WO2013063573A1 - Nozzle reactor systems and methods of use - Google Patents

Nozzle reactor systems and methods of use Download PDF

Info

Publication number
WO2013063573A1
WO2013063573A1 PCT/US2012/062424 US2012062424W WO2013063573A1 WO 2013063573 A1 WO2013063573 A1 WO 2013063573A1 US 2012062424 W US2012062424 W US 2012062424W WO 2013063573 A1 WO2013063573 A1 WO 2013063573A1
Authority
WO
WIPO (PCT)
Prior art keywords
nozzle
reactor
injection
nozzle reactor
stream
Prior art date
Application number
PCT/US2012/062424
Other languages
French (fr)
Inventor
Jose Armando Salazar
Mahendra Joshi
Christopher Daniel Ard
Original Assignee
Marathon Oil Canada Corporation
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 Corporation filed Critical Marathon Oil Canada Corporation
Publication of WO2013063573A1 publication Critical patent/WO2013063573A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/32Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G51/00Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/06Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural parallel stages only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • C10C3/002Working-up pitch, asphalt, bitumen by thermal means

Definitions

  • Nozzle reactors have long been used to cause materials to interact and achieve alteration of the mechanical or chemical composition of the materials. Typically, this involves injecting differing types of materials into a reactor chamber of a nozzle reactor and allowing the materials to interact.
  • the '615 Publication states that its disclosed nozzle reactor is designed to receive a bitumen/steam flow mixture into a single central nozzle reactor passage extending along the axial length of the nozzle reactor.
  • the reference states that the nozzle forms a flow r passageway of circular diametric cross-section having the following sections in sequence from the bitumen/steam flow mixture inlet: a first contraction section of reducing diameter for accelerating the flow and reducing the size of bitumen droplets; a diffuser section of expanding diameter to decelerate the flow and induce a shock wave; a second contraction section to accelerate the mixture more than the first contraction section; and an orifice outlet for producing an output jet or spray,
  • the '615 Publication further states that the disclosed nozzle reactor reduces bitumen droplet size from about 12,000 ⁇ to about 300 ⁇ .
  • the nozzle reactor of the '615 Publication receives a pre-mixed bitumen/steam liquid medium
  • the nozzle reactor technique of the '615 Publication requires implementation of one or more substantial pre-mixing steps in order to generate and deliver the desired bitumen'steam liquid medium to the central nozzle reactor passage.
  • the pre-mixed liquid medium (including bitumen in the mixture) inherently yields limited velocities of the medium through the nozzle reactor.
  • a nozzle reactor is described in U.S. Patent Application Publication No. 2004/0065589 (the '589 Publication),
  • the nozzle reactor discussed in the '589 Publication has two steam injectors disposed: (i) laterally separated from opposing sides of a central, axially extending vapor expansion feed stock injector, (ii) at an acute angle to the axis of the central vapor expansion feed stock injector.
  • the steam injectors are thus disposed for ejection from the steam injectors in the direction of travel of material feed stock injected by the feed stock injector.
  • Each of the three injectors has a discharge end feeding into a central reactor ring or tube extending coaxially from the central feed stock injector.
  • the central feed stock injector appears as if it may have a divergent-to-convergent axial cross-section with a nearly plugged convergent end; but as shown in related Canadian Patent Application No, 2,346,181 (the '181 Publication), the central feed stock injector has a straight- through bore.
  • nozzle reactors of the type shown in the '589 Publication are inefficient; (ii) typically and perhaps always provide only sonic or subsonic velocity of a feed stock into the associated reactor tube; and (iii) yield excessive un-cracked or insufficiently cracked heavy hydrocarbons.
  • These same nozzle reactors also typically yield excessive coke formation and scaling of the nozzle reactor walls, reducing the efficiency of the nozzle reactor and requiring substantial effort to remove the scale formation within the nozzle reactor.
  • the nozzle reactor provides a hydrocarbon cracking nozzle reactor.
  • the method includes generating a supersonic stream of cracking material and impacting hydrocarbon material with the supersonic stream of cracking material.
  • the nozzle reactor has a material feed passage extending into an interior reactor chamber section generally transverse to the exit or injection axis of at least one injection passage.
  • at least one injection passage is coaxial with the axis of an associated interior reactor chamber and at least one material feed passage is disposed to inject material feed to impact the cracking material injected at the ejection end of the injection passage.
  • the nozzle reactor has an injection passage abutting an interior reactor chamber and a material feed passage extending into the interior reactor chamber transverse to the axis of the injection passage and adjacent the ejection end of the injection passage.
  • the injection passage can be a non-linear injection passage injectingly penetrating the interior reactor chamber.
  • the injection passage can have a cross-sectional configuration in which opposing side wall portions are curved inwardly toward the central axis of the injection passage along the axial length of the injection passage.
  • the curved side wall portions of the injection passage has a smooth finish without sharp edges or sudden changes in surface contour, most preferably along the entire axial length of the injection passage.
  • the curved side wall portions of the injection passage can provide a nearly or substantially isentropic or frictionless passage for cracking material passing through the injection passage into the interior reactor chamber.
  • the nozzle reactor includes a material feed passage having at least one or more material feed ports, and if desired one or more partially or completely annular material feed ports, injectingly abutting the interior reactor chamber.
  • a material feed passage can include a reactor chamber material feed slot injectingly penetrating at least a substantial portion, or if desired, the entire outer circumferential periphery of an annular material feed port. The latter configuration can, in the case of a completely annular material feed port for example, provide impact of the material feed stream with the entire circumference of the injected cracking material stream,
  • the reactor chamber material feed slot or end of the annular material feed port is disposed axial ly adjacent the end of the injection passage injectingiy penetrating the interior reactor chamber. In this fashion, material feed can be injected through the material feed passage radially inwardly toward, and optionally transverse to, an adjacent cracking material injected through the injection passage.
  • the nozzle reactor comprises an annular or other port insert member mounted intermediate the interior reactor chamber and the injection passage.
  • the ejection port of the interior reactor chamber, opposite the injection passage, can provide a passage through which cracking material and other material can pass out of the reactor body.
  • the injection passage may have a frustoconical configuration.
  • Some embodiments of the present invention provide a conical, stepped, or telescoped interior reactor chamber, or a combined conical and otherwise shaped interior reactor chamber, extending along the axial length of the interior reactor chamber.
  • the interior reactor chamber can be configured to generally provide interfering, turbulence-inducing contact, optionally limited contact, between the cracking material and the material feed injected into the interior reactor chamber.
  • the injection passage includes an insert mounted within the injection passage and has a thin-thick-thin cross-section along the axial length of the insert.
  • the insert can have a radially outwardly curved periphery along the axial length of the insert.
  • Some embodiments provide a method of injecting cracking material and a feed material into a nozzle reactor, Some embodiments can include injecting cracking material from an injection passage into an interior reactor chamber along the axial length of the interior reactor chamber section and injecting feed material into the interior reactor chamber transverse to the axis of the interior reactor chamber. In some embodiments, the feed material is injected adjacent the end of the injection passage injectmgly abutting the interior reactor chamber. As a result, the cracking material impacts the feed material virtually immediately after ejection from the injection passage. This impact can thus take place before the velocity of the cracking material dimini shes appreciably.
  • cracking material comprises superheated steam and the feed material comprises pre-heated heavy hydrocarbons.
  • the heavy hydrocarbons can include or consist largely or even essentially of bitumen.
  • Cracking material also can include natural gas, carbon dioxide, or other gases.
  • the feed material is injected to impact the cracking material upon its ejection from the injection passage, at an angle of about 90°.
  • the bar pressure level of the superheated steam cracking material is substantially greater than, and preferably more than double, the pressure level within the interior reactor chamber.
  • the cracking material is injected through the injection passage into the interior reactor chamber at supersonic speeds. In some embodiments, the cracking material injection speed is twice the speed of sound or more.
  • Some embodiments provide reduced back flow and enhanced mechanical shear within the interior reactor chamber. Some embodiments may do so and accomplish substantial cracking of a desired hydrocarbon very quickly and generally without substantial regard to retention time of the material feeds within the reactor body. In other embodiments, increased retention time of the material feed within the reactor body can result in higher cracking rates.
  • Some embodiments of the apparatus and methods provide more efficient generation and transfer of kinetic energy from a cracking materia! to a material feed. Some embodiments also provide increased material processing capability and output and reduced uncracked material or other by-products in the output from the nozzle reactor or retained within the confines of the nozzle reactor, such as reduced scale formation on the side walls of the interior reactor chamber. Some embodiments also provide a relatively economical, durable, and easy-to-maintain or repair nozzle reactor.
  • Some embodiments provide mechanical cracking of hea vy oils or asphaltenes.
  • the cracking reaction can be caused primarily mechanically by the application of extreme shear rather than by temperature, retention time, or interaction with a catalyst.
  • the cracking may be selective, such as by selectively cracking primarily only the larger molecules making up certain heavy hydrocarbons in a hydrocarbon feed stock,
  • the nozzle reactor provides not only more selective and efficient cracking of material feed but also, or alternatively, reduced coke formation and reactor chamber scaling. In some embodiments, reactor chamber scaling may even be eliminated.
  • a nozzle reactor system generally comprises a first nozzle reactor and a second nozzle reactor. Each of the first nozzle reactor and the second nozzle reactor can be a nozzle reactor as described herein.
  • the nozzle reactor system can also include a first separation unit. The first separation unit is in fluid communication with an ejection end of the first nozzle reactor such tha material leaving the nozzle reactor flows into the separation unit.
  • the first separation unit includes a light stream outlet and a heavy stream outlet, The heavy stream outlet is in fluid communication with the material feed passage of the second nozzle reactor such that the heavy stream is injected into the nozzle reactor for further cracking.
  • a feed material cracking method includes a step of injecting a first stream of cracking material through an injection passage of a first nozzle reactor into an interior reaction chamber of a first nozzle reactor. The method further includes a step of injecting a material feed into the interior reactor chamber of the first nozzle reactor adjacent to the injection passage of the first nozzle reactor and transverse to the first stream of cracking material entering the interior reactor chamber of the first nozzle reactor from the injection passage of the first nozzle reactor to produce first light material and first heavy material. The method also includes a step of injecting a second stream of cracking material through an injection passage of a second nozzle reactor into a reaction chamber of a second nozzle reactor.
  • the method includes a step of injecting the first heavy material into the interior reactor chamber of the second nozzle reactor adjacent to the injection passage of the second nozzle reactor and transverse to the second stream of cracking material entering the interior reactor chamber of the second nozzle reactor from the injection passage of the second nozzle reactor to thereby produce second light material and second heavy material.
  • a nozzle reactor system comprises: a stream dividing apparatus comprising a first output port and a second output port; a first nozzle reactor having a feed material injection port in fluid communication with the first output port of the stream dividing apparatus, and an ejection end; a second nozzle reactor having a feed material injection port in fluid communication with the second output port of the stream dividing apparatus, and an ejection end; and a mixing apparatus having a first input port in fluid communication with the ejection end of the first nozzle reactor, and a second input port in fluid communication with the ejection end of the second nozzle reactor.
  • a material cracking method comprises mjecting a first material stream into a stream dividing apparatus and producing a first divided stream and a second divided stream, injecting the first divided stream into a first nozzle reactor and injecting the second divided stream into a second nozzle reactor, injecting a stream of cracking material into the first nozzle reactor and injecting a stream of cracking material into the second nozzle reactor, and combining a first nozzle reactor product from the first nozzle reactor and a second nozzle reactor product from the second nozzle reactor in a mixing apparatus,
  • Figure 1 is a cross-sectional, schematic view of one embodiment of a nozzle reactor suitable for use in various embodiments of the methods and systems described herein;
  • Figure 2 is a cross-sectional view of the nozzle reactor of Figure 1 , showing further construction details for the nozzle reactor;
  • Figure 3 shows a cross-sectional view of one embodiment of a nozzle reactor suitable for use in various embodiments of the systems and methods described herein;
  • Figure 4 shows a cross-sectional view of the top portion of the nozzle reactor shown in Figure 3:
  • Figure 5 shows a cross-sectional perspective view of the mixing chamber in the nozzle reactor shown in Figure 3;
  • Figure 6 shows a cross-sectional perspective view of the distributor from the nozzle reactor shown in Figure 3;
  • Figure 7 shows a cross-sectional view of another embodiment of a nozzle reactor suitable for use in various embodiments of the systems and methods described herein;
  • Figure 8 shows a cross-sectional view of the top portion of the nozzle reactor shown in Figure 7.
  • Figure 9 is a flow diagram illustrating a feed material cracking method according to various embodimenta disclosed herein;
  • Figure 10 is a block diagram illustrating a nozzle reactor system according to various embodiments disclosed herein;
  • Figure 1 1 is a block diagram illustrating a nozzle reactor system according to various embodiments described herein;
  • hydrocarbon and “hydrocarbons” as used herein may include organic material besides hydrogen and carbon, such as vanadyl, sulfur, nitrogen, and any other organic compound that may be in oil.
  • the nozzle reactor indicated generally at 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 an injection passage 15 extending into the interior reactor chamber 16 of the reactor body 14.
  • the central axis A of the injection passage 15 is coaxial with the central axis B of the interior reactor chamber 16.
  • the injection passage 15 has a circular diametric cross-section and, as shown in the axiaily-extending cross-sectional view of Figure 1 , opposing inwardly curved side wall portions 17, 19 (i.e., curved inwardly toward the central axis A of the injection passage 15) extending along the axial length of the injection passage 15.
  • the axially inwardly curved side wall portions 17, 19 of the injection passage 15 allow for a higher speed of injection gas when passing through the injection passage 15 into the interior reactor chamber 16.
  • the side wall of the injection passage 15 can provide one or more among: (i) uniform axial acceleration of cracking material passing through the injection passage; (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 injection passage 15 substantially isentropic.
  • a material feed passage 18 extends from the exterior of the reactor body 14 toward the interior reactor chamber 16 transversely to the axis B of the interior reactor chamber 16.
  • the material feed passage 18 penetrates an annular material 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 material feed port 20 includes an annular, radially extending reactor chamber feed slot 26 in material-injecting communication with the interior reactor chamber 16.
  • the material feed port 20 is thus configured to inject feed material: (i) at about a 90° angle to the axis of travel of cracking material injected from the injection passage 15; (ii) around the entire circumference of a cracking material injected through the injection passage 15; and (iii) to impact the entire circumference of the free cracking material stream virtually immediately upon its emission from the injection passage 15 into the interior reactor chamber 16.
  • the annular material feed port 20 may have a U-shaped or ( "' -shaped cross-section among others.
  • the annular materia! 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 material feed passage 18 toward the interior reactor chamber 16.
  • the junction of the annular material feed port 20 and material feed passage 1 8 can have a radiused cross-section.
  • the material feed passage 18, annular material feed port 20, and/or injection passage 15 may have differing orientations and configurations, and there can be more than one material feed port and associated structure.
  • the injection passage 15 may be located on or in the interior reactor chamber side 23 (and if desired may include an annular cracking material port) rather than at the reactor body injection end 12 of the reactor body 14, and the annular material feed port 20 may be non-annular and located at the reactor body injection end 12 of the reactor body 14.
  • the interior reactor chamber 16 can 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 material, such as superheated steam, natural gas, carbon dioxide, or other gas, to travel generally along and within the conical jet path C generated by the injection passage 15 along the axis B of the interior reactor chamber 16, whil e (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 materia] jet stream within the conical jet pat C and feed material, such as heavy hydrocarbons, injected through the annular material feed port 20.
  • a free jet of injected cracking material such as superheated steam, natural gas, carbon dioxide, or other gas
  • the reactor body 14 has an axial length (along axis B) that is muc greater than its width.
  • exemplary length-to-width ratios are typically in the range of 2 to 4 or more.
  • the dimensions of the various components of the nozzle reactor shown in Figure 1 are not limited, and may generally be adjusted based on the amount of material feed to be cracked inside the nozzle reactor.
  • Table 1 provides exemplary dimensions for the various components of the nozzle reactor based on the hydrocarbon input in barrels per day (BPD).
  • the reactor body 44 includes a generally tubular central section 46 and a frustoconical ejection end 48 extending from the central section 46 opposite an insert end 50 of the centra] section 46, with the insert end 50 in turn abutting the in jection nozzle 52.
  • the insert end 50 of the central section 46 consists of a generally tubular central body 51.
  • the central body 51 has a tubular material feed passage 54 extending from the external periphery 56 of the insert end 50 radially inwardly to injectingly communicate with the annular circumferential feed port depression or channel 58 in the otherwise planar, radially inwardly extending portion 59 of the axially stepped face 61 of the insert end 50.
  • the inwardly extending portion 59 abuts the planar radially internally extending portion 53 of a matingly stepped face 55 of the injection nozzle 52.
  • the feed port channel 58 and axially opposed radially internally extending portion 53 of the injection nozzle 52 cooperatively provide an annular feed port 57 disposed transversely laterally, or radially outwardly, from the axis A of a preferably non-linear injection passage 60 in the injection nozzle 5 ⁇ ..
  • the tubular body 1 of the insert end 50 is secured within and adjacent the interior periphery 64 of the reactor body 44.
  • the mechanism for securing the insert end 50 in this position may consist of an axially-extending nut-and-bolt arrangement (not shown) penetrating co-linearly mating passages (not shown) in: (i) an upper radially extending lip 66 on the reactor body 44; (ii) an abutting, radially outwardly extending thickened neck section 68 on the insert end 50; and (iii) in turn, the abutting injector nozzle 52.
  • Other mechanisms for securing the insert end 50 within the reactor body 44 may include a press fit (not shown) or mating threads (not shown) on the outer periphery 62 of the tubular body 51 and on the inner periphery 64 of the reactor body 44.
  • Seals, e.g., 70 may be mounted as desired between, for example, the radially extending lip 66 and the abutting the neck section 68 and the neck section 68 and the abutting injector nozzle 52.
  • the non-linear injection passage 60 has, from an axialiy-extending cross-sectional perspective, mating, radially inwardly curved opposing side wall sections 72, 74 extending along the axial length of the non-linear injection passage 60.
  • the entry end 76 of injection passage 60 provides a rounded circumferential face abutting an injection feed tube 78, which can be bolted (not shown) to the mating planar, radially outwardly extending distal face 80 on the injection nozzle 52.
  • the injection passage 60 is a DeLavai type of nozzle and has an axially convergent section 82 abutting an intermediate relatively narrower throat section 84, which in turn abuts an axially divergent section 86.
  • the injection passage 60 also has a circular diametric cross-section (i.e., in cross-sectional view perpendicular to the axis of the nozzle passage) all along its axial length.
  • the injection passage 60 may also present a somewhat roundly curved thick 82, less curved thicker 84, and relatively even less curved and more gently sloped relatively thin 86 axially extending cross-sectional configuration from the entry end 76 to the injection end 88 of the injection passage 60 in the injection nozzle
  • the injection passage 60 can thus be configured to present a substantially iseiitropic or frictionless configuration for the injection nozzle 52. This configuration may vary, however, depending on the application involved in order to yield a substantially isentropic configuration for the application.
  • the injection passage 60 is formed in a replaceable injection nozzle insert 90 press-fit or threaded into a mating injection nozzle mounting passage 92 extending axially through an injection nozzle body 94 of the injection nozzle 52.
  • the injection nozzle insert 90 is preferably made of hardened steel alloy, and the balance of the nozzle reactor 100 components other than seals, if any, are preferably made of steel or stainless steel.
  • the diameter D within the injection passage 60 is 140 mm.
  • the diameter E of the ejection passage opening 96 in the ejection end 48 of the reactor body 44 is 2.2 meters.
  • the axial length of the reactor body 44, from the injection end 88 of the injector passage 60 to the ejection passage opening 96, is 10 meters.
  • the interior peripheries 89, 91 of the insert end 50 and the tubular central section 46, respectively, cooperatively provide a stepped or telescoped structure expanding radially outwardly from the injection end 88 of the injection passage 60 toward the frustoconical end 48 of the reactor body 44,
  • the particular dimensions of the various components will vary based on the particular application for the nozzle reactor, generally 100. Factors taken into account in determining the particular dimensions include the physical properties of the cracking gas (density, enthalpy, entropy, heat capacity, etc.) and the pressure ratio from the entry end 76 to the injection end 88 of the injection passage 60.
  • the embodiment of Figure 2 may be used to, for example, crack heavy hydrocarbon material, including bitumen if desired, into lighter hydrocarbons and other components.
  • superheated steam (not shown) is injected into the injection passage 60.
  • the pressure differential can yield a steady increase in the kinetic energy of the cracking material as it moves along the axial length of the cracking material injection passage(s) 60,
  • the cracking material may thereby eject from the ejection end 88 of the injection passage 60 into the interior of the reactor body 44 at supersonic speed with a commensurately relatively high level of kinetic energy.
  • the level of kinetic energy of the supersonic discharge cracking material is therefore greater than can be achieved by certain prior art straight-through injectors or other injectors such as the convergent, divergent, convergent nozzle reactor of the '615 Publication.
  • a cracking material injection passage may not be as isentropic but may pro vide a substantial increase in the speed and kinetic energy of the cracking material as it moves through the injection passage 60.
  • an injection passage 60 may comprise a series of conical or toroidal sections (not shown) to provide varying cracking material acceleration through the passage 60 and, in certain embodiments, supersonic discharge of the cracking material from the passage 60.
  • heavy hydrocarbon feed stock (not shown) is pre-heated, for example at 2-1.5 bar, which is generally the same pressure as that in the reactor body 44.
  • the preheat should provide a feed, stock temperature of 300 to 500°, and most advantageously 400 to 450° C.
  • the preheated feed stock is injected into the material feed passage 54 and then through the mating annular feed port 57.
  • the feed stock thereby travels radially inwardly to impact a transversely (i.e., axially) traveling high speed cracking material jet (for example, steam, natural gas, carbon dioxide or other gas not.
  • a transversely (i.e., axially) traveling high speed cracking material jet for example, steam, natural gas, carbon dioxide or other gas not.
  • a catalyst can be introduced into the nozzle reactor to enhance cracking of the material feed stock by the cracking gas ejection stream.
  • KEj is the kinetic energy of the cracking material (referred to as the free jet) immediately upon emission from an injection nozzle
  • Ho is the enthalpy of cracking material upon entr ⁇ ' into the injection nozzle
  • Hj is the enthalpy of cracking material upon emission from the injection nozzle
  • KE 0 is the kinetic energy of the cracking material at the inlet of the nozzle.
  • thermodynamics an expression of the universal law of increasing entropy, stating that the entropy of an isolated system that is not in equilibrium will tend to increase over time, approaching a maximum value at equilibrium - means that no real process is perfectly isentropic.
  • a practically isentropic nozzle i.e., a nozzle commonly referred to as "isentropic” in the art
  • isentropic is one in which the increase in entropy through the nozzle results in a relatively complete or very high conversion of thermal energy into kinetic energy.
  • non-isentropic nozzles such as a straight-bore nozzle not only result in much less efficiency in conversion of thermal energy into kinetic energy but also can impose upper limits on the amount of kinetic energy available from them.
  • a practically "isentropic" converging/diverging nozzle such as shown in, for example, Figures 1 and 2, can yield, i.e.. eject, a gas jet that is supersonic. Consequently, the kinetic energy of the gas jet delivered by such an isentropic converging/diverging nozzle can be substantially greater tha that of the straight-bore nozzle, such as that shown in the ' 181 Publication.
  • certain embodiments disclosed above can provide a nozzle reactor providing enhanced transfer of kinetic energy to the material feed stock through many aspects such as, for example, by providing a supersonic cracking gas jet, improved orientation of the direction of flow of a cracking gas (or cracking gas mixture) with respect to that of the material feed stock, and/or more complete cracking gas stream impact with the material feed stock as a result of, for example, an annular material feed port and the telescoped reactor body interior, Certain embodiments also can result in reduced retention of by-products, such as coking, on the side walls of the reactor chamber.
  • Embodiments of the nozzle reactor can also be relatively rapid in operation, efficient, reliable, easy to maintain and repair, and relatively economical to make and use.
  • the injection material may comprise a cracking fluid or other motive material rather than, or in addition to, a cracking gas.
  • certain embodiments may utilize components that comprise motive material compatible components rather than, as described in particular embodiments above, cracking material compatible components such as, for example, the injection passage, e.g., 60, referenced above.
  • the motive material preferably is compressible.
  • the theoretically tested straight-through injection passage nozzle reactors of the prior art theoretically provide steam jet velocity at, or less than, the speed of sound.
  • the theoretically tested convergent/divergent injection passage nozzle reactors of the present application theoretically can provide a steam jet velocity in the interior reactor chamber well in excess of the speed of sound and, at 3 bar interior reactor chamber pressure, in excess of twice the speed of sound.
  • the associated kinetic energies of steam jets of the convergent/divergent injection passage nozzle reactors are theoretically significantly greater than the associated kinetic energies of the steam jets of the linear injection passage nozzle reactors.
  • the kinetic energies of cracking gas jet of the convergent/divergent injection passage nozzle reactors can also be significantly greater than the associated kinetic energies of the medium of the convergeni/divergent/conv rg nt injection passage of the type disclosed in the '615 Publication.
  • the velocity and kinetic energy of the bitumen/steam medium is designed to substantially decrease at least via the second convergent section, thus diminishing the ultimate velocity and kinetic energy of the medium when ejected from the '615 Publication's nozzle reactor, in addition, the '615 Publication's use of a mixed bitumen/steam medium itself reduces the velocity of the medium as compared to the velocities, and resulting shear, attainable by injection of separate steam and pre-heated bitumen feeds, for example.
  • Certain embodiments of the present reactor nozzle and method of use can therefore accomplish cracking of bitumen and other feed stocks primarily, or at least more substantially, by mechanical shear at a molecular level rather than by temperature, retention time, or involvement of catalysts.
  • the driving force of the hydrocarbon cracking process can be mechanical rather than chemical.
  • certain embodiments can utilize the greater susceptibility of at least certain heavy hydrocarbons to mechanical cracking in order to selectively crack particular hydrocarbons (such as relatively heavy bitumen for example) as opposed to other lighter hydrocarbons or other materials that may be in the material feed stock as it passes through the nozzle reactor.
  • the configuration of the nozzle reactor can reduce and even virtually eliminate back mixing while enhancing, for example, plug flow of the cracking ma terial and material feed mixture through the reactor body and cooling of the mixture through the reactor body. This can aid in not only enhancing mechanical cracking of the material feed but also in reducing coke formation and wall scaling within the reactor body. In combination with injection of a high velocity cracking material or other motive material from the injection nozzle into the reactor body, coke formation and wall scaling can be even more significantly reduced if not virtually or practically eliminated. In these embodiments, the nozzle reactor can thus provide more efficient and complete cracking, and if desired selective cracking, of heavy hydrocarbons, while reducing and in certain embodiments virtually eliminating wail scaling within the reactor body.
  • FIG. 3 to 8 Another embodiment of a nozzle reactor suitable for use in the methods and systems described herein is illustrated in Figures 3 to 8.
  • Figures 3 and 4 show cross-sectional views of one embodiment of a nozzle reactor 1000 suitable for use in the methods described herein.
  • the nozzle reactor 1000 includes a head portion 1002 coupled to a body portion 1004.
  • A. main passage 1006 extends through both the head portion 1002 and the body portion 1004.
  • the head and body portions 1002, 1004 are coupled together so that the central axes of the main passage 1006 in each portion 1002, 1004 are coaxial so that the main passage 1006 extends straight through the nozzle reactor 1000.
  • the term "coupled” means the joining of two members directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate member being attached to one another. Such joining may be permanent in nature or alternatively may be removable or releasable in nature.
  • the nozzle reactor 1000 includes a feed passage 1008 that is in fluid communication with the main passage 1006.
  • the feed passage 1008 intersects the main passage 1006 at a location between the portions 1002, 1004.
  • the main passage 1006 includes an entry opening 1010 at the top of the head portion 1002 and a exit opening 1 012 at the bottom of the body portion 1004.
  • the feed passage 1008 also includes an entry opening 1014 on the side of the body portion 1004 and an exit opening 1016 that is located where the feed passage 1008 meets the main passage 1006.
  • the nozzle reactor 1000 includes a reacting fluid that flows through the main passage 1006.
  • the reacting fluid enters through the entry' opening 1 010, travels the length of the main passage 1006, and exits the nozzle reactor 1000 out of the exit opening 1012.
  • a feed material flows through the feed passage 1008.
  • the feed material enters through the entry opening 1014, travels through the feed passage 1006, and exits into the main passage 1008 at exit opening 1016.
  • the main passage 1006 is shaped to accelerate the reacting fluid.
  • the main passage 1006 may have any suitable geometry that is capable of doing this.
  • the main passage 1006 includes a first region having a convergent section 1020 (also referred to herein as a contraction section), a throat 1022, and a divergent section 1024 (also referred to herein as an expansion section).
  • the first region is in the head portion 1002 of the nozzle reactor 1000.
  • the convergent section 1020 is where the main passage 1006 narrows from a wide diameter to a smaller diameter
  • the divergent section 1024 is where the main passage 1006 expands from a smaller diameter to a larger diameter.
  • the throat 1022 is the narrowest point of the main passage 1006 between the convergent section 1020 and the divergent section 1024.
  • the main passage 1006 appears to be pinched in the middle, making a carefully balanced, asymmetric hourglass-like shape. This configuration is commonly referred to as a convergent-divergent nozzle or "con-di nozzle”.
  • the convergent section of the main passage 1006 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 or Mach 1 at the throat 1022 provided that the pressure ratio is high enough. In this situation, the main passage 1006 is said to be in a choked flow condition,
  • Mach 1 can be a very high speed for a hot fluid since the speed of sound varies as the square root of absolute temperature. Thus the speed reached at the throat 1022 can be far higher than the speed of sound at sea level.
  • the divergent section 1024 of the main passage 1006 slows subsonic fluids, but accelerates sonic or supersonic fluids.
  • a convergent-divergent geometry can therefore accelerate fluids in a choked flow condition to supersonic speeds.
  • the convergent-divergent geometry ca be used to accelerate the hot, pressurized reacting 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 reacting fluid through the convergent-divergent nozzle is isentropic (fluid entropy is nearly constant).
  • the main passage 1006 only reaches a choked flow condition at the throat 1022 if the pressure and mass flow rate is sufficient to reach sonic speeds, otherwise supersonic flow is not achieved and the main passage will act as a venturi tube.
  • the entry pressure to the nozzle reactor 1000 should be significantly above ambient pressure
  • the pressure of the fluid at the exit of the divergent section 1024 of the main passage 1006 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 divergent section 1024 of the main passage 1006 forming an unstable jet that "flops" around and damages the main passage 1006.
  • the ambient pressure is no higher than approximately 2-3 times the pressure in the supersonic gas at the exit.
  • the supersonic reacting fluid collides and mixes with the feed material in the nozzle reactor 1000 to produce the desired reaction.
  • the high speeds involved and the resulting collision produces a significant amount of kinetic energy that helps facilitate the desired reaction.
  • the reacting fluid and/or the feed material may also be pre-heated to provide additional thermal energy to react the materials.
  • the nozzle reactor 1000 may be configured to accelerate the reacting fluid to at least approximately Mach 1 , at least approximately Mach 1.5, or, desirably, at least approximately Mach 2.
  • the nozzle reactor may also be configured to accelerate the reacting fluid to approximately Mach 1 to approximately Mach 7, approximately Mach 1.5 to approximately Mach 6, or, desirably, approximately Mach 2 to approximately Mach 5.
  • the main passage 1006 has a circular cross-section and opposing converging side walls 1026, 1028.
  • the side walls 1026, 1028 curve inwardly toward the central axis of the main passage 1006.
  • the side walls 1026, 1028 form the convergent section 1020 of the main passage 1006 and accelerate the reacting fluid as described above.
  • the main passage 1006 also includes opposing diverging side walls 1030, 1032.
  • the side walls 1030, 1032 curve outwardly (when viewed in the direction of flow) away from the central axis of the main passage 106.
  • the side wails 1030, 1032 form the divergent section 1024 of the main passage 106 that allows the sonic fluid to expand and reach supersonic velocities.
  • the side walls 1026, 1028, 1030, 1032 of the main passage 1006 provide uniform axial acceleration of the reacting fluid with minimal radial acceleration.
  • the side walls 1026, 1028, 1030, 1032 may also have a smooth surface or finish with an absence of sharp edges that may disrupt the flow.
  • the configuration of the side walls 1026, 1028, 1030, 1032 renders the main passage 1006 substantially isentropic.
  • the feed passage 1008 extends from the exterior of the body portion 1004 to an annular chamber 1034 formed by head and body portions 1002, 1004.
  • the portions 1002, 1 004 each have an opposing cavity so that when they are coupled together the cavities combine to form the annular chamber 1034.
  • a seal 1036 is positioned along the outer circumference of the annular chamber 1034 to prevent the feed material from leaking through the space between the head and body portions 1002, 1004,
  • the head and body portions 1002, 1004 may be coupled together in any suitable manner. Regardless of the method or devices used, the head and body portions 1002, 1004 should be coupled together in a way that prevents the feed material from leaking and withstands the forces generated in the interior, In one embodiment, the portions 1002, 1004 are coupled together using bolts that extend through holes in the outer flanges of the portions 1002, 1004.
  • the nozzle reactor 1000 includes a distributor 1040 positioned between the head and body portions 1002, 1004.
  • the distributor 1040 prevents the feed material from flowing directly from the opening 1041 of the feed passage 1008 to the main passage 1006. Instead, the distributor 1040 annular!y and uniformly distributes the feed materia! into contact with the reacting fluid flowing in the main passage 1006.
  • the distributor 1040 includes an outer circular wall 1048 that extends between the head and body portions 1002, 1004 and forms the inner boundary of the annular chamber 1034.
  • a sea! or gasket may be provided at the interface between the distributor 140 and the head and body portions 1002, 1004 to prevent feed material from leaking around the edges.
  • the distributor 1040 includes a plurality of holes 1044 that extend through the outer wall 1048 and into an interior chamber 1046.
  • the holes 1044 are evenly spaced around the outside of the distributor 1040 to provide even flow into the interior chamber 1046.
  • the interior chamber 1046 is where the main passage 1006 and the feed passage 1008 meet and the feed material comes into contact with the supersonic reacting fluid.
  • the distributor 1040 is thus configured to inject the feed material at about a 90° angle to the axis of tra vel of the reacting fluid in the main passage 1006 around the entire circumference of the reacting fluid.
  • the feed material thus forms an annul us of flow that extends toward the main passage 1006.
  • the number and size of the holes 1044 are selected to provide a pressure drop across the distributor 1040 that ensures that the flow through each hole 1044 is approximately the same.
  • the pressure drop across the distributor is at least approximately 2000 pascals, at least approximately 3000 pascals, or at least approximately 5000 pascals.
  • the distributor 1040 includes a wear ring 1050 positioned immediately adjacent to and downstream of the location where the feed passage 108 meets the main passage 1006. The collision of the reacting fluid and the feed material causes a lot of wear in this area.
  • the wear ring is a physically separate component that is capable of being periodically removed and replaced.
  • the distributor 1040 includes an annular recess 1052 that is sized to receive and support the wear ring 1050.
  • the wear ring 1050 is coupled to the distributor 1040 to prevent it from moving during operation.
  • the wear ring 1050 may be coupled to the distributor in any suitable manner.
  • the w r ear ring 1050 may be welded or bolted to the distributor 1040. If the wear ring 1050 is welded to the distributor 1040, as shown in Figure 5, the wear ring 1050 can be removed by grinding the weld off. In some embodiments, the weld or bolt need not protrude upward into the interior chamber 1046 to a significant degree.
  • the wear ring 1050 can be removed by separating the head portion 1002 from the body portion 1004. With the head portion 1002 removed, the distributor 1040 and/or the wear ring 1050 are readily accessible. The user can remove and/or replace the wear ring 1050 or the entire distributor 1040, if necessary.
  • the main passage 1006 expands after passing through the wear ring 1050.
  • This can be referred to as expansion area 1060 (also referred to herein as an expansion chamber).
  • the expansion area 1060 is formed largely by the distributor 1040, but can also be formed by the body portion 1004.
  • the main passage 1006 includes a second region having a converging-diverging shape.
  • the second region is in the body portion 1004 of the nozzle reactor 1000,
  • the main passage includes a convergent section 1070 (also referred to herein as a contraction section), a throat 1072, and a divergent section 1074 (also referred to herein as an expansion section).
  • the converging-diverging shape of the second region differs from that of the first region in that it is much larger, in one embodiment, the throat 1072 is at least 2-5 times as large as the throat 1022,
  • the second region provides additional mixing and residence time to react the reacting fluid and the feed material.
  • the main passage 1006 is configured to allow a portion of the reaction mixture to flow backward from the exit opening 1012 along the outer wail 1076 to the expansion area 1060, The backflow then mixes with the stream of material exiting the distributor 1040. This mixing action also helps drive the reaction to completion.
  • the dimensions of the nozzle reactor 1000 can vary based on the amount of material that is fed through it. For example, at a flow rate of approximately 590 kg/hr, the distributor 140 can include sixteen holes 144 that are 3 mm in diameter.
  • the dimensions of the various components of the nozzle reactor shown in Figures 3 and 4 are not limited, and may generally be adjusted based on the amount of feed flow rate if desired, Table 3 provides exemplary dimensions for the various components of the nozzle reactor 1000 based on a hydrocarbon feed input measured in barrels per day (BPD).
  • the nozzle reactor 1000 can be configured in a variety of ways that are different than the specific design shown in the Figures, For example, the location of the openings 1010, 1012, 1014, 1016 may be placed in any of a number of different locations. Also, the nozzle reactor 1000 may be made as an integral unit instead of comprising two or more portions 1002, 1004, Numerous other changes may be made to the nozzle reactor 1000.
  • FIG. 7 and 8 another embodiment of a nozzle reactor 2000 is shown. This embodiment is similar in many ways to the nozzle reactor 1000. Similar components are designated using the same reference number used to illustrate the nozzle reactor 1000. The previous discussion of these components applies equally to the similar or same components includes as part of the nozzle reactor 2000.
  • the nozzle reactor 2000 differs a few ways from the nozzle reactor 1000.
  • the nozzle reactor 2000 includes a distributor 2040 that is fomied as an integral part of the body portion 2004.
  • the wear ring 1050 is still a physically separate component that can be removed and replaced.
  • the wear ring 1050 depicted in Figure 18 is coupled to the distributor 2040 using bolts instead of by welding. It should be noted that the bolts are recessed in the top surface of the wear ring 1050 to prevent them from interfering with the flow of the feed material.
  • the head portion 1002 and the body portion 1004 are coupled together with a clamp 2080.
  • the seal which can be metal or plastic, resembles a "T" shaped cross- section.
  • the leg 2082 of the "T” forms a rib that is held by the opposing faces of the head and body portions 1002, 1004.
  • the two arms or lips 2084 form seals that create an area of sealing surface with the inner surfaces 2076 of the portions 1002, 1004. Internal pressure works to reinforce the seal.
  • the clamp 2080 fits over outer flanges 2086 of the head and body portions 1002, 1004.
  • the seal lips deflect against the inner surfaces 2076 of the portions 1002, 1004. This deflection elastically loads the lips 2084 against the inner surfaces 2076 forming a self-energized seal,
  • the clamp is made by Grayloc Products, located in Houston, XX.
  • a nozzle reactor system may be used to increase the overall conversion of material feed into lighter components via cracking.
  • the nozzle reactor system described herein may achieve this increase in overall conversion by utilizing a first nozzle reactor to conduct a first cracking step, and then passing any material not cracked or not sufficiently cracked by the first nozzle reactor into a second nozzle reactor that operates under conditions selected for cracking the uneracked or not sufficiently cracked material.
  • the nozzle reactor system 300 may generally include a first nozzle reactor 310 and a second nozzle reactor 320.
  • Nozzle reactor system 300 may also include a first separation unit 330.
  • First separation unit 330 may generally separate the materia] leaving first nozzle reactor 310 into a light stream and a heavy stream.
  • first separation unit 330 may include a light stream outlet 332 and a heavy stream outlet 334.
  • Heavy stream outlet 334 may be in fluid communication with the material feed passage of second nozzle reactor 320 so that the heavy components of heavy stream outlet 334 may be transported to second nozzle reactor 320 for cracking.
  • First and second nozzle reactors 310, 320 may generally include a nozzle reactor according to any embodiment or aspect described herein.
  • first and second nozzle reactors 310, 320 may each have a reactor body, an injection passage, and a material feed passage.
  • the reactor body may include an interior reactor chamber with an injection end and an ejection end.
  • the injection passage may be mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber.
  • the injection passage may have an enlarged volume injection section, an enlarged volume ejection section. and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section.
  • the injection passage may also have a material injection end and a material ejection end in injecting communication with the interior reactor chamber.
  • the material feed passage may penetrate the reactor body. The location of the material feed passage may be adjacent to the material ejection end of the injection passage and transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage.
  • First and second nozzle reactors 310, 320 may be identical or first and second nozzle reactors 310, 320 may be different.
  • second nozzle reactor 320 has a smaller interior body chamber volume than the interior reactor chamber volume of first nozzle reactor 310.
  • the interior reactor chamber volume of second nozzle reactor 320 may be 1/3 or less the interior reactor chamber volume of first nozzle reactor 310.
  • nozzle reactor system 300 may include more than two nozzle reactors. Other features of the nozzle reactor are described in greater detail above.
  • First separation unit 330 may generally include any type of separation unit capable of separating the lighter material that is the product of cracking the material feed fed into first nozzle reactor 310 from the heavy material that may generally be made up of material feed that was not cracked or not sufficiently cracked in first nozzle reactor 310.
  • suitable separation units include, but are not limited to, distillation units, gravity separation units, filtration units, and cyclonic separation units.
  • First separation unit 330 may be in fluid communication with the ejection end of first nozzle reactor 310 such that the material leaving first nozzle reactor 310 is fed into first separation unit 330. Any manner of fluid communication may be used between first nozzle reactor 310 and first separation unit 330. In one example, the fluid communication may be piping extending between the ejection end of first nozzle reactor 310 and first separation unit 330.
  • first separation unit 330 may generally include light stream outlet 332 and heavy stream outlet 334.
  • Light stream outlet 332 may generally include any materials having a predetermined property or properties, such as a molecular weight, boiling point, API gravity, or viscosity.
  • light stream outlet 332 may include, for example, a) material feed that is not cracked inside first nozzle reactor 310 but that possessed a predetermined property prior to being introduced into first nozzle reactor 310, and b) material feed that has been cracked inside first nozzle reactor 310 such that the cracked material obtains the predetermined property.
  • light stream outlet 332 may comprise uncracked hydrocarbons that had the predetermined property when injected into first nozzle reactor 310 and cracked hydrocarbon molecules that obtained the predetermined property upon being cracked inside of first nozzle reactor 310.
  • heavy stream outlet 334 may generally include any materials not having the predetermined property or properties.
  • heavy stream outlet 334 may include, for example, a) material feed that is not cracked inside first nozzle reactor 310 and that did not possess the predetermined property upon being introduced into first nozzle reactor 310, and b) material feed that has been cracked inside first nozzle reactor 310 but that did not result in the cracked material possessing the predetermined property.
  • heavy stream outlet 334 may include uncracked hydrocarbon molecules that did not have the predetermined property when injected into first nozzle reactor 310 and cracked hydrocarbon molecules that did not obtain the predetermined property upon being cracked inside of first nozzle reactor 310.
  • any property, property value or property range may be selected to determine whether a material is part of light stream outlet 332 or heavy stream outlet 334.
  • properties and property values that may be used to classify the material leaving first nozzle reactor 310 may include a molecular weight above a selected value, a molecular weight below a selected value, a molecular weight within a selected range, a boiling point above a selected value, a boiling point belo a selected value, a boiling point within a selected range, an API gravity above a selected value, an API gravity below a selected value, an API within a selected range, a viscosity above a selected value, a viscosity below a selected value, or a viscosity within a selected range.
  • multiple properties may be used to determine whether a material leaving first nozzle reactor 310 is part of light stream outlet 332 or heavy stream outlet 334.
  • the material may have to have both a molecular weight below a selected value and a boiling point below a selected value to be part of light stream outlet 332.
  • the value or range selected for the property is also not limited. The value or range of values selected may be based on known property values for useful fractions of a material feed.
  • a fluid communication may be established between heavy stream outlet 334 and second nozzle reactor 320. More specifically, a fluid communication may be established between heavy stream outlet 334 and the material feed passage of second nozzle reactor 320. However, fluid communication may also be established between heavy stream outlet 334 and any portion of second nozzle reactor 320. Any manner of fluid communication may be used between second nozzle reactor 320 and heavy stream outlet 334. In one example, the fluid communication may be piping extending between the heavy stream outlet 334 and second nozzle reactor 320, A pump may also be used in connection with the fluid communication to assist the flow of material through the fluid communication.
  • Second nozzle reactor 320 may be operated at different operating conditions than first nozzle reactor 310 so as to increase the likelihood of cracking the components of heavy stream outlet 334. It is generally theorized that nozzle reactors as described herein crack the molecules having the largest molecular mass first.
  • a relatively high operating temperature may be selected such that only a high boiling point fraction of the feed material is present in the reaction chamber as a liquid (or possibly a solid), while the remaining fractions are present in the reaction chamber as a gas.
  • the fraction that is present in the reaction chamber as a liquid or solid has the largest molecular mass and will be the first material cracked by the shock waves produced inside the nozzle reactor. Gaseous fractions may pass through the reaction chamber without being cracked.
  • second nozzle reactor 320 may then become part of the heavy stream fed to second nozzle reactor 320. If second nozzle reactor 320 is operated at the same operating conditions as first nozzle reactor 310, the heavy stream will remain in the gas phase and likely pass through second nozzle reactor 320 with no further cracking being accomplished. Accordingly, the operating conditions that may be altered between the first and second nozzle reactors 310, 320 are those which will increase the mass of the components of heavy stream outlet 334 as they enter second nozzle reactor 320. In other words, operating second nozzle reactor 320 under conditions that will transform the gaseous heavy stream into a liquid or solid may increase the rate at which second nozzle reactor 320 cracks the components of heavy stream outlet 334.
  • Exemplary operating conditions that may be altered between first nozzle reactor 310 and second nozzle reactor 320 and that will increase the mass of the components of heavy stream outlet 334 include decreasing the temperature of the components of heavy stream outlet 334, Reduction in temperature may be achieved by reducing the ratio of cracking material mass to material feed mass or by reducing the superheat in the cracking material whi le maintaining the ratio of cracking material mass to material feed mass.
  • nozzle reactor system 300 may further include a second separation unit 340.
  • Second separation unit 340 may be in fluid communication with the ejeciion end of second nozzle reactor 320 such that material leaving second nozzle reactor 320 is fed into second separation unit 340.
  • Second separation unit 340 may generally include a light stream outlet 342 and a heavy stream outlet 344.
  • second separation unit 340 may generally include any type of separation unit capable of separating lighter material that possesses a predetermined property when leaving second nozzle reactor 320 from the heavy material that does not possesses the predetermined property when leaving second nozzle reactor 320, Examples of suitable separation units include, but are not limited to, distillation units, gravity separation units, filtration units, and cyclonic separation units.
  • Second separation unit 340 may be in fluid communication with the ejection end of second nozzle reactor 320 such that the material leaving second nozzle reactor 320 is fed into second separation unit 340. Any manner of fluid communication may be used between second nozzle reactor 320 and second separation unit 340. In one example, the fluid communication may be piping extending between the ejection end of second nozzle reactor 320 and second separation unit 340.
  • second separation unit 340 may generally include light stream outlet 342 and heavy stream outlet 344
  • Light stream outlet 342 may generally include material that has a predetermined property or properties when leaving second nozzle reactor 320
  • heavy stream outlet 344 may generally be comprised of material tha does not have the predetermined property or properties when leaving second nozzle reactor 320
  • the predetermined property or properties used to separate streams in second separation unit 340 need not be the same predetermined property or properties used to separate streams in first separation unit 330. Alterna ively, the same predetermined property or properties may be used in both first separation unit 330 and second separation unit 340.
  • any property, property value or property value ranged may be selected as the parameter for separating light and heavy streams.
  • light stream outlet 342 may be in fluid communication with first nozzle reactor 310 or second nozzle reactor 320 via a recycle stream.
  • the materia! that makes up light stream outlet 342 may still be too large and heavy to be used as useful product, and thus requires further cracking.
  • Such cracking may take place in either first nozzle reactor 310 or second nozzle reactor 320 or both depending on the characteristics (such as molecular weight or boiling point) of the material that makes up light stream outlet 342. Accordingly, providing a fluid communication between light stream outlet 342 and first nozzle reactor 310 and/or second nozzle reactor 320 allows for this second attempt at cracking the material, although this time in an improved condition for cracking.
  • any manner of fluid communication may he used between light stream output 342 and first nozzle reactor 310 and/or second nozzle reactor 320.
  • the fluid communication may be piping extending between the light stream output 342 and the material feed passage of first nozzle reactor 310 and/or second nozzle reactor 320.
  • a similar recycle stream may be used to divert the material of heavy stream outlet 344 back to either first nozzle reactor 310 or second nozzle reactor 320.
  • the manner of providing such a recycle stream may be similar to the recycle stream as described above, such as by providing piping between heavy stream outlet 344 and either first nozzle reactor 310 or second nozzle reactor 320,
  • Similar recycle streams may also be provided between light stream outlet 332 and first nozzle reactor 310. Additionally, a portion of heavy stream outlet 334 may be recycled back to first nozzle reactor, while the remainder of heavy stream outlet 334 is injected into second nozzle reactor 320 as described in greater detail above. Furthermore, a portion of light stream 332 may be recycled back to first nozzle reactor 310.
  • nozzle reactor system is not limited to two nozzle reactors. Any number of nozzle reactors arranged in series may be used. Each nozzle reactor may operate at different conditions, with each nozzle reactor operating under conditions specifically selected to increase the likelihood of cracking a material that has passed through a previous nozzle reactor un cracked or not sufficiently cracked, Furthermore, the nozzle reactors may be arranged in parallel in addition to a series arrangement. For example, a first nozzle reactor may produce a heavy stream and a light stream, with the heavy stream being transported to a second nozzle reactor and a light stream being transported to a third nozzle reactor.
  • a material feed cracking method may generally allow for an increase in conversion of material feed into lighter components by utilizing two or more reactor nozzles.
  • the first reactor nozzle is utilized in a similar fashion to the detailed discussion above regarding the nozzle reactor.
  • an additional nozzle reactor is used to deal with the material that passes through the first nozzle reactor but that is not cracked or not sufficiently cracked. More specifically, the operating conditions of the second nozzle reactor may be selected so that the second nozzle reactor is more likely to break down material that passes through the first nozzle reactor uneracked or not sufficiently cracked.
  • the material feed cracking method may generally include a first step of injecting a first stream of cracking materia] through an injection passage of a first nozzle reactor into an interior reactor chamber of a first nozzle reactor. Materia! feed may then be injected into the interior reactor chamber of the first nozzle reactor adjacent to the injection passage of the first nozzle reactor and transverse to the first stream of cracking material entering the interior reaction chamber of the first nozzle reactor from the injection passage of the first nozzle reactor. In this manner, a first light material and a first heavy materia! may be produced. The method may then include a step of injecting a second stream of cracking material through an injection passage of a second nozzle reactor into an interior reactor chamber of a second nozzle reactor.
  • the first heavy material may be injected into the interior reactor chamber of the second nozzle reactor adjacent to the injection passage of the second nozzle reactor and transverse to the second stream of cracking material entering the mterior reactor chamber of the second nozzle reactor from the injection passage of the second nozzle reactor. In this manner, a second light material and a second heavy material may be produced.
  • each nozzle reactor may comprise a reactor body, an injection passage, and a material feed passage.
  • the reactor body may have an interior reactor chamber with an injection end and an ejection end.
  • the injection passage may be mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber.
  • the injection passage may have an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section.
  • the injection passage may also have a material injection end and a material ejection end in injecting communication with the interior reactor chamber.
  • the material feed passage may penetrate the reactor body. The location of the material feed passage may be adjacent to the material ejection end of the injection passage and transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage.
  • the first and second streams of cracking materia] may be any suitable cracking material for cracking the material feed.
  • the cracking material is a cracking gas, such as steam.
  • the first and second streams of cracking material may be introduced into the injection passages at any suitable temperature and pressure.
  • the first and second streams of cracking material are injected into the injection passage at a temperature of from about 600 °C to about 850 °C and at a pressure of from about 15 bar to about 200 bar.
  • the material feed may be any type of material that may be broken down into smaller and lighter components.
  • the material feed is a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaitene content.
  • the residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit.
  • the high asphaitene content may be an asphaitene content greater than 4 wt% of the residue.
  • Hydrocarbon sources such as these require cracking to break down the heavy and large molecules of the hydrocarbon into light components that may be beneficially used.
  • the material feed and first heavy stream may be introduced into the materia] feed passages at any suitable temperature and pressure.
  • the materia! feed and first heavy stream are injected into the material feed passages at a temperature of from about 300 °C to 500 °C and at a pressure of from about 2 about to about 15 bar.
  • the pressure inside the interior reactor chamber of the first and second nozzle reactor may range from about 0.5 bar to about 15 bar.
  • the ratio of cracking material to material feed may range from about 0.5: 1.0 to about 4: 1 ,
  • the ratio of cracking material to first heavy material may range from about 0.1 : 1.0 to about 3: 1.0.
  • the injection of the material feed and the first stream of cracking material may result in the production of first light materia! and first heavy material.
  • the nozzle reactor does not achieve total cracking of all material feed injected into the first nozzle reactor.
  • the short retention time of the material feed in the interior reactor chamber combined with the preference of the nozzle reactor to crack the largest molecules first does not allow for Shockwaves generated by the injection passage to crack all of the material feed, and some material feed will therefore pass all the way through the first nozzle reactor without being cracked.
  • fractions of the material feed in a gaseous phase when passing through the interior reactor chamber may pass through the nozzle reactor without being cracked, These gaseous fractions may be considered non-participating in that they will not be cracked by the shock waves, Where such material feed passing through the nozzle uncracked comprises large molecules, further work may need to be done to accomplish cracking of the material into useful material.
  • the operating conditions of the first nozzle reactor may be selected such that only a fraction of the material feed in the nozzle reactor is in a liquid or solid phase, while the remaining fractions of the material feed are in a gaseous phase. This may be achieved by, for example, pre-heating the material feed prior to injection into the nozzle reactor.
  • the bitumen may comprise a fraction having a boiling point higher than 200 deg C.
  • the pre-heating temperature may be selected such that only this fraction of the bitumen is in liquid or solid form, and therefore is the fraction most likely to be cracked by the first nozzle reactor.
  • the remaining fractions of the bitumen in the gaseous phase may pass through the first nozzle reactor uncracked, at which point they may be fed to a second nozzle reactor.
  • the temperature of the gaseous material leaving the first nozzle reactor may be altered such that the gas transforms into liquid or solid and thereby increases the chances of the material being cracked in the second nozzle reactor.
  • the first heavy material may be injected into the second nozzle reactor to undergo another attempt at cracking the material in the nozzle reactor.
  • the second nozzle reactor may be identical in size and dimension to the first nozzle reactor, or may be different than the first nozzle reactor.
  • the operating conditions of the second nozzle reactor are different from the operating conditions of the first nozzle reactor as described in greater detail above. For example, the temperature of the material injected into the second nozzle reactor may be reduced to add mass to the gaseous components being fed into the second nozzle reactor to better accomplish the cracking of the hydrocarbons that make up the first heavy material injected into the second nozzle reactor.
  • the first light material and the first heavy material leaving the first nozzle reactor may be separated prior to the introduction of the first heavy material into the second nozzle reactor.
  • the lighter and smaller components that make up the first light material may be separated for consumption or recycle while the heavy and large components that make up the first heavy material may be sent to the second nozzle reactor.
  • Sending only the first heavy material to the second nozzle reactor may be beneficial because the second nozzle reactor will function to specifically crack these components while not being impeded by the presence of the first light material.
  • Separation of the first light material and the first heavy material may be accomplished by any suitable means for separation of the components. Properties such as density and boiling point may be used to effect separation. Separation may include, but is not limited to, separation by distillation units, gravity separation units, filtration units, and cyclonic separation units.
  • the second light material and the second heavy material may also be separated. Any suitable means for separation, such as those mentioned above, may be used to effect the separation.
  • the method may further comprise a step of injecting the first light material, first heavy material, second light material, or second heavy material into the reaction chamber of the first nozzle reactor or second nozzle reactor.
  • the method may further comprise a step of injecting the first light material or second light material into the reaction chamber of the first nozzle reactor.
  • a nozzle reactor system includes two or more nozzle reactors aligned in parallel and used for upgrading hydrocarbon material.
  • Figure 10 illustrates a nozzle reactor system 400 including three nozzle reactors 401, 402, and 403 aligned in parallel.
  • the system also includes a stream dividing apparatus 10 located upstream of the nozzle reactors 401, 402, 403, and a product mixing apparatus 420 located downstream of the nozzle reactors 401, 402, 403. While not shown in Figure 10, the system can also include a stream heating unit located upstream of the nozzle reactors 401, 402, 402.
  • Stream dividing apparatus 410 is generally configured to receive a stream of material to be processed in the nozzle reactors and divide the stream of material into one stream for each nozzle reactor in the nozzle reactor system 400. Each stream produced can be easier to control and measure. As shown in Figure 10, three streams are produced by the stream dividing apparatus 410, with each stream being directed to one of the nozzle reactors 401, 402, 403. The product material leaving each of the nozzle reactors 401 , 402, 403 is then combined in a product mixing apparatus 420. A portion of the combined product can be recycled back to the stream dividing apparatus 410 for further processing in the nozzle reactors 401, 402, 403.
  • Nozzle reactors 401, 402, 403 may generally include a nozzle reactor according to any embodiment or aspect described herein.
  • nozzle reactors 401, 402, 403 each have a reactor body, an injection passage, and a material feed passage.
  • the reactor body includes an interior reactor chamber with an injection end and an ejection end.
  • the injection passage is mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber.
  • the injection passage has an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section.
  • the injection passage also has a material injection end and a material ejection end in injecting communication with the interior reactor chamber.
  • the material feed passage penetrates the reactor body.
  • nozzle reactors 401, 402, 403 are identical to one another in structure and dimension, although nozzle reactors that differ in either or both of these characteristics can also be used within the same nozzle reactor system 400.
  • the operating conditions of each nozzle reactor e.g., temperature, pressure, etc.
  • the number of nozzle reactors aligned in parallel in the nozzle reactor system 400 is not limited, In some embodiments, the amount of material needing to be upgraded and the relative capacity of each nozzle reactor that is part of the system 400 can play a role in the number of nozzle reactors selected for the system 400.
  • Stream dividing apparatus 410 generally includes any type of apparatus capable of dividing a larger stream into numerous smaller streams.
  • Stream dividing apparatus 410 can be adapted to create streams of equal volumetric flow rates or can create streams having different volumetric flow rates.
  • Stream dividing apparatus 410 can also be adapted to create any desired number of streams, but will generally be set up to create one stream for each nozzle reactor that is a part of the nozzle reactor system 400.
  • Exemplary stream dividing apparatus include, but are not limited to, flow control valves, limiting orifice valves, orifice plates, flow venturies, pipe tees, pipe manifolds, and baffle plates.
  • the stream dividing apparatus 410 can also produce stream of varying composition.
  • the stream dividing apparatus 410 can divide a stream of material based on molecular weight or density to produce a stream of material having a high molecular weight or high density, a stream of material ha ving a intermediate molecular weight or density, and a stream of material having a low molecular weight or density, While molecular weight is provided as example of the criteria on which the material can be divided, any other suitable criteria can be used for dividing the stream of material, including but not limited to, presence or absence of certain compounds or class of compounds, boiling point temperatures, and viscosity.
  • the stream dividing apparatus 410 can include but is not limited to vacuum or atmospheric distillation towers,
  • each stream can then be sent to a nozzle reactor in the nozzle reactor system 400 that is specifically tailored for upgrading streams having a specific composition
  • Nozzle reactors in the nozzle reactor system 400 can be tailored to upgrade a stream having a specific composition by any suitable manner, such as adjusting operating conditions (e.g., temperature, pressure, etc.) and/or by adjusting various dimensions of the nozzle reactor.
  • Each outlet of the stream dividing apparatus 410 is in fluid communication with the feed ma terial injection inlet of one of the nozzle reactors of the nozzle reactor system. In this manner, the material leaving the stream dividing apparatus 410 can be injected directly into one of the nozzle reactors 401 , 402, 403 for being subjected to cracking and upgrading.
  • Any manner of fluid communication may be used between the material dividing apparatus 410 and the feed material injection inlets of each nozzle reactors.
  • the fluid communication may be piping extending between an outlet of the stream dividing apparatus and the material feed injection inlet of each nozzle reactor.
  • the material feed fed into the stream dividing apparatus 410 and divided up into individual streams can include any type of material that may be broken down into smaller and lighter components.
  • the material feed is a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaltene content.
  • the residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit.
  • the high asphaltene content may be an asphaltene content greater than 4 wt% of the residue.
  • Hydrocarbon sources such as these require cracking to break down the heavy and large molecules of the hydrocarbon into light components that may be beneficially used.
  • the material feed is material stream exiting a nozzle reactor located upstream of the nozzle reactors 401 , 402, 403 aligned in parallel and part of th e nozzle reactor system 400.
  • the mixing apparatus 420 can include any suitable apparatus for receiving the material exiting each of the nozzle reactors 401, 402, 403 and combining the material back into one stream.
  • the mixing apparatus 420 generally includes a vessel with multiple input ports for receiving the material leaving each of the nozzle reactors 401, 402, 403 in the nozzle reactor system.
  • the mixing apparatus 420 is a Kenics mixer, in such configurations, the ejection ends of each nozzle reactor 401, 402, 403 is in fluid communication with the input port or ports of the mixing apparatus 420.
  • the fluid communication between the ejection ends of the nozzle reactors 401, 402, 403 and the injection port or ports of the mixing apparatus 420 can be established in any suitable manner, including the use of piping.
  • the vessel used for the mixing apparatus 420 can optionally include equipment for mixing the various material streams entering the mixing apparatus 420, such as a mixing blade.
  • the volume of the mixing apparatus 420 should generally be designed such that the mixing apparatus 420 is capable of receiving all of the product material leaving the nozzle reactors 401, 402, 403 of the nozzle reactor system 400.
  • the mixing apparatus 420 can also include an outlet port for allowing combined and optionally mixed material to leave the mixing apparatus 420 and be transported to further processing equipment located downstream of the nozzle reactor system 400.
  • the downstream processing equipment can serve as the mixing apparatus 420, and thereby both receive each stream leaving the nozzle reactors 401, 402, 403, and then subject the combined product streams to further processmg.
  • the product streams exiting the nozzle reactors 401, 402, 403 are subjecied to further processing prior to being combined in a mixing apparatus 420.
  • processing apparatus 501, 502, 503 are provided for each nozzle reactor 401, 402, 403.
  • the product stream leaving each nozzle reactor 401, 402, 403 is sent to a processing apparatus 501, 502, 503.
  • the product streams leaving each process apparatus 501 , 502, 503 is then sent to the mixing apparatus 420 described above for combining the product streams.
  • a portion of the combined product stream leaving mixing apparatus 420 can be recycled back to the nozzle reactors for further processing.
  • any suitable processing equipment can be used for the processing apparatus 501, 502, 503.
  • the processing equipment is equipment capable of further upgrading the product streams leaving the nozzle reactors 401 , 402, 403.
  • the processing equipment is a coil reactor, such as the coil reactors described in U.S. Patent Application No. 12/816,844 and U.S. Patent Application No. 13/292,747, both of which are hereby incorporated by reference,
  • Figure 11 illustrates only one piece of processing equipment located between each nozzle reactor and the mixing apparatus, multiple pieces of processing equipment can be provided per nozzle reactor.
  • each product stream leaving nozzle reactors 401, 402, 403, can be subjected to multiple pieces of processing equipment prior to being combined in the mixing apparatus 420.
  • the system 400 can further include separation apparatus located down stream of the mixing apparatus 420.
  • the separation apparatus can be used to separate the combined stream exiting mixing apparatus 420 into various streams based on any of a variety of criteria.
  • the combined stream can be separated based on the boiling points of the various components included in the combined stream. Any suitable separation apparatus can be used for this step, including, for example, distillation towers.
  • a material feed cracking method can generally include a first step of injecting a first material stream into a stream dividing apparatus and producing a first divided stream and a second divided stream. The method also includes a step of injecting the first divided stream into a first nozzle reactor and injecting the second divided stream into a second nozzle reactor. A next step includes injecting a stream of cracking material into the first nozzle reactor and injecting a stream of cracking material into the second nozzle reactor. A next step includes combining a first nozzle reactor product from the first nozzle reactor and a second nozzle reactor product from the second nozzle reactor in a mixing apparatus.
  • the stream dividing apparatus, the first nozzle reactor, the second nozzle reactor, and the mixing apparatus used in the method described above can all be similar or identical to the stream dividing apparatus, the nozzle reactor, and the mixing apparatus described in greater detail above.
  • the first material stream can include any type of material that may he broken down into smaller and lighter components.
  • the first material stream includes a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaltene content.
  • the residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit.
  • the high asphaltene content may be an asphaltene content greater than 4 wt% of the residue.
  • the first materia! stream can also include the material leaving the ejection end of a nozzle reactor located upstream of the stream dividing apparatus.
  • the first divided stream and the second divided stream can be a similar or identical, such as when the stream dividing apparatus performs a simple physical separation of the first material stream.
  • the first divided stream and the second divided stream can have different compositions, such as when the stream dividing apparatus is a distillation tower that separates the first material stream based on the boiling point of the various components of the first material stream.
  • the first divided stream and the second divided stream can also be equal in volumetric flow rate, or can have different volumetric flow rates, it can also have a third divided stream with a different volumetric flow rate used as a purge.
  • the first divided stream and the second divided stream can be injected into the first nozzle reactor and the second nozzle reactor, respectively, at any suitable temperature and pressure.
  • the first divided stream and the second divided tream are injected into the first nozzle reactor and the second nozzle reactor at a temperature of from about 300 °C to 500 °C and at a pressure of from about 0.5 about to about 15 bar.
  • the streams of cracking material injected into the first and second nozzle reactor can be any suitable cracking material for cracking the first divided stream and the second divided stream, In some embodiments, the cracking material is a cracking gas, such as steam.
  • the streams of cracking material can be injected into the nozzle reactors at any suitable temperature and pressure. In some embodiments, the streams of cracking material are injected into the nozzle reactors at a temperature of from about 600 °C to about 850 °C and at a pressure of from about 15 bar to about 200 bar.
  • the pressure inside each of the first and the second nozzle reactor may range from about 0.5 bar to about 15 bar.
  • the ratio of cracking material to material feed may range from about 0.1 :1 to about 4: 1.
  • the nozzle reactors operate to crack and upgrade the feed material injected into the nozzle reactor as a result of the feed material and the cracking material interacting within the nozzle reactor.
  • the product of this interaction leaves the ejection end of each nozzle reactor as a first nozzle reactor product and a second nozzle reactor product.
  • Each of these stream can be transported to and injected into a mixing apparatus for combining the individual streams into one larger stream.
  • the operating conditions of the mixing apparatus can be adjusted according to the material be injected into the mixing apparatus.
  • the temperature and pressure inside the mixing apparatus will be adjusted.
  • the mixing apparatus can have a temperature in the range of from 350 to 420 °C and a pressure in the range of from 0.2 to 15 bar.
  • the stream dividing apparatus will produce one divided stream for each nozzle reactor that is used in the nozzle reactor system.
  • each stream can be directed to a nozzle reactor tailored for upgrading of the specific material composition.
  • the parallel coniigurations described above and illustrated in Figures 10 and 11 ca be particularly advantageous in situations where events occur downstream of the parallel aligned nozzle reactors that require production to be reduced, such as in the event of a pipeline becoming unavailable or a product stream storage facility reaching capacity.
  • the nozzle reactors described herein provide optimum conversion and product quality when operated at specific flow velocities for both the cracking material stream and the feed material stream.
  • production can be reduced by completely shutting down one or more of the nozzle reactors while continuing to operate the remaining on-line nozzle reactors at optimum operating conditions.
  • the parallel alignment described herein allows nozzle reactors to continue to operate at optimum conditions while still providing a mechanism for lowering production in the case of downstream events.
  • VDU Vacuum Distillation Unit
  • the bottoms of the VDU are withdrawn from the VDU and comprise a heavy hydrocarbon source having a molecular weight range of from about 300 Daltons to 5,000 Daltons or more.
  • the heavy hydrocarbon source is pre-heated to a temperature of about 752 deg F (400 deg C). At this temperature, only the hydrocarbon fraction with a molecular weight larger then about 350 Dalton will be in the liquid and/or solid phase, while the remainder of the hydrocarbon source is in a gaseous state.
  • the hydrocarbon source is injected into an interior reactor chamber of a first nozzle reactor via the material feed passage of the first nozzle reactor.
  • superheated steam at a temperature of about 1256 deg F (680 deg C) is injected into the converging section of the injection passage of the first nozzle reactor at a flow rate of about 1.5 times the flow rate of the hydrocarbon source.
  • the first nozzle reactor has an overall length of 8,000 mm and an outside diameter of 1,600 mm.
  • the interior reactor chamber is 7,160 mm long with an injection end diameter of 262 mm and an ejection end diameter of 1 ,435 mm.
  • the injection passage has a length of 840 mm, with an enlarged volume injection section diameter of 207 mm, a reduced volume mid-section diameter of 70 mm and an enlarged volume ejection section diameter of 147 mm.
  • the pressure in the interior reactor chamber is about 2.
  • the hydrocarbon source and steam are retained in the first nozzle reactor for a time period of around 1.2 seconds. Shockwaves and thermal effects produced inside the nozzle convert approximately 45% per pass of the hydrocarbon source that has a boiling point of greater than 1050 deg F (566 deg C) into lighter hydrocarbons with a boiling point of less than 1050 deg F (566 cleg C), The nozzle reactor emits a mixture of steam, cracked hydrocarbons, and ncracked hydrocarbons at a temperature of about 788 deg F (420 deg C),
  • the mixture leaving the nozzle reactor is recycled to the same VDU as noted before.
  • Steam in the VDU is condensed.
  • the VDU separates the hydrocarbon into a gaseous hydrocarbon phase (C5 and smaller), gas oil, vacuum distillate and VDU bottoms having a molecular weight range of from 300 Daltons to 5,000 Daitons or more.
  • the gaseous hydrocarbon phase, gas oil and vacuum distillate are collected for consumption.
  • the VDU bottoms are split into two individual streams. A first stream comprising about 75% of the total VDU bottoms stream is recycled back to the first nozzle reactor, while a second stream comprising the remaining 25% is diverted to a second nozzle reactor. This split purges a fraction of the bottoms that has an increased amount of inorganic material, such as vanadium, nickel, and sulfur.
  • the second stream Prior to being introduced into the second nozzle reactor, the second stream is cooled to a temperature of about 700 deg F (371 deg C). At this temperature, all of the hydrocarbon material of the second stream is in the liquid phase.
  • the second stream is injected into an interior reactor chamber of a second nozzle reactor via the material feed passage of the second nozzle reactor, Simultaneously, steam at a temperature of 1256 deg F (680 deg C) is injected into the interior reactor chamber of the second nozzle reactor via the injection passage at a flow rate of about 2.0 times the flow ra te of the hydrocarbon injected into the second nozzle reactor.
  • the second nozzle reactor has an overall length of 7,000 mm and an outside diameter of 1,300 mm.
  • the interior reactor chamber is 6,400 mm long with an injection end diameter of 187 mm and an ejection end diameter of 1,231 mm.
  • the injection passage has a length of 600 mm, with an enlarged volume injection section diameter of 148 mm, a reduced volume mid-section diameter of 50 mm and an enlarged volume ejection section diameter of 105 mm.
  • the pressure in the interior reactor chamber is about 2.
  • the second stream and steam are injected into the second nozzle reactor for a time period of no more than 0.6 seconds. Shockwaves produced inside the nozzle reactor convert approximately 55% of the second stream into lighter hydrocarbons.
  • the nozzle reactor emits a mixture of steam, cracked hydrocarbons and uncracked hydrocarbons at a temperature of about 788 deg F.
  • the mixture leaving the second nozzle reactor is fed to a small Vacuum Separation Unit (VSU).
  • VSU Vacuum Separation Unit
  • the small VSU separates the mixture into a lighter hydrocarbon having a molecular weight in the range of from about 25 to about 200 Daltons and a heavier hydrocarbon stream having a molecular weight in the range of from about 200 to about 1 ,000 Daltons.
  • the light hydrocarbon stream is recycled back to the first and large VSU while the heavier hydrocarbon stream is cooled down to about 700 deg F (371 deg C) and collected as the final pitch stream for disposal.

Abstract

A nozzle reactor system for increasing the conversion rate of material feed injected into the nozzle reactor system. The system includes two or more nozzle reactors aligned in parallel. A main stream of material to be upgraded is divided such that one stream is produced for each nozzle reactor in the system. Each nozzle reactor includes an interior reactor chamber and an injection passage and a material feed passage that are each in material injecting communication with the interior reactor chamber. Furthermore, the injection passage is aligned transversely to the injection passage. The injection passage is configured to accelerate cracking material passed therethrough to a supersonic speed. The product produced from each of the nozzle reactors is combined into one product stream.

Description

IN THE UNITED STATES PATENT AND TRADEMARK OFFICE APPLICATION FOR LETTERS PATENT
NOZZLE REACTOR SYSTEMS AND METHOD OF USE
INVENTORS:
Jose Arm ndo Salazar
Mahendra Joshi
Christopher Ard
This application claims priority to U.S. Provisional Patent Application No. 61/553,009, filed October 28, 201 1, the entirety of which is hereby incorporated by reference,
Nozzle reactors have long been used to cause materials to interact and achieve alteration of the mechanical or chemical composition of the materials. Typically, this involves injecting differing types of materials into a reactor chamber of a nozzle reactor and allowing the materials to interact.
One example of a nozzle reactor disclosure is Canadian Patent Application No. 2,224,615
(the '615 Publication). This reference states that its disclosed nozzle reactor is designed to receive a bitumen/steam flow mixture into a single central nozzle reactor passage extending along the axial length of the nozzle reactor. The reference states that the nozzle forms a flowr passageway of circular diametric cross-section having the following sections in sequence from the bitumen/steam flow mixture inlet: a first contraction section of reducing diameter for accelerating the flow and reducing the size of bitumen droplets; a diffuser section of expanding diameter to decelerate the flow and induce a shock wave; a second contraction section to accelerate the mixture more than the first contraction section; and an orifice outlet for producing an output jet or spray, The '615 Publication further states that the disclosed nozzle reactor reduces bitumen droplet size from about 12,000 μπι to about 300 μηα.
Among other things, the nozzle reactor of the '615 Publication receives a pre-mixed bitumen/steam liquid medium, As a result, the nozzle reactor technique of the '615 Publication requires implementation of one or more substantial pre-mixing steps in order to generate and deliver the desired bitumen'steam liquid medium to the central nozzle reactor passage. In addition, the pre-mixed liquid medium (including bitumen in the mixture) inherently yields limited velocities of the medium through the nozzle reactor.
Another example of a nozzle reactor is described in U.S. Patent Application Publication No. 2004/0065589 (the '589 Publication), The nozzle reactor discussed in the '589 Publication has two steam injectors disposed: (i) laterally separated from opposing sides of a central, axially extending vapor expansion feed stock injector, (ii) at an acute angle to the axis of the central vapor expansion feed stock injector. The steam injectors are thus disposed for ejection from the steam injectors in the direction of travel of material feed stock injected by the feed stock injector. Each of the three injectors has a discharge end feeding into a central reactor ring or tube extending coaxially from the central feed stock injector. As shown in the '589 Publication, the central feed stock injector appears as if it may have a divergent-to-convergent axial cross-section with a nearly plugged convergent end; but as shown in related Canadian Patent Application No, 2,346,181 (the '181 Publication), the central feed stock injector has a straight- through bore.
As the '589 Publication explains, superheated steam is injected through the two laterally opposed steam injectors into the interior of reactor tube in order to impact a pre-heated, centrally-located feed stream of certain types of heavy hydrocarbon simultaneously injected through the vapor expansion feed stock injector into the interior of the reactor tube. The '589 Publication states that the object of '589 nozzle reactor is to crack the feed stream into lighter hydrocarbons through the impact of the steam feeds with the heavy hydrocarbon feed within the reactor tube. According to the '589 Publication, the types of heavy hydrocarbons processed with the '589 nozzle reactor are crude oil, atmospheric residue, and heavy distillates. With the nozzle reactors of either the '589 Publication and the ' 181 Publication, a central oil feed stock jet intersects the steam jets at some distance from the ejection of these jets from their respective injectors.
The applicants have discovered that, among other things, nozzle reactors of the type shown in the '589 Publication, the ' 181 Publication and associated methods of use: (i) are inefficient; (ii) typically and perhaps always provide only sonic or subsonic velocity of a feed stock into the associated reactor tube; and (iii) yield excessive un-cracked or insufficiently cracked heavy hydrocarbons. These same nozzle reactors also typically yield excessive coke formation and scaling of the nozzle reactor walls, reducing the efficiency of the nozzle reactor and requiring substantial effort to remove the scale formation within the nozzle reactor.
SUMMARY
Disclosed below are representative embodiments that are not intended to be limiting in any way. Instead, the present disclosure is directed toward features, aspects, and equivalents of the embodiments of the nozzle reactor and method of use described below. The disclosed ieatures and aspects of the embodiments can be used alone or in various combinations and subcombinations with one another.
Generally, a nozzle reactor having a variety of aspects and methods of use are described herein. In certain embodiments, the nozzle reactor provides a hydrocarbon cracking nozzle reactor. In certain embodiments, the method includes generating a supersonic stream of cracking material and impacting hydrocarbon material with the supersonic stream of cracking material.
In some embodiments of the nozzle reactor, the nozzle reactor has a material feed passage extending into an interior reactor chamber section generally transverse to the exit or injection axis of at least one injection passage. In some embodiments, at least one injection passage is coaxial with the axis of an associated interior reactor chamber and at least one material feed passage is disposed to inject material feed to impact the cracking material injected at the ejection end of the injection passage.
In some embodiments, the nozzle reactor has an injection passage abutting an interior reactor chamber and a material feed passage extending into the interior reactor chamber transverse to the axis of the injection passage and adjacent the ejection end of the injection passage. The injection passage can be a non-linear injection passage injectingly penetrating the interior reactor chamber.
In some embodiments, the injection passage can have a cross-sectional configuration in which opposing side wall portions are curved inwardly toward the central axis of the injection passage along the axial length of the injection passage. Preferably, the curved side wall portions of the injection passage has a smooth finish without sharp edges or sudden changes in surface contour, most preferably along the entire axial length of the injection passage. In some embodiments, the curved side wall portions of the injection passage can provide a nearly or substantially isentropic or frictionless passage for cracking material passing through the injection passage into the interior reactor chamber.
In some embodiments, the nozzle reactor includes a material feed passage having at least one or more material feed ports, and if desired one or more partially or completely annular material feed ports, injectingly abutting the interior reactor chamber. In some embodiments, a material feed passage can include a reactor chamber material feed slot injectingly penetrating at least a substantial portion, or if desired, the entire outer circumferential periphery of an annular material feed port. The latter configuration can, in the case of a completely annular material feed port for example, provide impact of the material feed stream with the entire circumference of the injected cracking material stream,
In some embodiments, the reactor chamber material feed slot or end of the annular material feed port is disposed axial ly adjacent the end of the injection passage injectingiy penetrating the interior reactor chamber. In this fashion, material feed can be injected through the material feed passage radially inwardly toward, and optionally transverse to, an adjacent cracking material injected through the injection passage.
In some embodiments, the nozzle reactor comprises an annular or other port insert member mounted intermediate the interior reactor chamber and the injection passage. The ejection port of the interior reactor chamber, opposite the injection passage, can provide a passage through which cracking material and other material can pass out of the reactor body. The injection passage may have a frustoconical configuration.
Some embodiments of the present invention provide a conical, stepped, or telescoped interior reactor chamber, or a combined conical and otherwise shaped interior reactor chamber, extending along the axial length of the interior reactor chamber. The interior reactor chamber can be configured to generally provide interfering, turbulence-inducing contact, optionally limited contact, between the cracking material and the material feed injected into the interior reactor chamber.
In some embodiments, the injection passage includes an insert mounted within the injection passage and has a thin-thick-thin cross-section along the axial length of the insert. The insert can have a radially outwardly curved periphery along the axial length of the insert.
Some embodiments provide a method of injecting cracking material and a feed material into a nozzle reactor, Some embodiments can include injecting cracking material from an injection passage into an interior reactor chamber along the axial length of the interior reactor chamber section and injecting feed material into the interior reactor chamber transverse to the axis of the interior reactor chamber. In some embodiments, the feed material is injected adjacent the end of the injection passage injectmgly abutting the interior reactor chamber. As a result, the cracking material impacts the feed material virtually immediately after ejection from the injection passage. This impact can thus take place before the velocity of the cracking material dimini shes appreciably.
In some embodiments, cracking material comprises superheated steam and the feed material comprises pre-heated heavy hydrocarbons. The heavy hydrocarbons can include or consist largely or even essentially of bitumen. Cracking material also can include natural gas, carbon dioxide, or other gases.
In some embodiments, the feed material is injected to impact the cracking material upon its ejection from the injection passage, at an angle of about 90°.
In some embodiments, the bar pressure level of the superheated steam cracking material is substantially greater than, and preferably more than double, the pressure level within the interior reactor chamber.
In some embodiments, the cracking material is injected through the injection passage into the interior reactor chamber at supersonic speeds. In some embodiments, the cracking material injection speed is twice the speed of sound or more.
Some embodiments provide reduced back flow and enhanced mechanical shear within the interior reactor chamber. Some embodiments may do so and accomplish substantial cracking of a desired hydrocarbon very quickly and generally without substantial regard to retention time of the material feeds within the reactor body. In other embodiments, increased retention time of the material feed within the reactor body can result in higher cracking rates.
Some embodiments of the apparatus and methods provide more efficient generation and transfer of kinetic energy from a cracking materia! to a material feed. Some embodiments also provide increased material processing capability and output and reduced uncracked material or other by-products in the output from the nozzle reactor or retained within the confines of the nozzle reactor, such as reduced scale formation on the side walls of the interior reactor chamber. Some embodiments also provide a relatively economical, durable, and easy-to-maintain or repair nozzle reactor.
Some embodiments provide mechanical cracking of hea vy oils or asphaltenes. In certain of these embodiments, the cracking reaction can be caused primarily mechanically by the application of extreme shear rather than by temperature, retention time, or interaction with a catalyst. In some embodiments, the cracking may be selective, such as by selectively cracking primarily only the larger molecules making up certain heavy hydrocarbons in a hydrocarbon feed stock,
In some embodiments, the nozzle reactor provides not only more selective and efficient cracking of material feed but also, or alternatively, reduced coke formation and reactor chamber scaling. In some embodiments, reactor chamber scaling may even be eliminated.
In some embodiments, a nozzle reactor system is disclosed. The nozzle reactor system generally comprises a first nozzle reactor and a second nozzle reactor. Each of the first nozzle reactor and the second nozzle reactor can be a nozzle reactor as described herein. The nozzle reactor system can also include a first separation unit. The first separation unit is in fluid communication with an ejection end of the first nozzle reactor such tha material leaving the nozzle reactor flows into the separation unit. The first separation unit includes a light stream outlet and a heavy stream outlet, The heavy stream outlet is in fluid communication with the material feed passage of the second nozzle reactor such that the heavy stream is injected into the nozzle reactor for further cracking.
In some embodiments, a feed material cracking method is disclosed. The method includes a step of injecting a first stream of cracking material through an injection passage of a first nozzle reactor into an interior reaction chamber of a first nozzle reactor The method further includes a step of injecting a material feed into the interior reactor chamber of the first nozzle reactor adjacent to the injection passage of the first nozzle reactor and transverse to the first stream of cracking material entering the interior reactor chamber of the first nozzle reactor from the injection passage of the first nozzle reactor to produce first light material and first heavy material. The method also includes a step of injecting a second stream of cracking material through an injection passage of a second nozzle reactor into a reaction chamber of a second nozzle reactor. Finally, the method includes a step of injecting the first heavy material into the interior reactor chamber of the second nozzle reactor adjacent to the injection passage of the second nozzle reactor and transverse to the second stream of cracking material entering the interior reactor chamber of the second nozzle reactor from the injection passage of the second nozzle reactor to thereby produce second light material and second heavy material.
In some embodiments, a nozzle reactor system comprises: a stream dividing apparatus comprising a first output port and a second output port; a first nozzle reactor having a feed material injection port in fluid communication with the first output port of the stream dividing apparatus, and an ejection end; a second nozzle reactor having a feed material injection port in fluid communication with the second output port of the stream dividing apparatus, and an ejection end; and a mixing apparatus having a first input port in fluid communication with the ejection end of the first nozzle reactor, and a second input port in fluid communication with the ejection end of the second nozzle reactor.
In some embodiments, a material cracking method comprises mjecting a first material stream into a stream dividing apparatus and producing a first divided stream and a second divided stream, injecting the first divided stream into a first nozzle reactor and injecting the second divided stream into a second nozzle reactor, injecting a stream of cracking material into the first nozzle reactor and injecting a stream of cracking material into the second nozzle reactor, and combining a first nozzle reactor product from the first nozzle reactor and a second nozzle reactor product from the second nozzle reactor in a mixing apparatus,
The foregoing and other features and advantages of the present application will become more apparent from the following detailed description, which proceeds with reference to the accompanying figures, in this regard, it is to be understood that the scope of the invention is to be determined by the claims as issued and not by whether given subject includes any or all features or aspects noted in this Summary or addresses any issues noted in the Background.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a cross-sectional, schematic view of one embodiment of a nozzle reactor suitable for use in various embodiments of the methods and systems described herein;
Figure 2 is a cross-sectional view of the nozzle reactor of Figure 1 , showing further construction details for the nozzle reactor;
Figure 3 shows a cross-sectional view of one embodiment of a nozzle reactor suitable for use in various embodiments of the systems and methods described herein; Figure 4 shows a cross-sectional view of the top portion of the nozzle reactor shown in Figure 3:
Figure 5 shows a cross-sectional perspective view of the mixing chamber in the nozzle reactor shown in Figure 3;
Figure 6 shows a cross-sectional perspective view of the distributor from the nozzle reactor shown in Figure 3;
Figure 7 shows a cross-sectional view of another embodiment of a nozzle reactor suitable for use in various embodiments of the systems and methods described herein; and
Figure 8 shows a cross-sectional view of the top portion of the nozzle reactor shown in Figure 7.
Figure 9 is a flow diagram illustrating a feed material cracking method according to various embodimenta disclosed herein;
Figure 10 is a block diagram illustrating a nozzle reactor system according to various embodiments disclosed herein;
Figure 1 1 is a block diagram illustrating a nozzle reactor system according to various embodiments described herein;
DETAILED DESCRIPTION
Before describing the details of the various embodiments herein, it should be appreciated that the term "hydrocarbon" and "hydrocarbons" as used herein may include organic material besides hydrogen and carbon, such as vanadyl, sulfur, nitrogen, and any other organic compound that may be in oil.
With reference to Figure 1, the nozzle reactor, indicated generally at 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 an injection passage 15 extending into the interior reactor chamber 16 of the reactor body 14. The central axis A of the injection passage 15 is coaxial with the central axis B of the interior reactor chamber 16.
With continuing reference to Figure 1 , the injection passage 15 has a circular diametric cross-section and, as shown in the axiaily-extending cross-sectional view of Figure 1 , opposing inwardly curved side wall portions 17, 19 (i.e., curved inwardly toward the central axis A of the injection passage 15) extending along the axial length of the injection passage 15. in certain embodiments, the axially inwardly curved side wall portions 17, 19 of the injection passage 15 allow for a higher speed of injection gas when passing through the injection passage 15 into the interior reactor chamber 16.
In certain embodiments, the side wall of the injection passage 15 can provide one or more among: (i) uniform axial acceleration of cracking material passing through the injection passage; (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 injection passage 15 substantially isentropic. These latter types of side wall and injection passage 15 features can be, among other things, particularly useful for pilot plant nozzle reactors of minimal size.
A material feed passage 18 extends from the exterior of the reactor body 14 toward the interior reactor chamber 16 transversely to the axis B of the interior reactor chamber 16. The material feed passage 18 penetrates an annular material 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 material feed port 20 includes an annular, radially extending reactor chamber feed slot 26 in material-injecting communication with the interior reactor chamber 16. The material feed port 20 is thus configured to inject feed material: (i) at about a 90° angle to the axis of travel of cracking material injected from the injection passage 15; (ii) around the entire circumference of a cracking material injected through the injection passage 15; and (iii) to impact the entire circumference of the free cracking material stream virtually immediately upon its emission from the injection passage 15 into the interior reactor chamber 16.
The annular material feed port 20 may have a U-shaped or ("'-shaped cross-section among others. In certain embodiments, the annular materia! 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 material feed passage 18 toward the interior reactor chamber 16. The junction of the annular material feed port 20 and material feed passage 1 8 can have a radiused cross-section.
In alternative embodiments, the material feed passage 18, annular material feed port 20, and/or injection passage 15 may have differing orientations and configurations, and there can be more than one material feed port and associated structure. Similarly, in certain embodiments the injection passage 15 may be located on or in the interior reactor chamber side 23 (and if desired may include an annular cracking material port) rather than at the reactor body injection end 12 of the reactor body 14, and the annular material feed port 20 may be non-annular and located at the reactor body injection end 12 of the reactor body 14.
In the embodiment of Figure 1 , the interior reactor chamber 16 can be bounded by stepped, telescoping side walls 28, 30, 32 extending along the axial length of the reactor body 14. in certain embodiments, the stepped side walls 28, 30, 32 are configured to: (i) allow a free jet of injected cracking material, such as superheated steam, natural gas, carbon dioxide, or other gas, to travel generally along and within the conical jet path C generated by the injection passage 15 along the axis B of the interior reactor chamber 16, whil e (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 materia] jet stream within the conical jet pat C and feed material, such as heavy hydrocarbons, injected through the annular material feed port 20.
As indicated by the drawing gaps 38, 40 in the embodiment of Figure 1, the reactor body 14 has an axial length (along axis B) that is muc greater than its width. In the Figure 1 embodiment, exemplary length-to-width ratios are typically in the range of 2 to 4 or more.
The dimensions of the various components of the nozzle reactor shown in Figure 1 are not limited, and may generally be adjusted based on the amount of material feed to be cracked inside the nozzle reactor. Table 1 provides exemplary dimensions for the various components of the nozzle reactor based on the hydrocarbon input in barrels per day (BPD).
Figure imgf000015_0001
With reference now to Figure 2 and the particular embodiment shown therein, the reactor body 44 includes a generally tubular central section 46 and a frustoconical ejection end 48 extending from the central section 46 opposite an insert end 50 of the centra] section 46, with the insert end 50 in turn abutting the in jection nozzle 52. The insert end 50 of the central section 46 consists of a generally tubular central body 51. The central body 51 has a tubular material feed passage 54 extending from the external periphery 56 of the insert end 50 radially inwardly to injectingly communicate with the annular circumferential feed port depression or channel 58 in the otherwise planar, radially inwardly extending portion 59 of the axially stepped face 61 of the insert end 50. The inwardly extending portion 59 abuts the planar radially internally extending portion 53 of a matingly stepped face 55 of the injection nozzle 52. The feed port channel 58 and axially opposed radially internally extending portion 53 of the injection nozzle 52 cooperatively provide an annular feed port 57 disposed transversely laterally, or radially outwardly, from the axis A of a preferably non-linear injection passage 60 in the injection nozzle 5^..
The tubular body 1 of the insert end 50 is secured within and adjacent the interior periphery 64 of the reactor body 44. The mechanism for securing the insert end 50 in this position may consist of an axially-extending nut-and-bolt arrangement (not shown) penetrating co-linearly mating passages (not shown) in: (i) an upper radially extending lip 66 on the reactor body 44; (ii) an abutting, radially outwardly extending thickened neck section 68 on the insert end 50; and (iii) in turn, the abutting injector nozzle 52. Other mechanisms for securing the insert end 50 within the reactor body 44 may include a press fit (not shown) or mating threads (not shown) on the outer periphery 62 of the tubular body 51 and on the inner periphery 64 of the reactor body 44. Seals, e.g., 70, may be mounted as desired between, for example, the radially extending lip 66 and the abutting the neck section 68 and the neck section 68 and the abutting injector nozzle 52.
The non-linear injection passage 60 has, from an axialiy-extending cross-sectional perspective, mating, radially inwardly curved opposing side wall sections 72, 74 extending along the axial length of the non-linear injection passage 60. The entry end 76 of injection passage 60 provides a rounded circumferential face abutting an injection feed tube 78, which can be bolted (not shown) to the mating planar, radially outwardly extending distal face 80 on the injection nozzle 52.
In the embodiment of Figure 2, the injection passage 60 is a DeLavai type of nozzle and has an axially convergent section 82 abutting an intermediate relatively narrower throat section 84, which in turn abuts an axially divergent section 86. The injection passage 60 also has a circular diametric cross-section (i.e., in cross-sectional view perpendicular to the axis of the nozzle passage) all along its axial length. In certain embodiments, the injection passage 60 may also present a somewhat roundly curved thick 82, less curved thicker 84, and relatively even less curved and more gently sloped relatively thin 86 axially extending cross-sectional configuration from the entry end 76 to the injection end 88 of the injection passage 60 in the injection nozzle
JZ,
The injection passage 60 can thus be configured to present a substantially iseiitropic or frictionless configuration for the injection nozzle 52. This configuration may vary, however, depending on the application involved in order to yield a substantially isentropic configuration for the application.
The injection passage 60 is formed in a replaceable injection nozzle insert 90 press-fit or threaded into a mating injection nozzle mounting passage 92 extending axially through an injection nozzle body 94 of the injection nozzle 52. The injection nozzle insert 90 is preferably made of hardened steel alloy, and the balance of the nozzle reactor 100 components other than seals, if any, are preferably made of steel or stainless steel.
In the particular embodiment shown in Figure 2, the diameter D within the injection passage 60 is 140 mm. The diameter E of the ejection passage opening 96 in the ejection end 48 of the reactor body 44 is 2.2 meters. The axial length of the reactor body 44, from the injection end 88 of the injector passage 60 to the ejection passage opening 96, is 10 meters.
The interior peripheries 89, 91 of the insert end 50 and the tubular central section 46, respectively, cooperatively provide a stepped or telescoped structure expanding radially outwardly from the injection end 88 of the injection passage 60 toward the frustoconical end 48 of the reactor body 44, The particular dimensions of the various components, however, will vary based on the particular application for the nozzle reactor, generally 100. Factors taken into account in determining the particular dimensions include the physical properties of the cracking gas (density, enthalpy, entropy, heat capacity, etc.) and the pressure ratio from the entry end 76 to the injection end 88 of the injection passage 60.
The embodiment of Figure 2 may be used to, for example, crack heavy hydrocarbon material, including bitumen if desired, into lighter hydrocarbons and other components. In order to do so in certain embodiments, superheated steam (not shown) is injected into the injection passage 60. The pressure differential from the entry end 76, where the pressure is relatively high, to the ejection end 88, where the pressure is relatively lower, aids in accelerating the superheated steam through the injection passage 60.
In certain embodiments having one or more non-linear cracking material injection passages, e.g., 60, such as the convergent/divergent configuration of Figure 2, the pressure differential can yield a steady increase in the kinetic energy of the cracking material as it moves along the axial length of the cracking material injection passage(s) 60, The cracking material may thereby eject from the ejection end 88 of the injection passage 60 into the interior of the reactor body 44 at supersonic speed with a commensurately relatively high level of kinetic energy. In these embodiments, the level of kinetic energy of the supersonic discharge cracking material is therefore greater than can be achieved by certain prior art straight-through injectors or other injectors such as the convergent, divergent, convergent nozzle reactor of the '615 Publication.
Other embodiments of a cracking material injection passage may not be as isentropic but may pro vide a substantial increase in the speed and kinetic energy of the cracking material as it moves through the injection passage 60. For example, an injection passage 60 may comprise a series of conical or toroidal sections (not shown) to provide varying cracking material acceleration through the passage 60 and, in certain embodiments, supersonic discharge of the cracking material from the passage 60.
In certain methods of use of the nozzle reactor embodiment illustrated in Figure 2, heavy hydrocarbon feed stock (not shown) is pre-heated, for example at 2-1.5 bar, which is generally the same pressure as that in the reactor body 44. In the case of bitumen feed stock, the preheat should provide a feed, stock temperature of 300 to 500°, and most advantageously 400 to 450° C. Contemporaneously, the preheated feed stock is injected into the material feed passage 54 and then through the mating annular feed port 57. The feed stock thereby travels radially inwardly to impact a transversely (i.e., axially) traveling high speed cracking material jet (for example, steam, natural gas, carbon dioxide or other gas not. shown) virtually immediately upon its ejection from the ejection end 88 of the injection passage 60. The collision of the radially injected feed stock with the axially traveling high speed steam jet delivers kinetic energy to the feed stock. The applicants believe that this process may continue, but with diminished intensity and productivity, through the length of the reactor body 44 as injected feed stock is forced along the axis of the reactor body 44 and yet constrained from avoiding contact with the jet stream by the telescoping interior walls, e.g., 89, 91 101 , of the reactor body 44. Depending on the nature of the feed stock and its pre-feed treatment, differing results can be procured, such as cracking of heavy hydrocarbons, including bitumen, into lighter hydrocarbons and, if present in the heavy hydrocarbons or injected material, other materials.
In some embodiments, a catalyst can be introduced into the nozzle reactor to enhance cracking of the material feed stock by the cracking gas ejection stream.
In the applicant's view, the methodology of nozzles of the type shown in the illustrated embodiments, to inject a cracking gas such as steam, can be based on the following equation h ; I I : Kb (1)
where KEj is the kinetic energy of the cracking material (referred to as the free jet) immediately upon emission from an injection nozzle, Ho is the enthalpy of cracking material upon entr}' into the injection nozzle, Hj is the enthalpy of cracking material upon emission from the injection nozzle, and KE0 is the kinetic energy of the cracking material at the inlet of the nozzle.
This equation derives from the first law of thermodynamics - that regarding the conservation of energy - in which the types of energy to be considered include: potential energy, kinetic energy, chemical energy, thermal energy, and work energy. In the case of the use of the nozzles of the illustrated embodiments to inject steam, the only significantly pertinent types of energy are kinetic energy and thermal energy. The others ~ potential, chemical, and work energy - can be zero or low enough to be disregarded. Also, the inlet kinetic energy can be low enough to be disregarded. Thus, the resulting kinetic energy of the cracking material as set forth in the above equation is simplified to the change in enthalpy ΔΗ.
The second law of thermodynamics - an expression of the universal law of increasing entropy, stating that the entropy of an isolated system that is not in equilibrium will tend to increase over time, approaching a maximum value at equilibrium - means that no real process is perfectly isentropic. However, a practically isentropic nozzle (i.e., a nozzle commonly referred to as "isentropic" in the art) is one in which the increase in entropy through the nozzle results in a relatively complete or very high conversion of thermal energy into kinetic energy. On the other hand, non-isentropic nozzles such as a straight-bore nozzle not only result in much less efficiency in conversion of thermal energy into kinetic energy but also can impose upper limits on the amount of kinetic energy available from them.
For example, since the velocity of an ideal gas through a nozzle is represented by the equation
V = (-2ΔΗ)172 (2)
and the velocity in a straight-bore nozzle is limited to the speed of sound, the kinetic energy of a gas jet delivered by a straight-bore nozzle is limited. However, a practically "isentropic" converging/diverging nozzle, such as shown in, for example, Figures 1 and 2, can yield, i.e.. eject, a gas jet that is supersonic. Consequently, the kinetic energy of the gas jet delivered by such an isentropic converging/diverging nozzle can be substantially greater tha that of the straight-bore nozzle, such as that shown in the ' 181 Publication.
It can thus be seen that certain embodiments disclosed above can provide a nozzle reactor providing enhanced transfer of kinetic energy to the material feed stock through many aspects such as, for example, by providing a supersonic cracking gas jet, improved orientation of the direction of flow of a cracking gas (or cracking gas mixture) with respect to that of the material feed stock, and/or more complete cracking gas stream impact with the material feed stock as a result of, for example, an annular material feed port and the telescoped reactor body interior, Certain embodiments also can result in reduced retention of by-products, such as coking, on the side walls of the reactor chamber. Embodiments of the nozzle reactor can also be relatively rapid in operation, efficient, reliable, easy to maintain and repair, and relatively economical to make and use.
It should be noted that, in certain embodiments including in conjunction with the embodiments shown in Figures 1 and 2 above, the injection material may comprise a cracking fluid or other motive material rather than, or in addition to, a cracking gas. Accordingly, it is to be understood that certain embodiments may utilize components that comprise motive material compatible components rather than, as described in particular embodiments above, cracking material compatible components such as, for example, the injection passage, e.g., 60, referenced above. When utilized in conjunction with an inwardly narrowed motive material injection passage, however, the motive material preferably is compressible.
The applicants believe that a non-linear injector passage nozzle reactor embodiment (as generally shown in Figure 1) and a linear injector passage nozzle reactor one inch in axial length provide the following theoretical results for 30 bar steam cracking material supplied at 660°C with interior reactor chamber pressures of 10 bar and 3 bar as shown. For both of these types of nozzle reactors, however, the injector passage configurations must be changed (by varying the position of the throat 84 and the diameter of the discharge or injection end 88) in order to deli ver 2 barrels per day (water volume) of steam at 10 bars and 3 bars. The results listed in Table 2 are based on the assumption of perfect gas behavior and the use of k (Cp/Cv, ratio of specific heats). Straight-Through C onvergent D ivergent
Injector Nozzle reactor Injection
10 bar 3 bar 10 bar 3 bar
Throat Diameter, mm 1.60 2.80 1 .20 1 .20
Steam Temp,, °C 560.0 544,3 464,4 296.7
Steam Velocity, m/s 647.1 690.0 914.1 1244.1
Mach Number 0.93 1.00 1.39 2.12
Kinetic energy, kW 0.72 1.12 1.43 2,64
Table 2
As can be seen from the results of applicants' calculations above, the theoretically tested straight-through injection passage nozzle reactors of the prior art theoretically provide steam jet velocity at, or less than, the speed of sound. In contrast, the theoretically tested convergent/divergent injection passage nozzle reactors of the present application theoretically can provide a steam jet velocity in the interior reactor chamber well in excess of the speed of sound and, at 3 bar interior reactor chamber pressure, in excess of twice the speed of sound. Similarly and as a result, the associated kinetic energies of steam jets of the convergent/divergent injection passage nozzle reactors are theoretically significantly greater than the associated kinetic energies of the steam jets of the linear injection passage nozzle reactors.
The applicants therefore believe that the theoretically tested convergent/divergent injection passage nozzle reactors of the present application are significantly closer to isentropic than the theoretically tested straight-through injection passage nozzle reactor, As shown by the theoretical kinetic energy data above, the applicants also believe that the theoretically tested convergent/divergent injection passage nozzle reactors can be 2 to 2.5 times more efficient than the theoretically tested straight-through injection passage nozzle reactors identified above, The above theoretical results were obtained using steam as the cracking material and therefore, are based on thermodynamic properties of steam. However, similar theoretical results can be obtained using other gaseous motive fluids as the cracking gas. Similarly, the kinetic energies of cracking gas jet of the convergent/divergent injection passage nozzle reactors can also be significantly greater than the associated kinetic energies of the medium of the convergeni/divergent/conv rg nt injection passage of the type disclosed in the '615 Publication.
In the convergent/divergent/convergent injection passage of the '615 Publication, however, the velocity and kinetic energy of the bitumen/steam medium is designed to substantially decrease at least via the second convergent section, thus diminishing the ultimate velocity and kinetic energy of the medium when ejected from the '615 Publication's nozzle reactor, in addition, the '615 Publication's use of a mixed bitumen/steam medium itself reduces the velocity of the medium as compared to the velocities, and resulting shear, attainable by injection of separate steam and pre-heated bitumen feeds, for example.
Certain embodiments of the present reactor nozzle and method of use can therefore accomplish cracking of bitumen and other feed stocks primarily, or at least more substantially, by mechanical shear at a molecular level rather than by temperature, retention time, or involvement of catalysts. Although such cracking of the hydrocarbon molecules yields smaller, charge imbalanced hydrocarbon chains which subsequently satisfy their charge imbalance by chemical interaction with other materials in the mixed jet stream or otherwise, the driving force of the hydrocarbon cracking process can be mechanical rather than chemical. In addition, certain embodiments can utilize the greater susceptibility of at least certain heavy hydrocarbons to mechanical cracking in order to selectively crack particular hydrocarbons (such as relatively heavy bitumen for example) as opposed to other lighter hydrocarbons or other materials that may be in the material feed stock as it passes through the nozzle reactor. Also, in certain embodiments, the configuration of the nozzle reactor can reduce and even virtually eliminate back mixing while enhancing, for example, plug flow of the cracking ma terial and material feed mixture through the reactor body and cooling of the mixture through the reactor body. This can aid in not only enhancing mechanical cracking of the material feed but also in reducing coke formation and wall scaling within the reactor body. In combination with injection of a high velocity cracking material or other motive material from the injection nozzle into the reactor body, coke formation and wall scaling can be even more significantly reduced if not virtually or practically eliminated. In these embodiments, the nozzle reactor can thus provide more efficient and complete cracking, and if desired selective cracking, of heavy hydrocarbons, while reducing and in certain embodiments virtually eliminating wail scaling within the reactor body.
Another embodiment of a nozzle reactor suitable for use in the methods and systems described herein is illustrated in Figures 3 to 8. Figures 3 and 4 show cross-sectional views of one embodiment of a nozzle reactor 1000 suitable for use in the methods described herein. The nozzle reactor 1000 includes a head portion 1002 coupled to a body portion 1004. A. main passage 1006 extends through both the head portion 1002 and the body portion 1004. The head and body portions 1002, 1004 are coupled together so that the central axes of the main passage 1006 in each portion 1002, 1004 are coaxial so that the main passage 1006 extends straight through the nozzle reactor 1000.
It should be noted that for purposes of this disclosure, the term "coupled" means the joining of two members directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate member being attached to one another. Such joining may be permanent in nature or alternatively may be removable or releasable in nature.
The nozzle reactor 1000 includes a feed passage 1008 that is in fluid communication with the main passage 1006. The feed passage 1008 intersects the main passage 1006 at a location between the portions 1002, 1004. The main passage 1006 includes an entry opening 1010 at the top of the head portion 1002 and a exit opening 1 012 at the bottom of the body portion 1004. The feed passage 1008 also includes an entry opening 1014 on the side of the body portion 1004 and an exit opening 1016 that is located where the feed passage 1008 meets the main passage 1006.
During operation, the nozzle reactor 1000 includes a reacting fluid that flows through the main passage 1006. The reacting fluid enters through the entry' opening 1 010, travels the length of the main passage 1006, and exits the nozzle reactor 1000 out of the exit opening 1012. A feed material flows through the feed passage 1008. The feed material enters through the entry opening 1014, travels through the feed passage 1006, and exits into the main passage 1008 at exit opening 1016.
The main passage 1006 is shaped to accelerate the reacting fluid. The main passage 1006 may have any suitable geometry that is capable of doing this. As shown in Figures 3 and 4, the main passage 1006 includes a first region having a convergent section 1020 (also referred to herein as a contraction section), a throat 1022, and a divergent section 1024 (also referred to herein as an expansion section). The first region is in the head portion 1002 of the nozzle reactor 1000. The convergent section 1020 is where the main passage 1006 narrows from a wide diameter to a smaller diameter, and the divergent section 1024 is where the main passage 1006 expands from a smaller diameter to a larger diameter. The throat 1022 is the narrowest point of the main passage 1006 between the convergent section 1020 and the divergent section 1024. When viewred from the side, the main passage 1006 appears to be pinched in the middle, making a carefully balanced, asymmetric hourglass-like shape. This configuration is commonly referred to as a convergent-divergent nozzle or "con-di nozzle".
The convergent section of the main passage 1006 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 or Mach 1 at the throat 1022 provided that the pressure ratio is high enough. In this situation, the main passage 1006 is said to be in a choked flow condition,
Increasing the pressure ratio further does not increase the Mach number at the throat 1022 beyond unity. However, the flowr downstream from the throat 1022 is free to expand and can reach supersonic velocities. It should be noted that Mach 1 can be a very high speed for a hot fluid since the speed of sound varies as the square root of absolute temperature. Thus the speed reached at the throat 1022 can be far higher than the speed of sound at sea level.
The divergent section 1024 of the main passage 1006 slows subsonic fluids, but accelerates sonic or supersonic fluids. A convergent-divergent geometry can therefore accelerate fluids in a choked flow condition to supersonic speeds. The convergent-divergent geometry ca be used to accelerate the hot, pressurized reacting 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 reacting fluid through the convergent-divergent nozzle is isentropic (fluid entropy is nearly constant). At subsonic flow the fluid is compressible so that sound, a small pressure wave, can propagate through it, At the throat 1022, where the cross sectional area is a minimum, the fluid velocity locally becomes sonic (Mach number = 1.0). As 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 fluid as viewed in the frame of reference of the nozzle (Mach number > 1 ,0).
The main passage 1006 only reaches a choked flow condition at the throat 1022 if the pressure and mass flow rate is sufficient to reach sonic speeds, otherwise supersonic flow is not achieved and the main passage will act as a venturi tube. In order to achieve supersonic flow, the entry pressure to the nozzle reactor 1000 should be significantly above ambient pressure,
The pressure of the fluid at the exit of the divergent section 1024 of the main passage 1006 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 divergent section 1024 of the main passage 1006 forming an unstable jet that "flops" around and damages the main passage 1006. In one embodiment, the ambient pressure is no higher than approximately 2-3 times the pressure in the supersonic gas at the exit.
The supersonic reacting fluid collides and mixes with the feed material in the nozzle reactor 1000 to produce the desired reaction. The high speeds involved and the resulting collision produces a significant amount of kinetic energy that helps facilitate the desired reaction. The reacting fluid and/or the feed material may also be pre-heated to provide additional thermal energy to react the materials. The nozzle reactor 1000 may be configured to accelerate the reacting fluid to at least approximately Mach 1 , at least approximately Mach 1.5, or, desirably, at least approximately Mach 2. The nozzle reactor may also be configured to accelerate the reacting fluid to approximately Mach 1 to approximately Mach 7, approximately Mach 1.5 to approximately Mach 6, or, desirably, approximately Mach 2 to approximately Mach 5.
As shown in Figure 4, the main passage 1006 has a circular cross-section and opposing converging side walls 1026, 1028. The side walls 1026, 1028 curve inwardly toward the central axis of the main passage 1006. The side walls 1026, 1028 form the convergent section 1020 of the main passage 1006 and accelerate the reacting fluid as described above.
The main passage 1006 also includes opposing diverging side walls 1030, 1032. The side walls 1030, 1032 curve outwardly (when viewed in the direction of flow) away from the central axis of the main passage 106. The side wails 1030, 1032 form the divergent section 1024 of the main passage 106 that allows the sonic fluid to expand and reach supersonic velocities.
The side walls 1026, 1028, 1030, 1032 of the main passage 1006 provide uniform axial acceleration of the reacting fluid with minimal radial acceleration. The side walls 1026, 1028, 1030, 1032 may also have a smooth surface or finish with an absence of sharp edges that may disrupt the flow. The configuration of the side walls 1026, 1028, 1030, 1032 renders the main passage 1006 substantially isentropic.
The feed passage 1008 extends from the exterior of the body portion 1004 to an annular chamber 1034 formed by head and body portions 1002, 1004. The portions 1002, 1 004 each have an opposing cavity so that when they are coupled together the cavities combine to form the annular chamber 1034. A seal 1036 is positioned along the outer circumference of the annular chamber 1034 to prevent the feed material from leaking through the space between the head and body portions 1002, 1004,
It should be appreciated that the head and body portions 1002, 1004 may be coupled together in any suitable manner. Regardless of the method or devices used, the head and body portions 1002, 1004 should be coupled together in a way that prevents the feed material from leaking and withstands the forces generated in the interior, In one embodiment, the portions 1002, 1004 are coupled together using bolts that extend through holes in the outer flanges of the portions 1002, 1004.
The nozzle reactor 1000 includes a distributor 1040 positioned between the head and body portions 1002, 1004. The distributor 1040 prevents the feed material from flowing directly from the opening 1041 of the feed passage 1008 to the main passage 1006. Instead, the distributor 1040 annular!y and uniformly distributes the feed materia! into contact with the reacting fluid flowing in the main passage 1006.
As shown in Figure 6, the distributor 1040 includes an outer circular wall 1048 that extends between the head and body portions 1002, 1004 and forms the inner boundary of the annular chamber 1034. A sea! or gasket may be provided at the interface between the distributor 140 and the head and body portions 1002, 1004 to prevent feed material from leaking around the edges.
The distributor 1040 includes a plurality of holes 1044 that extend through the outer wall 1048 and into an interior chamber 1046. The holes 1044 are evenly spaced around the outside of the distributor 1040 to provide even flow into the interior chamber 1046. The interior chamber 1046 is where the main passage 1006 and the feed passage 1008 meet and the feed material comes into contact with the supersonic reacting fluid. The distributor 1040 is thus configured to inject the feed material at about a 90° angle to the axis of tra vel of the reacting fluid in the main passage 1006 around the entire circumference of the reacting fluid. The feed material thus forms an annul us of flow that extends toward the main passage 1006. The number and size of the holes 1044 are selected to provide a pressure drop across the distributor 1040 that ensures that the flow through each hole 1044 is approximately the same. In one embodiment, the pressure drop across the distributor is at least approximately 2000 pascals, at least approximately 3000 pascals, or at least approximately 5000 pascals.
The distributor 1040 includes a wear ring 1050 positioned immediately adjacent to and downstream of the location where the feed passage 108 meets the main passage 1006. The collision of the reacting fluid and the feed material causes a lot of wear in this area. The wear ring is a physically separate component that is capable of being periodically removed and replaced.
As shown in Figure 6, the distributor 1040 includes an annular recess 1052 that is sized to receive and support the wear ring 1050. The wear ring 1050 is coupled to the distributor 1040 to prevent it from moving during operation. The wear ring 1050 may be coupled to the distributor in any suitable manner. For example, the wrear ring 1050 may be welded or bolted to the distributor 1040. If the wear ring 1050 is welded to the distributor 1040, as shown in Figure 5, the wear ring 1050 can be removed by grinding the weld off. In some embodiments, the weld or bolt need not protrude upward into the interior chamber 1046 to a significant degree.
The wear ring 1050 can be removed by separating the head portion 1002 from the body portion 1004. With the head portion 1002 removed, the distributor 1040 and/or the wear ring 1050 are readily accessible. The user can remove and/or replace the wear ring 1050 or the entire distributor 1040, if necessary.
As shown in Figures 3 and 4, the main passage 1006 expands after passing through the wear ring 1050. This can be referred to as expansion area 1060 (also referred to herein as an expansion chamber). The expansion area 1060 is formed largely by the distributor 1040, but can also be formed by the body portion 1004.
Following the expansion area 1060, the main passage 1006 includes a second region having a converging-diverging shape. The second region is in the body portion 1004 of the nozzle reactor 1000, In this region, the main passage includes a convergent section 1070 (also referred to herein as a contraction section), a throat 1072, and a divergent section 1074 (also referred to herein as an expansion section). The converging-diverging shape of the second region differs from that of the first region in that it is much larger, in one embodiment, the throat 1072 is at least 2-5 times as large as the throat 1022,
The second region provides additional mixing and residence time to react the reacting fluid and the feed material. The main passage 1006 is configured to allow a portion of the reaction mixture to flow backward from the exit opening 1012 along the outer wail 1076 to the expansion area 1060, The backflow then mixes with the stream of material exiting the distributor 1040. This mixing action also helps drive the reaction to completion.
The dimensions of the nozzle reactor 1000 can vary based on the amount of material that is fed through it. For example, at a flow rate of approximately 590 kg/hr, the distributor 140 can include sixteen holes 144 that are 3 mm in diameter. The dimensions of the various components of the nozzle reactor shown in Figures 3 and 4 are not limited, and may generally be adjusted based on the amount of feed flow rate if desired, Table 3 provides exemplary dimensions for the various components of the nozzle reactor 1000 based on a hydrocarbon feed input measured in barrels per day (BPD).
Table 3: Exemplar}' nozzle reactor specifications
Figure imgf000033_0001
It should be appreciated that the nozzle reactor 1000 can be configured in a variety of ways that are different than the specific design shown in the Figures, For example, the location of the openings 1010, 1012, 1014, 1016 may be placed in any of a number of different locations. Also, the nozzle reactor 1000 may be made as an integral unit instead of comprising two or more portions 1002, 1004, Numerous other changes may be made to the nozzle reactor 1000.
Turning to Figures 7 and 8, another embodiment of a nozzle reactor 2000 is shown. This embodiment is similar in many ways to the nozzle reactor 1000. Similar components are designated using the same reference number used to illustrate the nozzle reactor 1000. The previous discussion of these components applies equally to the similar or same components includes as part of the nozzle reactor 2000.
The nozzle reactor 2000 differs a few ways from the nozzle reactor 1000. The nozzle reactor 2000 includes a distributor 2040 that is fomied as an integral part of the body portion 2004. However, the wear ring 1050 is still a physically separate component that can be removed and replaced. Also, the wear ring 1050 depicted in Figure 18 is coupled to the distributor 2040 using bolts instead of by welding. It should be noted that the bolts are recessed in the top surface of the wear ring 1050 to prevent them from interfering with the flow of the feed material.
In Figures 7 and 8, the head portion 1002 and the body portion 1004 are coupled together with a clamp 2080. The seal, which can be metal or plastic, resembles a "T" shaped cross- section. The leg 2082 of the "T" forms a rib that is held by the opposing faces of the head and body portions 1002, 1004. The two arms or lips 2084 form seals that create an area of sealing surface with the inner surfaces 2076 of the portions 1002, 1004. Internal pressure works to reinforce the seal.
The clamp 2080 fits over outer flanges 2086 of the head and body portions 1002, 1004.
As the portions 1002, 1004 are drawn together by the clamp, the seal lips deflect against the inner surfaces 2076 of the portions 1002, 1004. This deflection elastically loads the lips 2084 against the inner surfaces 2076 forming a self-energized seal, In one embodiment, the clamp is made by Grayloc Products, located in Houston, XX.
In some embodiments, a nozzle reactor system may be used to increase the overall conversion of material feed into lighter components via cracking. The nozzle reactor system described herein may achieve this increase in overall conversion by utilizing a first nozzle reactor to conduct a first cracking step, and then passing any material not cracked or not sufficiently cracked by the first nozzle reactor into a second nozzle reactor that operates under conditions selected for cracking the uneracked or not sufficiently cracked material.
As shown in Figure 9, the nozzle reactor system 300 may generally include a first nozzle reactor 310 and a second nozzle reactor 320. Nozzle reactor system 300 may also include a first separation unit 330. First separation unit 330 may generally separate the materia] leaving first nozzle reactor 310 into a light stream and a heavy stream. Accordingly, first separation unit 330 may include a light stream outlet 332 and a heavy stream outlet 334. Heavy stream outlet 334 may be in fluid communication with the material feed passage of second nozzle reactor 320 so that the heavy components of heavy stream outlet 334 may be transported to second nozzle reactor 320 for cracking.
First and second nozzle reactors 310, 320 may generally include a nozzle reactor according to any embodiment or aspect described herein. In one aspect, first and second nozzle reactors 310, 320 may each have a reactor body, an injection passage, and a material feed passage. The reactor body may include an interior reactor chamber with an injection end and an ejection end. The injection passage may be mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber. Furthermore, the injection passage may have an enlarged volume injection section, an enlarged volume ejection section. and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section. The injection passage may also have a material injection end and a material ejection end in injecting communication with the interior reactor chamber. The material feed passage may penetrate the reactor body. The location of the material feed passage may be adjacent to the material ejection end of the injection passage and transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage.
First and second nozzle reactors 310, 320 may be identical or first and second nozzle reactors 310, 320 may be different. In one aspect of the embodiment, second nozzle reactor 320 has a smaller interior body chamber volume than the interior reactor chamber volume of first nozzle reactor 310. For example, the interior reactor chamber volume of second nozzle reactor 320 may be 1/3 or less the interior reactor chamber volume of first nozzle reactor 310. Additionally, nozzle reactor system 300 may include more than two nozzle reactors. Other features of the nozzle reactor are described in greater detail above.
First separation unit 330 may generally include any type of separation unit capable of separating the lighter material that is the product of cracking the material feed fed into first nozzle reactor 310 from the heavy material that may generally be made up of material feed that was not cracked or not sufficiently cracked in first nozzle reactor 310. Examples of suitable separation units include, but are not limited to, distillation units, gravity separation units, filtration units, and cyclonic separation units.
First separation unit 330 may be in fluid communication with the ejection end of first nozzle reactor 310 such that the material leaving first nozzle reactor 310 is fed into first separation unit 330. Any manner of fluid communication may be used between first nozzle reactor 310 and first separation unit 330. In one example, the fluid communication may be piping extending between the ejection end of first nozzle reactor 310 and first separation unit 330.
As noted above, first separation unit 330 may generally include light stream outlet 332 and heavy stream outlet 334. Light stream outlet 332 may generally include any materials having a predetermined property or properties, such as a molecular weight, boiling point, API gravity, or viscosity. As such, light stream outlet 332 may include, for example, a) material feed that is not cracked inside first nozzle reactor 310 but that possessed a predetermined property prior to being introduced into first nozzle reactor 310, and b) material feed that has been cracked inside first nozzle reactor 310 such that the cracked material obtains the predetermined property. Thus, where the material feed injected into first nozzle reactor 310 via the material feed passage is bitumen, light stream outlet 332 may comprise uncracked hydrocarbons that had the predetermined property when injected into first nozzle reactor 310 and cracked hydrocarbon molecules that obtained the predetermined property upon being cracked inside of first nozzle reactor 310. Correspondingly, heavy stream outlet 334 may generally include any materials not having the predetermined property or properties. As such, heavy stream outlet 334 may include, for example, a) material feed that is not cracked inside first nozzle reactor 310 and that did not possess the predetermined property upon being introduced into first nozzle reactor 310, and b) material feed that has been cracked inside first nozzle reactor 310 but that did not result in the cracked material possessing the predetermined property. Thus, where the material feed is bitumen, heavy stream outlet 334 may include uncracked hydrocarbon molecules that did not have the predetermined property when injected into first nozzle reactor 310 and cracked hydrocarbon molecules that did not obtain the predetermined property upon being cracked inside of first nozzle reactor 310.
Any property, property value or property range may be selected to determine whether a material is part of light stream outlet 332 or heavy stream outlet 334. Examples of properties and property values that may be used to classify the material leaving first nozzle reactor 310 may include a molecular weight above a selected value, a molecular weight below a selected value, a molecular weight within a selected range, a boiling point above a selected value, a boiling point belo a selected value, a boiling point within a selected range, an API gravity above a selected value, an API gravity below a selected value, an API within a selected range, a viscosity above a selected value, a viscosity below a selected value, or a viscosity within a selected range. Furthermore, multiple properties may be used to determine whether a material leaving first nozzle reactor 310 is part of light stream outlet 332 or heavy stream outlet 334. For example, the material may have to have both a molecular weight below a selected value and a boiling point below a selected value to be part of light stream outlet 332. The value or range selected for the property is also not limited. The value or range of values selected may be based on known property values for useful fractions of a material feed.
In order to transport the components of heavy stream outlet 334 to second nozzle reactor 320, a fluid communication may be established between heavy stream outlet 334 and second nozzle reactor 320. More specifically, a fluid communication may be established between heavy stream outlet 334 and the material feed passage of second nozzle reactor 320. However, fluid communication may also be established between heavy stream outlet 334 and any portion of second nozzle reactor 320. Any manner of fluid communication may be used between second nozzle reactor 320 and heavy stream outlet 334. In one example, the fluid communication may be piping extending between the heavy stream outlet 334 and second nozzle reactor 320, A pump may also be used in connection with the fluid communication to assist the flow of material through the fluid communication.
Second nozzle reactor 320 may be operated at different operating conditions than first nozzle reactor 310 so as to increase the likelihood of cracking the components of heavy stream outlet 334. It is generally theorized that nozzle reactors as described herein crack the molecules having the largest molecular mass first. In first nozzle reactor 310, a relatively high operating temperature may be selected such that only a high boiling point fraction of the feed material is present in the reaction chamber as a liquid (or possibly a solid), while the remaining fractions are present in the reaction chamber as a gas. As such, the fraction that is present in the reaction chamber as a liquid or solid has the largest molecular mass and will be the first material cracked by the shock waves produced inside the nozzle reactor. Gaseous fractions may pass through the reaction chamber without being cracked. These gaseous fractions may then become part of the heavy stream fed to second nozzle reactor 320. If second nozzle reactor 320 is operated at the same operating conditions as first nozzle reactor 310, the heavy stream will remain in the gas phase and likely pass through second nozzle reactor 320 with no further cracking being accomplished. Accordingly, the operating conditions that may be altered between the first and second nozzle reactors 310, 320 are those which will increase the mass of the components of heavy stream outlet 334 as they enter second nozzle reactor 320. In other words, operating second nozzle reactor 320 under conditions that will transform the gaseous heavy stream into a liquid or solid may increase the rate at which second nozzle reactor 320 cracks the components of heavy stream outlet 334. Exemplary operating conditions that may be altered between first nozzle reactor 310 and second nozzle reactor 320 and that will increase the mass of the components of heavy stream outlet 334 include decreasing the temperature of the components of heavy stream outlet 334, Reduction in temperature may be achieved by reducing the ratio of cracking material mass to material feed mass or by reducing the superheat in the cracking material whi le maintaining the ratio of cracking material mass to material feed mass.
In another aspect of this embodiment, nozzle reactor system 300 may further include a second separation unit 340. Second separation unit 340 may be in fluid communication with the ejeciion end of second nozzle reactor 320 such that material leaving second nozzle reactor 320 is fed into second separation unit 340. Second separation unit 340 may generally include a light stream outlet 342 and a heavy stream outlet 344.
Like first separation unit 330, second separation unit 340 may generally include any type of separation unit capable of separating lighter material that possesses a predetermined property when leaving second nozzle reactor 320 from the heavy material that does not possesses the predetermined property when leaving second nozzle reactor 320, Examples of suitable separation units include, but are not limited to, distillation units, gravity separation units, filtration units, and cyclonic separation units.
Second separation unit 340 may be in fluid communication with the ejection end of second nozzle reactor 320 such that the material leaving second nozzle reactor 320 is fed into second separation unit 340. Any manner of fluid communication may be used between second nozzle reactor 320 and second separation unit 340. In one example, the fluid communication may be piping extending between the ejection end of second nozzle reactor 320 and second separation unit 340.
As noted above, second separation unit 340 may generally include light stream outlet 342 and heavy stream outlet 344, Light stream outlet 342 may generally include material that has a predetermined property or properties when leaving second nozzle reactor 320, Correspondingly, heavy stream outlet 344 may generally be comprised of material tha does not have the predetermined property or properties when leaving second nozzle reactor 320, The predetermined property or properties used to separate streams in second separation unit 340 need not be the same predetermined property or properties used to separate streams in first separation unit 330. Alterna ively, the same predetermined property or properties may be used in both first separation unit 330 and second separation unit 340. As with first separation unit 330, any property, property value or property value ranged may be selected as the parameter for separating light and heavy streams.
In one aspect of the embodiment, light stream outlet 342 may be in fluid communication with first nozzle reactor 310 or second nozzle reactor 320 via a recycle stream. Despite possessing a predetermined property or properties, the materia! that makes up light stream outlet 342 may still be too large and heavy to be used as useful product, and thus requires further cracking. Such cracking may take place in either first nozzle reactor 310 or second nozzle reactor 320 or both depending on the characteristics (such as molecular weight or boiling point) of the material that makes up light stream outlet 342. Accordingly, providing a fluid communication between light stream outlet 342 and first nozzle reactor 310 and/or second nozzle reactor 320 allows for this second attempt at cracking the material, although this time in an improved condition for cracking. Any manner of fluid communication may he used between light stream output 342 and first nozzle reactor 310 and/or second nozzle reactor 320. In one example, the fluid communication may be piping extending between the light stream output 342 and the material feed passage of first nozzle reactor 310 and/or second nozzle reactor 320. A similar recycle stream may be used to divert the material of heavy stream outlet 344 back to either first nozzle reactor 310 or second nozzle reactor 320. The manner of providing such a recycle stream may be similar to the recycle stream as described above, such as by providing piping between heavy stream outlet 344 and either first nozzle reactor 310 or second nozzle reactor 320,
Similar recycle streams may also be provided between light stream outlet 332 and first nozzle reactor 310. Additionally, a portion of heavy stream outlet 334 may be recycled back to first nozzle reactor, while the remainder of heavy stream outlet 334 is injected into second nozzle reactor 320 as described in greater detail above. Furthermore, a portion of light stream 332 may be recycled back to first nozzle reactor 310.
In the above description, two nozzle reactors are discussed. However, the nozzle reactor system is not limited to two nozzle reactors. Any number of nozzle reactors arranged in series may be used. Each nozzle reactor may operate at different conditions, with each nozzle reactor operating under conditions specifically selected to increase the likelihood of cracking a material that has passed through a previous nozzle reactor un cracked or not sufficiently cracked, Furthermore, the nozzle reactors may be arranged in parallel in addition to a series arrangement. For example, a first nozzle reactor may produce a heavy stream and a light stream, with the heavy stream being transported to a second nozzle reactor and a light stream being transported to a third nozzle reactor.
In another embodiment, a material feed cracking method is disclosed. The material feed cracking method may generally allow for an increase in conversion of material feed into lighter components by utilizing two or more reactor nozzles. The first reactor nozzle is utilized in a similar fashion to the detailed discussion above regarding the nozzle reactor. However, an additional nozzle reactor is used to deal with the material that passes through the first nozzle reactor but that is not cracked or not sufficiently cracked. More specifically, the operating conditions of the second nozzle reactor may be selected so that the second nozzle reactor is more likely to break down material that passes through the first nozzle reactor uneracked or not sufficiently cracked.
The material feed cracking method may generally include a first step of injecting a first stream of cracking materia] through an injection passage of a first nozzle reactor into an interior reactor chamber of a first nozzle reactor. Materia! feed may then be injected into the interior reactor chamber of the first nozzle reactor adjacent to the injection passage of the first nozzle reactor and transverse to the first stream of cracking material entering the interior reaction chamber of the first nozzle reactor from the injection passage of the first nozzle reactor. In this manner, a first light material and a first heavy materia! may be produced. The method may then include a step of injecting a second stream of cracking material through an injection passage of a second nozzle reactor into an interior reactor chamber of a second nozzle reactor. Additionally, the first heavy material may be injected into the interior reactor chamber of the second nozzle reactor adjacent to the injection passage of the second nozzle reactor and transverse to the second stream of cracking material entering the mterior reactor chamber of the second nozzle reactor from the injection passage of the second nozzle reactor. In this manner, a second light material and a second heavy material may be produced.
The first and second nozzle reactors referred to above may generally include a nozzle reactor according to any embodiment or aspect described herein. In one aspect, each nozzle reactor may comprise a reactor body, an injection passage, and a material feed passage. The reactor body may have an interior reactor chamber with an injection end and an ejection end. The injection passage may be mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber. Furthermore, the injection passage may have an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section. The injection passage may also have a material injection end and a material ejection end in injecting communication with the interior reactor chamber. The material feed passage may penetrate the reactor body. The location of the material feed passage may be adjacent to the material ejection end of the injection passage and transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage.
The first and second streams of cracking materia] may be any suitable cracking material for cracking the material feed. In one aspect the cracking material is a cracking gas, such as steam. The first and second streams of cracking material may be introduced into the injection passages at any suitable temperature and pressure. In one embodiment, the first and second streams of cracking material are injected into the injection passage at a temperature of from about 600 °C to about 850 °C and at a pressure of from about 15 bar to about 200 bar.
The material feed may be any type of material that may be broken down into smaller and lighter components. In one aspect of this method, the material feed is a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaitene content. The residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit. The high asphaitene content may be an asphaitene content greater than 4 wt% of the residue. Hydrocarbon sources such as these require cracking to break down the heavy and large molecules of the hydrocarbon into light components that may be beneficially used.
The material feed and first heavy stream may be introduced into the materia] feed passages at any suitable temperature and pressure. In one embodiment, the materia! feed and first heavy stream are injected into the material feed passages at a temperature of from about 300 °C to 500 °C and at a pressure of from about 2 about to about 15 bar.
The pressure inside the interior reactor chamber of the first and second nozzle reactor may range from about 0.5 bar to about 15 bar. The ratio of cracking material to material feed may range from about 0.5: 1.0 to about 4: 1 , The ratio of cracking material to first heavy material may range from about 0.1 : 1.0 to about 3: 1.0.
As noted above, the injection of the material feed and the first stream of cracking material may result in the production of first light materia! and first heavy material. This is because the nozzle reactor does not achieve total cracking of all material feed injected into the first nozzle reactor. The short retention time of the material feed in the interior reactor chamber combined with the preference of the nozzle reactor to crack the largest molecules first does not allow for Shockwaves generated by the injection passage to crack all of the material feed, and some material feed will therefore pass all the way through the first nozzle reactor without being cracked. Specifically, fractions of the material feed in a gaseous phase when passing through the interior reactor chamber may pass through the nozzle reactor without being cracked, These gaseous fractions may be considered non-participating in that they will not be cracked by the shock waves, Where such material feed passing through the nozzle uncracked comprises large molecules, further work may need to be done to accomplish cracking of the material into useful material. In one aspect of this embodiment, the operating conditions of the first nozzle reactor may be selected such that only a fraction of the material feed in the nozzle reactor is in a liquid or solid phase, while the remaining fractions of the material feed are in a gaseous phase. This may be achieved by, for example, pre-heating the material feed prior to injection into the nozzle reactor. In an example where the material feed comprises bitumen, the bitumen may comprise a fraction having a boiling point higher than 200 deg C. The pre-heating temperature may be selected such that only this fraction of the bitumen is in liquid or solid form, and therefore is the fraction most likely to be cracked by the first nozzle reactor. The remaining fractions of the bitumen in the gaseous phase may pass through the first nozzle reactor uncracked, at which point they may be fed to a second nozzle reactor. The temperature of the gaseous material leaving the first nozzle reactor may be altered such that the gas transforms into liquid or solid and thereby increases the chances of the material being cracked in the second nozzle reactor.
Accordingly, the first heavy material may be injected into the second nozzle reactor to undergo another attempt at cracking the material in the nozzle reactor. The second nozzle reactor may be identical in size and dimension to the first nozzle reactor, or may be different than the first nozzle reactor. In one aspect of the embodiment, the operating conditions of the second nozzle reactor are different from the operating conditions of the first nozzle reactor as described in greater detail above. For example, the temperature of the material injected into the second nozzle reactor may be reduced to add mass to the gaseous components being fed into the second nozzle reactor to better accomplish the cracking of the hydrocarbons that make up the first heavy material injected into the second nozzle reactor.
In another aspect of this embodiment, the first light material and the first heavy material leaving the first nozzle reactor may be separated prior to the introduction of the first heavy material into the second nozzle reactor. In this manner, the lighter and smaller components that make up the first light material may be separated for consumption or recycle while the heavy and large components that make up the first heavy material may be sent to the second nozzle reactor. Sending only the first heavy material to the second nozzle reactor may be beneficial because the second nozzle reactor will function to specifically crack these components while not being impeded by the presence of the first light material.
Separation of the first light material and the first heavy material may be accomplished by any suitable means for separation of the components. Properties such as density and boiling point may be used to effect separation. Separation may include, but is not limited to, separation by distillation units, gravity separation units, filtration units, and cyclonic separation units.
As with the first light material and the first heavy material, the second light material and the second heavy material may also be separated. Any suitable means for separation, such as those mentioned above, may be used to effect the separation.
The method may further comprise a step of injecting the first light material, first heavy material, second light material, or second heavy material into the reaction chamber of the first nozzle reactor or second nozzle reactor. In addition or in place of such a recycle stream, the method may further comprise a step of injecting the first light material or second light material into the reaction chamber of the first nozzle reactor.
In some embodiments, a nozzle reactor system includes two or more nozzle reactors aligned in parallel and used for upgrading hydrocarbon material. Figure 10 illustrates a nozzle reactor system 400 including three nozzle reactors 401, 402, and 403 aligned in parallel. The system also includes a stream dividing apparatus 10 located upstream of the nozzle reactors 401, 402, 403, and a product mixing apparatus 420 located downstream of the nozzle reactors 401, 402, 403. While not shown in Figure 10, the system can also include a stream heating unit located upstream of the nozzle reactors 401, 402, 402. Stream dividing apparatus 410 is generally configured to receive a stream of material to be processed in the nozzle reactors and divide the stream of material into one stream for each nozzle reactor in the nozzle reactor system 400. Each stream produced can be easier to control and measure. As shown in Figure 10, three streams are produced by the stream dividing apparatus 410, with each stream being directed to one of the nozzle reactors 401, 402, 403. The product material leaving each of the nozzle reactors 401 , 402, 403 is then combined in a product mixing apparatus 420. A portion of the combined product can be recycled back to the stream dividing apparatus 410 for further processing in the nozzle reactors 401, 402, 403.
Nozzle reactors 401, 402, 403 may generally include a nozzle reactor according to any embodiment or aspect described herein. In some embodiments, nozzle reactors 401, 402, 403 each have a reactor body, an injection passage, and a material feed passage. The reactor body includes an interior reactor chamber with an injection end and an ejection end. The injection passage is mounted in the nozzle reactor in material injecting communication with the injection end of the interior reactor chamber. Furthermore, the injection passage has an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section. The injection passage also has a material injection end and a material ejection end in injecting communication with the interior reactor chamber. The material feed passage penetrates the reactor body. The location of the material feed passage is adjacent to the material ejection end of the injection passage and transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage. In some embodiments, nozzle reactors 401, 402, 403 are identical to one another in structure and dimension, although nozzle reactors that differ in either or both of these characteristics can also be used within the same nozzle reactor system 400. The operating conditions of each nozzle reactor (e.g., temperature, pressure, etc.) can also be identical in each nozzle reactor, or the nozzle reactors can operate under different operating conditions.
Although only three nozzle reactors are shown in the nozzle reactor system 400, the number of nozzle reactors aligned in parallel in the nozzle reactor system 400 is not limited, In some embodiments, the amount of material needing to be upgraded and the relative capacity of each nozzle reactor that is part of the system 400 can play a role in the number of nozzle reactors selected for the system 400.
Stream dividing apparatus 410 generally includes any type of apparatus capable of dividing a larger stream into numerous smaller streams. Stream dividing apparatus 410 can be adapted to create streams of equal volumetric flow rates or can create streams having different volumetric flow rates. Stream dividing apparatus 410 can also be adapted to create any desired number of streams, but will generally be set up to create one stream for each nozzle reactor that is a part of the nozzle reactor system 400. Exemplary stream dividing apparatus include, but are not limited to, flow control valves, limiting orifice valves, orifice plates, flow venturies, pipe tees, pipe manifolds, and baffle plates.
In some embodiments, the stream dividing apparatus 410 can also produce stream of varying composition. For example, the stream dividing apparatus 410 can divide a stream of material based on molecular weight or density to produce a stream of material having a high molecular weight or high density, a stream of material ha ving a intermediate molecular weight or density, and a stream of material having a low molecular weight or density, While molecular weight is provided as example of the criteria on which the material can be divided, any other suitable criteria can be used for dividing the stream of material, including but not limited to, presence or absence of certain compounds or class of compounds, boiling point temperatures, and viscosity. In embodiments where the stream dividing apparatus 410 produces streams of varying composition, the stream dividing apparatus 410 can include but is not limited to vacuum or atmospheric distillation towers,
When the stream dividing apparatus 410 produces streams of varying composition, each stream can then be sent to a nozzle reactor in the nozzle reactor system 400 that is specifically tailored for upgrading streams having a specific composition, Nozzle reactors in the nozzle reactor system 400 can be tailored to upgrade a stream having a specific composition by any suitable manner, such as adjusting operating conditions (e.g., temperature, pressure, etc.) and/or by adjusting various dimensions of the nozzle reactor.
Each outlet of the stream dividing apparatus 410 is in fluid communication with the feed ma terial injection inlet of one of the nozzle reactors of the nozzle reactor system. In this manner, the material leaving the stream dividing apparatus 410 can be injected directly into one of the nozzle reactors 401 , 402, 403 for being subjected to cracking and upgrading. Any manner of fluid communication may be used between the material dividing apparatus 410 and the feed material injection inlets of each nozzle reactors. In one example, the fluid communication may be piping extending between an outlet of the stream dividing apparatus and the material feed injection inlet of each nozzle reactor.
The material feed fed into the stream dividing apparatus 410 and divided up into individual streams can include any type of material that may be broken down into smaller and lighter components. In some embodiments, the material feed is a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaltene content. The residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit. The high asphaltene content may be an asphaltene content greater than 4 wt% of the residue. Hydrocarbon sources such as these require cracking to break down the heavy and large molecules of the hydrocarbon into light components that may be beneficially used. In some embodiments, the material feed is material stream exiting a nozzle reactor located upstream of the nozzle reactors 401 , 402, 403 aligned in parallel and part of th e nozzle reactor system 400.
The mixing apparatus 420 can include any suitable apparatus for receiving the material exiting each of the nozzle reactors 401, 402, 403 and combining the material back into one stream. In some embodiments, the mixing apparatus 420 generally includes a vessel with multiple input ports for receiving the material leaving each of the nozzle reactors 401, 402, 403 in the nozzle reactor system. In some embodiments, the mixing apparatus 420 is a Kenics mixer, in such configurations, the ejection ends of each nozzle reactor 401, 402, 403 is in fluid communication with the input port or ports of the mixing apparatus 420. As described in greater detail above with respect to the connection between the stream dividing apparatus 410 and the nozzle reactors 401 , 402, 403, the fluid communication between the ejection ends of the nozzle reactors 401, 402, 403 and the injection port or ports of the mixing apparatus 420 can be established in any suitable manner, including the use of piping.
The vessel used for the mixing apparatus 420 can optionally include equipment for mixing the various material streams entering the mixing apparatus 420, such as a mixing blade. The volume of the mixing apparatus 420 should generally be designed such that the mixing apparatus 420 is capable of receiving all of the product material leaving the nozzle reactors 401, 402, 403 of the nozzle reactor system 400. The mixing apparatus 420 can also include an outlet port for allowing combined and optionally mixed material to leave the mixing apparatus 420 and be transported to further processing equipment located downstream of the nozzle reactor system 400. In some embodiments, the downstream processing equipment can serve as the mixing apparatus 420, and thereby both receive each stream leaving the nozzle reactors 401, 402, 403, and then subject the combined product streams to further processmg.
In some embodiments, the product streams exiting the nozzle reactors 401, 402, 403 are subjecied to further processing prior to being combined in a mixing apparatus 420. As shown in Figure 11 , processing apparatus 501, 502, 503 are provided for each nozzle reactor 401, 402, 403. In such embodiments, the product stream leaving each nozzle reactor 401, 402, 403 is sent to a processing apparatus 501, 502, 503. The product streams leaving each process apparatus 501 , 502, 503 is then sent to the mixing apparatus 420 described above for combining the product streams. A portion of the combined product stream leaving mixing apparatus 420 can be recycled back to the nozzle reactors for further processing.
Any suitable processing equipment can be used for the processing apparatus 501, 502, 503. In some embodiments, the processing equipment is equipment capable of further upgrading the product streams leaving the nozzle reactors 401 , 402, 403. in some embodiments, the processing equipment is a coil reactor, such as the coil reactors described in U.S. Patent Application No. 12/816,844 and U.S. Patent Application No. 13/292,747, both of which are hereby incorporated by reference,
Although Figure 11 illustrates only one piece of processing equipment located between each nozzle reactor and the mixing apparatus, multiple pieces of processing equipment can be provided per nozzle reactor. In other words, each product stream leaving nozzle reactors 401, 402, 403, can be subjected to multiple pieces of processing equipment prior to being combined in the mixing apparatus 420.
Although not shown in Figures 10 or 11, the system 400 can further include separation apparatus located down stream of the mixing apparatus 420. The separation apparatus can be used to separate the combined stream exiting mixing apparatus 420 into various streams based on any of a variety of criteria. For example, in some embodiments, the combined stream can be separated based on the boiling points of the various components included in the combined stream. Any suitable separation apparatus can be used for this step, including, for example, distillation towers.
In some embodiments, a material feed cracking method is disclosed. Methods of the embodiments can generally include a first step of injecting a first material stream into a stream dividing apparatus and producing a first divided stream and a second divided stream. The method also includes a step of injecting the first divided stream into a first nozzle reactor and injecting the second divided stream into a second nozzle reactor. A next step includes injecting a stream of cracking material into the first nozzle reactor and injecting a stream of cracking material into the second nozzle reactor. A next step includes combining a first nozzle reactor product from the first nozzle reactor and a second nozzle reactor product from the second nozzle reactor in a mixing apparatus.
The stream dividing apparatus, the first nozzle reactor, the second nozzle reactor, and the mixing apparatus used in the method described above can all be similar or identical to the stream dividing apparatus, the nozzle reactor, and the mixing apparatus described in greater detail above. The first material stream can include any type of material that may he broken down into smaller and lighter components. In one aspect of this method, the first material stream includes a hydrocarbon source, such as heavy oil, bitumen, crude oil, or any residue with a high asphaltene content. The residue may be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit. The high asphaltene content may be an asphaltene content greater than 4 wt% of the residue. Hydrocarbon sources such as these require cracking to break down the heavy and large molecules of the hydrocarbon into light componenis that may be beneficially used. The first materia! stream can also include the material leaving the ejection end of a nozzle reactor located upstream of the stream dividing apparatus.
The first divided stream and the second divided stream can be a similar or identical, such as when the stream dividing apparatus performs a simple physical separation of the first material stream. Alternatively, the first divided stream and the second divided stream can have different compositions, such as when the stream dividing apparatus is a distillation tower that separates the first material stream based on the boiling point of the various components of the first material stream. The first divided stream and the second divided stream can also be equal in volumetric flow rate, or can have different volumetric flow rates, it can also have a third divided stream with a different volumetric flow rate used as a purge.
The first divided stream and the second divided stream can be injected into the first nozzle reactor and the second nozzle reactor, respectively, at any suitable temperature and pressure. In one embodiment, the first divided stream and the second divided tream are injected into the first nozzle reactor and the second nozzle reactor at a temperature of from about 300 °C to 500 °C and at a pressure of from about 0.5 about to about 15 bar. The streams of cracking material injected into the first and second nozzle reactor can be any suitable cracking material for cracking the first divided stream and the second divided stream, In some embodiments, the cracking material is a cracking gas, such as steam. The streams of cracking material can be injected into the nozzle reactors at any suitable temperature and pressure. In some embodiments, the streams of cracking material are injected into the nozzle reactors at a temperature of from about 600 °C to about 850 °C and at a pressure of from about 15 bar to about 200 bar.
The pressure inside each of the first and the second nozzle reactor may range from about 0.5 bar to about 15 bar. The ratio of cracking material to material feed may range from about 0.1 :1 to about 4: 1.
As described in greater detail above, the nozzle reactors operate to crack and upgrade the feed material injected into the nozzle reactor as a result of the feed material and the cracking material interacting within the nozzle reactor. The product of this interaction leaves the ejection end of each nozzle reactor as a first nozzle reactor product and a second nozzle reactor product. Each of these stream can be transported to and injected into a mixing apparatus for combining the individual streams into one larger stream. The operating conditions of the mixing apparatus can be adjusted according to the material be injected into the mixing apparatus. In some embodiments, the temperature and pressure inside the mixing apparatus will be adjusted. For example, the mixing apparatus can have a temperature in the range of from 350 to 420 °C and a pressure in the range of from 0.2 to 15 bar.
Although the above method is described in terms of two nozzle reactors, more than two nozzle reactors can be used. Generally speaking, the stream dividing apparatus will produce one divided stream for each nozzle reactor that is used in the nozzle reactor system. When the divided streams have varying compositions, each stream can be directed to a nozzle reactor tailored for upgrading of the specific material composition.
The parallel coniigurations described above and illustrated in Figures 10 and 11 ca be particularly advantageous in situations where events occur downstream of the parallel aligned nozzle reactors that require production to be reduced, such as in the event of a pipeline becoming unavailable or a product stream storage facility reaching capacity. Generally speaking, it is undesirable to reduce production by reducing the flow velocities of the cracking material and the feed material into the nozzle reactor because such alterations tend to negatively impact the conversion rate and product quality. The nozzle reactors described herein provide optimum conversion and product quality when operated at specific flow velocities for both the cracking material stream and the feed material stream. In the parallel con figuration described herein, production can be reduced by completely shutting down one or more of the nozzle reactors while continuing to operate the remaining on-line nozzle reactors at optimum operating conditions. Thus, the parallel alignment described herein allows nozzle reactors to continue to operate at optimum conditions while still providing a mechanism for lowering production in the case of downstream events.
Example 1
Cold Lake bitumen is injected into the lower section of a Vacuum Distillation Unit (VDU), The bottoms of the VDU are withdrawn from the VDU and comprise a heavy hydrocarbon source having a molecular weight range of from about 300 Daltons to 5,000 Daltons or more. The heavy hydrocarbon source is pre-heated to a temperature of about 752 deg F (400 deg C). At this temperature, only the hydrocarbon fraction with a molecular weight larger then about 350 Dalton will be in the liquid and/or solid phase, while the remainder of the hydrocarbon source is in a gaseous state. The hydrocarbon source is injected into an interior reactor chamber of a first nozzle reactor via the material feed passage of the first nozzle reactor.
Simultaneously, superheated steam at a temperature of about 1256 deg F (680 deg C) is injected into the converging section of the injection passage of the first nozzle reactor at a flow rate of about 1.5 times the flow rate of the hydrocarbon source.
The first nozzle reactor has an overall length of 8,000 mm and an outside diameter of 1,600 mm. The interior reactor chamber is 7,160 mm long with an injection end diameter of 262 mm and an ejection end diameter of 1 ,435 mm. The injection passage has a length of 840 mm, with an enlarged volume injection section diameter of 207 mm, a reduced volume mid-section diameter of 70 mm and an enlarged volume ejection section diameter of 147 mm. The pressure in the interior reactor chamber is about 2.
The hydrocarbon source and steam are retained in the first nozzle reactor for a time period of around 1.2 seconds. Shockwaves and thermal effects produced inside the nozzle convert approximately 45% per pass of the hydrocarbon source that has a boiling point of greater than 1050 deg F (566 deg C) into lighter hydrocarbons with a boiling point of less than 1050 deg F (566 cleg C), The nozzle reactor emits a mixture of steam, cracked hydrocarbons, and ncracked hydrocarbons at a temperature of about 788 deg F (420 deg C),
The mixture leaving the nozzle reactor is recycled to the same VDU as noted before. Steam in the VDU is condensed. The VDU separates the hydrocarbon into a gaseous hydrocarbon phase (C5 and smaller), gas oil, vacuum distillate and VDU bottoms having a molecular weight range of from 300 Daltons to 5,000 Daitons or more. The gaseous hydrocarbon phase, gas oil and vacuum distillate are collected for consumption. The VDU bottoms are split into two individual streams. A first stream comprising about 75% of the total VDU bottoms stream is recycled back to the first nozzle reactor, while a second stream comprising the remaining 25% is diverted to a second nozzle reactor. This split purges a fraction of the bottoms that has an increased amount of inorganic material, such as vanadium, nickel, and sulfur.
Prior to being introduced into the second nozzle reactor, the second stream is cooled to a temperature of about 700 deg F (371 deg C). At this temperature, all of the hydrocarbon material of the second stream is in the liquid phase. The second stream is injected into an interior reactor chamber of a second nozzle reactor via the material feed passage of the second nozzle reactor, Simultaneously, steam at a temperature of 1256 deg F (680 deg C) is injected into the interior reactor chamber of the second nozzle reactor via the injection passage at a flow rate of about 2.0 times the flow ra te of the hydrocarbon injected into the second nozzle reactor.
The second nozzle reactor has an overall length of 7,000 mm and an outside diameter of 1,300 mm. The interior reactor chamber is 6,400 mm long with an injection end diameter of 187 mm and an ejection end diameter of 1,231 mm. The injection passage has a length of 600 mm, with an enlarged volume injection section diameter of 148 mm, a reduced volume mid-section diameter of 50 mm and an enlarged volume ejection section diameter of 105 mm. The pressure in the interior reactor chamber is about 2.
The second stream and steam are injected into the second nozzle reactor for a time period of no more than 0.6 seconds. Shockwaves produced inside the nozzle reactor convert approximately 55% of the second stream into lighter hydrocarbons. The nozzle reactor emits a mixture of steam, cracked hydrocarbons and uncracked hydrocarbons at a temperature of about 788 deg F.
The mixture leaving the second nozzle reactor is fed to a small Vacuum Separation Unit (VSU). The small VSU separates the mixture into a lighter hydrocarbon having a molecular weight in the range of from about 25 to about 200 Daltons and a heavier hydrocarbon stream having a molecular weight in the range of from about 200 to about 1 ,000 Daltons. The light hydrocarbon stream is recycled back to the first and large VSU while the heavier hydrocarbon stream is cooled down to about 700 deg F (371 deg C) and collected as the final pitch stream for disposal.
In view of the many possible embodiments to which the principles of the disclosed invention may be applied, it should be recognized that the illustrated embodiments are only preferred examples of the invention and should not be taken as limiting the scope of the invention. Rather, the scope of the invention is defined by the following claims. We therefore claim as our in vention all that comes within the scope and spirit of these claims.

Claims

What is claimed is: L A nozzle reactor system comprising:
a stream dividing apparatus comprising a first output port and a second output port; a first nozzle reactor having a feed material injection port in fluid communication with the first output port of the stream dividing apparatus, and an ejection end;
a second nozzle reactor having a feed material injection port in fluid communication with the second output port of the stream dividing apparatus, and an ejection end; and
a mixing apparatus having a first input port in fluid communication wit the ejection end of the first nozzle reactor, and a second input port in fluid communication with the ejection end of the second nozzle reactor. 2, The nozzle reactor system as recited in claim 1, wherein:
the first nozzle reactor comprising in combination:
a reactor body having an interior reactor chamber with an injection end and an ejection end;
an injection passage mounted in the nozzle reactor in material injecting communication with the interior reactor chamber, the injection passage having (a) an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section, (b) a material injection end, and (c) a material ejection end in injecting commimication with the interior reactor chamber;
a material feed passage penetrating the reactor body and being (a) adjacent to the materia! ejection end of the injection passage and (b)transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage; and
the second nozzle reactor comprising in combination:
a reactor body having an interior reactor chamber with an injection end and an ejection end;
an injection passage mounted in the nozzle reactor in material injecting communication with the interior reactor chamber, the injection passage having (a) an enlarged volume injection section, an enlarged volume ejection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume ejection section, (b) a material injection end, and (c) a material ejection end in injecting communication with the interior reactor chamber;
a material feed passage penetrating the reactor body and being (a) adjacent to the material ejection end of the injection passage and (b)transverse to an injection passage axis extending from the material injection end to the material ejection end in the injection passage; and
The nozzle reactor system as claimed in claim 2, wherein the enlarged volume injection ction of each of the first and second nozzle reactors includes a converging central passage section, and the reduced volume mid-section and the enlarged volume ejection section of each of the first and second nozzle reactors includes a diverging central passage section,
4. The nozzle reactor system as claimed in claim 3, wherein the converging central passage section, the reduced volume mid-section, and the diverging central passage section of each of the first and second nozzle reactors provide a radially inwardly curved passage side wall
intermediate the material injection end and material ejection end in the injection passage of each of the first and second nozzle reactors. 5, The nozzle reactor system as claimed in claim 2, wherein (a) the interior reactor chamber of each of the first and second nozzle reactors has a central interior reactor chamber axis extending from the injection end to the ejection end of the interior reactor chamber and (b) an injection passage axis of each of the first and second nozzle reactors is coaxial with the central interior reactor chamber axis of each of the first and second nozzle reactors.
6. The nozzle reactor system as claimed in claim 2, wherein the enlarged volume injection section, reduced volume mid-section, and enlarged volume ejection section in the injection passage of each of the first and second nozzle reactors cooperatively pro vide a substantially isentropic passage for a cracking material through the injection passage of each of the first and second nozzle reactors.
7. The nozzle reactor system as claimed in claim 2, wherein the material feed passage of each of the first and second nozzle reactors is annular. 8, The nozzle reactor system as claimed in claim 2, wherein the interior reactor chamber of each of the first and second nozzle reactors includes a cross-sectional area and wherein the cross- sectional area alternates between maintaining constant and increasing in a direction from the injection end to the ejection end.
9, The nozzle reactor system as claimed in claim 1 , wherein the stream dividing apparatus comprises a distillation tower.
10, The nozzle reactor system as claimed in claim 1, further comprising:
an upstream nozzle reactor located upstream of the stream dividing apparatus and wherein an ejection of the upstream nozzle reactor is in fluid communication with an input port of the stream dividing apparatus.
11 , A material cracking method comprising:
injecting a first material stream into a stream dividing apparatus and producing a first divided stream and a second divided stream;
injecting the first divided stream into a first nozzle reactor and injecting the second divided stream into a second nozzle reactor;
injecting a stream of cracking material into the first nozzle reactor and injecting a stream of cracking material into the second nozzle reactor; and
combining a first nozzle reactor product from the first nozzle reactor and a second nozzle reactor product from the second nozzle reactor in a mixing apparatus.
12. The material cracking method as claimed in claim 1 1, wherein the first divided stream and the second divided stream are injected into the first and second nozzle reactor at a direction transverse to the direction the cracking material is injected into the first and second nozzle reactor.
13. The material cracking method as claimed in claim 11, wherein the cracking material is steam.
14. The material cracking method as claimed in claim 1 1, wherein the first material stream hydrocarbon material.
15. The material cracking method as claimed in claim 14, wherein the hydrocarbon material comprises bitumen. 16, The material cracking method as claimed in claim 1 1 , wherein the first divided stream has a different composition from the second divided stream.
17, The material cracking method as claimed in claim 11, wherein the first material stream comprises material collected from the ejection end of an upstream nozzle reactor,
PCT/US2012/062424 2011-10-28 2012-10-29 Nozzle reactor systems and methods of use WO2013063573A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161553009P 2011-10-28 2011-10-28
US61/553,009 2011-10-28

Publications (1)

Publication Number Publication Date
WO2013063573A1 true WO2013063573A1 (en) 2013-05-02

Family

ID=48168644

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/062424 WO2013063573A1 (en) 2011-10-28 2012-10-29 Nozzle reactor systems and methods of use

Country Status (2)

Country Link
US (1) US20130105361A1 (en)
WO (1) WO2013063573A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112135891A (en) * 2018-05-16 2020-12-25 迪傲公司 A turbomachinery chemical reactor and a method for cracking hydrocarbons in a process fluid

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013162667A2 (en) * 2012-02-09 2013-10-31 Marathon Canadian Oil Sands Holding Limited Nozzle reactor and method of use
US8715488B1 (en) 2013-01-07 2014-05-06 Clean Global Energy, Inc. Method and apparatus for making hybrid crude oils and fuels
JP5837725B1 (en) * 2015-01-14 2015-12-24 株式会社市丸技研 Piping structure of tire vulcanizer, circulation device, and tire vulcanizing method using tire vulcanizer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445799A (en) * 1993-10-20 1995-08-29 Mccants; Malcolm T. Apparatus and method for thermocracking a fluid
US6863867B2 (en) * 2001-05-07 2005-03-08 Uop Llc Apparatus for mixing and reacting at least two fluids
US20080154075A1 (en) * 2005-07-06 2008-06-26 Bryce Alan Williams Process for the Production of Olefins
US20090324463A1 (en) * 2006-07-12 2009-12-31 Bozzano Andrea G Reactor System With Interstage Product Removal
US20100264062A1 (en) * 2009-04-15 2010-10-21 Marathon Oil Canada Corporation Nozzle reactor and method of use
US7927565B2 (en) * 2005-01-03 2011-04-19 Marathon Oil Canada Corporation Nozzle reactor and method of use

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445799A (en) * 1993-10-20 1995-08-29 Mccants; Malcolm T. Apparatus and method for thermocracking a fluid
US6863867B2 (en) * 2001-05-07 2005-03-08 Uop Llc Apparatus for mixing and reacting at least two fluids
US7927565B2 (en) * 2005-01-03 2011-04-19 Marathon Oil Canada Corporation Nozzle reactor and method of use
US20080154075A1 (en) * 2005-07-06 2008-06-26 Bryce Alan Williams Process for the Production of Olefins
US20090324463A1 (en) * 2006-07-12 2009-12-31 Bozzano Andrea G Reactor System With Interstage Product Removal
US20100264062A1 (en) * 2009-04-15 2010-10-21 Marathon Oil Canada Corporation Nozzle reactor and method of use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112135891A (en) * 2018-05-16 2020-12-25 迪傲公司 A turbomachinery chemical reactor and a method for cracking hydrocarbons in a process fluid
CN112135891B (en) * 2018-05-16 2022-07-12 迪傲公司 Turbomachinery chemical reactor and method for cracking hydrocarbons in a process fluid

Also Published As

Publication number Publication date
US20130105361A1 (en) 2013-05-02

Similar Documents

Publication Publication Date Title
CA2592950C (en) Nozzle reactor and method of use
US7927565B2 (en) Nozzle reactor and method of use
US8636958B2 (en) Nozzle reactor and method of use
US8449763B2 (en) Nozzle reactor and method of use
US20110084000A1 (en) Systems and methods for processing nozzle reactor pitch
WO2013063573A1 (en) Nozzle reactor systems and methods of use
US20130105362A1 (en) Systems and methods for integrating bitumen extraction with bitumen upg...
US20140110307A1 (en) Dual reactor for improved conversion of heavy hydrocarbons
US20130048539A1 (en) Methods and Systems for Upgrading Hydrocarbon
US8435402B2 (en) Nozzle reactor and method of use
CA2833952A1 (en) Heavy hydrocarbon reactor
US20130299387A1 (en) Methods and systems for upgrading hydrocarbon
US20130251597A1 (en) Nozzle reactor and method of use
US20130043033A1 (en) Upgrading hydrocarbon material on offshore platforms
US20130092599A1 (en) Methods and systems for upgrading hydrocarbon
US20130161238A1 (en) Methods and Systems for Removing Material from Bitumen-Containing Solvent
CA2787192A1 (en) Upgrading hydrocarbon material on offshore platforms
WO2010121041A1 (en) Nozzle reactor and method of use
WO2014003704A1 (en) Methods and systems for upgrading hydrocarbon residuum
WO2013119778A1 (en) Systems and methods for integrating bitumen extraction with bitumen upgrading
CA2787591A1 (en) Methods and systems for upgrading hydrocarbon
OA16337A (en) Systems and methods for processing nozzle reactor pitch.

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: 12843221

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12843221

Country of ref document: EP

Kind code of ref document: A1