WO2012145204A2 - Réacteur à hydrocarbures lourds - Google Patents

Réacteur à hydrocarbures lourds Download PDF

Info

Publication number
WO2012145204A2
WO2012145204A2 PCT/US2012/033013 US2012033013W WO2012145204A2 WO 2012145204 A2 WO2012145204 A2 WO 2012145204A2 US 2012033013 W US2012033013 W US 2012033013W WO 2012145204 A2 WO2012145204 A2 WO 2012145204A2
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
approximately
heavy hydrocarbon
hydrocarbon material
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2012/033013
Other languages
English (en)
Other versions
WO2012145204A3 (fr
Inventor
Jose Armando SALAZAR-GUILLEN
Christopher Ard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Marathon Oil Canada Corp
Original Assignee
Marathon Oil Canada Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Marathon Oil Canada Corp filed Critical Marathon Oil Canada Corp
Priority to BR112013027199A priority Critical patent/BR112013027199A2/pt
Priority to CA2833952A priority patent/CA2833952A1/fr
Publication of WO2012145204A2 publication Critical patent/WO2012145204A2/fr
Publication of WO2012145204A3 publication Critical patent/WO2012145204A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B01J19/0026—Avoiding carbon deposits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam

Definitions

  • Conventional thermal cracking is the thermal decomposition of high molecular weight constituents (higher molecular weight and higher boiling than gasoline constituents) to form lower molecular weight (and lower boiling) species. Many of these processes use catalysts to crack residual and other heavy feedstocks, alkylation, polymerization, and isomerization. Catalytic cracking is one of the leading processes for upgrading lighter oils (e.g., conventional crude oil) into high quality fuel. Hydrocracking, a catalytic cracking process conducted in the presence of hydrogen, is especially suitable for producing yielding gasoline and/or jet fuels.
  • Thermal cracking processes such as visbreaking, an abbreviated term for viscosity breaking or viscosity lowering, are used to convert heavy, high viscosity, high boiling hydrocarbons to lower viscosity fractions suitable for further processing or use in heavy fuel oil. These processes may accomplish one or more of the following objectives. First, they reduce the viscosity of the feed stream, which may include heavy hydrocarbon sources such as the residue from distillation operations, the residue from hydroskimming operations, natural bitumen from sources such as tar sands, and even certain high viscosity crude oils.
  • heavy hydrocarbon sources such as the residue from distillation operations, the residue from hydroskimming operations, natural bitumen from sources such as tar sands, and even certain high viscosity crude oils.
  • Middle distillates are often used as a diluent for heavy hydrocarbons to lower their viscosity to a marketable level. Cracking the residual hydrocarbons reduces the diluent requirement so that the saved middle distillates can be diverted to higher value products.
  • the feed is passed through one or more tubes in a furnace.
  • the heavy hydrocarbon material is heated to a high temperature causing partial vaporization and mild cracking. Conversion is achieved primarily as a result of temperature and residence time, which is why this process is described as being high temperature (e.g., 455 to 510 °C) and short residence time.
  • the short residence time is the principal reason that this is considered a mild thermal reaction.
  • the product that exits the tube is quenched to halt the cracking reactions. This may be done by heat exchange with the feed material, which saves energy, or with a stream of cold material such as gas oil to achieve the same effect.
  • Processes for cracking heavy hydrocarbon material also produce a significant amount of gaseous hydrocarbons as a by-product. Although these can be separated for other uses, it is preferable to limit the amount of gases produced to maximize liquid yields.
  • a reactor for cracking heavy hydrocarbon material into distillates includes a tube having an internal passage through which the heavy hydrocarbon material passes.
  • the heavy hydrocarbon undergoes cracking reactions as it travels through the reactor thereby producing the distillates.
  • the heavy hydrocarbon can react with a cracking fluid in the reactor that facilitates the cracking reactions.
  • the reactor may be oriented vertically so that the fluid in the reactor moves downward through the internal passage.
  • the internal passage may lie substantially on a plane so that the reactor appears to be flat.
  • the internal passage may include alternating linear sections and curved sections that form a zig-zag or serpentine shape.
  • the tube can be at least approximately 6 inches in width.
  • the internal passage has a cylindrical shape and its diameter is at least approximately 6 inches.
  • the reactor can be used as part of a method for cracking the heavy hydrocarbon material and forming distillates.
  • the method includes reacting the heavy hydrocarbon material with a cracking fluid such as steam or natural gas in the reactor.
  • a cracking fluid such as steam or natural gas in the reactor.
  • the temperature and residence time of the heavy hydrocarbon material is sufficient to convert a substantial amount of it to distillates.
  • the residence time and linear velocity of the fluid in the reactor may be
  • the reactor is part of a multiple reactor system for cracking heavy hydrocarbon material.
  • the reactor is the second reactor in the system and is positioned in series after a first reactor.
  • the heavy hydrocarbon material begins to crack in the first reactor into lighter hydrocarbon material.
  • the second reactor provides the residence time at high temperature that further drives conversion of the heavy hydrocarbon material into distillates.
  • the first reactor may be a nozzle reactor.
  • the cracking fluid is accelerated to supersonic speed in the nozzle reactor and mixed with the heavy hydrocarbon material in the feed to initiate cracking.
  • the cracking fluid functions as a hydrogen source thereby minimizing coke formation due to excessive hydrogen loss from the heavy hydrocarbon material.
  • the effluent from the second reactor is separated to isolate any remaining heavy hydrocarbon material.
  • the heavy hydrocarbon material may be recycled back to the first reactor until it is completely eliminated.
  • the recycled heavy hydrocarbon material does not produce significant amounts of coke due to the hydrogen rich environment supplied by the cracking fluid.
  • the entire process may be operated without the use of a catalyst or added hydrogen.
  • the raw feed is combined with the effluent from the second reactor and separated into distillates and heavy hydrocarbon material.
  • Any suitable separation process may be used such as distillation.
  • the distillates continue on to further processing and the heavy hydrocarbon material is fed into the reactor system. This design allows the distillates from the feed and the reactor effluent to be separated in a single step with the same separation unit. It also increases the concentration of heavy hydrocarbon material in the feed to the reactor system.
  • the raw feed may be fed directly into the reactor system before being separated into its constituent fractions. For example, this may be desirable when the raw feed is largely made up of heavy hydrocarbon material.
  • the raw feed may be separated in a first separation unit, the heavy hydrocarbon material fed into the reactor system, and the effluent separated in a second separation unit.
  • the term "heavy hydrocarbon material” is used to refer to the hydrocarbon fraction that has a boiling point at or above 525 °C. This material may be obtained from a number of sources such as the residue from distillation operations such as atmospheric or vacuum distillation, the residue from hydroskimming operations, natural sources such as tar sands (including oil sands and oil shale), and even certain high viscosity crude oils.
  • sources such as the residue from distillation operations such as atmospheric or vacuum distillation, the residue from hydroskimming operations, natural sources such as tar sands (including oil sands and oil shale), and even certain high viscosity crude oils.
  • distillates is used to refer to the hydrocarbon fraction that has a boiling point below 525 °C.
  • coke precursor is used to refer to carbon based material that is not soluble in toluene. It should be appreciated that all pressures are given as gauge pressures unless noted otherwise.
  • Figure 1 is a schematic representation of one embodiment of a system for cracking heavy hydrocarbon material.
  • Figure 2 is a schematic representation of another embodiment of a system for cracking heavy hydrocarbon material that includes recycle of unconverted heavy hydrocarbon material.
  • Figure 3 shows one embodiment of a nozzle reactor that may be used in the process.
  • Figure 4 shows one embodiment of a nozzle reactor coupled in series to a coil reactor.
  • Figure 5 shows one embodiment of a nozzle reactor coupled in series to a tubular reactor.
  • Figures 6 and 7 shows different embodiments of a tubular reactor having a serpentine shape.
  • Figure 8 shows an exemplary embodiment of a method for cracking heavy hydrocarbon material.
  • Figure 1 shows one embodiment of a system 100 for cracking heavy hydrocarbon material.
  • the system includes a first reactor 102 and a second reactor 104 positioned in series.
  • the first reactor 102 partially upgrades the heavy hydrocarbon material and the second reactor 104 further upgrades it until it reaches the overall desired conversion level.
  • the second reactor 104 discharges an upgraded effluent material 110.
  • a feed 106 includes heavy hydrocarbon material and is fed into the first reactor 102.
  • a cracking fluid 108 is also fed into the first reactor.
  • the feed 106 may enter the first reactor 102 without being separated, it is often desirable to separate the heavy hydrocarbon material before it enters the first reactor 102 to prevent eliminate or reduce the amount of distillates present in the feed 106.
  • the feed 106 may come from a variety of sources. Examples of suitable sources include the residual fraction of distillation operations such as atmospheric or vacuum distillation or from the residual fraction of hydroskimming operations. Other sources include natural sources such as oil sands (which includes tar sands, oil shale, etc.) or even certain high viscosity crude oils. The concentration of heavy hydrocarbon material in the feed 106 varies depending on its source and whether it was processed previously.
  • composition of the feed 106 can vary widely, but often includes asphaltenes, resins, aromatic hydrocarbons, and alkanes in varying amounts.
  • Asphaltenes are large polycyclic molecules that are commonly defined as those molecules that are insoluble in n-heptane and soluble in toluene.
  • Resins are also polycyclic but have a lower molecular weight than
  • Aromatic hydrocarbons are derivatives of benzene, toluene and xylene.
  • the feed may also include 12 to 25 wt% micro carbon as detennined using ASTM D4530-07.
  • the feed 106 can include heavy hydrocarbon material and other lower boiling fractions. In most situations, it is advantageous to separate distillates from the feed 106 so that it is composed entirely or almost entirely of heavy hydrocarbon material when it enters the first reactor 102. Any suitable separation process (e.g., distillation, etc.) may be used to separate the distillates.
  • the feed 106 includes at least approximately 95 wt% heavy hydrocarbon material, at least approximately 98 wt% heavy hydrocarbon material, or, desirably, at least approximately 99 wt% heavy hydrocarbon material. It should be appreciated that in other embodiments, the feed 106 may include a substantial amount of distillates.
  • the feed 106 is preheated before it enters the nozzle reactor to a temperature that is just below the temperature at which cracking occurs. This imparts the maximum amount of energy to the feed 106 without initiating cracking.
  • the feed 106 may be heated to a temperature that is no more than 400 °C.
  • the feed 106 may be heated to at least approximately 350 °C.
  • the feed 106 may be heated to approximately 350 °C to 400 °C.
  • the cracking fluid 108 may be any material that when combined with the feed 106 in the first reactor 102 and the second reactor 104 cracks the heavy hydrocarbon material and/or serves as a hydrogen donor to the heavy hydrocarbon material.
  • the cracking fluid 108 may be supplied as a superheated fluid. Suitable cracking fluids include steam, natural gas, methanol, ethanol, ethane, propane, other gases, or combinations thereof. In one embodiment, the cracking fluid 108 is superheated steam, natural gas, or a combination of both.
  • the cracking fluid 108 may help to prevent the formation of coke in the system 100 by functioning as a hydrogen donor in the cracking reactions.
  • the hydrogen from the cracking fluid 108 is transferred to the heaviest hydrocarbons thereby preventing them from becoming hydrogen depleted in the extreme conditions of the reactors 102, 104.
  • the cracking fluid 108 may be heated and pressurized before it is introduced to the first reactor 102.
  • the heat and pressure give the cracking fluid 108 added energy that is transferred to the heavy hydrocarbon material causing it to crack or scission.
  • the cracking fluid 108 may be provided in an amount and at a temperature sufficient to heat the feed 106 to the desired temperature and initiate the cracking reactions.
  • the amount of heat supplied in the cracking fluid 108 may be determined using a mass and energy balance.
  • the cracking fluid 108 is supplied at a temperature of at least approximately 550 °C or at least approximately 600 °C. In another embodiment, the cracking fluid 108 is supplied at a temperature of approximately 550 °C to 700 °C or approximately 600 °C to 650 °C. In yet another embodiment, the cracking fluid 108 is supplied at a temperature of no more than approximately 700 °C.
  • the cracking fluid 108 is pressurized to at least approximately 1380 kPa or at least approximately 3100 kPa. In another embodiment, the cracking fluid 108 is pressurized to approximately 1380 kPa to 6200 kPa or approximately 3100 kPa to 5170 kPa. In yet another embodiment, the cracking fluid 108 is pressurized no more than approximately 6200 kPa or no more than approximately 5170 °C.
  • the ratio of cracking fluid 108 to feed 106 supplied to the first reactor 102 varies depending on a number of factors. In general, it is desirable to minimize the amount of cracking fluid 108 to reduce cost while still successfully cracking the heavy hydrocarbons. In one embodiment, the ratio of cracking fluid 108 to feed 106 is no more than 2.0 or no more than 1.7. In another embodiment, the ratio of cracking fluid 108 to feed 106 may be approximately 0.5 to 2.0 or approximately 1.0 to 1.7. In yet another embodiment, the ratio of cracking fluid 108 to feed 106 is at least approximately 0.5 or at least approximately 1.0
  • the first reactor 102 may be any suitable reactor capable of at least partially upgrading heavy hydrocarbon material.
  • the first reactor 102 is a nozzle reactor.
  • a nozzle reactor includes any type of apparatus having a convergent and/or divergent internal shape in which one or more materials are injected for the purpose of chemically and/or mechanically interacting with each other. Any of the nozzle reactors disclosed in the documents incorporated by reference can be used.
  • the nozzle reactor includes a first entry opening that receives the cracking fluid, a second entry opening that receives the feed, and an exit opening.
  • the first entry opening, the second entry opening, and the exit opening are in fluid communication with each other. This can be accomplished in any of a number of ways.
  • the first entry opening can lead to a first input passage or injection passage.
  • the second entry opening can intersect and/or be combined with the first input passage and then lead to the exit opening.
  • the first input passage is shaped to accelerate the cracking fluid.
  • the first input passage may have any suitable geometry that is capable of doing this.
  • the first input passage includes a convergent section where the passage narrows from a wide diameter to a smaller diameter in the direction of the flow.
  • the first input passage includes a divergent section where the passage expands from a smaller diameter to a larger diameter in the direction of the flow.
  • the first input passage includes a convergent section followed by a divergent section. The first input passage appears to be pinched in the middle, making a carefully balanced, asymmetric hourglass-shape. This configuration is commonly referred to as convergent-divergent nozzle or "con-di nozzle”.
  • the convergent section of the first input passage accelerates subsonic fluids since the mass flow rate is constant and the material must accelerate to pass through the smaller opening.
  • the flow will reach sonic velocity at the narrowest point (i.e., the nozzle throat) provided that the nozzle pressure ratio is high enough. In this situation, the first input passage is said to be choked.
  • the divergent section of the first input passage slows subsonic fluids, but accelerates sonic or supersonic fluids.
  • a convergent-divergent geometry can therefore accelerate fluids that have choked in the convergent section to supersonic speeds.
  • the convergent-divergent geometry can be used to accelerate the hot, pressurized cracking fluid to supersonic speeds, and upon expansion, to shape the exhaust flow so that the heat energy propelling the flow is maximally converted into kinetic energy.
  • the flow rate of the fluid through the convergent-divergent nozzle is isentropic (fluid entropy is nearly constant).
  • the fluid is compressible so that sound, a small pressure wave, can propagate through it.
  • the cross sectional area increases the gas begins to expand and the gas flow increases to supersonic velocities where a sound wave cannot propagate backwards through the gas as viewed in the frame of reference of the nozzle (Mach number > 1.0).
  • the first input passage will only choke at the throat if the pressure and mass flow rate is sufficient to reach sonic speeds, otherwise supersonic flow is not achieved and the first input passage will act as a Venturi tube. In order to achieve supersonic flow, the entry pressure to the nozzle should be significantly above ambient pressure.
  • the pressure of the gas at the exit of the expansion portion of the first input passage can be low, but should not be too low.
  • the exit pressure can be significantly below ambient pressure since pressure cannot travel upstream through the supersonic flow. However, if the pressure is too far below ambient, then the flow will cease to be supersonic or the flow will separate within the expansion portion of the nozzle forming an unstable jet that may "flop' around within the nozzle.
  • the ambient pressure is no higher than
  • the supersonic flow collides and mixes with the heavy hydrocarbon material in the nozzle reactor. In this way, the nozzle reactor generates a tremendous amount of thermal and kinetic energy that is used to crack the heavy hydrocarbon material.
  • the nozzle reactor is configured to accelerate the cracking fluid to at least approximately Mach 1, at least approximately Mach 1.5, or, desirably, at least approximately Mach 2. In another embodiment, the nozzle reactor accelerates the cracking fluid to approximately Mach 1 to 7, approximately Mach 1.5 to 6, or, desirably, approximately Mach 2 to 5.
  • the cracking produced in the nozzle reactor is influenced by a number of factors such as temperature, residence time, pressure, and impact force. Without wishing to be bound by theory, it appears that the mechanical forces exerted on the heavy hydrocarbon material due to the impact of the cracking fluid are a significant factor in the success of the system 100. The impact force directly cleaves the molecule apart and/or weakens it making it more susceptible to chemical attack.
  • the nozzle reactor is the same or substantially similar to the nozzle reactor disclosed in the '597 patent or the '741 publication.
  • the nozzle reactor includes an interior reactor chamber, a first input passage or injection passage, and a second input passage or material feed passage.
  • the interior reactor chamber has an injection end and an ejection end.
  • the first input passage is positioned in fluid communication with the injection end of the interior reactor chamber.
  • the first input passage is roughly shaped like an hourglass with enlarged openings at the entrance (the enlarged volume injection section) and exit (the enlarged volume ejection section) and a constricted or narrow section in the middle.
  • the cracking fluid 108 enters the nozzle reactor through the first input passage.
  • the cracking fluid 108 enters the first input passage at a material injection end and exits the passage at a material ejection end.
  • the first input passage opens to the interior reactor chamber.
  • the heavy hydrocarbon material enters the nozzle reactor through the second input passage, which is in fluid communication with the interior reactor chamber and is generally located adjacent to the location where the cracking fluid 108 exits the first input passage.
  • the second input passage is positioned transverse to the direction of the first input passage.
  • the nozzle reactor 10 has a reactor body injection end 12, a reactor body 14 extending from the reactor body injection end 12, and an ejection port 13 in the reactor body 14 opposite its injection end 12.
  • the reactor body injection end 12 includes a first input passage 15 extending into the interior reactor chamber 16 of the reactor body 14.
  • the central axis A of the first input passage 15 is coaxial with the central axis B of the interior reactor chamber 16.
  • the first input passage 15 has a circular diametric cross-section and, as shown in the axially-extending cross-sectional view of Figure 3, opposing inwardly curved side wall portions 17, 19 (i.e., curved inwardly toward the central axis A of the first input passage 15) extending along the axial length of the first input passage 15.
  • the axially inwardly curved side wall portions 17, 19 of the first input passage 15 facilitate high speed injection of the cracking fluid 108 as it passes through the first input passage 15 into the interior reactor chamber 16.
  • the curved side wall portions 17, 19 also form convergent-divergent sections in the first input passage 15.
  • the side wall of the first input passage 15 can provide one or more of the following: (i) uniform axial acceleration of the cracking fluid 108 passing through the first input passage 15; (ii) minimal radial acceleration of such material; (iii) a smooth finish; (iv) absence of sharp edges; and (v) absence of sudden or sharp changes in direction.
  • the side wall configuration can render the first input passage 15 substantially isentropic.
  • a second input passage 18 extends from the exterior of the reactor body 14 toward the interior reaction chamber 16 transversely to the axis B of the interior reactor chamber 16.
  • the second input passage 18 16 netrates an annular feed port 20 adjacent the interior reactor chamber wall 22 at the interior reactor chamber injection end 24 abutting the reactor body injection end 12.
  • the feed port 20 includes an annular, radially extending reactor chamber feed slot 26 in fluid communication with the interior reactor chamber 16.
  • the feed port 20 is thus configured to inject the feed 106: (i) at about a 90° angle to the axis of travel of the cracking fluid 108 injected from the first input passage 15; (ii) around the entire circumference of a cracking fluid 108 injected through the first input passage 15; and (iii) to impact the entire circumference of the cracking fluid stream virtually immediately upon its emission from the first input passage 15 into the interior reactor chamber 16.
  • the annular feed port 20 may have a U-shaped or C-shaped cross-section among others.
  • the annular feed port 20 may be open to the interior reactor chamber 16, with no arms or barrier in the path of fluid flow from the second input passage 18 toward the interior reactor chamber 16.
  • the junction of the annular feed port 20 and the second input passage 18 can have a radiused cross-section.
  • the interior reactor chamber 16 may be bounded by stepped, telescoping side walls 28, 30, 32 extending along the axial length of the reactor body 14.
  • the stepped side walls 28, 30, 32 are configured to: (i) allow a free jet of injected cracking fluid 108 to travel generally along and within the conical jet path C generated by the first input passage 15 along the axis B of the interior reactor chamber 16, while (ii) reducing the size or involvement of back flow areas (e.g., 34, 36) outside the conical or expanding jet path C, thereby forcing increased contact between the high speed cracking fluid stream within the conical jet path C and the feed 106 injected through the annular feed port 20.
  • back flow areas e.g., 34, 36
  • the reactor body 14 has an axial length (along axis B) that is much greater than its width.
  • exemplary length-to-width ratios are typically in the range of 2 to 7 or more.
  • the dimensions of the various components of the nozzle reactor shown in Figure 3 are not limited, and may generally be adjusted based on the amount of feed flow rate.
  • Table 1 provides exemplary dimensions for the various components of the nozzle reactor 10 based on the hydrocarbon input in barrels per day (BPD).
  • the feed 106 which includes the heavy hydrocarbon material, is injected into the interior reactor chamber 16 via the second input passage 18.
  • the feed 106 may be pretreated prior to entering the nozzle reactor 10 to alter the amount or fraction of heavy hydrocarbon material.
  • the feed 106 may also be pretreated to alter other characteristics of the feed.
  • the feed 106 includes the heavy fraction from a separation unit.
  • a raw feed may be separated using a distillation column and the heavy fraction sent to the nozzle reactor 10.
  • the effluent produced by the nozzle reactor 10 and/or the second reactor 104 can be added to the raw feed and separated from any remaining heavy hydrocarbon material in the same separation unit used to provide the feed 106.
  • the feed 106 and the cracking fluid 108 are simultaneously injected into the interior reactor chamber 16 through the second input passage 18 and the first input passage 15.
  • the configuration of the first input passage IS is such that the cracking fluid 108 is accelerated to supersonic speed and enters the interior reactor chamber 16 at supersonic speed.
  • the cracking fluid 108 produces shock waves that facilitate mechanical and chemical scission of the heavy hydrocarbon material. In this manner, the heavy hydrocarbon material may be broken down into distillates.
  • the nozzle reactor's conversion rate of heavy hydrocarbon material into distillates varies depending on the inputs, conditions, and a number of other factors.
  • the conversion rate of the nozzle reactor 10 is at least approximately 2%, at least approximately 4%, or, desirably, at least approximately 8%.
  • the conversion rate of the nozzle reactor 10 is approximately 2% to 25%, approximately 4% to 20%, or, desirably, approximately 8% to 16%.
  • the second reactor 104 may be any suitable reactor capable of further upgrading the heavy hydrocarbon material.
  • the second reactor 104 is a tubular reactor.
  • the tubular reactor provides sufficient residence time at high temperature and high velocity to provide the overall desired level of conversion of heavy hydrocarbon material.
  • the tubular reactor includes a tube or pipe having an internal passage that generally has a uniform cross-sectional shape and may be linear or non-linear.
  • Figure 4 shows one embodiment of a reactor system 11 that includes the first reactor 10 and a tubular reactor 112 is a coiled shape.
  • the reactor 112 is one example of a non-linear tubular reactor.
  • the non-linear shape of the reactor 112 forces the material to repeatedly change direction as it passes through the tube. This causes greater mixing and faster reaction time between the heavy hydrocarbon material and the cracking fluid 108.
  • the coil configuration affects the temperature and pressure distribution as well as the product yields.
  • the reactor 112 is spiral shaped, but it should be appreciated that the reactor 112 may have any suitable non-linear shape. Other suitable shapes include a single row, split, reversed split, etc. Coil reactors typically increase the rate of conversion of heavy hydrocarbon materials as well as the amount converted.
  • the feed 106 and cracking fluid 108 pass directly from the nozzle reactor 10 to the reactor 112. This quick transition allows the materials to enter the reactor 112 without losing too much heat or velocity. It should be appreciated, however, that the materials may undergo some form of processing or treatment after leaving the nozzle reactor 10 but before entering the reactor 112.
  • Figure 5 shows another embodiment of a reactor system 13 including the nozzle reactor 10 and another embodiment of a tubular reactor 50.
  • the tubular reactor 50 has a roughly serpentine shape.
  • the reactor 50 is positioned immediately following the nozzle reactor 10.
  • the mixture of the feed 106 and the cracking fluid 108 exits the nozzle reactor 10 and immediately enters the reactor 50.
  • the reactor 50 provides the residence time at high temperature that allows the cracking process to continue until the desired conversion level is reached.
  • the reactor 50 includes a tube having an internal passage 52.
  • the reactor 50 is oriented vertically so that the effluent from the nozzle reactor 10 moves downward through the reactor 50. Gravity helps to maintain the desired flow rate and velocity in the reactor 50.
  • the internal passage includes alternating linear sections 54 and curved sections 56.
  • the sections 54, 56 are oriented in a single plane so that the reactor 50 is roughly flat. In this way, the reactor 50 can be positioned vertically in a plant type environment without taking up a lot of space.
  • the internal passage includes at least three, four, or five alternating linear sections 54 and curved sections 56.
  • the linear sections 54 slope downward in the direction of fluid flow.
  • the curved sections 56 curve less than a full 180° to provide the linear sections 54 with a downward slope. In one embodiment, the curved sections curve approximately 150° up to 180° or approximately 170° to 180°.
  • the linear sections 54 may be any suitable length. In one embodiment, the linear sections 54 are approximately 3 to 10 feet in length.
  • the internal passage 52 may have any suitable shape or configuration.
  • the tube is a round pipe so that the internal passage 52 has a cylindrical shape and a circular cross sectional shape.
  • the internal passage 52 may different cross- sectional shapes such as square or rectangular.
  • the reactor 50 may be relatively large to provide a high amount of throughput.
  • the internal passage 52 is at least approximately 6 inches wide, at least
  • the width of the internal passage 52 should be measured at its widest point for non- circular cross sectional shapes. If the internal passage 52 is circular, then the width is the diameter.
  • the height of the reactor 50 and the length of the linear sections 54 may be closely related. As shown in Figure 6, the length L
  • the temperature is at least approximately 410 °C or at least approximately 430 °C. In another embodiment, the temperature is approximately 410 °C to 490 °C or approximately 430 °C to 460 °C. In yet another embodiment, the temperature is no more than approximately 490 °C or no more than approximately 480 °C.
  • the residence time and linear velocity of the heavy hydrocarbon material in the tubular reactor may be adjusted as necessary to provide the desired conversion rate and product characteristics.
  • the residence time is at least approximately 0.0S s, at least approximately 0.10 s, or, desirably, at least approximately 0.15 s.
  • the residence time is approximately 0.05 s to 1.5 s, approximately 0.10 s to 1.4 s, or, desirably, approximately 0.15 s to 1.3 s.
  • the residence time is no more than approximately 2 s, no more than approximately 1.5 s, no more than approximately 1.4 s, or, desirably, no more than approximately 1.3 s.
  • the linear velocity of the heavy hydrocarbon material in the tubular reactor may be at least approximately 4 m/s, at least approximately 5 m/s, or, desirably, at least approximately 6 m/s. In another embodiment, the linear velocity is approximately 4 to 40 m/s, approximately 5 to 35 m/s, or, desirably 4 to 32 m/s. In yet another embodiment, the linear velocity is no more than approximately 40 m/s, no more than approximately 35 m/s, or, desirably, no more than approximately 32 m/s. [0085]
  • the pressure gauge in the tubular reactor may vary as required to sustain the cracking reactors. In one embodiment, the tubular reactor may be at a pressure of approximately -34 kPa to 240 kPa or approximately -34 kPa to 140 kPa.
  • tubular reactor has been described primarily in conjunction with another reactor, it should be appreciated that the tubular reactor can be used along without any other reactors.
  • the tubular reactor may be made of any suitable material such as metal, composites, and so forth.
  • the tubular reactor is made of SS-316.
  • the system 100 cracks the heavy hydrocarbon material to produce lighter, lower molecular weight hydrocarbons.
  • the heavy hydrocarbon material is broken down into light hydrocarbon liquid distillate.
  • the light hydrocarbon liquid distillate includes hydrocarbons having a molecular weight less than about 300 Daltons. In certain embodiments, about 25% to about 50% of the heavy hydrocarbon material cracked in the system 100 is converted into distillates.
  • the system 100 may provide a much higher conversion rate than other comparable systems.
  • the conversion rate of heavy hydrocarbon material into distillates in the system 100 varies depending on the inputs, conditions, and a number of other factors.
  • the conversion rate of the system 100 is at least approximately 15%, at least approximately 30%, or, desirably, at least approximately 35%.
  • the total residence time of the heavy hydrocarbon material in the nozzle reactor and the tubular reactor may vary widely. In one embodiment, the total residence time is at least approximately 0.2 s or at least approximately 0.3 s. In another embodiment, the total residence time is approximately 0.2 s to 2 s or approximately 0.3 s to 1.2 s. In yet another embodiment, the residence time is no more than approximately 2 s or no more than approximately 1.8 s.
  • one significant advantage of the system 100 is that it produces very little, if any, coke and minimizes the amount of gas generated. This makes it possible to operate the system 100 for long periods of time without cleaning.
  • the system 100 may be operated indefinitely. Minimizing coke production also means that more of the heavy hydrocarbon material is conserved so that it can be used to produce higher value products than coke.
  • the amount of coke produced by the system 100 can be determined by measuring the amount of coke precursors present in the feed 106 and the effluent 110.
  • the feed 106 may include 0.1 wt% to 0.2 wt% of coke precursors and the effluent 120 may include 1 wt% to 2 wt% of coke precursors. This represents a substantial improvement over other technologies.
  • the effluent 110 may include no more than 5 wt% of coke precursors or no more than 3 wt% of coke precursors.
  • heavy hydrocarbon material may pass through the system 100 without being cracked.
  • This material may be referred to as non- participating heavy hydrocarbons or uncracked heavy hydrocarbons, since the reactors 102, 104 did not act on this material to crack it into lighter hydrocarbons.
  • Heavy hydrocarbon material that is cracked but still qualifies as heavy hydrocarbon material may also be referred to as non- participating heavy hydrocarbons.
  • the effluent 110 from the system 100 may be transported to a separation unit that separates it into its constituent fractions.
  • the separation unit may be any suitable separator capable of separating the effluent 110. Examples of suitable separation units include, but are not limited to, atmospheric or vacuum distillation units, gravity separation units, filtration units, and cyclonic separation units.
  • suitable separation units include, but are not limited to, atmospheric or vacuum distillation units, gravity separation units, filtration units, and cyclonic separation units.
  • the non-participating hydrocarbons may be subjected to further processing to upgrade it into more useful material. Various types of processing may be performed on the non- participating hydrocarbon for upgrading the non-participating hydrocarbon.
  • the remaining fractions may be used as end products or be subjected to further processing.
  • FIG. 2 another embodiment of a system 150 for cracking heavy hydrocarbon material is shown.
  • the system 150 is similar to the system 100 except that the non- participating heavy hydrocarbons 152 are separated from the effluent 110 in separation unit 154 and recycled back to the first reactor 102.
  • the non-participating heavy hydrocarbons 152 can be recycled back in perpetuity because the hydrogen interaction with the cracking fluid 108 minimizes or prevents coke formation.
  • no more than approximately 10 wt% (or 0 to 10 wt%) of the heavy hydrocarbons 152 are purged to increase process reliability and maintain a constant concentration of contaminants such as metals and sulfur in the material being recycled.
  • the system 150 may provide a significantly higher conversion rate than other comparable systems including hydrocrackers.
  • the conversion rate of heavy hydrocarbon material into distillates in the system 150 varies depending on the inputs, conditions, and a number of other factors.
  • the conversion rate of heavy hydrocarbon material in the system 150 may be at least approximately 65%, at least approximately 75%, or, desirably, at least approximately 90%.
  • most or at least substantially all of the heavy hydrocarbon material that enters the system 150 is cracked to distillates. The amount of non-participating heavy hydrocarbon material and/or coke left over from the process may be minor.
  • the system 150 is similar to the system shown in Figure 2 except that the feed 106 is a raw feed and it enters the separation unit 154 without entering the reactors 102, 104.
  • the feed 106 may be combined with the effluent 110 before entering the separation unit 154 or the feed 106 and the effluent 1 10 may separately enter the separation unit 154.
  • the heavy hydrocarbon material is separated from the feed 106 and the effluent 10 and fed back to the first reactor 102 in the manner shown in Figure 2.
  • the non-participating hydrocarbons may be injected into a third and fourth reactor positioned in series.
  • the third reactor may be a nozzle reactor that is designed similarly or identical to the first nozzle reactor.
  • the fourth reactor may be a tubular reactor that is similar or identical to the second reactor.
  • the dimensions of the additional nozzle and tubular reactor may be identical to the dimensions of the first nozzle and tubular reactor, or they may be scaled up or down.
  • the non-participating hydrocarbon stream may also be pretreated before entering the third and fourth reactor in a similar or identical way as those described above.
  • the systems 100, 150 crack the heavy hydrocarbon material without the use of a catalyst or added elemental hydrogen.
  • the systems 100, 150 are not catalytic cracking processes or hydro-cracking processes.
  • a method 210 for cracking heavy hydrocarbon material is depicted in Figure 5.
  • the method includes the step 200 of reacting the heavy hydrocarbon material and the cracking fluid 108 in the first reactor 102 to form a first effluent material.
  • the first effluent material is reacted in the second reactor 104 to form a second effluent material.
  • the first effluent is discharged directly from the first reactor 102 to the second reactor 104 without undergoing any intermediate processing or storage.
  • the second effluent material is separated at step 204 to isolate the non-participating heavy hydrocarbon material from distillates 212 and gas 214. T e non-participating heavy hydrocarbon material 152 is then recycled back to the first reactor 102. In some embodiments the separation and recycling step may be skipped in favor of sending the effluent on for further processing (e.g., catalytic cracking, hydro-cracking, etc.).
  • This example compares the conversion of heavy hydrocarbon material in a nozzle and coil reactor versus a nozzle reactor alone.
  • the hydrocarbon material used in this example is Cold Lake raw bitumen and it has the properties shown in Table 2.
  • the cracking fluid is steam.
  • the nozzle reactor is substantially the same as the nozzle reactor shown and described in U.S. Patent Application Publication No. 2009/0266741.
  • the specifications of the nozzle reactor are given in Table 3.
  • the coil reactor is a 2194.4 cm long tube that has an internal diameter of 1.6 cm that is uniform throughout its entire length.
  • the coil reactor has a spiral shape.
  • Each run is conducted as follows.
  • the cracking fluid is superheated to approximately 650 °C and approximately 2000 kPa.
  • the cracking fluid is sent to the nozzle reactor where it reaches a supersonic velocity of approximately Mach 2.8.
  • the heavy hydrocarbon material is preheated to a temperature of approximately 380 °C and injected into the nozzle reactor where it reacts with the superheated cracking fluid.
  • the nozzle reactor converts part of the heavy hydrocarbon material into lighter hydrocarbons that have a boiling point below 525 °C.
  • the partially upgraded feed from the nozzle reactor is discharged to the coil reactor.
  • the coil reactor provides the residence time at cracking temperatures of 420 to 470 °C to further convert the heavy hydrocarbon material into lighter distillates.
  • This example demonstrates that the coil reactor increases the conversion of the heavy hydrocarbon material versus the nozzle reactor alone.
  • the coil reactor provides increased residence time at high temperature, which drives conversion of the heavy hydrocarbon material.
  • This example demonstrates the nozzle and coil reactor combination is more efficient than the nozzle and straight tubular reactor.
  • the reaction rate constant of the nozzle/coil combination is twice that of the nozzle/straight tubular combination.
  • Example 3 The procedure for this example is the same as Example 1. One run was performed using only the nozzle reactor and another run used both the nozzle reactor and the coil reactor. The carbon pro ile for each run is shown in Table 6.
  • the word “or” when used without a preceding "either” shall be interpreted to be inclusive (e.g., “x or y” means one or both x or y).
  • the term “and/or” shall also be interpreted to be inclusive (e.g., "x and/or y” means one or both x or y).
  • a stated range of 1 to 10 should be considered to include and provide support for claims that recite any and all subranges or individual values that are between and/or inclusive of the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 5.5 to 10, 2.34 to 3.56, and so forth) or any values from 1 to 10 (e.g., 3, 5.8, .9994, and so forth).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un réacteur permettant de craquer des hydrocarbures lourds, comprenant un tube ayant un passage interne rempli d'un fluide qui comprend un matériau de type hydrocarbure lourd. Le réacteur est orienté verticalement de sorte que le fluide se déplace vers le bas à travers le passage interne du tube. Le passage interne comprend des sections linéaires et des sections incurvées alternées. Le passage interne est orienté de sorte qu'il se trouve sur un seul plan. Le réacteur peut être combiné avec un autre réacteur pour former un système de réacteurs.
PCT/US2012/033013 2011-04-22 2012-04-11 Réacteur à hydrocarbures lourds Ceased WO2012145204A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR112013027199A BR112013027199A2 (pt) 2011-04-22 2012-04-11 Reator de hidrocarboneto pesado
CA2833952A CA2833952A1 (fr) 2011-04-22 2012-04-11 Reacteur a hydrocarbures lourds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161478252P 2011-04-22 2011-04-22
US61/478,252 2011-04-22
US13/292,747 2011-11-09
US13/292,747 US20120267286A1 (en) 2011-04-22 2011-11-09 Heavy hydrocarbon reactor

Publications (2)

Publication Number Publication Date
WO2012145204A2 true WO2012145204A2 (fr) 2012-10-26
WO2012145204A3 WO2012145204A3 (fr) 2012-12-27

Family

ID=47020467

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/033013 Ceased WO2012145204A2 (fr) 2011-04-22 2012-04-11 Réacteur à hydrocarbures lourds

Country Status (4)

Country Link
US (1) US20120267286A1 (fr)
BR (1) BR112013027199A2 (fr)
CA (1) CA2833952A1 (fr)
WO (1) WO2012145204A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8435402B2 (en) 2010-03-29 2013-05-07 Marathon Canadian Oil Sands Holding Limited Nozzle reactor and method of use
US8586515B2 (en) 2010-10-25 2013-11-19 Marathon Oil Canada Corporation Method for making biofuels and biolubricants
FR3016536A1 (fr) * 2014-01-21 2015-07-24 Innoveox Dispositif d'injection d'oxydant pour une installation de traitement d'un effluent aqueux par oxydation hydrothermale
CN110314622B (zh) * 2019-07-23 2021-08-24 山东建筑大学 一种混合、反应、分离一体化液-液螺旋管旋流反应器

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464503A (en) * 1993-10-28 1995-11-07 Texaco Inc. Tire liquefying process reactor discharge system and method
US5624642A (en) * 1994-10-14 1997-04-29 Amoco Corporation Hydrocarbon processing apparatus
US6423279B1 (en) * 2000-10-16 2002-07-23 Harvest Energy Technology, Inc. Compact endothermic catalytic reaction apparatus
US6906164B2 (en) * 2000-12-07 2005-06-14 Eastman Chemical Company Polyester process using a pipe reactor

Also Published As

Publication number Publication date
BR112013027199A2 (pt) 2017-01-03
US20120267286A1 (en) 2012-10-25
WO2012145204A3 (fr) 2012-12-27
CA2833952A1 (fr) 2012-10-26

Similar Documents

Publication Publication Date Title
US8636958B2 (en) Nozzle reactor and method of use
US10011788B2 (en) Integrated slurry hydroprocessing and steam pyrolysis of crude oil to produce petrochemicals
US9284497B2 (en) Integrated solvent deasphalting and steam pyrolysis process for direct processing of a crude oil
AU2010307276A1 (en) Systems and methods for processing nozzle reactor pitch
US20140110307A1 (en) Dual reactor for improved conversion of heavy hydrocarbons
US20080099376A1 (en) Upgrading heavy hydrocarbon oils
US20130306519A1 (en) Nozzle reactor and method of use
US20110308995A1 (en) Dual reactor for better conversion of heavy hydrocarbons
US20120267286A1 (en) Heavy hydrocarbon reactor
US20130197289A1 (en) Integrated solvent deasphalting and steam pyrolysis process for direct processing of a crude oil
US20130105362A1 (en) Systems and methods for integrating bitumen extraction with bitumen upg...
US8435402B2 (en) Nozzle reactor and method of use
WO2013063573A1 (fr) Systèmes de réacteur à tuyères et procédés d'utilisation
US20110180454A1 (en) Methods for preparing solid hydrocarbons for cracking
US20130299387A1 (en) Methods and systems for upgrading hydrocarbon
US20130251597A1 (en) Nozzle reactor and method of use
US20130341245A1 (en) Methods and Systems for Upgrading Hydrocarbon Residuum
EP4551669A1 (fr) Systèmes et procédés de production de produits oléfiniques
CN119522269A (zh) 由烃类原料生产烯烃产品的系统和方法
WO2013056247A1 (fr) Procédés et systèmes de valorisation d'hydrocarbures
US20130161238A1 (en) Methods and Systems for Removing Material from Bitumen-Containing Solvent
WO2014003704A1 (fr) Procédés et systèmes de traitement de résidus d'hydrocarbures
OA16337A (en) Systems and methods for processing nozzle reactor pitch.
WO2010121041A1 (fr) Reacteur a buse et procede d'utilisation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12773978

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2833952

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013027199

Country of ref document: BR

122 Ep: pct application non-entry in european phase

Ref document number: 12773978

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 112013027199

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20131022