WITH ELECTROMAGNETIC ENERGY

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent

Application No. 62/120,670 filed February 25, 2015, which is hereby incorporated by reference.

FIELD

[0002] The present disclosure relates generally to refining of hydrocarbons. More particularly, the present disclosure relates to refining of hydrocarbons by exposure to electromagnetic energy.

BACKGROUND

[0003] Hydrocarbons, including heavy crude oil and bitumen, have previously been upgraded by exposure to microwaves as described in, for example, Mohammed et al., "Upgrading Heavy Crude Oil Potentials through Microwave Assisted Distillation", (201 1), Journal of Innovative Research in Engineering and Science 2(3), 137, and Britten et al., "Heavy petroleum upgrading by microwave irradiation", (2005), WIT Transactions on Modelling and Simulation, 41 , 103.

[0004] United States Patent No. 8,431 ,015 to Banerjee et al. describes applying microwaves to hydrocarbons, such as heavy oil or bitumen, recovered from underground reservoirs. The microwaves heat the hydrocarbons to temperatures of between 250°C and 450°C to upgrade the hydrocarbons by cracking. This process lowers the viscosity of the hydrocarbons for transportation in a pipeline to offsite locations, such as a refinery.

[0005] Banerjee et al. adds a microwave energy absorbing substance to the hydrocarbons before applying the microwaves. The energy absorbing substance may include halides of Na, Al, Fe, Ni, and Zn, particulate carbon graphite particles, metal particles, or semiconductor materials. Banerjee et al. states that utilizing the microwave energy absorbing substance to absorb microwave energy and transfer heat to the hydrocarbons through conduction makes attaining the desired temperatures feasible. [0006] United States Publication No. 201 1/0094738 to Safinya describes use of an upgrader which applies microwave radiation to reduce the viscosity of and increase the API gravity of crude oil. Hydrocarbons, such as crude oil or heavy oil, are transported on a perforated belt and microwave radiation from antennas at least partially upgrades heavy oil into upgraded oil, such as medium-gravity oil and/or light-gravity oil. Safinya also uses an upgrader with an upstream reboiler to heat the oil to between 250°C and 500°C prior to irradiation. Safinya adds an electron activator to the oil prior to heating it for faster, more efficient absorption of microwaves, resulting in more efficient cracking of the oil.

[0007] United States Publication No. 201 1/0294223 to Safinya et al. describes a reaction vessel used for characterizing parameters useful for designing and executing production and upgrading plans for hydrocarbons. Samples of hydrocarbons are placed in the vessel and electromagnetic radiation is used to provide rapid, even, and tunable heating to the hydrocarbons. An electromagnetic radiation attenuating material is included either as part of the vessel or dispersed within the hydrocarbons. The electromagnetic radiation is absorbed by the electromagnetic radiation attenuating material, resulting in an increase in heat of the electromagnetic radiation attenuating material. The increase in heat is passed on to the hydrocarbons and the hydrocarbons are recovered as gases which are analyzed to determine the makeup of the gases. This data, among other data, facilitates planning and execution of production and upgrading of hydrocarbons.

[0008] The prior art carries out upgrading of hydrocarbons at high temperatures and generally uses an electromagnetic radiation absorbing material to reach these temperatures. The prior processes reduce the viscosity of the hydrocarbons. There is therefore a need for a system and apparatus to treat hydrocarbons at lower temperatures and for producing hydrocarbons with a higher viscosity than the feedstock.

SUMMARY

[0009] It is an object of the present disclosure to obviate or mitigate at least one disadvantage of previous methods of refining hydrocarbons by exposure to electromagnetic (EM) energy.

[0010] Herein disclosed are methods of refining hydrocarbons where feedstock hydrocarbons are exposed to EM energy, resulting in vaporization of selected hydrocarbons. Exposure to the EM energy occurs at temperatures, for example about 250°C or lower, below a reference vaporization temperature of at least some of the vaporized selected hydrocarbons. The feedstock hydrocarbons are exposed to the EM energy without the need for any added catalyst, significant water content, or other EM energy absorbing material. Refining of the hydrocarbons by the EM energy may be carried out to an intermediate stage or a complete stage by applying the EM energy for a longer period of time, at a greater EM power, or both. The EM energy may be microwave energy.

[0011] The methods may be applied to a variety of feedstock hydrocarbons. The feedstock hydrocarbons may include hydrocarbons having an API of 24° or lower such as heavy oil or bitumen. The feedstock hydrocarbons may also include lighter hydrocarbons including crude oil. The feedstock hydrocarbons may also include byproducts of other processes, such as coke, asphalt, bunker oil, or pyrolysis bunker oil.

[0012] Refining the feedstock hydrocarbons may result in separation of the selected hydrocarbons from a secondary product. The selected hydrocarbons may include light and medium carbon chain lengths, such as about C6 to about C30.

[0013] Refining heavier feedstock hydrocarbons to an intermediate stage may result in a secondary product including an intermediate hydrocarbon product having a higher viscosity than the hydrocarbon feedstock. The higher viscosity intermediate product has an increased viscosity compared with the feedstock hydrocarbons. The higher viscosity intermediate product may be solid or substantially solid at room temperature. The higher viscosity intermediate product may be hardened bitumen which is essentially solid at 20°C. The higher viscosity intermediate product may also be refined to obtain asphalt as a byproduct.

[0014] Refining to a complete or substantially complete stage results in recovery of the selected hydrocarbons and a secondary product which includes a residual product. The residual product includes a high proportion of carbon, such as 90% or greater.

[0015] The methods may be applied in a vessel. The vessel may be divided into an

EM exposure zone and a recovery zone above the EM exposure zone. The vessel may include a shield positioned between the EM exposure zone and the recovery zone. EM energy is provided to the EM exposure zone. The shield may be gas-permeable and EM energy-impermeable to contain the EM energy in the EM exposure zone and allow the selected hydrocarbons to flow as gases into the recovery zone. The recovery zone facilitates condensation and recovery of the selected hydrocarbons. [0016] The methods disclosed herein facilitate refining hydrocarbons comprising the steps of treating feedstock hydrocarbons at an EM exposure temperature with EM energy to produce selected hydrocarbons. At least a portion of the selected hydrocarbons may be vaporized at a vaporization temperature below a reference vaporization temperature of at least one hydrocarbon species present in the selected hydrocarbons. The reference vaporization temperature would be the normal vaporization temperature at 760 mmHg, the standard vaporization temperature at 1 bar (750.06 mmHg), or the otherwise calculated vaporization temperature in view of the pressure during vaporization by exposure to the EM energy. Vaporizing separates the selected hydrocarbons from the feedstock hydrocarbons and any secondary product. The selected hydrocarbons may be recovered, for example by condensing the selected hydrocarbons.

[0017] In some aspects, the present disclosure describes a method and apparatus for refining hydrocarbons. The method includes treating feedstock hydrocarbons at a low temperature with EM energy for vaporizing selected hydrocarbons. The selected

hydrocarbons are vaporized at temperatures below reference vaporization temperatures of at least a portion of the species included within the selected hydrocarbons. The vaporized hydrocarbons may be condensed from the vapour phase for recovery. A remaining secondary product may include a higher viscosity hydrocarbon product with a greater viscosity than the feedstock hydrocarbons, such as a hardened bitumen that is substantially solid at ambient temperature.

[0018] In some aspects, the present disclosure describes a method of refining hydrocarbons including: treating feedstock hydrocarbons with EM energy at a first EM exposure temperature for vaporizing selected hydrocarbons at a first vaporization temperature. The first vaporization temperature is equal to or lower than the first EM exposure temperature. The first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the selected hydrocarbons.

[0019] In some aspects, the present disclosure describes a vessel for treating feedstock hydrocarbons with EM energy, the vessel including: a body; an EM exposure zone defined within the body for receiving the hydrocarbons; an EM energy source in

communication with the EM exposure zone for providing the EM energy to the EM exposure zone for exposing the feedstock hydrocarbons to the EM energy to vaporize selected hydrocarbons; a recovery zone in communication with the EM exposure zone for receiving the selected hydrocarbons from the EM exposure zone; and a first shield positioned within the body between the EM exposure zone and the recovery zone. The first shield is gas- permeable and EM energy-impermeable for allowing the selected hydrocarbons to flow from the EM exposure zone to the recovery zone and for maintaining the EM energy in the EM exposure zone.

[0020] In some aspects, the present disclosure describes a method of transporting hydrocarbons comprising: providing feedstock hydrocarbons having an API gravity of about 24° or lower; at a first location, treating the feedstock hydrocarbons with EM energy at a first EM exposure temperature for vaporizing first selected hydrocarbons at a first vaporization temperature and resulting in a higher viscosity hydrocarbon product having a greater viscosity than the feedstock hydrocarbons and substantially maintaining its shape at 20 °C; and transporting the higher viscosity hydrocarbon product from the first location to a second location. The first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the first selected hydrocarbons. The first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the selected hydrocarbons.

[0021] In some aspects, the present disclosure describes a hardened hydrocarbon product prepared from a feedstock bitumen or heavy oil by exposure of feedstock bitumen or heavy oil to EM energy, the hardened hydrocarbon product substantially maintaining its shape at 20 °C. The hardened hydrocarbon product may have a kinematic viscosity of about 5,000,000,000 cSt at 20 °C and may have an initial boiling temperature corresponding to a temperature of at least 250°C for 5% mass recovery as determined by high temperature simulated distillation.

[0022] Other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached figures, in which features sharing reference numerals with the final two digits in common correspond to similar features across multiple figures (e.g. the waveguide 20, 120, 220, 320, 420, etc.). [0024] Fig. 1 is a partial cutaway perspective view of vessel for exposing hydrocarbons to electromagnetic energy (EM energy);

[0025] Fig. 2 is a cross-sectional elevation view of the vessel of Fig. 1 ;

[0026] Fig. 3 is a cross-sectional elevation view of the vessel of Fig. 1 in operation;

[0027] Fig. 4 is a cross-sectional perspective view of a further vessel for exposing hydrocarbons to EM energy;

[0028] Fig. 5 is a cross-sectional elevation view of a further vessel for exposing hydrocarbons to EM energy;

[0029] Fig. 6 is a cross-sectional elevation view of a further vessel for exposing hydrocarbons to EM energy;

[0030] Fig. 7 is a schematic of a method of transporting a high-viscosity intermediate product;

[0031] Fig. 8 is a schematic of a method of transporting a high-viscosity intermediate product for further refinement;

[0032] Fig. 9 is a schematic of a test-scale vessel;

[0033] Fig. 10 is a graph of temperature in a liquid bitumen sample during the course of an example application of a method disclosed herein;

[0034] Fig. 1 1 is a graph of carbon chain length population distributions in selected hydrocarbons recovered during the example application of Fig. 10;

[0035] Fig. 12 is a graph of carbon chain length population distributions in feedstock bitumen and hardened bitumen in the example application of Fig. 10;

[0036] Fig. 13 is high temperature distillation data from hardened bitumen resulting from an example application of a method disclosed herein;

[0037] Fig. 14 is a graph of the carbon chain length population distribution of light hydrocarbons recovered during an example application of a method disclosed herein;

[0038] Fig. 15 is a graph of temperatures in a vessel during the course of an example application of a method disclosed herein;

[0039] Fig. 16 is a graph of the carbon chain length population distributions in light hydrocarbons recovered and other data acquired during the example application of Fig. 15;

[0040] Fig. 17 is a graph of carbon chain length population distributions in feedstock bitumen, recovered selected hydrocarbons, and hardened bitumen from the example application of Fig. 15; [0041] Fig. 18 is a graph of carbon chain length population distributions in feedstock bitumen, recovered selected hydrocarbons, and hardened bitumen from the example application of Fig. 15;

[0042] Fig. 19 is a graph of carbon chain length population distributions in feedstock bitumen, recovered selected hydrocarbons, and hardened bitumen from the example application of Fig. 15;

[0043] Fig. 20 is a graph of carbon chain length population distributions in feedstock bitumen and hardened bitumen from the example application of Fig. 15;

[0044] Fig. 21 is a graph of carbon chain length population distributions in feedstock bitumen and hardened bitumen from the example application of Fig. 15; and

[0045] Fig. 22 is high temperature distillation data from hardened bitumen resulting from the example application of Fig. 15.

DETAILED DESCRIPTION

[0046] Generally, the present disclosure provides methods and apparatuses for refining hydrocarbons using electromagnetic energy (EM energy).

[0047] The methods may be used to refine produced hydrocarbons, and may be used for example with crude oil. The hydrocarbons may have an API gravity of 24° or less, such as heavy oil or bitumen. The methods may also be applied to hydrocarbons with diluent added, such as Western Canadian Select. The methods may also be applied to byproducts of other processes, such as coke, asphalt, bunker oil, or pyrolysis bunker oil.

[0048] In the methods disclosed herein, feedstock hydrocarbons are exposed to EM energy. The EM energy may be any high frequency EM energy, such as radio waves from about 3 kHz to about 3000 GHz. The EM energy may be radio waves having a frequency from 3 kHz to 300 MHz. The EM energy may be high to ultra high frequency radio waves having frequencies in the range of about 8 kHz to about 300 MHz. The EM energy may be microwaves, which may have frequencies in the range of about 300 MHz to about 300 GHz. Commonly used commercial and industrial microwave frequencies are 915 MHz and 2,450 MHz.

[0049] The methods disclose herein may be carried out inside a vessel.

[0050] Figs. 1 to 3 show a vessel 10. The vessel 10 includes a body 12. A plate 14 extends across a cavity defined within the body 12, separating the cavity into an EM exposure zone 16 and a recovery zone 18. The EM exposure zone 16 is below the recovery zone 18.

[0051] The vessel 10 includes a waveguide 20. The waveguide 20 extends into the

EM exposure zone 16 for providing EM energy into the EM exposure zone 16. In the embodiment shown in Figs. 1 to 3, the waveguide 20 extends into the reaction 16, passing through the recovery zone 18 and the plate 14. However, the waveguide does not need to be positioned above the recovery zone as shown in these figures. Other configurations are shown in Figs. 4 and 5 and other configurations will be known to a person skilled in this field. The waveguide 20 includes a window 22. The window 22 functions as an EM energy permeable gas impermeable shield at a portion of the waveguide 20 within the EM exposure zone 16 for providing the EM energy into the EM exposure zone 16 but preventing potentially combustible gases (e.g. gaseous selected hydrocarbons, etc.) from flowing into the waveguide 20. The window 22 may be made from any suitable material, such as glass, which allows passage of EM energy and which blocks gases. An EM energy source 24 is connected to the waveguide 20 for providing the EM energy to the waveguide 20.

[0052] The plate 14 includes apertures 15 for allowing flow of fluids across the plate

14 (e.g. gaseous selected hydrocarbons, etc.). Figure 1 shows only exemplary apertures on one side of the plate 14 but generally the plate will include multiple apertures positioned throughout. The plate 14 functions as a gas permeable, EM energy impermeable shield. Confining the EM energy to the EM exposure zone 16 facilitates increased efficiency in exposure of hydrocarbons to the EM energy and mitigates the risk that gaseous selected hydrocarbons will be ignited in the recovery zone 18. As shown in the figures, the plate 14 includes metals or other conductive materials which will prevent passage of the EM energy into the recovery zone 18 and confine the EM energy to the EM exposure zone 16. The apertures 15 may be smaller than the wavelength of the EM energy being used in the vessel 10.

[0053] A lower outlet 26 and an upper outlet 28 are both positioned in the body 12 in the recovery zone 18 and may be connected to a collection vessel (not shown) to recover selected hydrocarbons by condensation after the selected hydrocarbons are vaporized in the EM exposure zone 16. The number and location of outlets is determined by the properties of the selected hydrocarbons to be recovered from the feedstock. The vessel may include one outlet, two outlets as shown in the figures, or more than two outlets. A lower cooling coil 27 and an upper cooling coil 29 are shown in Figs. 2 and 3 but are not required. The cooling coils 27, 29 facilitate condensation and recovery of the selected hydrocarbons at the lower outlet 26 and the upper outlet 28, respectively. The outlets 26, 28 and cooling coils 27, 29 facilitate condensing and recovering the selected hydrocarbons in the recovery zone 18.

[0054] The feedstock hydrocarbons may contain other components or contaminants such as sulfur. The vessel 10 may also collect these contaminants. For example, the vessel may include copper or other catalysts to capture sulfur (not shown).

[0055] An injection port may be included to selectively provide motive flow to vaporized selected hydrocarbons in the EM exposure zone 16, for example non-condensible gases may be injected into the vessel 10 to urge vaporized selected hydrocarbons to cross the plate 14 into the recovery zone 18. Injection of non-condensible gases to provide motive flow may for example be used with alternative vessel designs in which the recovery zone is offset in the body horizontally from the EM exposure zone but not vertically from the EM exposure zone, in which the recovery zone and the EM exposure zone are located in separate vessel bodies, or in which the recovery zone is otherwise not located above the EM exposure zone, and in which normal flow of vapour upwards is not applied for condensation as in the vessel 10.

[0056] Fig. 3 shows the vessel 10 being used to refine feedstock hydrocarbons 40 in the EM exposure zone 16 by exposure to EM energy 42 provided into the EM exposure zone 16 through the waveguide 20. The feedstock hydrocarbons 40 interact with the EM energy 42 in the EM exposure zone 16, resulting in gaseous selected hydrocarbons 44 and a higher viscosity hydrocarbon product 48. The gaseous selected hydrocarbons 44 flow through the plate 14 into the recovery zone 18, and condense as liquid selected hydrocarbons 46 near the lower and upper cooling coils 27, 29. Although the cooling coils 27, 29 are included in the vessel 10, cooling coils are optional and not required. Condensation of the liquid selected hydrocarbons 46 may be facilitated by selecting an appropriate location for the outlets 26, 28 along the body 12 based on the expected reaction conditions and the feedstock

hydrocarbons 40 which are intended to be used. The liquid selected hydrocarbons 46 are recovered through the lower and upper outlets 26, 28. Where the methods are applied to a vessel other than the vessel 10 with additional outlets, the additional outlets would also serve as recovery points for the liquid selected hydrocarbons 46. Once the liquid selected hydrocarbons 46 have been recovered, the higher viscosity hydrocarbon product 48 remains in the bottom of the EM exposure zone 16. The higher viscosity hydrocarbon product 48 is shown at the bottom of EM exposure zone 16, however, during the reaction, the higher viscosity hydrocarbon product 48 may be in liquid form and mixed with any feedstock hydrocarbons 40 remaining in the EM exposure zone 16.

[0057] If the reaction is continued through prolonged exposure to the EM energy 42, additional gaseous selected hydrocarbons 44 will volatize from the higher viscosity hydrocarbon product 48, leaving a carbon residue (not shown). As described above, the carbon residue includes primarily elemental carbon, and may include common minor components such as sulfur (about 1 to 10% by mass) and metals (below about 500 mg/kg).

[0058] Fig. 4 shows an alternate configuration for a vessel 1 10 wherein the waveguide 120 enters the body 1 12 at the EM exposure zone 1 16 directly, rather than passing through the recovery zone and plate as shown in Figs. 1 to 3.

[0059] Fig. 5 shows an alternate configuration for a vessel 210 which includes a secondary waveguide, a secondary EM exposure zone, a secondary recovery zone, and additional plates to function as EM shields. The vessel 210 includes a secondary EM exposure zone waveguide 230 and window 231 in communication with a secondary EM exposure zone 232 defined between a first secondary EM exposure zone plate 234 and a second secondary EM exposure zone plate 236. A secondary recovery zone 237 is defined above the second secondary EM exposure zone plate 236. A secondary recovery zone outlet 238 extends through the body 212 into the secondary recovery zone 237 for providing fluid communication with the secondary recovery zone 237. The secondary recovery zone outlet 238 and a secondary EM exposure zone cooling coil 239 facilitate recovery of additional selected hydrocarbons resulting from exposure of selected hydrocarbons in the secondary EM exposure zone 232 to secondary EM energy from the secondary EM exposure zone waveguide 230.

[0060] The first secondary EM exposure zone plate 234 and second secondary EM exposure zone plate 236 each provide a gas permeable EM energy impermeable shield. The plates 234, 236 each include apertures 235 for allowing flow of fluids across the plates 234, 236. The plates 234, 236 each include metals or other conductive materials which prevent passage of the EM energy from the secondary EM exposure zone waveguide 230 into the recovery zone 218 and confine the EM energy to the secondary EM exposure zone 232. The plates 234, 236 define the secondary EM exposure zone 232 and the secondary recovery zone 237 and confine secondary EM energy from the secondary EM exposure zone waveguide 230 to the secondary EM exposure zone 232. Confinement of the secondary EM energy to the secondary EM exposure zone 232 facilitates increased efficiency in exposure of selected hydrocarbons in the secondary EM exposure zone 232 to the secondary EM energy and mitigates the risk that gaseous selected hydrocarbons will be ignited in the recovery zone 218.

[0061] In operation of the vessel 210, the waveguide 220 provides EM energy to the

EM exposure zone 216 to treat feedstock hydrocarbons in the EM exposure zone 216 (not shown in the vessel 210, but similar to the feedstock hydrocarbons 40 in the EM exposure zone 16 of the vessel 10 shown in Fig. 3). Selected hydrocarbons are vaporized during exposure of the feedstock hydrocarbons to the EM energy in the EM exposure zone 216. The selected hydrocarbons flow upwards and a portion are recondensed and recovered at the outlets 226, 226. Any remaining vaporized selected hydrocarbons flow through the apertures 235 in the first secondary EM exposure zone plate 234 into the secondary EM exposure zone 232. In the secondary EM exposure zone 232, treatment of the selected hydrocarbons with the secondary EM energy results in additional selected hydrocarbons. Without being bound by any theory, the additional selected hydrocarbons are understood to arise from catabolic chemical reactions induced in the selected hydrocarbons by the secondary EM energy. The additional selected hydrocarbons may be condensed in the secondary recovery zone 237 and recovered through the secondary recovery zone outlet 238.

[0062] EM energy may be applied to the secondary EM exposure zone waveguide

230 independently of the waveguide 220 in the first EM exposure zone 216. The waveguide 220 and the secondary EM exposure zone waveguide 230 may be connected to separate EM sources, a single EM source with separate outputs, or a single EM source with one. Correspondingly, a secondary EM source for the secondary waveguide 230 may be the same EM source used for the waveguide 220 or a separate EM source. Regardless of whether the secondary EM source is the same EM source is applied to the waveguide 220, the EM energy provided to the waveguide 220 and the additional EM energy applied to the secondary waveguide 230 may have the same or distinct properties depending on the application. [0063] Fig. 6 shows an alternate configuration for a vessel 310 which includes a secondary waveguide, a secondary EM exposure zone, and an additional plate to function as an EM shield. The secondary EM exposure zone waveguide 330 and window 331 are in communication with a secondary EM exposure zone 370 defined between an EM exposure zone plate 372 and a recovery zone plate 374. The recovery zone 318 is defined above the recovery zone plate 374.

[0064] The EM exposure zone plate 372 and the recovery zone plate 374 each provide a gas permeable EM energy impermeable shield. The plates 372, 374 each include apertures 375 for allowing flow of fluids across the plates 372, 374. The plates 372, 374 each include metals or other conductive materials which prevent passage of the EM energy from the secondary EM exposure zone waveguide 330 into the recovery zone 318 and confine the EM energy to the secondary EM exposure zone 370. The plates 372, 374 define the secondary EM exposure zone 370 and the recovery zone 318 and confine secondary EM energy from the secondary EM exposure zone waveguide 330 to the secondary EM exposure zone 370. Confinement of the secondary EM energy to the secondary EM exposure zone 370 facilitates increased efficiency in exposure of selected hydrocarbons in the secondary EM exposure zone 370 to the secondary EM energy and mitigates the risk that gaseous selected hydrocarbons will be ignited in the recovery zone 318.

[0065] In operation of the vessel 310, the waveguide 320 provides EM energy to the EM exposure zone 316 to treat feedstock hydrocarbons in the EM exposure zone 316 (not shown in the vessel 310, but similar to the feedstock hydrocarbons 40 in the EM exposure zone 16 of the vessel 10 shown in Fig. 3). Selected hydrocarbons are vaporized during exposure of the feedstock hydrocarbons to the EM energy in the EM exposure zone 316. The selected hydrocarbons flow upwards through the apertures 375 into the secondary EM exposure zone 370. In the secondary EM exposure zone 370, treatment of the selected hydrocarbons with the secondary EM energy results in additional selected hydrocarbons. The additional selected hydrocarbons may be condensed in the recovery zone 318 and recovered through the recovery zone outlets 326, 328.

[0066] As with the vessel 210, EM energy may be applied to the secondary EM exposure zone waveguide 330 independently of the waveguide 320 in the first EM exposure zone 316. The waveguide 320 and the secondary EM exposure zone waveguide 330 may be connected to separate EM sources, a single EM source with separate outputs, or a single EM source with one. Correspondingly, a secondary EM source for the secondary waveguide 330 may be the same EM source used for the waveguide 320 or a separate EM source. Regardless of whether the secondary EM source is the same EM source is applied to the waveguide 320, the EM energy provided to the waveguide 320 and the secondary waveguide 330 may have the same or distinct properties depending on the application.

[0067] Additional EM exposure zones, recovery zones, or both, either above or below those shown in Figs. 5 and 6, may be defined in a vessel as desired for any given application by adding the corresponding secondary plate(s), secondary waveguide(s), and secondary recovery port(s). For example, with reference to the vessel 210, an additional EM exposure zone may also be defined between the plate 214 and the lower secondary EM exposure zone plate 234 by introducing an additional waveguide between the plate 214 and the lower secondary EM exposure zone plate 234, providing a total of three EM exposure zones and one recovery zone (not shown). Similarly, designs in which the EM exposure zone(s) and recovery zone(s) are arranged horizontally may be applied, in some cases using non condensible gases to move vaporized selected hydrocarbons between the various zones. In addition, vessels in accordance with the description herein may include EM exposure zone(s) and recovery zone(s) in separate vessels, for example as shown in the schematics of methods of transportation shown in Figs. 7 and 8.

[0068] Exposure of the feedstock hydrocarbons to the EM energy vaporizes mainly light and medium chain hydrocarbons from the feedstock hydrocarbons. The vaporized hydrocarbons rise through the vessel into the recovery zone and are recovered through known means, such as condensation. Depending on the desired products, exposure of the feedstock hydrocarbons to the EM energy may be carried out to refine the feedstock hydrocarbons to an intermediate stage of refinement or a complete stage of refinement.

[0069] The chain length of the hydrocarbons which are vaporized and recovered can be controlled using a number of factors such as the temperature and pressure in the vessel and exposure time of the hydrocarbons to the EM energy. For example, recovery of longer chain hydrocarbons may be facilitated by reducing the exposure time of the vapor phase to the EM energy through a shorter EM exposure zone, applying a vacuum to evacuate the vapor phase more quickly, increasing the temperature of the EM exposure zone, or a combination thereof. Further, recovery of hydrocarbons having selected chain lengths may be facilitated by increasing the exposure time of the vapor phase to the EM energy in the EM exposure zone, recovery and condensation of vapors at different heights in the recovery zone, including additional EM exposure zones and waveguides within the recovery zone, or a combination thereof. Selected hydrocarbons may be further exposed to EM energy, either by retaining the selected hydrocarbons in the EM exposure zone or by treating the selected hydrocarbons in a secondary EM exposure zone, resulting in secondary selected

hydrocarbons with shorter chain lengths. For example, if the selected hydrocarbons include a large proportion of hydrocarbons having C20 carbon chain length or longer, these selected hydrocarbons may be further processed, either by retaining them in the EM exposure zone or by treating them in a secondary EM exposure zone, resulting in secondary selected hydrocarbons having shorter carbon chain lengths, such as C7 and C8 chain length fractions.

[0070] The selected hydrocarbons are generally more valuable hydrocarbons that can be sold at higher prices than the feedstock hydrocarbons. For example, the selected hydrocarbons may include light hydrocarbons having chain lengths from C2 to C30, from C4 to C22, from C5 to C20, from C6 to C15, or from C7 to C12, or may include at least 50% by volume C7 and C8. The selected hydrocarbons may include for example one or more of gasoline, naphtha, diesel, and kerosene fractions. Although the meaning of light

hydrocarbons as defined in the industry may differ somewhat, as referred to herein light hydrocarbons means hydrocarbons generally having a carbon chain length of about C2 to about C30.

[0071] Exposure to the EM energy results in an increase in temperature of the feedstock hydrocarbons and vaporization of the selected hydrocarbons from the feedstock hydrocarbons. Without being bound by any theory, the selected hydrocarbons are believed include hydrocarbons already present in the feedstock hydrocarbons, hydrocarbons which are the result of chemical reactions induced by the EM energy, or a combination of both.

[0072] An EM exposure temperature is the maximum temperature in any component of the system during vaporization of the selected hydrocarbons. The EM exposure temperature is expected to be observed in a liquid phase of heavier chain hydrocarbons from the feedstock hydrocarbons and any developing liquid phase selected hydrocarbons or secondary products. Vaporization of the selected hydrocarbons may occur at a vaporization temperature at or below the EM exposure temperature. The vaporization temperature for at least some of the selected hydrocarbons may be lower than an expected reference vaporization temperature which would be observed through convection or other heating methods which do not include exposure to the EM energy.

[0073] Once exposure to the EM energy begins, the liquid temperature of the feedstock hydrocarbons increases until a threshold liquid phase temperature is reached. The threshold liquid phase temperature is the liquid phase temperature of the feedstock hydrocarbons at the onset of the selected hydrocarbons being vaporized. A corresponding threshold vapour phase temperature may be observed above the liquid phase feedstock hydrocarbons. As EM energy exposure continues, there may be an increase in both liquid phase and vapour phase temperatures until a plateau temperature or range of temperatures is reached. Plateau temperatures may be identified in each of the liquid and vapour phases and may be at different values at different location within a given system being treated with the EM energy. At the plateau temperatures, vaporization of the selected hydrocarbons may occur at a greater rate than at temperatures below the plateau temperatures. If the feedstock hydrocarbons are pre-heated by convection or other means other than the EM energy to the threshold liquid temperature or the plateau liquid temperature, vaporization of the selected hydrocarbons begins sooner after the onset of the treatment with the EM energy.

[0074] The vaporization temperature at which at least some of the hydrocarbons vaporize may be significantly lower than the a reference temperature at which at least one species from the selected hydrocarbons would be expected to vaporize in conventional methods such as by convection or other heating, and below the conventionally recognized boiling points for these hydrocarbons. For example, where the reaction is carried out at 760 mmHg, the vaporization temperatures may be lower than the normal boiling points of at least some of the selected hydrocarbons. In another example, where the reaction is carried out at 1 bar, the vaporization temperatures may be lower than the standard boiling points of at least some of the selected hydrocarbons. Similarly, where the reaction is carried out under vacuum or under pressure, the vaporization temperatures may be lower than an expected reference vaporization temperature at the pressure of the reaction of at least some of the selected hydrocarbons.

[0075] Previous methods which applied EM energy to hydrocarbons for upgrading required high temperatures, in some cases of 450°C and higher. In contrast, the refining methods described herein may be carried out by exposing the feedstock hydrocarbons to EM energy, and vaporization of the selected hydrocarbons, at or below EM exposure temperatures. The EM exposure temperatures for vaporization of the selected hydrocarbons may be lower than a reference temperature required to vaporize at least one of the selected hydrocarbons in conventional refining methods, or in previous microwave-based upgrading methods. In the present methods, the EM exposure temperatures may be below 250°C, below 200°C, below 150°C, below 100°C, or below 60°C. The feedstock hydrocarbons may be exposed to the EM energy without the need for any added catalyst, significant water content, or other EM energy absorbing material. Since higher temperatures are not required and may be avoided, these added EM energy absorbing materials are not necessary in the present methods.

[0076] In the present methods, the EM exposure temperature may be below the normal vaporization temperatures of at least some of the vaporized selected hydrocarbons are observed both in the liquid-phase feedstock hydrocarbons and in the vapor-phase light hydrocarbons. Table 1 shows normal (i.e. at normal atmospheric pressure of 760 mmHg) vaporization temperatures for linear saturated hydrocarbons having carbon chain lengths from 4 to 15 when using convection or other heating means. These and additional normal boiling points are also illustrated graphically in Fig. 16 alongside data from Example 5.

Table 1

n-Hydrocarbon Normal Vaporization Temperature (°C)

Tetradecane 254

Pentadecane 270

[0077] The temperatures observed in the method of Example 1 are shown in Table 2 and discussed in detail below. Briefly, the highest liquid-phase temperature observed during Example 1 was 106 °C and the highest vapour-phase temperature observed during Example 1 was 74 °C. The observed threshold and plateau liquid phase temperatures and the observed threshold and plateau vapor phase temperatures were below these temperatures of 106 °C and 74 °C. However, Fig. 1 1 and Table 3 show that the majority of the

hydrocarbons recovered by condensation in Example 1 had carbon chain lengths between C4 and C14, and that at least about 40% of the recovered hydrocarbons were of chain lengths from C8 to C14. As shown above in Table 1 , the normal vaporization temperature of n-octane is 125 °C and the normal vaporization temperature of tetradecane is 254 °C. Thus, by exposure of the feedstock hydrocarbons to EM energy, these fractions are vaporized under atmospheric pressure at significantly lower temperatures than would typically be required using convection or other conventional heating methods. When using convection heating under normal conditions, vaporization of carbon chain lengths of C8 (n-octane having a boiling point of 125 °C) or greater would not be expected at the low temperatures at which vaporization of selected hydrocarbons may be achieved with the present methods, such as a maximum EM exposure temperature of 106 °C in Example 1 .

[0078] The temperatures observed in the method of Example 5 are shown in Table 4 and discussed in detail below. Briefly, the EM exposure temperature was the highest liquid- phase temperature observed during Example 5 was 125 °C and the highest vapour-phase temperature observed during Example 5 was 107 °C. The observed threshold and plateau liquid phase temperatures and the observed threshold and plateau vapor phase

temperatures were below these temperatures of 125 °C and 107 °C. However, Figs. 16 to 19 show that the about 85% (w/w) of the hydrocarbons recovered by condensation in Example 5 had carbon chain lengths between C7 and C10, and that about 35% (w/w) of the recovered hydrocarbons were of chain lengths from C9 to C14. As shown above in Table 1 , the normal vaporization temperature of nonane is 151 °C and the normal vaporization temperature of tetradecane is 254 °C. Thus, by exposure of the feedstock hydrocarbons to EM energy, these fractions are vaporized under atmospheric pressure at significantly lower temperatures than would typically be required using convection or other conventional heating methods, since the EM exposure temperature was 125 °C. When using convection heating under normal conditions, vaporization of carbon chain lengths of C9 (n-nonane having a boiling point of 151 °C) or greater would not be expected at the low temperatures seen in the present methods, such as a maximum EM exposure temperature of 125 °C in Example 5.

[0079] As set out above, it has been found by the present inventor that the high temperatures in conventional methods are not necessary to refine feedstock hydrocarbons and obtain the selected recovered hydrocarbons. Previous methods were directed to upgrading the hydrocarbons by thermally cracking long chain hydrocarbon molecules and providing in deasphalted oil. Such previous methods result in a hydrocarbon product having a reduced viscosity, which was advantageous for pipeline transport of the hydrocarbon. In contrast, the present methods refine the hydrocarbons, and any upgrading of the feedstock hydrocarbons which results from the refining procedure is at EM exposure temperatures below the temperatures at which comparable thermal cracking reactions would be expected. When refining a heavier feedstock hydrocarbon such as heavy oil or bitumen, the present methods may produce an intermediate product having a higher viscosity then the feedstock hydrocarbons. The higher viscosity intermediate product produced by the present methods may be transported as a solid product at ambient temperature rather than pipelined. Further, when the present refining methods are carried to completion, the methods are able to extract more hydrocarbons from the feedstock, leaving only a carbon ash residual product, as compared to the prior processes which leave petroleum coke as a waste byproduct. Wthout being bound by any theory, it is thought that the use of the lower temperatures in combination with the EM energy results in the production of the increased viscosity hydrocarbon product and more complete refining of the hydrocarbon product.

[0080] The EM energy is applied to the feedstock hydrocarbons for a period of time selected to result in either the higher viscosity intermediate product or to fully refine the hydrocarbons, leaving the carbon residue in the vessel (in addition to recovering the selected hydrocarbons in either case). The period of time is determined with reference to a number of factors including the power and frequency of the EM energy source, the properties and volume of feedstock hydrocarbons, the properties and volume of the selected hydrocarbons, and the temperature. For example, for a barrel of bitumen at about 20°C, 10 hours of exposure to EM energy at a frequency of 915 MHz may result in recovery of the selected hydrocarbons and the intermediate hardened bitumen product, with a maximum EM exposure temperature of between about 105 °C and 125 °C in the liquid phase of the reaction mixture. The longer time frame is required since the barrel of bitumen begins the process at ambient temperature. If the barrel of bitumen is preheated to about 60 °C, the treatment time frame may be reduced to about 5 hours with some loss of lighter fractions, particularly where pentane diluent is included in the bitumen. If the barrel of bitumen is preheated to about 80 °C, the treatment time frame may be further reduced to about 4 hours. By preheating the barrel of bitumen, less treatment time is required since the barrel will already be closer to the EM exposure temperature and the vaporization temperature once treatment with the EM energy begins.

[0081] Refining heavier feedstock hydrocarbons, such as those having an API gravity of about 24° or lower, to the intermediate stage results in recovery of the selected hydrocarbons described herein and a higher viscosity intermediate hydrocarbon product. The higher viscosity intermediate product has a higher viscosity than the feedstock hydrocarbons. The higher viscosity intermediate product may be hardened or solid at room or ambient temperature (about 20°C). Where the feedstock hydrocarbon is bitumen, the higher viscosity intermediate product may be hardened bitumen which is essentially solid at 20 °C. Reference to hardened or solid is meant to also include substantially hardened or substantially solid. The higher viscosity intermediate hydrocarbon product may maintain its form at room temperature, although it may still be somewhat malleable.

[0082] Previous methods that applied EM energy to hydrocarbons resulted in upgraded hydrocarbons with a lower viscosity and higher API gravity than the starting hydrocarbons, essentially synthetic crude. In contrast to previous methods which applied microwaves, often in combination with microwave absorbing additives, to thermally upgrade and increase the API gravity of hydrocarbons, the methods described herein produce the higher viscosity intermediate product which has a greater viscosity and lower API gravity than the feedstock hydrocarbons.

[0083] Where the higher viscosity intermediate product is in a hardened or solid form, it may be transported as a solid product. This provides an alternative to pipelining the hydrocarbons. Transporting a solid may have less environmental concerns than transporting a liquid hydrocarbon. The hardened or solid intermediate product may be transported in containers designed for solid cargo, such as tractor trailers, train cars, or shipping containers. Costs may be reduced since there is no need to add diluent or otherwise treat the hydrocarbons to meet pipeline requirements.

[0084] Fig. 7 shows a schematic of a method 50 of refining feedstock hydrocarbons

60 and transporting a resulting higher viscosity intermediate product 62 from a first location 51 to a second location 61 . In the method 50, the feedstock hydrocarbons 60 are provided to a first reactor vessel 52 and exposed to EM energy in the first reactor vessel 52, resulting in the higher viscosity intermediate product 62 and vaporization of selected hydrocarbons 64. The selected hydrocarbons 64 may be recovered, for example through condensation in a separate condensing vessel 54 or in the first reactor vessel 52 (for example if using one of the vessels shown in Figs. 1 to 6), and may be stored in a first storage facility 55. The higher viscosity intermediate product 62 is loaded on to a transport 56 (e.g. a rail car, cargo container, etc.). Where the feedstock hydrocarbons 60 include bitumen, the higher viscosity intermediate product 62 may substantially maintain its shape at 20 °C to simplify transport in solid form on the transport 56. The transport 56 may be used to convey the higher viscosity intermediate product 62 to a second location in solid form.

[0085] The intermediate product may also be further refined. It may be refined using conventional methods or may be exposed to additional EM energy as set out above to recover additional selected hydrocarbons, until only a carbon ash residue is left as a byproduct. In contrast, previous refining methods typically result in petroleum coke, asphalt, other residue, or combinations as byproducts. The intermediate product may also be refined to obtain asphalt by varying intensity, duration, wavelength, or other properties of the EM energy applied.

[0086] Refining of the feedstock hydrocarbons to a complete or substantially complete stage results in the selected hydrocarbons described above and a carbon ash residue. When the complete stage is reached, essentially all recoverable hydrocarbons in the feedstock hydrocarbons may be recovered as selected hydrocarbons, leaving the carbon residue. The carbon residue includes primarily elemental carbon, with common minor components including sulfur (about 1 to 10% by mass), and metals (below about 500 mg/kg). The complete stage may be reached by exposure of the feedstock hydrocarbons to the EM energy for a greater period of time, at greater EM energy power, or both, relative to the conditions applied for the intermediate stage.

[0087] This carbon residue is in contrast to the petroleum coke produced as a byproduct of conventional upgrading which consists of heavier hydrocarbons and asphaltenes. The present methods are able to refine those heavier hydrocarbons and asphaltenes into selected hydrocarbons and leave less byproduct.

[0088] Fig. 8 shows a method 150 of refining the feedstock hydrocarbons 160 and transporting the higher viscosity intermediate product 162 from the first vessel 152 at the first location to a second vessel 158 at a second location. In the second vessel 158, the higher viscosity intermediate product 162 may be exposed to EM energy in the second vessel 158, resulting in vaporization of additional selected hydrocarbons 167. The additional selected hydrocarbons 167 may be recovered, for example through condensation in the second vessel 158 or in a separate condensing vessel 157, and may be stored in a second storage facility 159. After vaporization of substantially all of the additional selected hydrocarbons 166, a residual product 168 substantially comprised of carbon ash may remain.

[0089] The methods may be applied to a variety of feedstock hydrocarbons. The feedstock hydrocarbons may include hydrocarbons having an API gravity of 24° or lower such as heavy oil or bitumen. Diluent is often added to bitumen prior to transport by pipeline to a refinery. If the feedstock hydrocarbons are bitumen with diluent or other solvents, the methods may also be used to recover the diluent or solvent. The feedstock hydrocarbons may also include lighter hydrocarbons including crude oil with an API gravity of above 24°. The feedstock hydrocarbons may also include byproducts of other processes, such as coke, asphalt, bunker oil, or pyrolysis bunker oil.

[0090] Example 1

[0091] In one example application of the methods, a one-barrel equivalent sample

(159 liters) of feedstock diluted bitumen was treated with EM energy in a test-scale vessel. The feedstock bitumen was purchased with diluent, some of which had evaporated during storage prior to Example 1 . The feedstock bitumen was placed in a test-scale vessel and exposed to microwaves with a frequency of 915 MHz for about 10.5 hours.

[0092] In summary, during this example application, liquid feedstock diluted bitumen temperatures reached about 100°C during exposure to EM energy. Vapour temperatures of up to between about 25°C and about 75°C were observed, depending on the location in the test-scale vessel. The selected hydrocarbons were recovered by condensation at vapour temperatures of between about 30°C and about 50°C. Onset of collection of the selected hydrocarbons at condensation vapour temperatures of about 30°C began when the feedstock bitumen temperature reached about 60°C. As the feedstock bitumen was further treated with the EM energy, temperatures in the feedstock bitumen increased to about 100°C and recovery of the selected hydrocarbons increased.

[0093] Fig. 9 shows a schematic of the test scale vessel 410 identifying collection zones and associated outlets, and temperature sensors, which are referenced below. The waveguide 420 and other features have been excluded from Fig. 9 for simplicity. The test scale vessel 410 includes the following temperature sensors, which have numeral in the figures and the indicated annotated names in the below Tables 2 and 4:

1) sensor 490 in the EM exposure zone 416 below the resting point of the liquid bitumen in the EM exposure zone 416 ("Bit");

2) sensor 491 in the EM exposure zone 416 above the resting point of the liquid bitumen within the EM exposure zone 416 ("Vap1 ");

3) sensor 492 in the recovery zone 418 below the first outlet 480 ("Vap2");

4) sensor 494 in the recovery zone 418 at the first outlet 480 ("R1 "),

5) sensor 496 in the recovery zone 418 at a second outlet 482 ("R2"), and

6) sensor 498 in the recovery zone 418 at a third outlet 484 ("R3").

[0094] At the top of the vessel 410, a fourth outlet 486 is present without a temperature sensor.

[0095] Table 2 provides a timeline of observations taken at intervals during the method. In Table 2, the temperatures provided are taken from temperature sensors in the test-scale vessel described above with reference to Fig. 9.

Table 2: Observations during Example 1

Time Observation Temperature (°C)

(hr)

Bit Vap1 Vap2 R1 R2 R3

4.5 Recovery of selected 50 44 37 27 21 23 hydrocarbons by condensation

begins at highest recovery port

5.5 Recovery of selected 60 49 41 30 22 22 hydrocarbons by condensation

begins at lowest recovery port

6.0 Microwave power reaches 8 kw 66 52 43 31 22 23

6.75 Continuous recovery of selected 76 56 47 33 26 26 hydrocarbons by condensation at

all recovery ports

8.25 Cooling coils run briefly 94 67 60 50 40 38

8.5 Significant recovery of selected 95 68 60 50 40 37 hydrocarbons by condensation at

all recovery ports

10.5 Prior to Microwave power being 102 74 62 45 31 26 deactivated

10.6 Microwave power deactivated 106 68 59 39 30 30

1 1 .25 All recovery ports closed and (no data)

hardened bitumen remaining in

test vessel left to cool

21 .25 Test vessel opened and hardened (no data)

bitumen recovered from test

vessel

[0096] As indicated above, the test-scale vessel included four recovery ports.

Temperature sensors 494, 496, 498 were located at three of the four ports only (the three data sets reported below at 480, 482, 484). However, selected hydrocarbons were recovered at all four ports 480, 482, 484, and 486, and the selected hydrocarbons from all four ports were analyzed to assess the chain lengths of the selected hydrocarbons (see Fig. 1 1). [0097] With the exception of the temperatures reported at Bit, all temperatures in the above table are vapour temperatures (Vap1 , Vap2, R1 , R2, and R3). The temperatures reported at Bit are measured within the liquid feedstock bitumen and, as the reaction progresses, within liquid-phase hardened bitumen mixed with the feedstock bitumen.

[0098] Fig. 10 is a graph of the Bit temperature readings throughout Example 1 . The maximum observed temperature of the liquid bitumen was 106 °C. The bitumen had a temperature of 60 °C when production of selected hydrocarbons began and when significant recovery of selected hydrocarbons was observed, the liquid bitumen temperature was 95 °C. The highest vapour temperature observed over the liquid bitumen in the EM exposure zone was 74 °C. The lowest vapour temperature at which selected hydrocarbons were condensed and recovered was 26 °C.

[0099] Fig. 1 1 is a graph of the population distribution by volume of carbon chain lengths in the recovered selected hydrocarbons at each of the outlets 480, 482, 484, and 486. About 99% of the recovered carbon chain lengths ranged from C4 to C14, with at least 40% being C8 to C14. The measured volumes shown in Fig. 1 1 can be further summarized as follows for each of outlets :

Table 3: Summary of Population Distributions in Fig. 1 1

[00100] Ports 480, 482, and 484 are the same ports for which temperature data is shown for selected points in time in Table 2. Port 486 is at a higher position on the test-scale vessel than 484. The selected hydrocarbons recovered at each port were predominantly heptanes and octanes. No vacuum was applied to the test-scale vessel during the experiment of Example 1 .

[00101] The most common fractions of selected hydrocarbons recovered at all four ports were C7 and C8. Significant amounts (at least 1 % by volume) of the selected hydrocarbons having chain lengths of each of C9 to C14 were also observed, with amounts of between 2% and 16% by volume for each of C9 and C10. The boiling points of n-heptane and n-octane are 98 °C and 125°C, respectively. The boiling points of n-nonane and n- decane are 151 °C and 175°C, respectively. The boiling points of n-undecane through tetradecane range between 196°C and 254°C. While heptane would boil at the highest observed Bit temperatures, it is unexpected that the gaseous hydrocarbons would include the recovered quantifies of octane, nonane, decane, undecane, dodecane, tridecane, or tetradecane. Convection or other heating to 106°C would not be expected to result in vaporization of C8 or greater chain lengths without application of vacuum or otherwise altering the pressure or other conditions relevant to vaporization.

[00102] Fig. 12 is the population of hydrocarbons by chain length in feedstock bitumen (black squares) and hardened bitumen following exposure to EM energy (white diamonds). The population percentages are assessed by volume. For each of the feedstock bitumen and the hardened bitumen, the solid lines show the percentage present of a given hydrocarbon chain length. The dashed lines show the total percentage of hydrocarbons of a given chain length or shorter. The hardened bitumen had a greater percentage of C18 and longer chain lengths, and a lower percentage of C17 and shorter chain lengths, than the feedstock bitumen.

[00103] The data in Figs. 10 to 12 show that exposure of bitumen or other hydrocarbons to EM energy results in vaporization and recovery of selected hydrocarbons including light hydrocarbons (C14 or below in Example 1 ) from the bitumen at vapour temperatures far below the normal vaporization temperature for hydrocarbons with these chain lengths. The data also shows that the remaining hardened bitumen has an increased population of all fractions beginning with C20, and a decreased population of C19 and all fractions below C19. Recovery of the selected hydrocarbons had an onset temperature in the bitumen of 60°C and 49 °C immediately above the bitumen (time 5.5 hours). The temperature at the first recovery port to produce condensed selected hydrocarbons was 30°C. At peak recovery of the selected hydrocarbons (time 8.5 hours), the temperature in the bitumen was 95 °C, the vapour temperature immediately above the bitumen was 68 °C, and the temperature proximate the recovery ports for the selected hydrocarbons were between 37 and 50°C (time 8.5 hours). These temperatures are far below the boiling points of C14 (n- tetradecane having a boiling point of 254°C) and C8 (n-octane having a boiling point of 125°C), each of which were recovered by condensation (in addition to C9 to C13 fractions; see Fig. 1 1).

[00104] Fig. 10 shows that the feedstock in this sample took about 8 hours to reach 60 °C, at which point the selected hydrocarbons were recovered. However, if the feedstock bitumen is initially heated to about 60 °C with corresponding vapour temperatures from about 20 °C to about 50 °C, recovery of the selected hydrocarbons begins about one hour following exposure to EM energy. However, preheating alone without exposure to the EM energy does not result in vaporization of the selected hydrocarbons.

[00105] At the temperatures observed in the EM exposure zone, which did not exceed 106 °C, no hydrocarbons above C7 to would be expected to be vaporized ad distilled, and yet chain lengths as high as C12 were present in amounts over 1 % in the selected hydrocarbons recovered in Example 1 .

[00106] At the temperatures observed in the recovery zone, it would not be expected that hydrocarbons with unbranched chain lengths as high as those observed would remain gaseous to travel upwards and condense above the shield between the EM exposure zone and the recovery zone. It would be expected that such hydrocarbons would either not pass the shield or would condense directly on top of the shield. However, recovery of carbon chains of C7 to C12 in amounts over 1 % w/w was observed at recovery ports 480 and 482, and recovery of carbon chains of C7 to C10 in amounts over 2 % w/w was observed at all three recovery ports 480, 482, and 484.

[00107] In Example 1 , vaporization of hydrocarbons, and maintenance of the vapor state, were each observed at much lower temperatures for the carbon chain lengths vaporized and recovered than would be expected at atmospheric pressure based on the normal vaporization temperatures shown in Table 1 . Vaporization of the selected

hydrocarbons resulted from a total of about 10 hours of exposure to 915 MHz microwave energy at about 8 kw peak power.

[00108] Example 2

[00109] Fig. 13 shows high temperature simulated distillation ("HTSD") data of hardened bitumen prepared by a second example application of the methods provided herein. The hardened bitumen is shown as a plot of white diamonds. Control groups of

Checham bitumen (black "x"), Albian bitumen (black triangles), and Western Canadian Select bitumen (black horizontal bars) are also included in Fig. 13. A mass recovery of 5% is observed at over 270 °C in the hardened bitumen. A dashed line on the graph shows 270 °C for comparison with the control samples. The control samples showed 5% mass recovery at 38 °C (Western Canadian Select), 41 °C (Albian), and 100 °C (Canadian Select). At 270 °C, the control samples showed between 20 and 30 % of mass recovered. The relatively higher distillation temperatures of early mass recovery in the hardened bitumen compared with the temperatures observed in the three control samples is indicative of the lower population of short chain hydrocarbons in the hardened bitumen compared to the feedstock bitumen.

[00110] Example 3

[00111] Fig. 14 is the population of hydrocarbons by chain length in the recovered selected hydrocarbons from a third example application of the methods. The data in Fig. 14 is analogous to that of Fig. 1 1 but with the population distribution centered on a higher carbon chain length than in Example 1 . The chain lengths of the recovered selected hydrocarbons in Example 3 ranged from C6 to C30, with the most populated fractions being C13 to C18, particularly C16. Compared with Example 1 , the reaction in Example 3 was taken to a stage of refinement where the byproduct is the carbon residue. As described above, the carbon residue observed in Example 3 was primarily elemental carbon, and also included 6.23% by mass sulfur, and below about 500 mg/kg metals.

[00112] Compared with Example 1 , the total time spent in the reaction was greater in Example 3 than in Example 1 . However, the vessel used in Example 3 essentially lacked the recovery zone of the vessel of Example 1 . Rather, vacuum was applied to the vessel immediately above the gas permeable EM energy impermeable shield to draw off any volatile fractions. Wthout being bound by any theory, the longer chain lengths of the selected hydrocarbons in Example 3 may have been due to a shorter residence time in the EM exposure zone of the vessel of Example 3. With a shorter residence time in the EM exposure zone, the feedstock hydrocarbons would have less exposure to the EM energy.

[00113] Example 4

[00114] In a fourth example application of the methods, feedstock bitumen was refined to hardened bitumen. The hardened bitumen had a kinematic viscosity of about

5,000,000,000 cSt at 20°C and about 17,000,000 cSt at 40°C.

[00115] Example 5

[00116] In another example application of the methods, a one-barrel equivalent sample (159 liters) of feedstock diluted bitumen was treated with EM energy in the same test-scale vessel as used in Example 1 . About 2.55% pentane diluent was present in the bitumen. The feedstock bitumen was placed in the test-scale vessel and exposed to microwaves with a frequency of 915 MHz for about 10.5 hours.

[00117] In summary, during this example application, liquid feedstock diluted bitumen temperatures reached a maximum of about 125 °C during exposure to EM energy. Vapour temperatures of up to between about 100 °C and about 105 °C were observed, depending on the location in the test-scale vessel. The selected hydrocarbons were recovered by condensation at vapour temperatures in the range of between about 44°C and about 64°C. Onset of collection of the selected hydrocarbons at condensation vapour temperatures of between 55 and 60 °C began when the feedstock bitumen temperature reached about 75 °C, with similar vapour temperatures immediately above the feedstock bitumen. As the feedstock bitumen was further treated with the EM energy, temperatures in the feedstock bitumen increased to about 125°C and recovery of the selected hydrocarbons increased.

[00118] Table 4 provides a timeline of observations taken at intervals during Example 5. In Table 4, the temperatures provided are taken from temperature sensors in the test- scale vessel. The temperature sensors are positioned as indicated above in respect of Table 2 described in Example 1 .

Table 4: Observations during Example 5

Time Temperature (°C)

Observation

(hr) Bit Vap1 Vap2 R1 R2 R3

10.6 Microwave power deactivated 120 96 85 48 40 41

[00119] As indicated above, the test-scale vessel included four recovery ports.

Temperature sensors 494, 496, 498 were located at three of the four ports only (the three data sets reported below at 480, 482, 484). However, selected hydrocarbons were recovered at all four ports 480, 482, 484, and 486, and the selected hydrocarbons from all four ports were analyzed to assess the chain lengths of the selected hydrocarbons (see Fig. 16). Unlike Example 1 , carbon chain distribution data for Example 5 is a pool of the fractions collected at all four ports 480, 482, 484, and 486.

[00120] With the exception of the temperatures reported at Bit, all temperatures in the above table are vapour temperatures (Vap1 , Vap2, R1 , R2, and R3). The temperatures reported at Bit are measured within the liquid feedstock bitumen and, as the reaction progresses, within liquid-phase hardened bitumen mixed with the feedstock bitumen.

[00121] Fig. 15 is a graph of the (Vap1 , Vap2, R1 , R2, and R3) temperature readings throughout Example 5. The maximum observed temperature of the liquid bitumen was 125 °C. The highest value graphed on Fig. 15 is 121 , but at a higher resolution than Fig. 15, data up to 125 °C was observed. The bitumen had a temperature of about 65 °C when production of selected hydrocarbons began and when significant recovery of selected hydrocarbons was observed, the liquid bitumen temperature was 79 °C. The highest vapour temperature observed over the liquid bitumen in the EM exposure zone was 107 °C at 10.0 hours.

[00122] Fig. 15 shows that the feedstock in this sample took about 3.5 hours to reach 60 °C, at which point the selected hydrocarbons were recovered. As above, preheating the bitumen by convection or other heating may abridge this time.

[00123] Fig. 16 is a graph of the population distribution by volume of carbon chain lengths in the recovered selected hydrocarbons (white circles). The populations for the same carbon lengths are also shown for the feedstock hydrocarbon (black squares) and the hardened bitumen secondary product (white diamonds). The normal boiling points are also shown as a bar graph for each of the carbon lengths on a separate y axis. The maximum temperature observed at any points in the experiment is shown for reference (solid line at 125 °C). The range of the lower condensation temperatures observed (dashed lines between 44 °C and 64 °C).

[00124] About 97% w/w of the recovered carbon chain lengths ranged from C6 to C14, with 35% w/w being C9 to C14, which have boiling points beginning at 151 °C, above the maximum temperature of 125 °C observed in the EM exposure zone. The selected hydrocarbons recovered at each port were predominantly heptane (27 %) and octane (32 %). No vacuum was applied to the test-scale vessel during the experiment of Example 1 .

[00125] The boiling point of n-octane is 98 °C. While octane would boil at the highest observed Bit temperatures, it is unexpected that the gaseous hydrocarbons would include the recovered quantifies of nonane, decane, undecane, dodecane, tridecane, tetradecane, or pentadecane. Convection or other heating to 125 °C would not be expected to result in vaporization of C9 or greater chain lengths without application of vacuum or otherwise altering the pressure or other conditions relevant to vaporization.

[00126] At the temperatures observed in the EM exposure zone, which did not exceed 125 °C, no hydrocarbons above C8 to would be expected to be vaporized ad distilled, and yet chain lengths as high as C14 were present in amounts over 1 % in the selected hydrocarbons recovered in Example 5.

[00127] Figs. 17 to 21 show the w/w% populations of hydrocarbons by chain length in feedstock bitumen (black squares), hardened bitumen following exposure to EM energy (white diamonds), and selected hydrocarbons (white circles). The population percentages are assessed by volume. For each of the feedstock bitumen and the hardened bitumen, the solid lines show the percentage present of a given hydrocarbon chain length. The dashed lines show the total percentage of hydrocarbons of a given chain length or shorter.

[00128] Fig. 22 shows HTSD data of hardened bitumen prepared in Example 5.

HTSD data is shown for feedstock bitumen (black squares), hardened bitumen following exposure to EM energy (white diamonds), and selected hydrocarbons (white circles). A mass recovery of 5% is observed at 259 °C in the hardened bitumen. The feedstock bitumen showed 5% mass recovery at 74 °C and at 253 °C showed 21 % mass recovery. The relatively higher distillation temperatures of early mass recovery in the hardened bitumen compared with the temperatures observed in the feedstock bitumen is indicative of the lower population of short chain hydrocarbons in the hardened bitumen compared to the feedstock bitumen. [00129] The data in Figs. 15 to 22 show that exposure of bitumen or other

hydrocarbons to EM energy results in vaporization and recovery of selected hydrocarbons including light hydrocarbons (C14 or below in Example 1 ) from the bitumen at vapour temperatures far below the normal vaporization temperature for hydrocarbons with these chain lengths.

[00130] The data in Figs. 17 to 21 also shows that the remaining hardened bitumen has an increased population relative to the feedstock hydrocarbons of the all fractions beginning with C13, a decreased population of C8 to C12, and no C7 or lower. Recovery of the selected hydrocarbons had an onset temperature in the bitumen of 65 °C and immediately above the bitumen of 64 °C (time 4.0 hours). At peak recovery of the selected hydrocarbons (time 6.0 hours), the temperature in the bitumen was 79 °C, the vapour temperature immediately above the bitumen was 74 °C, and the temperature above the plate 414 and proximate the recovery ports for the selected hydrocarbons were between 56 and 59 °C (time 6.0 hours). These temperatures are far below the boiling points of C14 (n- tetradecane having a boiling point of 254 °C) and C8 (n-octane having a boiling point of 125 °C), each of which were recovered by condensation (in addition to C9 to C13 fractions). Vaporization of the selected hydrocarbons resulted from a total of about 10.5 hours of exposure to 915 MHz microwave energy at about 5 kw set-point peak power.

[00131] In the preceding description, for purposes of explanation, numerous details are set forth to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that these specific details are not required.

[00132] The above-described embodiments are intended to be examples only.

Alterations, modifications and variations can be effected to the particular embodiments by those of skill in the art. The scope of the claims should not be limited by the particular embodiments set forth herein, but should be construed in a manner consistent with the specification as a whole.