the oil. Removal of the components is accomplished by an adsorptive process in which the oil is initially heated or treated by various means and then contacted with sorbent to adsorb portions of the asphaltenic material.
• the sorbent can be but is not limited to a solid in a fixed bed, a fluidized bed, a surfaced, or a porous membrane.
• One means of initial treatment is to heat the oil to disrupt the ordered structure and to separate the most aromatic and refractory molecules from peptizing molecules that associate with them to keep them in solution.
• Another possible treatment is mild pyrolysis.
• Another possible treatment is to add an amount chemical additive or low polarity or other solvent (polar, aromatic, acid or base) to destabilize the ordered structure but not sufficient to completely precipitate asphaltenes from solution. Combinations of these treatments are also possible.
• the asphaltenic components are then adsorbed onto a stationary phase material.
• the sorbent can be one with high surface energy that is selective to adsorption of asphaltene component molecules such as highly pericondensed aromatic molecules.
• examples of the sorbents which may be particularly useful include but not limited to metals, ceramics, zeolites, clays, silica, limestone, glass, quartz, sand, alumina, or high surface energy carbonaceous materials such as petroleum coke, coal, charcoal, activated carbon, or similar materials.
• Other stationary phases such as salts or acids or bases might be useful also.
• Alberta oil sands bitumen shipped to U.S. refineries will be near 1.44 million barrels per day. This is an energy security issue since U.S. relations with Canada are cordial. Additional heavy oils will come from U.S. enhanced oil recovery production and other imports.
• the petroleum industry is currently undergoing a major paradigm shift in converting refineries to be able to process the heavier feeds.
• Alberta bitumens are solids or very viscous materials. To ship these materials in pipelines, a significant decrease in viscosity is required. About 25% by volume light oil diluent or 50% by volume light synthetic crude oil is added to the bitumen to lower the viscosity to meet pipeline specifications.
• the mixture of the diluent and heavy bitumen is then shipped to the U.S. to refineries that are capable of processing the Canadian material.
• the solvent is removed by distillation at the refinery, which is energy intensive.
• diluent is pipelined back to Canada for re-use since there is a limited supply.
• the pericondensed asphaltene component molecules present in bitumen cause association effects in the oil since they can be modeled as being surrounded by other molecules of intermediate aromaticity and polarity that act as peptizing agents. This results in associated complexes which act as particles in the oil, resulting in significant viscosity increases above the viscosity of the base solvent oil.
• the associated complexes can be broken apart in a reversible manner by heating the oil to temperatures below the point where cracking reactions begin. Heating exposes the highly pericondensed aromatic core materials by freeing them from peptizing molecules which act as solubilizing agents.
• the associated complexes can also be destabilized by mild pyrolysis or by adding materials to the oil such as solvents or other chemical additives.
• Viscosity can be reduced by removing relatively small portions of the asphaltenes.
• This invention describes a novel method for viscosity reduction by selective removal of portions of the most refractory pericondensed aromatic or other types of asphaltene components that act as viscosity builders in the oil. Removal of the components is accomplished by an adsorptive process in which the oil is initially heated or treated by various means and then contacted with sorbent to adsorb portions of the asphaltenic material.
• the sorbent can be a solid in a fixed bed, a fluidized bed, a surface, or a porous membrane.
• One means of initial treatment is to heat the oil to disrupt the ordered structure and to separate the most aromatic and refractory molecules from peptizing molecules that associate with them to keep them in solution.
• Another possible treatment is mild pyrolysis.
• Another possible treatment is to add an amount of chemical additive or low polarity or other solvent to destabilize the ordered structure but not sufficient to completely precipitate asphaltenes from solution. Combinations of these treatments are also possible.
• the asphaltenic components are then adsorbed onto a stationary phase material. After treatment, the total amount of diluent required would be less that that used without the treatment.
• the sorbent can be one with high surface energy that is selective to adsorption of asphaltene component molecules such as highly pericondensed aromatic molecules.
• asphaltene component molecules such as highly pericondensed aromatic molecules.
• examples of the sorbents which may be particularly useful include but not limited to metals, ceramics, zeolites, clays, silica, limestone, glass, quartz, sand, alumina, or high surface energy carbonaceous materials such as petroleum coke, coal, charcoal, activated carbon, or similar materials.
• Other sorbents such as salts or acids or bases might be useful also.
• This invention describes a new process for lowering the viscosity of heavy oil by the selective removal of the most pericondensed aromatic or other asphaltenic components from oil using an adsorptive process. This is accomplished by initially treating the oil to destabilize the solvent phase / dispersed phase ordered structure to separate the peptizing molecules from the polar asphaltenic and pericondensed aromatic molecules in the oil. Initial treatment can include heating, mild pyrolysis, and/or addition of a solvent or chemical additive.
• portions of these materials can be selectively adsorbed onto high surface energy solid sorbents such as metals, ceramics, zeolites, clays, silica, limestone, glass, quartz, sand, alumina, or high surface energy carbonaceous materials such as petroleum coke, coal, charcoal, activated carbon, acids, bases, salts, or similar materials.
• high surface energy solid sorbents such as metals, ceramics, zeolites, clays, silica, limestone, glass, quartz, sand, alumina, or high surface energy carbonaceous materials such as petroleum coke, coal, charcoal, activated carbon, acids, bases, salts, or similar materials.
• sorbents can be regenerated using small portions of strong solvent formulations. The potential use of carbon based sorbents is attractive since they can be used as part of the fuel for the process and would not need to be rinsed with solvent to desorb the aromatic material.
• Fig. 1 shows an Apparatus Used for Heated Sorbent Filtration
• Fig. 2 shows Table 1 - Sorbent Asphaltene Removal Results for Lloydminster Vacuum Residuum
• Fig. 3 shows Table 2 - Sorbent Asphaltene Removal Results for Cold Lake Vacuum Residuum
• Fig. 4 shows Table 3 - Viscosity Reduction for Diluted Cold Lake Residuum Processed by Sorbent Treatment at 250 °C
• Fig. 5 shows Table 4 - Elevated Temperature Pouring Sorbent Experiment Viscosities with Athabasca Bitumen
• Fig. 6 shows Table 5 - Asphaltene Determinator Results for Original Athabasca Bitumen
• Fig. 7 shows Table 6 - Asphaltene Determinator Results for Athabasca Bitumen Poured at 150
• the present invention includes a variety of aspects, which may be combined in different ways.
• the following descriptions are provided to list elements and describe some of the embodiments of the present invention. These elements are listed with initial embodiments, however it should be understood that they may be combined in any manner and in any number to create additional embodiments.
• the variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described systems, techniques, and applications. Further, this description should be understood to support and encompass descriptions and claims of all the various embodiments, systems, techniques, methods, devices, and applications with any number of the disclosed elements, with each element alone, and also with any and all various permutations and combinations of all elements in this or any subsequent application.
• Tests were conducted to percolate heated residuum through the various sorbents.
• the two oils used were Lloydminster and Cold Lake vacuum residua.
• the residua and sorbents were heated to 250 °C. Once the oven was turned on, it took 100 minutes to reach 250 °C. The oven was maintained at this temperature for 60 minutes, and then the conduit pipe was rotated and the heated oil was poured into the heated sorbent. The oil was separated from the sorbent through the medium glass frit filter below the bed of sorbent. Oil that percolated through the sorbent was collected in the glass Petri dish.
• the oil was analyzed before and after the sorbent tests using the Asphaltene Determinator to determine if pericondensed asphaltene material was removed by the sorbent.
• Complex viscosities were measured at 10 rad/sec with a Malvern Kinexus dynamic shear rheometer. Complex viscosity measurements were made at a frequency of 10 Hz at 50 °C, which is a pipeline specification temperature, and at 60 °C, which is a temperature used for paving asphalt viscosity measurements.
• the sorbents tested were 20-4 mesh Caballo lignite coal, 6 mesh glass beads, 70-100 mesh glass beads, 20-40 mesh petroleum coke from a Canadian oil, and size C 316 stainless steel HelipakTM material (small wire coils).
• the amount retained could be minimized by pumping heated oil through a bed of heated sorbent. Once the sorbent is no longer active, it can be regenerated by rinsing with a small portion of a strong chromatographic extraction solvent such as toluene :ethanol (85:5 v:v) and then re -used. For the carbon-based sorbents, the spent sorbent with adsorbed material could be burned as fuel for the process.
• a strong chromatographic extraction solvent such as toluene :ethanol (85:5 v:v)
• Residua solutions consisting of 22 wt. % heptane and cyclohexane respectively were made for the control Cold Lake poured material and the Cold Lake material that was poured through 70-100 mesh glass bead and Helipak stainless steel sorbents, respectively. Complex viscosities were measured for these solutions at 19 °C. The results are shown in Table 3 (see Figure 4). When compared to the heptane solutions of the control material, the data show a 22.6 % decrease in viscosity for a solution of the material poured through glass beads. A similar effect was observed for cyclohexane solutions of the control and material poured through the stainless steel sorbent, where a 56.0 % decrease in viscosity was noted.
• Viscosity and Asphaltene Determinator data were evaluated from Canadian Athabasca bitumen sorbent pouring experiments conducted at 150, 200, and 250 °C using three sorbents: glass beads, petroleum coke, and stainless steel Helipak wire. Since the bitumen is an atmospheric residuum, unlike a vacuum residuum, it contains volatile components that can be lost in open vessel elevated temperature experiments.
• the viscosity of the whole bitumen is 18.2 Pa s and 9.11 Pa S at 50 and 60 °C, respectively.
• the corresponding dynamic viscosities of the heptane maltenes following gravimetric removal of the 11.8 wt.% gravimetric heptane asphaltenes are 1.43 and 0.697 Pa s at 50 and 60 °C, respectively. This reflects a 92% decrease in viscosity at 60 °C by removing the asphaltenes, which is similar in magnitude to the results reported by Kharrat (2009) using asphaltene removal by solvent precipitation. The effect of asphaltene removal from this material on viscosity is significant.
• Dynamic viscosities at 50 and 60 °C of the original bitumen and the bitumen poured through the sorbents at 150, 200, and 250 °C are provided in Table 4 (see Figure 5). Percent viscosity decrease values relative to the original unpoured bitumen are tabulated. The viscosities at 60 °C showed significant decreases relative to the unpoured material for bitumen poured at 150 °C. The poured control material with no sorbent also showed a viscosity decrease. This is possibly due to adsorption of components onto the 3 mm thick coarse sintered glass filter which likely acted as a sorbent. Volatiles loss ranged from 2.2 - 2.9 wt. % at 150 °C.
• the Asphaltene Determinator separation results for the original bitumen are provided in Table 5 (see Figure 6).
• the data for the material poured at 150 °C are provided in Table 6 (see Figure 7).
• the Coking Index ratio is the ratio of the peak area of the cyclohexane soluble material to the peak area for the methylene chloride:methanol (98:2 v:v) peak area.
• Values above 1 indicate a material that has not been subjected to severe pyrolysis (severe cracking). Pyrolysis decreases the amount of cyclohexane soluble peak material and increases the amount of pre-coke pericondensed aromatics that are represented by the methylene chloride: methanol peak (Schabron et al. 2010).
• the AD Asphalt Aging Index is an indicator of oxidation severity. It is the ratio of the pericondensed aromatic toluene soluble material to the ratio of the pericondensed aromatic heptane soluble material that absorbs light at 500 nm. Values near 1 or below indicate little oxidation, and values increase with oxidation to values of 3 or higher.
• the data for the evaporative light scattering detector (ELSD) were corrected for the volatiles loss that occurred from the heptane soluble material in the ELSD evaporator.
• the data show very little apparent difference between the poured bitumen materials and the original unpoured control.
• certain embodiments of the inventive technology may be described as a hydrocarbon viscosity reduction method that comprises the steps of: treating a hydrocarbon having asphaltenes therein (as a component of the hydrocarbon) to generate a treated hydrocarbon, wherein the hydrocarbon has a first viscosity; contacting the treated hydrocarbon with a sorbent (whether as a result of pouring or other means); and adsorbing at least a portion of the asphaltenes onto the sorbent, thereby removing the at least a portion of the asphaltenes from the hydrocarbon so as to generate a viscosity reduced hydrocarbon having a second viscosity that is lower than the first viscosity.
• hydrocarbon may include, but is not necessarily limited to, bitumen, shale oil, coal oil, coal tar, biological oil, heavy oil or residuum. It may be or include atmospheric bitumen or vacuum bitumen. It is note that the sorbent is preferably a solid sorbent, and may be either a stationary phase or fluidized sorbent.
• Solid sorbents include but are not limited to: fixed bed sorbent, fluidized bed sorbent, surfaced sorbent, porous membrane sorbent, high surface energy sorbent, highly aromatic sorbent, sorbent that is selective to adsorption of asphaltenes, metal sorbent, steel sorbent, steel wire sorbent, steel wire coil sorbent, metal wire sorbent, metal wire coil sorbent, ceramic sorbent, zeolite sorbent, clay sorbent, silica sorbent, limestone sorbent, glass sorbent, mesh glass sorbent, glass bead sorbent, mesh glass bead sorbent, quartz sorbent, sand sorbent, alumina sorbent, and high surface energy carbonaceous material sorbent, salt sorbent, acid sorbent, base sorbent, carbon based sorbent, and high surface energy carbonaceous materials (e.g., petroleum coke, ground petroleum coke, coal-based sorbents, charcoal, activated carbon). It is
• the step of treating a hydrocarbon may involve heating the hydrocarbon to above or below a cracking temperature (any temperature that effects cracking of the hydrocarbon; typically at or above 340C). Heating of the hydrocarbon may be accomplished, in part or whole, via heating from a heat source that is upstream of the sorbent. Such heating step may be, but need not be, supplemented with heating from the sorbent itself (in such case, the method further includes the step of heating the sorbent to generate a heated sorbent). It is of note that in particular embodiments, the heating of the hydrocarbon may be achieved exclusively by heat transfer from the sorbent.
• heating of the hydrocarbon may be accomplished strictly via heating from a source other than the sorbent (e.g., upstream of the sorbent, in a heated vessel, for example), strictly via heating from a heated sorbent, or via combination of the two.
• a source other than the sorbent e.g., upstream of the sorbent, in a heated vessel, for example
• heating from a heated sorbent or via combination of the two.
• the treated hydrocarbon upon contact with the sorbent, has been heated via both heat transfer occurring upstream of the sorbent (e.g., in a heating vessel) and heat transfer from the sorbent (via a heated sorbent)
• the respective temperatures to which the two heating operations raise the hydrocarbon need not be the same.
• the temperature to which a heating vessel upstream of the heated sorbent raises the hydrocarbon may be less than, or greater than, or even equal to, the temperature to which the heated sorbent raises (or lowers) the hydrocarbon.
• the heated sorbent (where heated implies heating to some temperature that is above ambient temperature) may actually cool the hydrocarbon heated upstream of the sorbent (i.e., reduce the temperature it achieved from heating upstream of the sorbent).
• the steps of treating the hydrocarbon may involve contacting the untreated hydrocarbon with the sorbent, particularly in those cracking heat embodiments where the sorbent is at a cracking temperature.
• the step of contacting the treated hydrocarbon with the sorbent may occur later (perhaps immediately later, such as even fractions of a second later, particularly where the required heating (whether to a cracking temperature or not) is to be supplied entirely by the sorbent), after the sorbent heating effectively treats the hydrocarbon. Further, in those embodiments involving cooling of the hydrocarbon, the hydrocarbon that contacts the sorbent, whether heated or not, is still a treated hydrocarbon.
• heating regardless of whether the heat source is "upstream" of the sorbent or is the sorbent itself, can utilize any of the well known manners of heating a substance - convection, radiation, conduction, heating element, oven, flame, heated gas, heated liquid, solar, hot solvent, electric, fuel, microwave oven, geothermal, nuclear, external or internal fuel combustion, heating coil, burning deposited material from the sorbent, chemical reaction, and friction, etc.
• Cracking heat treatment embodiments may, but need not, involve the step of cooling the cracked hydrocarbon to a temperature below a cracking temperature (such that the treated hydrocarbon (i.e., the hydrocarbon as it is when it contacts the sorbent) might not even be at a cracking temperature).
• a cracking temperature such that the treated hydrocarbon (i.e., the hydrocarbon as it is when it contacts the sorbent) might not even be at a cracking temperature).
• the intent of the cracking is to create an irreversibly modified hydrocarbon; even if a cracked hydrocarbon is cooled it will have properties that enhance asphaltene adsorption (in this invention).
• such cooling can take place, in embodiments where the heat is applied upstream of the sorbent, even where the sorbent is heated (although certainly it could also take in the case where the sorbent is not heated).
• the temperature of the treated hydrocarbon in such case, merely a heated (and not cracked) hydrocarbon should never have reached a cracking temperature, and upon contact with the sorbent, should be elevated sufficiently above ambient but below a minimum cracking temperature.
• any embodiments, whether involving heating of the hydrocarbon or not, may further comprise the step of rinsing the sorbent with an aromatic solvent after asphaltene adsorption, in order to cleanse the sorbent and prepare it for additional runs.
• the aromatic solvent may be a strong chromatographic extraction solvent such as a halogenated solvent, an aromatic solvent, an alcohol, or a mixture thereof.
• the step of heating the hydrocarbon occurs for a heating time, and such time may be optimized (perhaps minimized).
• energy efficient/environmental pollutant emissions reduction benefits may be realized.
• Another additional benefit attendant the inventive methods is a reduction of the amount of subsequent hydrogen addition required due to the formation of double bonds and unstable liquids; this benefit may be most pronounced in the case of mild pyrolysis.
• sorbent contact times may be optimized (lowered to a minimum amount necessary to achieve a desired amount of asphaltene adsorption), to enhance process efficiency. It is of note that while certain hydrocarbon treatment embodiments that involve heating may be solventless, some may be supplemented with addition of a solvent or chemical additive.
• treatment of the hydrocarbon may, in some embodiments, may be entirely heat free, and be accomplished exclusively with solvent and/or chemical additive addition to an untreated hydrocarbon to generate a treated hydrocarbon that, upon contact with an appropriate sorbent, will have at least some asphaltenes adsorbed thereto.
• the solvent may be a low polarity solvent; whether it be conventionally referred to as a solvent or a chemical additive, it may be a polar material, an aromatic material, or and an acid or base (as but a few characterizations).
• addition of the substance does not effect asphaltene precipitation.
• the step of adsorbing at least a portion of the asphaltenes onto the sorbent may comprise the step of adsorbing at least a portion of the most pericondensed aromatic structures of the hydrocarbon, the most pericondensed, aromatic and refractory structures of the hydrocarbon, and/or the most pericondensed and highest surface energy pre-coke asphaltene materials.
• the method may further comprise the step of adding a diluent amount to the viscosity reduced hydrocarbon so as to generate a diluted hydrocarbon having a diluted hydrocarbon viscosity that is no greater than a certain viscosity (e.g., a viscosity governed by pipeline specifications, such as a maximum viscosity allowable for hydrocarbons to be pumped through the pipeline).
• the diluent amount is preferably less than that untreated hydrocarbon diluent amount required to reduce viscosity of an untreated hydrocarbon to the diluted hydrocarbon viscosity.
• another aspect of the inventive technology may be described as a new method for transporting a hydrocarbon, comprising the steps of: treating an untreated hydrocarbon to generate a treated hydrocarbon, and thereby lowering viscosity of the untreated hydrocarbon to a treated hydrocarbon viscosity; adding an amount of diluent to the treated hydrocarbon to generate a diluted hydrocarbon, thereby further lowering the treated hydrocarbon viscosity to a pipeline specification viscosity, wherein the amount of diluent is less than a conventional amount of diluent required to reduce the viscosity of the untreated hydrocarbon to the pipeline specification viscosity; and pumping the diluted hydrocarbon.
• the step of treating an untreated hydrocarbon may comprise the step of removing at least a portion of asphaltenes from the untreated hydrocarbon. This may be done via any of the methods specifically described herein.
• the amount of diluent may be a weight percentage of diluent for a given weight of treated hydrocarbon, while the conventional amount of diluent may be a weight percentage of diluent for a given weight of untreated hydrocarbon.
• the pipeline specification viscosity may be the maximum viscosity allowable for hydrocarbons to be pumped through the pipeline.
• the method may further comprise the step of removing the diluent from the diluted hydrocarbon (after transport via pumping).
• required diluent reduction may effect a reduction in greenhouse gas emissions (if only because less energy is required to eliminate the reduced amount of diluent from the post- transit hydrocarbon). Reduced diluent requirements may also result in reduced hydrocarbon piping costs, and increased hydrocarbon transportation operation efficiencies.
• the basic concepts of the present invention may be embodied in a variety of ways. It involves both heating techniques as well as devices to accomplish the appropriate heating.
• the heating techniques are disclosed as part of the results shown to be achieved by the various devices described and as steps which are inherent to utilization. They are simply the natural result of utilizing the devices as intended and described.
• devices are disclosed, it should be understood that these not only accomplish certain methods but also can be varied in a number of ways. Importantly, as to all of the foregoing, all of these facets should be understood to be encompassed by this disclosure.
• each of the various elements of the invention and claims may also be achieved in a variety of manners.
• an element is to be understood as encompassing individual as well as plural structures that may or may not be physically connected.
• This disclosure should be understood to encompass each such variation, be it a variation of an embodiment of any apparatus embodiment, a method or process embodiment, or even merely a variation of any element of these.
• the words for each element may be expressed by equivalent apparatus terms or method terms— even if only the function or result is the same. Such equivalent, broader, or even more generic terms should be considered to be encompassed in the description of each element or action.
• Opportunity Crudes Report II Technologies and Strategies for Meeting Evolving Market and Environmental Challenges, Hydrocarbon Publishing Company, an updated and expanded study of the 2006 report titled Opportunity Crudes: Technical Challenges and Economic Benefits. Ovalles, C. et al. Characterization and Preparative Separation of Heavy Crude Oils, their fractions and thermally Cracked Products by the Asphaltene solubility Fractions Method, Prepr. Pap.-Am. Chem. Soc. Div. Pet. Chem. 2011, 56(1), 8
• each of the viscosity reduction devices as herein disclosed and described, ii) the related methods disclosed and described, iii) similar, equivalent, and even implicit variations of each of these devices and methods, iv) those alternative designs which accomplish each of the functions shown as are disclosed and described, v) those alternative designs and methods which accomplish each of the functions shown as are implicit to accomplish that which is disclosed and described, vi) each feature, component, and step shown as separate and independent inventions, vii) the applications enhanced by the various systems or components disclosed, viii) the resulting products produced by such systems or components, ix) each system, method, and element shown or described as now applied to any specific field or devices mentioned, x) methods and apparatuses substantially as described hereinbefore and with reference to any of the accompanying examples, xi) an apparatus for performing the methods described herein comprising means for performing the steps, xii) the various combinations and permutations of each of
• any claims set forth at any time are hereby incorporated by reference as part of this description of the invention, and the applicant expressly reserves the right to use all of or a portion of such incorporated content of such claims as additional description to support any of or all of the claims or any element or component thereof, and the applicant further expressly reserves the right to move any portion of or all of the incorporated content of such claims or any element or component thereof from the description into the claims or vice-versa as necessary to define the matter for which protection is sought by this application or by any subsequent continuation, division, or continuation-in-part application thereof, or to obtain any benefit of, reduction in fees pursuant to, or to comply with the patent laws, rules, or regulations of any country or treaty, and such content incorporated by reference shall survive during the entire pendency of this application including any subsequent continuation, division, or continuation-in- part application thereof or any reissue or extension thereon.

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• 2012
  • 2012-01-13 CA CA2829291A patent/CA2829291A1/en not_active Abandoned
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  • 2012-01-13 EP EP12754614.1A patent/EP2683795A4/de not_active Withdrawn
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