WO2002024835A2 - Products produced from rapid thermal processing of heavy hydrocarbon feedstocks - Google Patents
Products produced from rapid thermal processing of heavy hydrocarbon feedstocks Download PDFInfo
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- WO2002024835A2 WO2002024835A2 PCT/CA2001/001316 CA0101316W WO0224835A2 WO 2002024835 A2 WO2002024835 A2 WO 2002024835A2 CA 0101316 W CA0101316 W CA 0101316W WO 0224835 A2 WO0224835 A2 WO 0224835A2
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- feedstock
- liquid product
- product
- heat carrier
- reactor
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
- C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- 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
-
- 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
Definitions
- the present invention relates to the rapid thermal processing of viscous oil feedstocks. More specifically, this invention relates to the use of pyrolysis in order to upgrade and reduce the viscosity of these oils.
- Heavy oil and bitumen resources are supplementing the decline in the production of conventional light and medium crude oil, and production form these resources is expected to dramatically increase.
- Pipeline expansion is expected to handle the increase in heavy oil production, however, the heavy oil must be treated in order to permit its transport by pipeline.
- Heavy oil and bitumen crudes are either made transportable by the addition of diluents or they are upgraded to synthetic crude.
- diluted crudes or upgraded synthetic crudes are significantly different from conventional crude oils.
- bitumen blends or synthetic crudes are not easily processed in conventional fluid catalytic cracking refineries. Therefore, in either case the refiner must be configured to handle either diluted or upgraded feedstocks.
- feedstocks are also characterized as comprising significant amounts of BS&W (bottom sediment and water). Such feedstocks are not suitable for transportable by pipeline, or upgrading due to the sand, water and corrosive properties of the feedstock.
- feedstocks characterized as having less than 0.5 wt.% BS&W are transportable by pipeline, and those comprising greater amount of BS&W require some degree of processing and treatment to reduce the BS&W content prior to transport.
- processing may include storage to let the water and particulates settle, followed by heat treatment to drive of water and other components.
- these manipulations are expensive and time consuming.
- Heavy oils and bitumens can be upgraded using a range of rapid processes including thermal (e.g. US 4,490,234; US 4,294,686; US 4,161,442), hydrocracking (US 4,252,634) visbreaking (US 4,427,539; US 4,569,753; US 5,413,702) or catalytic cracking (US 5,723,040; US 5,662,868; US 5,296,131; US 4,985,136; US 4,772,378; US 4,668,378, US 4,578,183) procedures.
- thermal e.g. US 4,490,234; US 4,294,686; US 4,161,442
- hydrocracking US 4,252,634
- visbreaking US 4,427,539; US 4,569,753; US 5,413,702
- catalytic cracking US 5,723,040; US 5,662,868; US 5,296,131; US 4,985,136; US 4,772,378; US 4,668,378, US 4,578,183
- FCC fluid catalytic cracking
- many compounds present within the crude feedstocks interfere with these process by depositing on the contact material itself.
- These feedstock contaminants include metals such as vanadium and nickel, coke precursors such as Conradson carbon and asphaltenes, and sulfur, and the deposit of these materials results in the requirement for extensive regeneration of the contact material. This is especially true for contact material employed with FCC processes as efficient cracking and proper temperature control of the process requires contact materials comprising little or no combustible deposit materials or metals that interfere with the catalytic process.
- pretreatment of the feedstock via visbreaking US 5,413,702; US 4,569,753; US 4,427,539), thermal (US 4,252,634; US 4,161,442) or other processes, typically using FCC-like reactors, operating at temperatures below that required for cracking the feedstock (e.g US 4,980,045; US 4,818,373 and US 4,263,128;) have been suggested.
- These systems operate in series with FCC units and function as pre-treaters for FCC.
- These pretreatment processes are designed to remove contaminant materials from the feedstock, and operate under conditions that mitigate any cracking. This ensures that any upgrading and controlled cracking of the feedstock takes place within the FCC reactor under optimal conditions.
- US 4,294,686 discloses a steam distillation process in the presence of hydrogen for the pretreatment of feedstock for FCC processing. This document also indicates that this process may also be used to reduce the viscosity of the feedstock such that the feedstock may be suitable for transport within a pipeline. However, the use of short residence time reactors to produce a transportable feedstock is not disclosed.
- the present invention is directed to the upgrading of heavy hydrocarbon feedstocks, for example but not limited to heavy oil or bitumen feedstocks, that utilizes a short residence pyrolytic reactor operating under conditions that cracks and chemically upgrades the feedstock.
- the feedstock used within this process may comprise significant levels of BS&W and still be effectively processed, thereby increasing the efficiency of feedstock handling.
- the process of the present invention provides for the preparation of a partially upgraded feedstock exhibiting reduced viscosity and increased API gravity.
- the process described herein selectively removes metals, salts, water and nitrogen from the feedstock, while at the same time maximizes the liquid yield, and minimizing coke and gas production.
- this process reduces the viscosity of the feedstock to an extent which can permit pipeline transport of the feedstock without addition of diluents.
- the partially upgraded product optionally permits transport of the feedstock offsite, to locations better equipped to handle refining. Such facilities are typically located at a distance from the point where the crude feedstock is obtained.
- the present invention relates to the rapid thermal processing of viscous oil feedstocks. More specifically, this invention relates to the use of pyrolysis in order to upgrade and reduce the viscosity of these oils.
- a method for upgrading a heavy hydrocarbon feedstock comprising: i) introducing a particulate heat carrier into an upflow reactor; ii) introducing the heavy hydrocarbon feedstock into the upflow reactor at at least one location above that of the particulate heat carrier so that a loading ratio of the particulate heat carrier to feedstock is from about 10:1 to about 200:1; iii) allowing the heavy hydrocarbon feedstock to interact with the heat carrier with a residence time of less than about 1 second, to produce a product stream; iv) separating the product stream from the particulate heat carrier; v) regenerating the particulate heat carrier; and vi) collecting a gaseous and liquid product from the product stream, wherein the liquid product exhibits an increased API gravity, a reduced pour point, reduced viscosity and a reduced level of contaminants over that of said feedstock.
- the loading ratio of the method as outlined above is from about 20 : 1 to about 30:1.
- This invention also includes the method as outlined above wherein the heavy hydrocarbon feedstock is either heavy oil or bitumen. Furthermore, the feedstock is preheated prior to its introduction into the upflow reactor.
- the present invention also relates to the method as defined above, wherein the temperature of the upflow reactor is less than 750 ° C, wherein the residence time is from about 0.5 to about 2 seconds, and wherein the particulate heat carrier is silica sand.
- This invention is also directed to the above method wherein the contaminants, including Conradson carbon (coke), BS&W, nickel and vanadium are removed from the feedstock or deposited onto the heat carrier
- the present invention also includes the method as defined above, wherein said product stream of a first pyrolysis run is separated into a lighter fraction and a heavier fraction, collecting the lighter fraction from the product stream, and recycling the heavier fraction back into the upflow reactor for further processing within a second pyrolysis run to produce a second product stream.
- the further processing includes mixing the heavier fraction with the particulate heat carrier, wherein the temperature of the particulate heat carrier of the second pyrolysis run is at about, or above, that used in the processing of the feedstock within the first pyrolysis run.
- the temperature of the heat carrier within the first pyrolysis run is from about 300 °C to about 590 °C
- the temperature of the second pyrolysis run is from about 530 °C to about 700 °C.
- the residence time of the second pyrolysis run is the same as, or longer than, the residence time of the first pyrolysis run.
- the heavier fraction may be added to unprocessed feedstock prior to being introduced into the upflow reactor for the second pyrolysis run.
- the present invention is also directed to an upgraded heavy oil characterized by the following properties: i) an API gravity from about 13 to about 23; ii) a density from about 0.92 to about 0.98; iii) a viscosity at 40°C (cSt) from about 15 to about 300; and iv) a reduced Vanadium content of about 60 to about 100 ppm; and v) a reduced Nickel content of about 10 to about 50 ppm.
- This invention also embraces an upgraded bitumen characterized by the following properties: i) an API gravity from about 10 to about 21; ii) a density from about 0.93 to about 1.0; iii) a viscosity at 40 °C (cSt) from about 15 to about 300; and iv) a reduced Vanadium content of about 60 to about 100 ppm; and v) a reduced Nickel content of about 10 to about 50 ppm.
- the present invention also pertains to a liquid product characterized in having at least one of the following properties: i) less than 50% of the components evolving at temperatures above 538 °C during simulated distillation; ii) from about 60% to about 95 % of the product evolving below 538° during simulated distillation; iii) from about 1.0% to about 10% of the liquid product evolving below 193 °C during simulated distillation; iv) from about 2% to about 6% of the liquid product evolving between 193-
- the present invention embraces a vacuum gas oil (VGO) characterised with a measured analine point from about 110 °F to about 130 °F, and a calculated analine point from about 125 °F to about 170 °F. Furthermore, the VGO may be further characterized by having a hydrocarbon profile comprising about 38% mono-aromatics.
- VGO vacuum gas oil
- the present invention also pertains to a method for upgrading a heavy hydrocarbon feedstock comprising: i) introducing a particulate heat carrier into an upflow reactor; ii) introducing a feedstock into the upflow reactor at at least one location above that of the particulate heat carrier so that a loading ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from about
- the present invention addresses the need within the art for a rapid upgrading process of a heavy oil or bitumen feedstock involving a partial chemical upgrade or mild cracking of the feedstock.
- This product may, if desired, be transportable for further processing and upgrading.
- the process as described herein also reduces the levels of contaminants within feedstocks, thereby mitigating contamination of catalytic contact materials with components present in heavy oil or bitumen feedstocks.
- the vacuum gas oil fraction (VGO) of the liquid product of the present invention is a suitable feedstock for catalytic cracking purposes, and exhibits a unique hydrocarbon profile, including high levels of reactive compounds including mono-aromatics and thiophene aromatics.
- Mono-aromatics and thiophene aromatics have a plurality of side chains available for cracking, and provide high levels of conversion during catalytic cracking.
- a range of heavy hydrocarbon feedstocks may be processed by the methods as described herein, including feedstocks comprising significant amounts of BS&W.
- Feedstocks comprising significant BS&W content are non-transportable due to their corrosive properties.
- Current practices for the treatment of feedstocks to decrease their BS&W content are time consuming and costly, and still require further processing or partial upgrading prior to transport.
- the methods described herein permit the use of feedstocks having a substantial BS&W component, and produce a liquid product that is partially upgraded and suitable for pipeline or other methods, of transport.
- the present invention therefore provides for earlier processing of feedstocks and reduces associated costs and processing times.
- FIGURE 1 is a schematic drawing of an embodiment of the present invention relating to a system for the pyrolytic processing of feedstocks.
- FIGURE 2 is a schematic drawing of an embodiment of the present invention relating to the feed system for introducing the feedstock to the system for the pyrolytic processing of feedstocks.
- FIGURE 3 is a schematic drawing of an embodiment of the present invention relating to the feed system for introducing feedstock into the second stage of a two stage process using the system for the pyrolytic processing of feedstocks as described herein.
- FIGURE 4 is a schematic drawing of an embodiment of the present invention relating to the recovery system for obtaining feedstock to be either collected from a primary condenser, or recycled to the second stage of a two stage process using the system for the pyrolytic processing of feedstocks as described herein.
- FIGURE 5 is a schematic drawing of an embodiment of the present invention relating to a multi stage system for the pyrolytic processing of feedstocks. DESCRIPTION OF PREFERRED EMBODIMENT
- the present invention relates to the rapid thermal processing of viscous crude oil feedstocks. More specifically, this invention relates to the use of pyrolysis in order to upgrade and reduce the viscosity of these oils.
- feedstock it is generally meant a heavy hydrocarbon feedstock comprising, but not limited to, heavy oil or bitumens.
- feedstock may also include other hydrocarbon compounds such as petroleum crude oil, atmospheric tar bottom products, vacuum tar bottoms, coal oils, residual oils, tar sands, shale oil and asphaltic fractions.
- the feedstock may comprise significant amounts of BS&W (Bottom Sediment and Water), for example, but not limited to, a BS&W content of greater than 0.5% (wt%).
- Feedstock may also include pre-treated (pre-processed) feedstocks as defined below, however, heavy oil and bitumen are the preferred feedstock.
- Bitumens typically comprise a large proportion of complex polynuclear hydrocarbons (asphaltenes) that add to the viscosity of this feedstock and some form of pretreatment of this feedstock is required for transport. Such pretreatment typically includes dilution in solvents prior to transport.
- tar-sand derived feedstocks are pre-processed prior to upgrading, as described herein, in order to concentrate bitumen.
- pre-processing may also involve methods known within the art, including hot or cold water treatments, or solvent extraction that produces a bitumen-gas oil solution.
- These pre-processing treatments typically reduce the sand content of bitumen.
- one such water pre-processing treatment involves the formation of a tar-sand containing bitumen- hot water/NaOH slurry, from which the sand is permitted to settle, and more hot water is added to the floating bitumen to dilute out the base and ensure the removal of sand.
- Cold water processing involves crushing tar-sand in water and floating the bitumen containing tar-sands in fuel oil, then diluting the bitumen with solvent and separating the bitumen from the sand-water residue.
- a more complete description of the cold water process is disclosed in US 4,818,373 (which is incorporated by reference).
- Such pre-processed or pre-treated feedstocks may also be used for further processing as described herein.
- Bitumens may be upgraded using the process of this invention, or other processes such as FCC, visbraking, hydrocracking etc.
- Pre-treatment of tar sand feedstocks may also include hot or cold water treatments, for example, to partially remove the sand component prior to upgrading the feedstock using the process as described herein, or other upgrading processes including FCC, hydrocracking, coking, visbreaking etc. Therefore, it is to be understood that the term "feedstock” also includes pre-treated feedstocks, including, but not limited to those prepared as described above.
- lighter feedstocks may also be processed following the method of the invention as described herein.
- liquid products obtained from a first pyrolytic treatment as described herein may be further processed by the method of this invention (for example composite recycle and multi stage processing; see Figure 5 and Examples 3 and 4) to obtain a liquid product characterized as having reduced viscosity, a reduced metal (especially nickel, vanadium) and water content, and a greater API.
- liquid products obtained from other processes as known in the art for example, but not limited to US 5,662,868; US 4,980,045; US 4,818,373; US 4,569,753; US 4,435,272; US 4,427,538; US 4,427,539; US 4,328,091; US 4,311,580; US 4,243,514; US 4,294,686, may also be used as feedstocks for the process described herein. Therefore, the present invention also contemplates the use of lighter feedstocks including gas oils, vacuum gas oils, topped crudes or pre-processed liquid products, obtained from heavy oils or bitumens.
- lighter feedstocks may be treated using the process of the present invention in order to upgrade these feedstocks for further processing using, for example, but not limited to, FCC, visbreaking, or hydrocracking etc, or for transport and further processing.
- the liquid product arising from the process as described herein may be suitable for transport within a pipeline to permit further processing of the feedstock elsewhere. Typically, further processing occurs at a site distant from where the feedstock is obtained.
- the liquid product produced using the present method may also be directly input into a unit capable of further upgrading the feedstock, such as, but not limited to, FCC, coking, visbreaking, hydrocraking, or pyrolysis etc.
- the pyrolytic reactor of the present invention partially upgrades the feedstock while at the same time acts as a pre-treater of the feedstock for further processing, as disclosed in, for example, but not limited to US 5,662,868; US 4,980,045; US 4,818,373; US 4,569,753; US 4,435,272; US 4,427,538; US 4,427,539; US 4,328,091; US 4,311,580; US 4,243,514; US 4,294,686 (all of which are incorporated by reference herein).
- the feedstocks of the present invention are processed using a fast pyrolysis reactor, such as that disclosed in US 5,792,340 (WO 91/11499; EP 513,051) involving contact times between the heat carrier and feedstock from about 0.01 to about 2 sec.
- a fast pyrolysis reactor such as that disclosed in US 5,792,340 (WO 91/11499; EP 513,051) involving contact times between the heat carrier and feedstock from about 0.01 to about 2 sec.
- Other known riser reactors with short residence times may also be employed, for example, but not limited to US 4,427,539, 4,569,753, 4,818,373, 4,243,514 (which are incorporated by reference).
- the heat carrier used within the pyrolysis reactor exhibits low catalytic activity.
- a heat carrier may be an inert particulate solid, preferably sand, for example silica sand.
- silica sand it is meant a sand comprising greater than about 80% silica, preferably greater than about 95% silica, and more preferably greater than about 99% silica.
- silica sand may include, but are not limited to, from about 0.01% (about 100 ppm) to about 0.04% (400 ppm) iron oxide, preferably about ⁇ .035% (358ppm); about ⁇ .00037% (3.78 ppm) potassium oxide; about 0.00688%) (68.88 ppm) aluminum oxide; about 0.0027 (27.25) magnesium oxide; and about 0.0051% (51.14 ppm) calcium oxide.
- the above composition is an example of a silica sand that can be used as a heat carrier as described herein, however, variations within the proportions of these ingredients within other silica sands may exist and still be suitable for use as a heat carrier.
- Other known inert particulate heat carriers or contact materials for example kaolin clays, rutile, low surface area alumina, oxides of magnesium aluminum and calcium as described in US 4,818,373 or US 4,243,514, may also be used.
- the liquid product produced from the processing of heavy oil is characterized in having the following properties:
- yields of liquid product of at least 60 vol% preferably the yields are greater than about 70 vol%, and more preferably they are greater than about 80%.
- liquid product obtained from processing bitumen feedstock which is not to be considered limiting, is characterized as having:
- the high yields and reduced viscosity of the liquid product produced according to this invention may permit the liquid product to be transported by pipeline to refineries for further processing with the addition of little or no diluents. Furthermore, the liquid products exhibit reduced levels of contaminants (e.g. metals and water), with the content of sulphur and nitrogen slightly reduced. Therefore, the liquid product may also be used as a feedstock, either directly, or following transport, for further processing using, for example, FCC, hydrocracking etc.
- contaminants e.g. metals and water
- liquid products of the present invention may be characterised using Simulated Distillation (SimDist) analysis, as is commonly known in the art, for example but not limited to ASTM D 5307-97 or HT 750 (NCUT).
- SimDist analaysis indicates that liquid products obtained following processing of heavy oil or bitumen can be characterized by any one of, or a combination of, the following properties (see Examples 1, 2 and 5):
- VGO vacuum gas oil
- the vacuum gas oil (VGO) fraction produced as a distilled fraction obtained from the liquid product of rapid thermal processing as described herein, may be used as a feedstock for catalytic cracking in order to covert the heavy compounds of the VGO to a range of lighter weight compounds for example, gases (C 4 and lighter), gasoline, light cracked oil, and heavy gas oil.
- gases C 4 and lighter
- the quality and characteristics of the VGO fraction may be analysed using standard methods known in the art, for example Microactivity testing (MAT) testing, K-f actor and analine point analysis. Analine point analysis determines the minimum temperature for complete miscibility of equal volumes of analine and the sample under test.
- MAT Microactivity testing
- K-f actor K-f actor
- Analine point analysis determines the minimum temperature for complete miscibility of equal volumes of analine and the sample under test.
- analine point for petroleum products and hydrocarbon solvents is typically carried out using ASTM Method D611.
- a product characterized with a high analine point is low in aromatics, naphthenes, and high in paraffins (higher molecular weight components).
- VGOs of the prior art are characterized as having low analine points and therefore have poor cracking characteristics are undesired as feedstocks for catalytic cracking. Any increase in analine point over prior art feedstocks is remedial, and it is desired within the art to have a VGO characterized with a high analine point.
- analine points correlate well with cracking characteristics of a feed, and the calculated analine points obtained from MAT.
- VGOs of the present invention are unique compared to prior art VGOs.
- VGOs of the present invention are characterized by having a unique hydrocarbon profile comprising about 38% mono- aromatics plus thiophene aromatics. These types of molecules have a plurality of side chains available for cracking, and provide higher levels of conversion, than compounds with reduced levels of mono-aromatics and thiophene aromatic compounds, typical of the prior art.
- the increased amounts of mono- aromatic and thiophene aromatic may result in the descrepancy between the catalytic cracking properties observed in MAT testing and the determined analine point.
- VGO s obtained from heavy hydrocarbon feedstocks, produced as described herein are characterized as having an analine point of about 110°F to about 170 °F depending upon the feedstock.
- the VGO exhibits an analine point of from about 110° to about 135 °F
- VGO obtained from Athabaska resid exhibits an analine point of about 148 °F
- the VGO obtained from Kerrobert heavy crude is from about 119° to about 158 °F.
- VGO is hydrotreated, for example Athabaskan bitumen VGO, using standard methods known in the art, for example, using a reactor at about 720 °F, running at 1500psig, with a space velocity of 0.5 , and a hydrogen rate of 3625 SCFB, the analine point increases from about 133 ° to about to about 158 ° . Similar hydrotreating of an Athabaska- VGO resid increase the analine point to about 170 °F.
- the API increases, for example, from about 14.2 (for ATB-VGO) to about 22.4 (for Hydro-ATB-VGO), or from about 11.8 (for ATB-VGO resid) to about 20 (for Hydro-ATB-VGO resid), with a decrease in the sulfur level from about 3.7 wt% to about 0.27 wt% (for ATB-VGO and Hydro-ATB- VGO, respectively; see Example 6).
- the fast pyrolysis system includes a feed system generally indicated as (10; also see Figures 2 and 3), that injects the feedstock into a reactor (20), a heat carrier separation system that separates the heat carrier from the product vapour (e.g .100 and 180) and recycles the heat carrier to the reheating/regenerating system (30), a particulate inorganic heat carrier reheating system (30) that reheats and regenerates the heat carrier, and primary (40) and secondary (50) condensers that collect the product.
- a feed system generally indicated as (10; also see Figures 2 and 3
- a heat carrier separation system that separates the heat carrier from the product vapour (e.g .100 and 180) and recycles the heat carrier to the reheating/regenerating system (30)
- a particulate inorganic heat carrier reheating system (30) that reheats and regenerates the heat carrier
- primary (40) and secondary (50) condensers that collect the product.
- the pre-heated feedstock enters the reactor just below the mixing zone (170) and is contacted by the upward flowing stream of hot inert carrier within a transport fluid, typically a recycle gas supplied by a recycle gas line (210).
- a transport fluid typically a recycle gas supplied by a recycle gas line (210).
- a through and rapid mixing and conductive heat transfer from the heat carrier to the feedstock takes place in the short residence time conversion section of the reactor.
- the feedstock may enter the reactor through at least one of several locations along the length of the reactor.
- the different entry points indicated in Figures 1 and 2 are non-limiting examples of such entry locations. By providing several entry points along the length of the reactor, the length of the residence time within the reactor may be varied.
- the feedstock enters the reactor at a location lower down the reactor, while, for shorter residence times, the feedstock enters the reactor at a location higher up the reactor.
- the introduced feedstock mixes with the upflowing heat carrier within a mixing zone (170) of the reactor.
- the product vapours produced during pyrolysis are cooled and collected using a suitable condenser means (40, 50) in order to obtain a liquid product.
- the inert heat carrier Following pyrolysis of the feedstock in the presence of the inert heat carrier, some contaminants present within the feedstock are deposited onto the inert heat carrier. These contaminants include metals (especially nickel and vanadium), coke, and to some extent nitrogen and sulphur.
- the inert heat carrier therefore requires regeneration (30) before re-introduction into the reaction stream.
- the heat carrier may be regenerated via combustion within a fluidized bed at a temperature of about 600 to about 900 °C.
- deposits may also be removed from the heat carrier by an acid treatment, for example as disclosed in US 4, 818,373 (which is incorporated by reference).
- the heated, regenerated, heat-carrier is then re-introduced to the reactor (20) and acts as heat carrier for fast pyrolysis.
- the feed system (10) provides a preheated feedstock to the reactor (20).
- the feed system (generally shown as 10, Figures 1 and 2 ) is designed to provide a regulated flow of pre-heated feedstock to the reactor unit (20) .
- the feed system shown in Figure 2 includes a feedstock pre-heating surge tank (110), heated using external band heaters (130) to 80 °C, and is associated with a recirculation/transfer pump (120).
- the feedstock is constantly heated and mixed in this tank at 80 °C.
- the hot feedstock is pumped from the surge tank to a primary feed tank (140), also heated using external band heaters (130), as required.
- the primary feed tank (140) may also be fitted with a recirculation/delivery pump (150).
- Heat traced transfer lines (160) are maintained at about 150°C and pre-heat the feedstock prior to entry into the reactor via an injection nozzle (170).
- Atomization at the injection nozzle (70) positioned near the mixing zone (170) within reactor (20) may be accomplished by any suitable means.
- the nozzle arrangement should provide for a homogeneous dispersed flow of material into the reactor. For example, which is not considered limiting in any manner, mechanical pressure using single-phase flow atomization, or a two-phase flow atomization nozzle may be used. With a two phase flow atomization nozzle, pre-heated air, nitrogen or recycled by-product gas may be used as a carrier. Instrumentation is also dispersed throughout this system for precise feedback control (e.g. pressure transmitters, temperature sensors, DC controllers, 3-way valves gas flow metres etc.) of the system.
- Conversion of the feedstock is initiated in the mixing zone (170; e.g. Figure 1) under moderate temperatures (typically less than 750 °C) and continues through the conversion section within the reactor unit (20) and connections (e.g. piping, duct work) up until the primary separation system (e.g. 100) where the bulk of the heat carrier is removed from the product vapour stream.
- the solid heat carrier and solid coke by- product are removed from the product vapour stream in a primary separation unit.
- the product vapour stream is separated from the heat carrier as quickly as possible after exiting from the reactor (20), so that the residence time of the product vapour stream in the presence of the heat carrier is as short as possible.
- the primary separation unit may be any suitable solids separation device, for example but not limited to a cyclone separator, a U-Beam separator, or Rams Horn separator as are known within the art.
- a cyclone separator is shown diagrammatically in Figures 1, 3 and 4.
- the solids separator for example a primary cyclone (100), is preferably fitted with a high-abrasion resistant liner. Any solids that avoid collection in the primary collection system are carried downstream and recovered in a secondary collection system (180).
- the secondary separation unit may be the same as the primary separation unit, or it may comprise an alternate solids separation device, for example but not limited to a cyclone separator, a 1/4 turn separator, for example a Rams Horn separator, or an impingement separator, as are known within the art.
- a secondary cyclone separator (180) is graphically represented in Figures 1 and 4, however, other separators may be used as a secondary separator unit.
- the solids that have been removed in the primary and secondary collection systems are transferred to a vessel for regeneration of the heat carrier, for example, but not limited to a direct contact reheater system (30).
- a direct contact reheater system (30) the coke and by-product gasses are oxidized to provide processes thermal energy which is directly carried to the solid heat carrier, as well as regenerating the heat carrier.
- the temperature of the direct contact reheater is maintained independent of the feedstock conversion (reactor) system.
- other methods for the regeneration of the heat carrier may be employed, for example but not limited to, acid treatment.
- the hot product stream from the secondary separation unit is quenched in a primary collection column (or primary condenser, 40; Figure 1).
- the vapour stream is rapidly cooled from the conversion temperature to less than about 400 °C. Preferably the vapour stream is cooled to about 300°C.
- Product is drawn from the primary column and pumped (220) into product storage tanks.
- a secondary condenser (50) can be used to collect any material that evades the primary condenser (40).
- Product drawn from the secondary condenser (50) is also pumped (230) into product storage tanks.
- the remaining non-condensible gas is compressed in a blower (190) and a portion is returned to the heat carrier regeneration system (30) via line (200), and the remaining gas is returned to the reactor (20) by line (210) and acts as a heat carrier, and transport, medium.
- the reactor used with the process of the present invention is capable of producing high yields of liquid product for example at least greater than 60 vol%, preferably the yield is greater than 70 vol%, and more preferably the yield is greater than 80%, with minimal byproduct production such as coke and gas.
- residence times within the reactor for example up to about 5 sec, may be obtained if desired by introducing the feedstock within the reactor at a position towards the base of the reactor, by increasing the length of the reactor itself, by reducing the velocity of the heat carrier through the reactor (provided that there is sufficient velocity for the product vapour and heat carrier to exit the reactor), or a combination thereof.
- the preferred residence time is from about 0.5 to about 2sec.
- the liquid product arising from the processing of heavy oil as described herein has significant conversion of the resid fraction when compared to heavy oil or bitumen feedstock.
- the liquid product of the present invention produced from the processing of heavy oil is characterized, for example, but which is not to be considered limiting, as having an API gravity of at least about 13 ° , and more preferably of at least about 17°.
- higher API gravities may be achieved with a reduction in volume.
- one liquid product obtained from the processing of heavy oil using the method of the present invention is characterized as having from about 10 to about 15% by volume bottoms, from about 10 to about 15% by volume light ends, with the remainder as middle distillates.
- the viscosity of the liquid product produced from heavy oil is substantially reduced from initial feedstock levels, of from 250 cSt @ 80 °C, to product levels of 4.5 to about 10 cSt @ 80°C, or from about 6343 cSt @ 40°C, in the feedstock, to about 15 to about 35 cSt @40°C in the liquid product.
- initial feedstock levels of from 250 cSt @ 80 °C
- product levels of 4.5 to about 10 cSt @ 80°C, or from about 6343 cSt @ 40°C, in the feedstock, to about 15 to about 35 cSt @40°C in the liquid product.
- liquid yields of greater than 80 vol% and API gravities of about 17, with viscosity reductions of at least about 25 times that of the feedstock are obtained (@40°C).
- These viscosity levels are suitable for pipeline transport of the liquid product.
- ASTM D 5307-97, HT 750, (NCUT)) analysis further reveals substantially different properties between the feedstock and liquid product as produced herein.
- For heavy oil feedstock approx. 1% (wt%) of the feedstock is distilled off below about 232°C (Kerosene fraction), approx. 8.7% from about 232°to about 327°C (Diesel fraction), and 51.5 % evolved above 538 °C (Vacuum resid fraction; see Example 1 for complete analysis).
- SimDist analysis of the liquid product produced as described above may be characterized as having, but is not limited to having, the following properties: approx.4% (wt%) evolving below about 232 °C (Kerosene fraction), approx.
- the present invention is directed to a liquid product obtained from single stage processing of heavy oil may that may be characterised by at least one of the following properties:
- 193-232 °C Preferably from about 2.8% to about 5% evolves between 193-232°C (diesel fraction);
- a liquid product obtained from processing bitumen feedstock following a single stage process is characterized as having, and which is not to be considered as limiting, an increase in API gravity of at least about 10 (feedstock API is typically about 8.6). Again, higher API gravities may be achieved with a reduction in volume.
- the product obtained from bitumen is also characterised as having a density from about 0.93 to about 1.0 and a greatly reduced viscosity of at least about 20 fold lower than the feedstock (i.e. from about 15 g/ml to about 60 g/ml at 40°C in the product, v. the feedstock comprising about 1500 g/ml).
- the present invention is also directed to a liquid product obtained from single stage processing of bitumen which is characterised by having at least one of the following properties:
- 193 °C Preferably from about 1.2% to about 5% evolves below 193 °C (i.e. before the naphtha/kerosene fraction);
- the liquid product produced as described herein also exhibits a high degree of stability. Analysis of the liquid product over a 30 day period indicates negligible change in SimDist profile, viscosity, API and density for liquid products produced from either heavy oil or bitumen feedstocks (see Example 1 and 2).
- further processing of the liquid product obtained from the process of heavy oil or bitumen feedstock may take place following the method of this invention.
- Such further processing may utilize conditions that are very similar to the initial fast pyrolysis treatment of the feedstock, or the conditions may be modified to enhance removal of lighter products (a single-stage process with a mild crack) followed by more severe cracking of the recycled fraction (i.e. a two stage process).
- liquid product from a first pyrolytic treatment is recycled back into the pyrolysis reactor in order to further upgrade the properties of the final product to produce a lighter product.
- liquid product from the first round of pyrolysis is used as a feedstock for a second round of pyrolysis after the lighter fraction of the product has been removed from the product stream.
- a composite recycle may also be carried out where the heavy fraction of the product stream of the first process is fed back (recycled) into the reactor along with the addition of fresh feedstock (e.g. Figure 3, described in more detail below).
- the second method for upgrading a feedstock to obtain liquid products with desired properties involves a two-stage pyrolytic process (see Figures 2 and 3).
- This two stage processes comprises a first stage where the feedstock is exposed to conditions that mildly cracks the hydrocarbon components in order to avoid overcracking and excess gas and coke production.
- An example of these conditions includes, but is not limited to, injecting the feedstock at about 150°C into a hot gas stream comprising the heat carrier at the inlet of the reactor.
- the feedstock is processed with a residence time less than about one second within the reactor at less than 500 °C, for example 300 °C.
- the product, comprising lighter materials (low boilers) is separated (100, and 180, Figure 3), and removed following the first stage in the condensing system (40).
- the heavier materials (240), separated out at the bottom of the condenser (40) are collected subjected to a more severe crack within the reactor (20) in order to render a liquid product of reduced viscosity and high yield.
- the conditions utilized in the second stage include, but are not limited to, a processing temperature of about 530° to about 590°C.
- Product from the second stage is processed and collected as outlined in Figure 1 using a primary and secondary cyclone (100, 180, respectively) and primary and secondary condensers (40 and 50, respectively).
- an example of the product, which is not to be considered limiting, of the first stage (light boilers) is characterized with a yield of about 30 vol%, an API of about 19, and a several fold reduction in viscosity over the initial feedstock.
- the product of the high boiler fraction, produced following the processing of the recycle fraction in the second stage is typically characterized with a yield greater than about 75 vol%, and an API gravity of about 12, and a reduced viscosity over the feedstock recycled fraction.
- SimDist analysis for liquid product produced from heavy oil feedstock is characterized with approx. 7.4% (wt%) of the feedstock was distilled off below about 232 °C (Kerosene fraction v. 1.1% for the feedstock), approx.
- Alternate conditions of a two stage process may include a first stage run where the feedstock is preheated to 150 °C and injected into the reactor and processed at about 530° to about 620 °C, and with a residence time less than one second within the reactor (see Figure 2).
- the product is collected using primary and secondary cyclones (100 and 180, respectively, Figures 2 and 4), and the remaining product is transferred to a hot condenser (250).
- the condensing system ( Figure 4) is engineered ' to selectively recover the heavy ashphaltene components using a hot condenser (250) placed before the primary condenser (40).
- the heavy alsphaltenes are collected and returned to the reactor (20) for further processing (i.e. the second stage).
- the second stage utilizes reactor conditions operating at higher temperatures, or longer residence times, or at higher temperatures and longer residence times (e.g. injection at a lower point in the reactor), than that used in the first stage to optimize the liquid product. Furthermore, a portion of the product stream may be recycled to extinction following this method.
- multi-stage processing comprises introducing the primary feedstock (raw feed) into the primary condenser (see figure 5) via line 280, and using the primary feedstock to rapidly cool the product vapours within the primary condenser.
- Product drawn from the primary condenser is then recycled to the reactor via line 270 for combined "first stage” and "second stage” processing (i.e. recycled processing).
- the recycled feedstock is exposed to conditions that mildly crack the hydrocarbon components in order to avoid overcracking and excess gas and coke production.
- An example of these conditions includes, but is not limited to, injecting the feedstock at about 150°C into a hot gas stream comprise the heat carrier at the inlet of the reactor.
- the feedstock is processed with a residence time of less than about two seconds within the reactor at a temperature of between about 500°C to about 600°C.
- the residence time is from about 0.8 to about 1.3 sec
- the reactor temperature is from about 520° to about 580°C
- the product, comprising lighter materials (low boilers) is separated (100, and 180, Figure 5), and removed in the condensing system (40).
- the heavier materials (240), separated out at the bottom of the condenser (40) are collected and reintroduced into the reactor (20) via line 270.
- the feedstock is recycled through the reactor .in order to produce a product that can be collected from the second condenser, thereby upgrading and optimizing the properties of the liquid product.
- feeds systems may also be used as required for one, two, composite or multi stage processing.
- the feedstock (primary feedstock or raw feed) is obtained from the feed system (10), and is transported within line (280; which may be heated as previously described) to a primary condenser (40).
- the primary product obtained from the primary condenser may also be recycled back to the reactor (20) within a primary product recycle line (270).
- the primary product recycle line may be heated if required, and may also comprise a pre-heater unit (290) as shown in Figure 5, to re-heat the recycled feedstock to desired temperature for introduction within the reactor (20).
- product with yields of greater than 60, and preferably above 75% (wt%), and with the following characteristics, which are not to be considered limiting in any manner, may be produced from either bitumen or heavy oil feedstocks: an API from about 14 to about 19; viscosity of from about 20 to about 100 (cSt @40°C); and a low metals content (see Example 5).
- liquid products obtained following multi-stage processing of heavy oil can be characterized by comprising at least one of the following properties:
- 193 °C Preferably from about 1.2% to about 5%, and more preferably from about 1.3% to about 4.8% evolves below 193 °C (i.e. before the naphtha/kerosene fraction);
- the liquid product obtained from multi-stage processing of bitumen may be charachterized as having at least one of the following properties:
- the conditions of processing include a reactor temperature from about 500 ° to about 620 ° C. Loading ratios for particulate heat carrier (silica sand) to feedstock of from about 20:1 to about 30:1 and residence times from about 0.35 to about 0.7 sec. These conditions are outlined in more detail below (Table 2).
- the pour point of the feedstock improved and was reduced from 32 °F to about
- the Conradson carbon reduced from 12. wt% to about 6.6 wt%.
- Simulated distillation (SimDist) analysis of feedstock and liquid product obtained from several separate runs is present in Table 5.
- SimDist analysis followed the protocol outlined in ASTM D 5307-97, which reports the residue as anything with a boiling point higher than 538 °C.
- Other mthods for SimDist may also be used, for example HT 750 (NCUT; which includes boiling point distribution through to 750 °C).
- the feedstock can be further characterized with approx.0.1 % of its components evolving below 193 °C (naphtha kerosene fraction), v. approx. 6% for the liquid product.
- the diesel fraction also demonstrates significant differences between the feedstock and liquid product with 8.7% and 14.2% evolving at this temperature range (232-327 °C), respectively.
- API 15.9 15.9 15.8 15.8
- feedstock V 209 ppm feedstock Ni 86 ppm
- undiluted bitumen may be processed according to the method of this invention to produce a liquid product with reduced viscosity from greater than 1300 cSt (@40°C) to about 25.6 - 200 cSt (@40°C (depending on the run conditions; see also Tables 8 and 9), with yields of over 75% to about 85%, and an improvement in the product API from 8.6 to about 12 - 13.
- the liquid product exhibits substantial upgrading of the feedstock. SimDist analysis,and other properties of the liquid product are presented in Table 8, and stability studies in Table 9.
- Table 8 Properties and SimDist anlaysis of feedstock and liquid product after single stage processing (Reactor temp. 545 °C).
- API - 8.5 12.9 12.7 12.6 12.6
- Kerosene 193-232 1.0 2.6 2.6 ' 2.6 2.7
- the pyrolysis reactor as described in US 5,792,340 may be configured so that the recovery condensers direct the liquid products into the feed line to the reactor (see Figures 3 and 4).
- the conditions of processing included a reactor temperature ranging from about 530° to about 590°C. Loading ratios for particulate heat carrier to feedstock for the initial and recycle run of about 30: 1 , and residence times from about 0.35 to about 0.7 sec were used. These conditions are outlined in more detail below (Table 10). Following pyrolysis of the feedstock, the lighter fraction was removed and collected using a hot condenser placed before the primary condenser (see Figure 4), while the heavier fraction of the liquid product was recycled back to the reactor for further processing (also see Figure 3).
- the API gravity increased from 11.0 in the heavy oil feedstock to about 13 to about 18.5 after the first treatment cycle, and further increases to about 17 to about 23 after a second recycle treatment.
- a similar increase in API is observed for bitumen having a API of about 8.6 in the feedstock, which increase to about 12.4 after the first run and to 16 following the recycle run.
- With the increase in API there is an associated increase in yield from about 77 to about 87% after the first run, to about 67 to about 79% following the recycle run. Therefore associated with the production of a lighter product, there is a decrease in liquid yield.
- an upgraded lighter product may be desired for transport, and recycling of liquid product achieves such a product.
- Example 4 Two-Stage treatment of Heavy Oil Heavy oil or bitumen feedstock may also be processed using a two-stage pyrolytic process which comprises a first stage where the feedstock is exposed to conditions that mildly crack the hydrocarbon components in order to avoid overcracking and excess gas and coke production. Lighter materials are removed following the processing in the first stage, and the remaining heavier materials are subjected to a more severe crack at a higher temperature.
- the conditions of processing within the first stage include a reactor temperature ranging from about 510 to about 530°C (data for 515 °C given below), while in the second stage, a temperature from about 590° to about 800 °C (data for 590 °C presented in table 11) was employed.
- the loading ratios for particulate heat carrier to feedstock range of about 30:1, and residence times from about 0.35 to about 0.7 sec for both stages. These conditions are outlined in more detail below (Table 11).
- the product of the first stage (light boilers) is characterized with a yield of about 30 vol%, an API of about 19, and a several fold reduction in viscosity over the initial feedstock.
- the product of the high boiling point fraction, produced following the processing of the recycle fraction in the second stage, is typically characterized with a yield greater than about 75 vol%, and an API gravity of about 12, and a reduced viscosity over the feedstock recycled fraction.
- Example 5 “Multi-Stage” treatment of Heavy Oil and Bitumen, using Feedstock for Quenching within Primary Condenser.
- Heavy oil or bitumen feedstock may also be processed using a "Multi-stage" pyrolytic process as outlined in Figure 5.
- the pyrolysis reactor described in US 5,792,340 is configured so that the primary recovery condenser directs the liquid product into the feed line back to the reactor, and feedstock is introduced into the system at the primary condenser where it quenches the product vapours produced during pyrolysis.
- the conditions of processing included a reactor temperature ranging from about 530° to about 590°C. Loading ratios for particulate heat carrier to feedstock for the initial and recycle run of from about 20: 1 to about 30:1, and residence times from about 0.35 to about 1.2 sec were used. These conditions are outlined in more detail below (Table 12). Following pyrolysis of the feedstock, the lighter fraction is forwarded to the secondary condenser while the heavier fraction of the liquid product obtained from the primary condenser is recycled back to the reactor for further processing (Figure 5).
- Table 12 Charaterization of the liquid product obtained following Multi-Stage processing of Saskatchewan Heavy Oil and Bitumen Crack Temp. °C Viscosity ® Yield wt% Density ® API° Yield
- the liquid products produced from multi-stage processing of feedstock exhibit properties suitable for transport with greatly reduced viscosity down from 6343 cSt (@40°C) for heavy oil and 30380 cSt (@40°C) for bitumen.
- the API increased from 11 (heavy oil) to from 15.9 to 18.2, and from 8.6 (bitumen) to 14.7.
- yeilds for heavy oil under these reaction conditions are from 59 to 68 % for heavy oil, and 82% for bitumen.
- Table 13 Properties and SimDist of liquidjproducts prepared from Heavy Oil using the multi-stage Process (for feedstock properties see Tables 1 and 5).
- the kerosene and diesel fractions also demonstrates significant differences between the feedstock and liquid product with 1 % of the feedstock fraction evolving between 193-232°C v.2.8 to 5% for the liquid product, and with 8.7%) (feedstock) and 18.9 to 23.1% (liquid product) evolving at this temperature range (232- 327°C; diesel).
- Simulated distillation analysis demonstrates that over 50% of the components within the feedstock evolve at temperatures above 538 °C (vacuum resid fraction) while 80.5% of the liquid product evolves below 538 °C.
- the feedstock can be further characterized with approx. 0.1 % of its components evolving below 193 °C (naphtha/kerosene fraction), v. 6.2% for the liquid product.
- the diesel fraction also demonstrates significant differences between the feedstock and liquid product with 8.7% (feedstock) and 19.7% (liquid product) evolving at this temperature range (232-327 °C).
- VGO Vacuum Gas Oil
- Vacuum Gas Oil was obtained from a range of heavy hydrocarbon feedstocks, including:
- Athabasca bitumen (ATB; ATB-VGO(243) and ATB-VGO(255))
- Kerrobert heavy crude • a Kerrobert heavy crude (KHC) .
- VGO products were obtained using the methods as outlined in Example 4 (two stage; at a reactor temperature of 560°- 578 °C with a residence time of 1.209 seconds), except for ATB-VGO (255) which was obtained using the method of Example 1 with an increased residence time (1.705 seconds) and lower reactor temperature (490°C).
- the liquid product following thermal processing of the above feedstocks was distilled to produce a VGO fraction using standard procedures disclosed in ASTM D2892 and ASTM D5236.
- reactor temperature 720 °F reactor pressure 15 psig; Space Velocity 0.5; Hydrogen rate 3625 SCFB.
- ANS Alaskan North Slope crude oil
- the analine point Based upon the calculated analine points, the analine point all increased and are more in keeping with the data determined from MAT testing.
- the analine point of:
- ATB-VGO-resid 148 °F
- Hydro-ATB-VGO is 158°F
- Hydro-ATB-VGO-resid is l70°F.
- VGOs prepared from liquid products following rapid thermal processing as described herein are substantially different from VGOs obtained from similar feedstocks that have been only processed using conventional methods (e.g. distillation), for example ANS- VGO.
- Further analysis of the above VGOs obtained following rapid therml processing indicates that they are characterized by having a unique hydrocarbon profile comprising about 38% mono-aromatics plus thiophene aromatics. These types of molecules have a plurality of side chains available for cracking, and provide higher levels of conversion.
Abstract
Description
Claims
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BR0113937-1A BR0113937A (en) | 2000-09-18 | 2001-09-18 | Beneficial heavy oil and bitumen, liquid product and vacuum gas oil |
ES01971568T ES2395116T3 (en) | 2000-09-18 | 2001-09-18 | Products produced from rapid thermal processing of heavy hydrocarbon raw materials |
CA2422534A CA2422534C (en) | 2000-09-18 | 2001-09-18 | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
AT01971568T ATE532842T1 (en) | 2000-09-18 | 2001-09-18 | PRODUCT PRODUCED BY RAPID THERMAL TREATMENT OF HEAVY HYDROCARBON INSERTS |
AU2001291563A AU2001291563A1 (en) | 2000-09-18 | 2001-09-18 | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
MXPA03002341A MXPA03002341A (en) | 2000-09-18 | 2001-09-18 | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks. |
DK01971568.9T DK1332199T3 (en) | 2000-09-18 | 2001-09-18 | Products made by rapid thermal treatment of heavy hydrocarbon raw materials |
EP01971568A EP1332199B8 (en) | 2000-09-18 | 2001-09-18 | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
NO20031230A NO330786B1 (en) | 2000-09-18 | 2003-03-17 | Process for Preparing a Vacuum Gas Oil (VGO) |
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US8105482B1 (en) * | 1999-04-07 | 2012-01-31 | Ivanhoe Energy, Inc. | Rapid thermal processing of heavy hydrocarbon feedstocks |
US8062503B2 (en) * | 2001-09-18 | 2011-11-22 | Ivanhoe Energy Inc. | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
EP1332199B8 (en) | 2000-09-18 | 2012-03-14 | Ivanhoe HTL Petroleum Ltd | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
US7572365B2 (en) * | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
US7572362B2 (en) * | 2002-10-11 | 2009-08-11 | Ivanhoe Energy, Inc. | Modified thermal processing of heavy hydrocarbon feedstocks |
DK3252128T3 (en) | 2006-04-03 | 2019-04-01 | Pharmatherm Chemicals Inc | THERMAL EXTRACTION PROCEDURE FOR PREPARING A TAX EXTRACT |
US7758746B2 (en) | 2006-10-06 | 2010-07-20 | Vary Petrochem, Llc | Separating compositions and methods of use |
US8062512B2 (en) * | 2006-10-06 | 2011-11-22 | Vary Petrochem, Llc | Processes for bitumen separation |
EP2069467B1 (en) | 2006-10-06 | 2014-07-16 | Vary Petrochem, LLC | Separating compositions and methods of use |
CA2624746C (en) * | 2007-03-12 | 2015-02-24 | Robert Graham | Methods and systems for producing reduced resid and bottomless products from heavy hydrocarbon feedstocks |
WO2011038027A1 (en) * | 2009-09-22 | 2011-03-31 | Neo-Petro, Llc | Hydrocarbon synthesizer |
US20110094937A1 (en) * | 2009-10-27 | 2011-04-28 | Kellogg Brown & Root Llc | Residuum Oil Supercritical Extraction Process |
US20110284359A1 (en) | 2010-05-20 | 2011-11-24 | Uop Llc | Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas |
US8499702B2 (en) | 2010-07-15 | 2013-08-06 | Ensyn Renewables, Inc. | Char-handling processes in a pyrolysis system |
CA2714842C (en) * | 2010-09-22 | 2012-05-29 | Imperial Oil Resources Limited | Controlling bitumen quality in solvent-assisted bitumen extraction |
WO2012061742A1 (en) | 2010-11-05 | 2012-05-10 | ThermoChem Recovery International | Solids circulation system and method for capture and conversion of reactive solids |
WO2012092520A1 (en) | 2010-12-29 | 2012-07-05 | Ivanhoe Energy Inc. | Improved reactor feed nozzles |
EA201390974A1 (en) | 2010-12-29 | 2014-06-30 | Айванхо Энерджи Инк. | METHOD, SYSTEM AND DEVICE FOR THE DISTRIBUTION OF TRANSPORTING GAS |
WO2012092613A2 (en) | 2010-12-30 | 2012-07-05 | Ivanhoe Energy Inc. | Method, system, and apparatus for separation in processing of feedstocks |
US9011646B2 (en) | 2011-01-28 | 2015-04-21 | Mccutchen Co. | Mechanical pyrolysis in a shear retort |
US9441887B2 (en) | 2011-02-22 | 2016-09-13 | Ensyn Renewables, Inc. | Heat removal and recovery in biomass pyrolysis |
CN102116144A (en) * | 2011-03-08 | 2011-07-06 | 西南石油大学 | Integrated method for thin oil blending, viscosity reduction, extraction and transportation of thickened oil |
PL2865735T3 (en) | 2011-03-29 | 2018-08-31 | Fuelina Technologies, Llc | Method and apparatus for making a hybrid fuel |
US9062525B2 (en) | 2011-07-07 | 2015-06-23 | Single Buoy Moorings, Inc. | Offshore heavy oil production |
US9347005B2 (en) | 2011-09-13 | 2016-05-24 | Ensyn Renewables, Inc. | Methods and apparatuses for rapid thermal processing of carbonaceous material |
US10041667B2 (en) | 2011-09-22 | 2018-08-07 | Ensyn Renewables, Inc. | Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same |
US10400175B2 (en) | 2011-09-22 | 2019-09-03 | Ensyn Renewables, Inc. | Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material |
US9044727B2 (en) * | 2011-09-22 | 2015-06-02 | Ensyn Renewables, Inc. | Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material |
AU2012315914B2 (en) | 2011-09-27 | 2015-07-09 | Thermochem Recovery International, Inc. | System and method for syngas clean-up |
US9109177B2 (en) | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
US9670413B2 (en) | 2012-06-28 | 2017-06-06 | Ensyn Renewables, Inc. | Methods and apparatuses for thermally converting biomass |
WO2014031965A2 (en) | 2012-08-24 | 2014-02-27 | Ensyn Renewables, Inc. | Systems and methods for the devolatilization of thermally produced liquids |
US9707532B1 (en) | 2013-03-04 | 2017-07-18 | Ivanhoe Htl Petroleum Ltd. | HTL reactor geometry |
TWI645026B (en) | 2013-06-26 | 2018-12-21 | 安信再生公司 | Systems and methods for renewable fuel |
EP3227411B1 (en) | 2014-12-03 | 2019-09-04 | Drexel University | Direct incorporation of natural gas into hydrocarbon liquid fuels |
DK3337966T3 (en) | 2015-08-21 | 2022-02-28 | Ensyn Renewables Inc | HEATING SYSTEM WITH LIQUID BIOMASS |
ES2940894T3 (en) | 2016-02-16 | 2023-05-12 | Thermochem Recovery Int Inc | Two-stage integrated power product gas generation system and method |
WO2017164888A1 (en) | 2016-03-25 | 2017-09-28 | Thermochem Recovery International, Inc. | Three-stage energy-integrated product gas generation system and method |
US10364398B2 (en) | 2016-08-30 | 2019-07-30 | Thermochem Recovery International, Inc. | Method of producing product gas from multiple carbonaceous feedstock streams mixed with a reduced-pressure mixing gas |
MX2019007698A (en) | 2016-12-29 | 2019-10-04 | Ensyn Renewables Inc | Demetallization of liquid biomass. |
CA2963436C (en) | 2017-04-06 | 2022-09-20 | Iftikhar Huq | Partial upgrading of bitumen |
US9920926B1 (en) | 2017-07-10 | 2018-03-20 | Thermochem Recovery International, Inc. | Pulse combustion heat exchanger system and method |
US10099200B1 (en) | 2017-10-24 | 2018-10-16 | Thermochem Recovery International, Inc. | Liquid fuel production system having parallel product gas generation |
US11555157B2 (en) | 2020-03-10 | 2023-01-17 | Thermochem Recovery International, Inc. | System and method for liquid fuel production from carbonaceous materials using recycled conditioned syngas |
US11466223B2 (en) | 2020-09-04 | 2022-10-11 | Thermochem Recovery International, Inc. | Two-stage syngas production with separate char and product gas inputs into the second stage |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929619A (en) * | 1973-07-19 | 1975-12-30 | Exxon Research Engineering Co | Hydrocracking process with tri-metallic catalyst |
US4080285A (en) * | 1976-07-12 | 1978-03-21 | Gulf Research & Development Company | Thermal cracking of shale oil |
US5626742A (en) * | 1995-05-02 | 1997-05-06 | Exxon Reseach & Engineering Company | Continuous in-situ process for upgrading heavy oil using aqueous base |
US5807478A (en) * | 1997-05-16 | 1998-09-15 | Exxon Research And Engineering Company | Bitumen modification using fly ash derived from bitumen coke |
WO2000061705A1 (en) * | 1999-04-07 | 2000-10-19 | Ensyn Group Inc. | Rapid thermal processing of heavy hydrocarbon feedstocks |
Family Cites Families (89)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2735804A (en) * | 1956-02-21 | Stack | ||
US2573906A (en) * | 1944-12-18 | 1951-11-06 | Universal Oil Prod Co | Multistage catalytic conversion of bituminous solids |
US3039955A (en) * | 1958-08-21 | 1962-06-19 | United Eng & Constructors Inc | Pyrolysis process |
CA932686A (en) | 1970-03-02 | 1973-08-28 | Crown Zellerbach Corporation | Process for pyrolytically degrading bark |
US3853498A (en) * | 1972-06-28 | 1974-12-10 | R Bailie | Production of high energy fuel gas from municipal wastes |
JPS5139644B2 (en) * | 1972-11-30 | 1976-10-29 | ||
US4039390A (en) * | 1973-09-13 | 1977-08-02 | Occidental Petroleum Corporation | Feed system for pyrolysis reactors |
CA1050736A (en) * | 1974-05-24 | 1979-03-20 | Occidental Petroleum Corporation | Mixing of particulate materials |
US4153514A (en) * | 1975-02-27 | 1979-05-08 | Occidental Petroleum Corporation | Pyrolysis process for solid wastes |
DE2508707C2 (en) * | 1975-02-28 | 1982-09-23 | Metallgesellschaft Ag, 6000 Frankfurt | Process for the treatment of vapors resulting from the smoldering of oil shale |
US4049540A (en) | 1975-03-08 | 1977-09-20 | Chiyoda Chemical Engineering & Construction Co. Ltd. | Process for the thermal cracking of heavy oils with a fluidized particulate heat carrier |
US4083751A (en) * | 1975-08-11 | 1978-04-11 | Occidental Petroleum Corporation | Continuous feed pyrolysis chamber for decomposing solid waste |
US4211606A (en) * | 1975-08-19 | 1980-07-08 | Chikul Olga S | Method for thermal processing bitumen-containing materials and device for realization of same |
US4322222A (en) * | 1975-11-10 | 1982-03-30 | Occidental Petroleum Corporation | Process for the gasification of carbonaceous materials |
US4069107A (en) * | 1976-05-03 | 1978-01-17 | Edward Koppelman | Continuous thermal reactor system and method |
US4102773A (en) * | 1976-06-25 | 1978-07-25 | Occidental Petroleum Corporation | Pyrolysis with cyclone burner |
US4085030A (en) * | 1976-06-25 | 1978-04-18 | Occidental Petroleum Corporation | Pyrolysis of carbonaceous materials with solvent quench recovery |
US4141794A (en) * | 1976-06-25 | 1979-02-27 | Occidental Petroleum Corporation | Grid-wall pyrolysis reactor |
CA1108545A (en) | 1976-06-25 | 1981-09-08 | Charles K. Choi | Process and apparatus for rapid pyrolysis of carbonaceous materials |
US4064018A (en) * | 1976-06-25 | 1977-12-20 | Occidental Petroleum Corporation | Internally circulating fast fluidized bed flash pyrolysis reactor |
US4057490A (en) * | 1976-07-12 | 1977-11-08 | Gulf Research & Development Company | Thermal cracking process employing crushed oil shale as fuel |
US4097362A (en) * | 1976-07-12 | 1978-06-27 | Gulf Research & Development Company | Method for enhancing distillate liquid yield from an ethylene cracking process |
US4147593A (en) * | 1976-07-21 | 1979-04-03 | Occidental Petroleum Corporation | Flash pyrolysis of organic solid waste employing ash recycle |
US4087347A (en) * | 1976-09-20 | 1978-05-02 | Chevron Research Company | Shale retorting process |
US4090285A (en) * | 1977-02-14 | 1978-05-23 | Bochat Elbert E | Process and product for fitting a brake shoe to a brake drum |
CA1097245A (en) * | 1977-11-22 | 1981-03-10 | Chandra P. Khulbe | Thermal hydrocracking of heavy hydrocarbon oils with heavy oil recycle |
US4298453A (en) * | 1977-12-27 | 1981-11-03 | Mobil Oil Corporation | Coal conversion |
US4161442A (en) | 1978-01-05 | 1979-07-17 | Mobil Oil Corporation | Processing of tar sands |
US4243514A (en) * | 1979-05-14 | 1981-01-06 | Engelhard Minerals & Chemicals Corporation | Preparation of FCC charge from residual fractions |
US4263128A (en) * | 1978-02-06 | 1981-04-21 | Engelhard Minerals & Chemicals Corporation | Upgrading petroleum and residual fractions thereof |
US4284494A (en) * | 1978-05-01 | 1981-08-18 | Engelhard Minerals & Chemicals Corporation | Control of emissions in FCC regenerator flue gas |
US4280876A (en) * | 1978-10-27 | 1981-07-28 | Occidental Research Corporation | Coal pyrolysis process |
US4604268A (en) * | 1979-04-19 | 1986-08-05 | Kay Alan R | Methods of desulfurizing gases |
US4260456A (en) * | 1979-05-29 | 1981-04-07 | Tosco Corporation | Single retort manufacturing technique for producing valuable char and gases from coke |
CA1156952A (en) * | 1979-06-08 | 1983-11-15 | Zacharia M. George | Formation of coke from heavy crude oils in the presence of calcium carbonate |
US4232514A (en) * | 1979-06-20 | 1980-11-11 | General Motors Corporation | Dump control for turbine engine gate valve actuator |
US4311580A (en) | 1979-11-01 | 1982-01-19 | Engelhard Minerals & Chemicals Corporation | Selective vaporization process and dynamic control thereof |
US4328091A (en) * | 1979-11-01 | 1982-05-04 | Engelhard Minerals & Chemicals Corporation | Selective vaporization process |
US4448589A (en) * | 1980-01-23 | 1984-05-15 | Kansas State University Research Foundation | Pyrolytic conversion of carbonaceous solids to fuel gas in quartz sand fluidized beds |
US4305809A (en) * | 1980-03-06 | 1981-12-15 | Mobil Oil Corporation | Fixed sulfur petroleum coke fuel and method for its production |
US4294686A (en) * | 1980-03-11 | 1981-10-13 | Gulf Canada Limited | Process for upgrading heavy hydrocarbonaceous oils |
US4446009A (en) | 1980-06-02 | 1984-05-01 | Engelhard Corporation | Selective vaporization process and apparatus |
JPS5718783A (en) * | 1980-07-09 | 1982-01-30 | Terukatsu Miyauchi | Pyrolysis of heavy oil |
US4428862A (en) * | 1980-07-28 | 1984-01-31 | Union Oil Company Of California | Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons |
ATE18253T1 (en) | 1981-08-21 | 1986-03-15 | Kiyoshige Hayashi | REFINING PROCESS TO INCREASE THE YIELD OF HEAVY OIL FEED DISTILLATES. |
US4569753A (en) | 1981-09-01 | 1986-02-11 | Ashland Oil, Inc. | Oil upgrading by thermal and catalytic cracking |
US4490234A (en) | 1982-02-22 | 1984-12-25 | Beckman Instruments, Inc. | Method for measuring ionic concentration utilizing an ion-sensing electrode |
US4409416A (en) * | 1982-03-01 | 1983-10-11 | Snell George J | Lignin cracking process using fast fluidized bed reactions |
GB2117394B (en) | 1982-03-22 | 1986-05-21 | Engelhard Corp | Decarbonizing and demetallizing petroleum stocks |
US4435272A (en) * | 1982-04-16 | 1984-03-06 | Engelhard Corporation | Process for upgrading crude oil and residual fractions thereof by vaporizing the charge in a falling curtain of contact particles |
US4427539A (en) | 1982-09-07 | 1984-01-24 | Ashland Oil, Inc. | Demetallizing and decarbonizing heavy residual oil feeds |
US4507195A (en) * | 1983-05-16 | 1985-03-26 | Chevron Research Company | Coking contaminated oil shale or tar sand oil on retorted solid fines |
JPS60248793A (en) * | 1984-05-22 | 1985-12-09 | Fuji Standard Res Kk | Thermal decomposition of heavy oil |
US4818373A (en) * | 1984-10-19 | 1989-04-04 | Engelhard Corporation | Process for upgrading tar and bitumen |
US4578183A (en) | 1984-11-30 | 1986-03-25 | Mobil Oil Corporation | Feed mixing technique for fluidized catalytic cracking of hydrocarbon oil |
US4828681A (en) * | 1984-12-24 | 1989-05-09 | Exxon Research & Engineering Company | Process of thermally cracking hydrocarbons using particulate solids as heat carrier |
JPH0662958B2 (en) * | 1985-02-28 | 1994-08-17 | 富士スタンダ−ドリサ−チ株式会社 | Pyrolysis of heavy oil |
EP0226483B1 (en) * | 1985-11-12 | 1989-06-14 | Institut Français du Pétrole | Process and apparatus for the catalytic cracking of a hydrocarbon feedstock submitted to a pretreatment with solid particles having a poor activity |
US4747938A (en) * | 1986-04-17 | 1988-05-31 | The United States Of America As Represented By The United States Department Of Energy | Low temperature pyrolysis of coal or oil shale in the presence of calcium compounds |
US4816136A (en) * | 1986-05-27 | 1989-03-28 | Exxon Research And Engineering Company | Low severity fluid coking |
US4693808A (en) * | 1986-06-16 | 1987-09-15 | Shell Oil Company | Downflow fluidized catalytic cranking reactor process and apparatus with quick catalyst separation means in the bottom thereof |
CA1283880C (en) | 1987-05-07 | 1991-05-07 | Dave A. Berg | Method and apparatus for rapid thermal processing |
US4919898A (en) * | 1987-08-11 | 1990-04-24 | Stone & Webster Engineering Corp. | Particulate solids cracking apparatus |
US4814067A (en) * | 1987-08-11 | 1989-03-21 | Stone & Webster Engineering Corporation | Particulate solids cracking apparatus and process |
DE3828633A1 (en) | 1987-08-29 | 1989-03-09 | Asea Brown Boveri | Process for the utilisation (valorisation) of starting material containing halogenated hydrocarbons |
US4985136A (en) * | 1987-11-05 | 1991-01-15 | Bartholic David B | Ultra-short contact time fluidized catalytic cracking process |
US4980045A (en) | 1988-08-02 | 1990-12-25 | Chevron Research Company | Heavy oil pretreatment process with reduced sulfur oxide emissions |
US5092984A (en) * | 1989-12-29 | 1992-03-03 | Institute Of Gas Technology | Pyrolysis of coal |
US5792340A (en) * | 1990-01-31 | 1998-08-11 | Ensyn Technologies, Inc. | Method and apparatus for a circulating bed transport fast pyrolysis reactor system |
CA2009021C (en) | 1990-01-31 | 2001-09-11 | Barry A. Freel | Method and apparatus for a circulating bed transport fast pyrolysis reactor system |
US5626741A (en) * | 1990-03-26 | 1997-05-06 | Amoco Corporation | Catalytic cracking with quenching |
US5077261A (en) * | 1990-06-25 | 1991-12-31 | Phillips Petroleum Company | Sulfur absorbants |
CA2022721C (en) * | 1990-08-03 | 1999-10-26 | Teresa Ignasiak | Process for converting heavy oil deposited on coal to distillable oil in a low severity process |
US5136117A (en) * | 1990-08-23 | 1992-08-04 | Battelle Memorial Institute | Monomeric recovery from polymeric materials |
US5102854A (en) * | 1991-03-08 | 1992-04-07 | Phillips Petroleum Company | Adsorbent compositions for the removal of hydrogen sulfide from fluid streams |
US5120428A (en) * | 1991-06-06 | 1992-06-09 | Energy Mines & Resources Canada | Deashing of heavy hydrocarbon residues |
US5370848A (en) * | 1991-06-20 | 1994-12-06 | Phillips Petroleum Company | Sulfur absorbents |
US5413702A (en) * | 1992-02-21 | 1995-05-09 | Mobil Oil Corporation | High severity visbreaking of residual oil |
US5296131A (en) * | 1992-12-02 | 1994-03-22 | Mobil Oil Corporation | Process for short contact time cracking |
US5264623A (en) * | 1993-01-04 | 1993-11-23 | Energy Mines & Resources Canada | Method of producing calcium salts from biomass |
US5370789A (en) * | 1994-02-03 | 1994-12-06 | Energy Mines & Resources Canada | Ultrapyrolytic heavy oil upgrading in an internally circulating aerated bed |
US5662868A (en) * | 1994-09-22 | 1997-09-02 | Stone & Webster Engineering Corporation | Short residence time cracking apparatus and process |
US5723040A (en) | 1994-09-22 | 1998-03-03 | Stone & Webster Engineering Corporation | Fluid catalytic cracking process and apparatus |
US5952539A (en) | 1996-02-23 | 1999-09-14 | Exxon Chemical Patents Inc. | Dual process for obtaining olefins |
US5858213A (en) * | 1996-07-30 | 1999-01-12 | Exxon Research And Engineering Company | Monitoring for coke formation during hydrocarbon feed processing |
US5904839A (en) * | 1997-06-06 | 1999-05-18 | Exxon Research And Engineering Co. | Process for upgrading heavy oil using lime |
US5928501A (en) * | 1998-02-03 | 1999-07-27 | Texaco Inc. | Process for upgrading a hydrocarbon oil |
BR9913487A (en) * | 1998-09-03 | 2001-05-22 | Dow Chemical Co | Autothermal process for producing olefins and catalyst composition |
EP1332199B8 (en) | 2000-09-18 | 2012-03-14 | Ivanhoe HTL Petroleum Ltd | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
-
2001
- 2001-09-18 EP EP01971568A patent/EP1332199B8/en not_active Expired - Lifetime
- 2001-09-18 US US09/955,267 patent/US7270743B2/en not_active Expired - Fee Related
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- 2001-09-18 BR BR0113937-1A patent/BR0113937A/en not_active IP Right Cessation
- 2001-09-18 DK DK01971568.9T patent/DK1332199T3/en active
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- 2001-09-18 PT PT01971568T patent/PT1332199E/en unknown
- 2001-09-18 CA CA2422534A patent/CA2422534C/en not_active Expired - Fee Related
-
2003
- 2003-03-17 NO NO20031230A patent/NO330786B1/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929619A (en) * | 1973-07-19 | 1975-12-30 | Exxon Research Engineering Co | Hydrocracking process with tri-metallic catalyst |
US4080285A (en) * | 1976-07-12 | 1978-03-21 | Gulf Research & Development Company | Thermal cracking of shale oil |
US5626742A (en) * | 1995-05-02 | 1997-05-06 | Exxon Reseach & Engineering Company | Continuous in-situ process for upgrading heavy oil using aqueous base |
US5807478A (en) * | 1997-05-16 | 1998-09-15 | Exxon Research And Engineering Company | Bitumen modification using fly ash derived from bitumen coke |
WO2000061705A1 (en) * | 1999-04-07 | 2000-10-19 | Ensyn Group Inc. | Rapid thermal processing of heavy hydrocarbon feedstocks |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014140175A1 (en) * | 2013-03-14 | 2014-09-18 | Fluid Oil Limited | Gravitational collision enhanced upgrading of heavy oils |
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AR033838A1 (en) | 2004-01-07 |
NO20031230D0 (en) | 2003-03-17 |
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CA2422534A1 (en) | 2002-03-28 |
BR0113937A (en) | 2004-01-13 |
DK1332199T3 (en) | 2012-02-06 |
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