CA2977686A1 - Method and apparatus for refining hydrocarbons with electromagnetic energy - Google Patents
Method and apparatus for refining hydrocarbons with electromagnetic energy Download PDFInfo
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- CA2977686A1 CA2977686A1 CA2977686A CA2977686A CA2977686A1 CA 2977686 A1 CA2977686 A1 CA 2977686A1 CA 2977686 A CA2977686 A CA 2977686A CA 2977686 A CA2977686 A CA 2977686A CA 2977686 A1 CA2977686 A1 CA 2977686A1
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 544
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 541
- 238000000034 method Methods 0.000 title claims abstract description 136
- 238000007670 refining Methods 0.000 title claims abstract description 27
- 239000010426 asphalt Substances 0.000 claims abstract description 150
- 238000011084 recovery Methods 0.000 claims abstract description 126
- 230000008016 vaporization Effects 0.000 claims abstract description 114
- 238000009834 vaporization Methods 0.000 claims abstract description 95
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 238000009833 condensation Methods 0.000 claims description 36
- 230000005494 condensation Effects 0.000 claims description 36
- 238000009835 boiling Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000005484 gravity Effects 0.000 claims description 12
- 238000004891 communication Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims 2
- 230000004888 barrier function Effects 0.000 claims 1
- 238000002309 gasification Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 description 30
- 239000013067 intermediate product Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 16
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 239000008186 active pharmaceutical agent Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 9
- 101100532656 Rattus norvegicus Sec31a gene Proteins 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- 239000010779 crude oil Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 230000005670 electromagnetic radiation Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000010432 diamond Substances 0.000 description 5
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- -1 heavy oil or bitumen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 230000005855 radiation Effects 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
-
- 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
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/308—Gravity, density, e.g. API
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
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
BACKGROUND
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.
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.
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
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.
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.
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.
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.
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.
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.
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.
BRIEF DESCRIPTION OF THE DRAWINGS
DETAILED DESCRIPTION
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.
exposure zone 16 and a recovery zone 18. The EM exposure zone 16 is below the recovery zone 18.
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.
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.
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.
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.
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.
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).
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.
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.
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.
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.
exposure zone plate 372 and a recovery zone plate 374. The recovery zone 318 is defined above the recovery zone plate 374.
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.
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.
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.
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.
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.
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.
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.
energy, and vaporization of the selected hydrocarbons, at or below EM exposure
[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) Butane -1 Pentane 36 Hexane 69 Heptane 98 Octane 125 Nonane 151 Decane 174 Undecane 196 Dodecane 216 Tridecane 235 n-Hydrocarbon Normal Vaporization Temperature ( C) Tetradecane 254 Pentadecane 270
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.
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. Without 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.
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.
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.
Costs may be reduced since there is no need to add diluent or otherwise treat the hydrocarbons to meet pipeline requirements.
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.
energy applied.
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.
The feedstock hydrocarbons may also include byproducts of other processes, such as coke, asphalt, bunker oil, or pyrolysis bunker oil.
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.
and recovery of the selected hydrocarbons increased.
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").
Table 2: Observations during Example 1 Time Observation Temperature ( C) (hr) Bit Vap1 Vap2 R1 R2 R3 0.0 Microwave power exposure 15 17 17 17 17 18 begins at 1 kw and ramps upward 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 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 11.25 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
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. 11).
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.
Table 3: Summary of Population Distributions in Fig. 11 Chain Lengths 480 482 484 486 C4-C14 99% 99% 99% 99%
C6-C10 91% 91% 94% 88%
C7-C8 70% 71% 74% 63%
C8-C14 45% 44% 41% 71%
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.
see Fig. 11).
energy does not result in vaporization of the selected hydrocarbons.
[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.
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.
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.
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.
Table 4: Observations during Example 5 Time Temperature ( C) Observation (hr) Bit Vap1 Vap2 R1 R2 R3 0.0 Microwave power exposure 19 19 19 16 15 16 begins at 1 kw and ramps upward 4.0 Recovery of selected 65 64 61 46 38 38 hydrocarbons by condensation begins 6.0 Significant recovery of selected 79 74 69 59 56 hydrocarbons by condensation at all recovery ports 10.5 Prior to Microwave power being 121 97 86 48 40 deactivated Time Temperature ( C) Observation (hr) Bit Vap1 Vap2 R1 R2 R3 10.6 Microwave power deactivated 120 96 85 48 40 41
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.
No vacuum was applied to the test-scale vessel during the experiment of Example 1.
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.
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.
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.
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.
Claims (84)
treating feedstock hydrocarbons with electromagnetic (EM) energy at a first EM
exposure temperature for vaporizing selected hydrocarbons at a first vaporization temperature;
wherein the first vaporization temperature is equal to or lower than the first EM
exposure temperature; and the first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the selected hydrocarbons.
recovering the higher viscosity product comprises transporting the higher viscosity hydrocarbon product from a first location to a second location; and treating the feedstock hydrocarbons with the EM energy takes place at the first location.
wherein the second vaporization temperature is equal to or lower than the second EM
exposure temperature; and the second vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the additional selected hydrocarbons.
treating the higher viscosity hydrocarbon product with additional EM energy at a second EM exposure temperature for vaporizing additional selected hydrocarbons at a second vaporization temperature;
wherein the second vaporization temperature is equal to or lower than the second EM
exposure temperature; and the second vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the additional selected hydrocarbons.
energy.
vaporizing the selected hydrocarbons takes place in an EM exposure zone;
recovering the selected hydrocarbons takes place in a recovery zone; and the EM exposure zone is separated from the recovery zone by a gas permeable, EM
energy impermeable barrier.
recovering the selected hydrocarbons comprises condensing the selected hydrocarbons in the recovery zone at a first condensation temperature; and the first condensation temperature is lower than the first vaporization temperature.
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 being 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.
exposure zone.
exposure zone.
the first shield comprises a plate with a plurality of apertures;
the plate comprises a conductive material; and a diameter of each of the apertures is smaller than the wavelength of the EM
energy.
a second shield positioned in the body between the first shield and the recovery zone for defining a secondary EM exposure zone between the first shield and the second shield;
and a secondary EM energy source in communication with the secondary EM exposure zone for providing additional EM energy to the secondary EM exposure zone for exposing the selected hydrocarbons to the additional EM energy in the secondary EM
exposure zone;
wherein the second shield is gas permeable and EM energy impermeable for allowing the selected hydrocarbons to flow from the secondary EM exposure zone to the recovery zone and for maintaining the additional EM energy in the secondary EM exposure zone.
a second shield positioned in the body for defining the recovery zone between the first shield and the second shield;
a third shield positioned in the body for defining a secondary EM exposure zone between the second shield and the third shield;
a secondary EM energy source in communication with the secondary EM exposure zone for providing additional EM energy to the secondary EM exposure zone for exposing selected hydrocarbons in the secondary EM exposure zone to the additional EM
energy in the secondary EM exposure zone; and a secondary recovery zone defined across the third shield from the secondary EM
exposure zone;
wherein the second shield is gas permeable and EM energy impermeable for allowing the selected hydrocarbons to flow from the recovery zone to the secondary EM
exposure zone and for maintaining the additional EM energy in the secondary EM exposure zone; and the third shield is gas permeable and EM energy impermeable for allowing the selected hydrocarbons to flow from the secondary EM exposure zone to the secondary recovery zone and for maintaining the additional EM energy in the secondary EM
exposure zone.
providing feedstock hydrocarbons having an API gravity of about 24° or lower;
at a first location, treating the feedstock hydrocarbons with electromagnetic (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;
wherein the first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the first selected hydrocarbons; and the first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the selected hydrocarbons.
exposure temperature for vaporizing additional selected hydrocarbons at a second vaporization temperature;
wherein the second vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the additional selected hydrocarbons;
and the first vaporization temperature is lower than a reference vaporization temperature of at least one hydrocarbon species of the selected hydrocarbons.
about 3% or less of hydrocarbons having chain lengths of C12; about 2% or less of hydrocarbons having chain lengths of C12; about 10% or less of hydrocarbons having chain lengths of C16 or less; about 8% or less of hydrocarbons having chain lengths of C16 or less;
about 6% or less of hydrocarbons having chain lengths of C16 or less; about 20% or less of hydrocarbons having chain lengths of C22 or less; about 18% or less of hydrocarbons having chain lengths of C22 or less; about 36% or less of hydrocarbons having chain lengths of C30 or less; about 32% or less of hydrocarbons having chain lengths of C30 or less; or about 50%
or less of hydrocarbons having chain lengths of C45 or less.
about 7% or less of hydrocarbons having chain lengths of C12 or less, as compared to the feedstock bitumen; about 7% or less of hydrocarbons having chain lengths of C16 or less, as compared to the feedstock bitumen; or about 7% or less of hydrocarbons having chain lengths of C22 or less, as compared to the feedstock bitumen.
and about 1.0 % of hydrocarbons having a chain length of C9 to C12; between about 1.0 % and about 2.0 % of hydrocarbons having a chain length of C13 to C22; between about 1.0 % and about 2.0 % of hydrocarbons having a chain length of C13 to C30; between about 1.0 % and about 2.0 % of hydrocarbons having a chain length of C13 to C45; between about 0.2 and 0.9 % per carbon chain length species of hydrocarbons of C46 or greater.
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US11214740B2 (en) | 2017-03-14 | 2022-01-04 | Solideum Holdings Inc. | Endogenous asphaltenic encapsulation of bituminous materials with recovery of light ends |
CN110485959B (en) * | 2019-08-21 | 2021-08-31 | 中国地质调查局油气资源调查中心 | Shale oil gas microwave resonance impact synergistic yield increase technical method |
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US5055180A (en) * | 1984-04-20 | 1991-10-08 | Electromagnetic Energy Corporation | Method and apparatus for recovering fractions from hydrocarbon materials, facilitating the removal and cleansing of hydrocarbon fluids, insulating storage vessels, and cleansing storage vessels and pipelines |
US5181998A (en) * | 1989-12-27 | 1993-01-26 | Exxon Research And Engineering Company | Upgrading of low value hydrocarbons using a hydrogen donor and microwave radiation |
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