EP2336274A1 - Verwendung von verbesserten schweren Kohlenwasserstoffeinsätzen in Pipelines - Google Patents

Verwendung von verbesserten schweren Kohlenwasserstoffeinsätzen in Pipelines Download PDF

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Publication number
EP2336274A1
EP2336274A1 EP10184110A EP10184110A EP2336274A1 EP 2336274 A1 EP2336274 A1 EP 2336274A1 EP 10184110 A EP10184110 A EP 10184110A EP 10184110 A EP10184110 A EP 10184110A EP 2336274 A1 EP2336274 A1 EP 2336274A1
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EP
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Prior art keywords
feedstock
heat carrier
product
fraction
reactor
Prior art date
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Granted
Application number
EP10184110A
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English (en)
French (fr)
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EP2336274B1 (de
Inventor
Barry A. Freel
Robert G. Graham
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Ivanhoe HTL Petroleum Ltd
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Ensyn Petroleum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • 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
    • 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
    • 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
    • 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
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW
    • 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
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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. There is therefore a need within the art for an efficient method for upgrading feedstock comprising a significant BS&W content prior to transport or further processing of the feedstock.
  • 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
  • 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
  • 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.
  • 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 pre-heated 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.
  • This invention also includes an upflow pyrolysis reactor for heavy hydrocarbon feedstock upgrading comprising:
  • the present invention also relates to the upflow reactor as defined above, wherein the plurality of locations, includes locations distributed along the length of said reactor.
  • the upflow reactor may comprise a hot condenser means prior to the condensing means.
  • the particulate heat carrier is silica sand, and the loading ratio is from about 20:1 to about 30:1.
  • the upflow reactor as defined above may also comprise a heavy fraction product recirculation means from the hot condensing means to the injection means of the upflow reactor.
  • the present invention also pertains to a method for upgrading a heavy hydrocarbon feedstock comprising:
  • 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.
  • 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.
  • 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. These 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.
  • lighter feedstocks including gas oils, vacuum gas oils, topped crudes or pre-processed liquid products,
  • 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.
  • 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 ( WO91/11499 ; 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 ( WO91/11499 ; 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 0.035% (358 ppm); about 0.00037% (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:
  • 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):
  • 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.
  • the suitable conditions for a the pyrolytic treatment of feedstock, and the production of a liquid product is described in US 5,792,340 , which is incorporated herein by reference.
  • This process utilizes sand (silica sand) as the heat carrier, and a reactor temperature ranging from about 480° to about 620°C, loading ratios of heat carrier to feedstock from about 10:1 to about 200:1, and residence times from about 0.35 to about 0.7 sec.
  • the reactor temperature ranges from about 500° to about 550°C.
  • the preferred loading ratio is from about 15:1 1 to about 50:1, with a more preferred ratio from about 20:1 1 to about 30:1.
  • 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:
  • 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:
  • 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.
  • 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:
  • 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).
  • Table 3 Metal Analysis of Liquid Products (ppm) 1) Component Saskatchewan Heavy Oil Run @ 620°C Run @ 592°C Run @ 560°C Aluminum ⁇ 1 ⁇ 1 11 ⁇ 1 Iron ⁇ 1 2 4 ⁇ 1 Nickel 44 10 12 9 Zinc 2 ⁇ 1 2 1 Calcium 4 2 3 1 Magnesium 3 1 2 ⁇ 1 Boron 21 42 27 ⁇ 1 Sodium 6 5 5 4 Silicon 1 10 140 4 Vanadium 127 39 43 39 Potassium 7 7 ⁇ 1 4 Water(wt%) 0.78 0.19 0.06 .10 Sulphur (wt%) 3.6 3.5 3.9 3.5 1) Copper, tin, chromium, lead, cadmium, titanium, molybdenum, barium and manganese all showed less than 1 ppm in feedstock and liquid products.
  • Table 4 Gas analysis of Pyrolysis runs Gas (wt%) Run @620°C Run @ 560°C Total Gas Yield 11.8 7.2 Ethylene 27.0 16.6 Ethane 8.2 16.4 Propylene 30.0 15.4 Methane 24.0 21.0
  • the pour point of the feedstock improved and was reduced from 32°F to about -54°F.
  • 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.
  • Stability of the liquid product was also determined over a 30 day period (Table 6). No significant change in the viscosity, API or density of the liquid product was observed of a 30 day period.
  • 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).
  • 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.
  • 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).
  • Table 11 Two-Stage Runs of Saskatchewan Heavy Oil Crack Temp. °C Viscosity @ 80°C (cSt) Yield wt% Density @ 15°C g/ml API° Yield Vol% 1) 515 5.3 29.8 0.943 18.6 31.4 590 52.6 78.9 0.990 11.4 78.1 515 &590 nd nd nd 13.9 86.6 "nd" means not determined 1)Light condensible materials were not captured. Therefore these values are conservative estimates.
  • 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.
  • 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 liquid products prepared from Heavy Oil using the multi- stage Process (for feedstock properties see Tables 1 and 5).
  • 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).

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BR0009652B1 (pt) 2012-04-03
PT1169412E (pt) 2013-09-23
NO20014868D0 (no) 2001-10-05
US20120279825A1 (en) 2012-11-08
BR0009652A (pt) 2002-03-26
NO20014868L (no) 2001-12-06
PT2336274E (pt) 2013-09-25
ES2429816T3 (es) 2013-11-18
AU3798300A (en) 2000-11-14
MXPA01010120A (es) 2002-08-12
EP2336274B1 (de) 2013-06-19
EP1169412B1 (de) 2013-06-19
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CA2369288A1 (en) 2000-10-19
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