This patent application claims priority to U.S. Provisional Patent Application No. 61/169,569, filed April 15, 2009, and U.S. Patent Application No. 12/466,923, filed May 15, 2009, each of which is hereby incorporated by reference. In the event of a conflict, the subject matter explicitly recited or shown herein controls over any subject matter incorporated by reference. All definitions of a term (express or implied) contained in any of the subject matter incorporated by reference herein are hereby disclaimed.

BACKGROUND

Some nozzle reactors operate to cause interactions between materials and achieve alteration of the physical or chemical composition of one or more of the materials. Such interaction and alteration typically occurs by injecting the materials into a reactor chamber in the nozzle reactor. The manner in which the materials are injected into the reactor chamber and the configuration of the various components of the nozzle reactor may both contribute to how the materials interact and what types of alterations are achieved.

U.S. Patent No. 7,618,597 describes various configurations for a nozzle reactor wherein the cracking material and the material to be cracked are injected into the reactor chamber of the nozzle reactor at approximately transverse directions. Additionally, the nozzle reactors described in the '597 patent describe a cracking material injection pathway capable of accelerating the cracking material to a supersonic speed as it enters the reactor chamber. These features of the disclosed nozzle reactors, along with additional features, can help to achieve increased conversion rates of material to be cracked injected into the nozzle reactor. Additionally, these features can help to ensure that the material to be cracked is sufficiently altered (e.g., broken down into smaller compounds having a sufficiently low molecular weight for the desired product).

While the nozzle reactors disclosed in the '597 patent can provide an increase in conversion rates of the material to be cracked passing therethrough, it is still possible that material to be cracked will pass through the disclosed nozzle reactors unaltered. Such unaltered material may therefore not be suitable for use as a desired end product of the nozzle reactor process. In some instances, the unaltered material may have to be discarded as a waste product of the process, which clearly makes the process less economical.

One option for dealing with material that passes through the '597 nozzle reactors unaltered is to recycle the unaltered material back through the nozzle reactor. However, such a recycle stream does not always lead alteration of the recycled material. The nozzle reactors disclosed in the '597 reference can be operating under conditions that do not provide the best environment for the recycled material to be altered. Accordingly, the recycled material may remain unaltered no matter how many times it is re-injected into the same 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 features and aspects of the embodiments can be used alone or in various combinations and sub- combinations with one another.

In some embodiments, a method of cracking residual oil is disclosed. The method includes the steps of providing a nozzle reactor, injecting a stream of cracking material through the first material injector into the reactor body, and injecting residual oil through the second material feed port into the reactor body and transverse to the stream of cracking material entering the reactor body from the first material injector to produce cracked residual oil and uncracked residual oil. The residual oil can include distillation bottoms, asphaltenes, or stripped hydrocarbon material.

In some embodiments, a method of modifying a refinery plant including at least one of a coker, a hydrocracker, and a deasphalting unit is disclosed. The method includes the step of replacing at least one of the coker, hydrocracker, and deasphalting unit with a nozzle reactor.

In some embodiments, a refinery plant is disclosed. The refinery plant includes a refinery residue-producing processing unit that includes a refinery residue outlet and a nozzle reactor located downstream of the refinery residue-producing processing unit. The nozzle reactor is in fluid communication with the refinery residue outlet of the refinery residue-producing processing unit, such that refinery residue from the refinery residue-producing processing unit may be injected into the nozzle reactor. In some embodiments, a feed material cracking method is disclosed. The method includes the steps of injecting a stream of cracking material through a cracking material injector into a reaction chamber, and a step of injecting residual oil into the reaction chamber adjacent to the cracking material injector and transverse to the stream of cracking material entering the reaction chamber from the cracking material injector. In some embodiments, a nozzle reactor system of the type useable to inject a first material and a second material to cause interaction between the first material and the second material is disclosed. The nozzle reactor system includes a first nozzle reactor, a second nozzle reactor, and a first separation unit in fluid communication with the first nozzle reactor. The first separation unit includes a light stream outlet and a heavy stream outlet in fluid communication with the second nozzle reactor.

In some embodiments, a material cracking method is disclosed. The material cracking method includes injecting a first stream of cracking material through a injection passage of a first nozzle reactor into an interior reactor chamber of a first nozzle reactor, 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, 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, and 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.

The foregoing and other features and advantages of the present application will become apparent from the following detailed description, which proceeds with reference to the accompanying figures. It is thus to be understood that the scope of the invention is to be determined by the claims as issued and not by whether a claim includes any or all features or advantages recited in this Brief Summary or addresses any issue identified in the Background BRIEF DESCRIPTION OF THE DRAWINGS

The preferred and other embodiments are disclosed in association with the accompanying drawings in which:

Figure 1 is a flow diagram illustrating a feed material cracking method according to an embodiment disclosed herein.

Figure 2 is a cross-sectional, schematic view of one embodiment of a nozzle reactor.

Figure 3 is a cross-sectional view of the nozzle reactor of Figure 2, showing further construction details for the nozzle reactor.

Figure 4 is a cross-sectional view of an alternative embodiment of a nozzle reactor. Figure 5 is a cross-sectional, schematic view of one embodiment of an injection nozzle for use with a nozzle reactor.

Figure 6 is an end view of the injection nozzle of Figure 5 taken from the inlet end of the nozzle.

Figure 7 is a cross-sectional, schematic view of one embodiment of an injection nozzle for use with a nozzle reactor, with the nozzle having a material feed injection passage formed in the nozzle body.

Figure 8 is a cross-sectional, schematic view of one embodiment of an injection nozzle for use with a nozzle reactor, with the nozzle having a material feed injection passage formed in the flow directing insert. Figure 9 is a flow diagram illustrating a feed material cracking method according to an embodiment disclosed herein.

Figure 10 is a flow diagram illustrating a feed material cracking method according to an embodiment disclosed 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.

In some embodiments disclosed herein, methods of cracking residual oil are disclosed. With reference to Figure 1, the methods generally include a step 1000 of providing a nozzle reactor, a step 1100 of inj ecting a stream of cracking material into the reactor body of the nozzle reactor, and a step 1200 of injecting residual oil into the reactor body of the nozzle reactor. The nozzle reactor provided in step 1000 can generally include any suitable nozzle reactor for altering the physical or chemical structure of the feed material injected into the nozzle reactor. The nozzle reactor can generally include a reactor body where the cracking material and feed material interact to alter the feed material, a cracking material injector for injecting cracking material into the reactor body, and a feed material injector for injecting feed material into the reactor body. The cracking material injector and the feed material injector can be the same injection passageway or can be separate injection passageways, or a combination of both.

In some embodiments, the nozzle reactor provided in step 1000 is similar or identical to the nozzle reactors disclosed in U.S. Patent No. 7,618,597. With reference to Figure 2, a nozzle reactor 10 as disclosed in the '597 patent includes 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 2, the injection passage 15 has a circular diametric cross-section and, as shown in the axially-extending cross-sectional view of Figure 2, 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 cracking material when passing through the injection passage 15 into the interior reactor chamber 16.

In certain embodiments, the side wall of the injection passage 15 provides 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 can have a U-shaped or C-shaped cross-section among others. In certain embodiments, the annular material feed port 20 is 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 18 can have a radiused cross-section.

In alternative embodiments, the material feed passage 18, annular material feed port 20, and/or injection passage 15 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 is located on or in the interior reactor chamber side 23 (and if desired can 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. With continuing reference to Figure 2, the interior reactor chamber 16 is 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, while (ii) reducing the size or involvement of back flow areas, e.g., 34, 36, outside the conical or expanding jet path C, thereby forcing increased contact between the high speed cracking material jet stream within the conical jet path 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 Figure 2, the reactor body 14 has an axial length (along axis B) that is much greater than its width. Exemplary length-to-width ratios are typically in the range of 2 to 4 or more.

The dimensions of the various components of the nozzle reactor illustrated in Figure 2 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).

With reference now to Figure 3, 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 central section 46, with the insert end 50 in turn abutting the injection nozzle

52. The insert end 50 of the central section 46 includes 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 iηjectingly 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 52.

The tubular body 51 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 can include 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 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, can be mounted as desired between, for example, the radially extending Hp 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 axially-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.

With continuing reference to Figure 3, the injection passage 60 is a DeLaval 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 presents 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

52.

The injection passage 60 can thus be configured to present a substantially isentropic or frictionless configuration for the injection nozzle 52. This configuration can 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 .

An exemplary diameter D within the injection passage 60 is 140 mm. An exemplary diameter E of the ejection passage opening 96 in the ejection end 48 of the reactor body 44 is 2.2 meters. An exemplary 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 nozzle reactors disclosed herein can be used to, for example, crack heavy hydrocarbon material, including residual oil, 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 illustrated in Figure 3, 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 thereby ejects 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.

Other embodiments of a cracking material injection passage may not be as isentropic but may provide 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 can 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 3, the material to be cracked (not shown) is pre-heated, for example at 2-15 bar, which is generally the same pressure as that in the reactor body 44. In some embodiments, the preheat should provide a feed stock temperature of 300°C to 500°C, and most advantageously 400°C 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 heavy hydrocarbons into lighter hydrocarbons and, if present in the heavy hydrocarbons or injected material, other materials.

With reference now to Figure 4, an embodiment of the nozzle reactor, generally 110, has a nozzle 111 and a reactor body 128 with an insert end 112 intermediate the reactor body 128 injector insert 130. The insert end 112 has a conical interior periphery section 113 that: (i) extends, and expands outwardly, from the injection end 114 of the injection passage 116 of the nozzle 111; and (ii) terminates with a maximum diameter at the abutting tubular interior periphery section 115 of the insert end 112 opposite the ejection end 114 of the injection passage 116. This alternative embodiment also has a feed material injection passage 118 formed of a material feed line or tube 120 in communication with an annular material feed distribution channel 122, which in turn is in communication with an axially narrower annular material feed injection ring or port 124. The material feed injection ring 124 is laterally adjacent the ejection end 114 of the injection passage 116 to radially inwardly inject material feed stock, into contact with axially injected cracking material (not shown) virtually immediately upon the ejection of the cracking material from the ejection end 114 into the interior 126 of the reactor body 128.

The injection passage 116 can be configured to eject a free stream of cracking material, such as super-heated steam (not shown) for example, generally conically with an included angle of about 18°. The conical interior section 113 can be configured to surround or interfere with such a free stream of cracking material ejection stream. In certain such embodiments, after engaging the injected material feed stock adjacent the ejection end 114, the resulting jet mixture - a mixture of cracking material and material feed stock - preferably makes at least intermittent interrupting contact with the tubular interior section 113 and, if desired, the downstream tubular interior section 115. This intermittent, interrupting contact increases turbulence and concentrates shear stresses into an axially shortened reaction zone within the reactor body 128. Preferably, however, the jet mixture travels through the interior 126 of the reactor body 128 with minimal backflow of any components of the jet mixture, resulting in more rapid plug flow of all jet mixture components through the reactor body 128. Once the material feed stock is cracked by the cracking material ejection stream adjacent the injection end 114, the configuration of the reactor body facilitates substantially immediate cooling of the jet mixture. This cooling of the jet mixture acts to arrest the chemical reaction between the material feed stock and the cracking material ejection stream.

The applicants believe that, in certain embodiments, sufficient steam cracking of at least certain heavy hydrocarbons may be achieved at jet velocities above about 300 meters per second while the retention time in the reactor body zone providing such extreme shear can be very short, on the order of only about 0.01 seconds. In such embodiments, cracking of material feed stock can be caused by extreme shear of the cracking material. In certain of these types of embodiments, the retention time of the material feed or cracking material in the reactor body 128 therefore can have little or no impact on such cracking or, if desired, any other substantial cracking. In other embodiments, an increased retention time of the material feed or cracking material in the reactor body 128 can result in increased cracking rates.

In some embodiments, a catalyst can be introduced into the nozzle reactor to enhance cracking of the material feed stock by the cracking material ejection stream. In the applicant's view, the methodology of nozzles of the type shown in the illustrated embodiments, to inject a cracking material such as steam, can be based on the following equation

KE ₁ = H ₁ - H ₀ + KE ₀ (1) where KE ₁ 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 entry into the injection nozzle, H ₁ is the enthalpy of cracking material upon emission from the injection nozzle, and KE ₀ 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 ΔH.

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 = (-2ΔH) ^1/2 (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 those disclosed herein, 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 than that of the straight-bore nozzle.

It can thus be seen that nozzle reactors as described herein can provide 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 material (or cracking material mixture) with respect to that of the material feed stock, and/or more complete cracking material 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 2-4 above, the injection material may comprise a cracking fluid or other motive material rather than, or in addition to, a cracking material. 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.

In some embodiments, a nozzle reactor of the present application can include an injection passage that has a flow directing insert around which a first material can flow to increase the velocity of the first material in preparation for an interaction with a second material to alter the mechanical or chemical composition of the first and/or second materials. For example, as shown in Figures 5 and 6, an injection nozzle 150 includes an injection nozzle body 152 having an injection passage 154 extending axially through the body. In certain implementations, the passage 154 has a constant diameter along the axial length of the passage. In other implementations, the diameter of the passage 154 varies, such as decreasing along the axial length of the passage, i.e., narrowing of the passage, or increasing along the axial length of the passage, i.e., widening of the passage, or various combinations of both. A flow directing insert 166 is positioned within the injection passage 154, but remains out of direct contact with the inner surface of the injection passage through use of a supporting insert 156. The flow directing insert 166 can be coupled to the supporting insert 156, which is inserted and secured within a mating supporting insert recess 170 formed in the injection nozzle body 152.

The supporting insert 156 can include one or more support rods 168 connected to a cylindrical portion 165 of the flow directing insert 166. The cylindrical portion 165 includes outer peripheral surfaces that run parallel to the axis of the insert 156. The supporting insert 156 includes a generally annular shaped fluid flow passage 172 corresponding to the injection passage 154 of the injection nozzle body 152 such that when inserted in the recess 170, the interior periphery of the passage 172 is generally flush with the interior periphery of passage 154. Cross-sectional areas of the fluid flow passage 172 on planes perpendicular to the axis of the fluid flow passage 172 remain substantially the same extending the axial length of the passage 172. In other words, an outer diameter and inner diameter of the fluid flow passage 172 remain generally unchanged throughout the passage.

In some implementations, the inserts 156, 158 are replaceable. In specific implementations, the insert 156, with insert 158 secured thereto, can include external threads and can be removably secured within the mating supporting insert recess 170 by threadably engaging internal threads formed in the recess. In other specific implementations, the insert 158 is press- fit into the recess 170. Yet in other implementations, the insert 156 is bonded to the recess 170 by applying a bonding material, such as a heat-activated adhesive, pressure-activated adhesive, pressure-activated adhesive, or other similar adhesive, between the outer periphery of the insert and the recess, and activating the bonding material.

Fluid, such as cracking material, is allowed to flow through the nozzle 150 by first passing through a flow inlet opening 174 in the supporting insert 156, the fluid flow passage 172 and a flow outlet opening 176 in the supporting insert. As shown in Figure 5, the fluid flows around the cylindrical portion 165 and the support rods 168 as it flows through the fluid flow passage 172 at a generally constant velocity. Preferably, the number and cross-sectional area of the support rods 168 are minimized so as not to substantially disrupt the flow of fluid through the fluid flow passage 172.

When the flow directing insert is positioned within the injection passage 154, a generally annular fluid flow passage 180, defined between the surface of the injection passage and the exterior surface of the flow directing insert 158, is formed.

The flow directing insert 158 includes a diverging, or expanding, portion 164, a converging, or contracting, portion 166 and a transitioning portion 167 coupling the diverging and converging portions. In the illustrated embodiments, the diverging and converging portions 164, 166 are generally frustoconically shaped and conically shaped, respectively, with abutting base surfaces proximate the transitioning portion 167. The diameter of the diverging portion increases and the diameter of the converging portion decreases along the axial length of the flow directing insert 158 in the fluid flow direction as indicated in Figure 5. Accordingly, the annular fluid flow passage 180 between the diverging portion 164 of the flow directing insert 158 and the outer periphery of the injection passage 154, i.e., converging region 200, narrows in the fluid flow direction and the annular fluid flow passage between the converging portion 166 of the flow direction insert and the outer periphery of the injection passage, i.e., diverging region 204, widens in the fluid flow direction. As can be recognized, the annular fluid flow passage 180 is most narrow between the transition portion 167 of the insert 158 and the outer periphery of the injection passage 154, i.e., transition, or throat, region 202.

Fluid flowing through the fluid flow passage 172 in the supporting insert 156 exits through the outlet opening 176 of the passage 172 and into the annular fluid flow passage 180. The nozzle can be configured such that fluid flowing through the fluid flow passage 172 and into the annular fluid flow passage 180 flows at a velocity less than the speed of sound, i.e., subsonic flow. As the fluid flows through the fluid flow passage 180, the narrowing of the converging region and the widening of the diverging region help to induce a back pressure, i.e., pressure is higher at the entry of the passage 180 than at the exit of the passage, which increases the velocity of the fluid. The fluid velocity can be increased such that as the fluid exits the transition region its velocity is at or above the speed of sound, i.e., supersonic flow. The fluid remains at supersonic flow through the diverging region and as it exits the nozzle 150 at the end of the diverging region. Like the reactor body injection end 12 of Figure 2, the injection nozzle 52 of Figure 3, and the reactor body injection insert 130 of Figure 4, the nozzle 150 can be coupled to a reactor chamber. Further, the fluid flowing through the nozzle can be a cracking material that, upon exiting from the nozzle, immediately contacts radially inwardly injected material feed stock proximate the nozzle exit to induce interaction between the cracking material and the material feed.

Alternatively, with reference to Figure 7, a feed material injection passage 190 extends from an exterior of injection nozzle body 191 toward the injection passage 193. The material feed injection passage 190 penetrates an annular material feed port 192 adjacent the outer periphery of the injection passage 193 proximate transition region 195. The annular material feed port 192 includes an annular, radially extending chamber feed slot 194 in material -injecting communication with an exit of the transition region 195. Similar to Figure 2, the feed port 192 is configured to inject feed material: (i) at about a 90° angle to the axis of travel of cracking material flowing through the transition region 195; (ii) around the entire circumference of cracking material flowing out of the transition region; and (iii) to impact the entire circumference of the free cracking material virtually immediately upon its emission from the transition region into diverging region 197.

With reference to Figure 8, nozzle 210 is similar to the nozzle 150 of Figures 5 and 6 and nozzle 189 of Figures 7, except that feed material injection passage 210 is formed in the flow directing insert 212 and axially extends from an end of the flow directing insert toward a transitioning portion 214 of the insert. The injection passage 210 penetrates a disk-shaped feed slot 216 in material-injecting communication with an exit of a transition region 218. Feed material can be injected through the passage 210 through the feed slot 216 and around the entire circumference of cracking matπtial flowing out of the transition region 218 at a 90° angle to the axis of travel of fluid, e.g., cracking material, flowing through the transition region. The feed material then impacts the entire circumference of the fluid as described above.

Certain embodiments of the present reactor nozzle and method of use can therefore accomplish cracking of hydrocarbon material, such as residual oil, 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 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 material 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 wall scaling within the reactor body.

The dimensions of the various components of the nozzle reactor provided in step 1000 are not limited, and can generally be adjusted based on the amount of hydrocarbon (e.g., residual oil) to be cracked inside the nozzle reactor. Table 2 provides exemplary dimensions for the various components of a nozzle reactor based on the hydrocarbon input in barrels per day (BPD).

As can be seen from Table 2, the first material injector may be small relative to the reactor body. The size of the first material injector is beneficial in that the first material injector may be a replaceable insert that is easily removed from the reactor body. As such, other first material injectors having different internal dimensions and providing different types of injection flow properties for the cracking material can be used to increase the versatility of the nozzle reactor as a whole. To the contrary, conventional units used for processing residual oil are large and cumbersome apparatus that do not provide versatility. In step 1100, a stream of cracking material is injected into the nozzle reactor. In some embodiments, the stream of cracking material is injected into the reactor body of the nozzle reactor via the injection passage. The cracking material may be any suitable material for cracking the feed material, including those materials described in greater detail above. In some embodiments, the cracking material is steam.

In a step 1200, residual oil is injected into the reactor body via the material feed passage. The residual oil can be any refinery residue produced during any part of a refinement process. In some embodiments, refinery residue can be defined as the remainder of any stream of material fed to a unit of a refinement process after removal of a part or parts of the stream of material or as a part of any stream of material removed from the stream of material after having been fed to a unit of refinement process. The residual oil can be a mixture of various refinery residues. The residual oil can also be a refinery residue mixed with other waste materials, such as slop oil. In some embodiment, the residual oil includes hydrocarbon material remaining after separation is performed on a hydrocarbon source or hydrocarbon material removed from a hydrocarbon source. The hydrocarbon residual oil can have an average molecular weight greater than about 300 Daltons. The hydrocarbon source from which residual oil is separated is not limited and can be any hydrocarbon source that requires refinery processing to produce useful lighter hydrocarbon material. Examples of hydrocarbon sources include, but are not limited to, heavy oil, bitumen, crude oil, and kerogen from oil shale processing. In some embodiments, the residual oil includes distillation bottoms. Distillation bottoms can include the remaining portion or portions of a material fed to a distillation unit that has not separated from the feedstock via evaporation. In a typical distillation unit, the distillates are the components that are evaporated and then condensed as a means of separating each component from the feed. The varying boiling points of each of the components allow for their separation from the feed and from each other. The heaviest component (or components) of the material being distilled does not undergo evaporation, but rather is separated from the feed by virtue of being the only remaining component (or components) after all other lighter components have been evaporated out of the feed. As such, the heaviest component (or components) of the distilled material can be considered distillation bottoms. The distillation bottoms can be bottoms from any type of distillation unit, including an atmospheric distillation unit or a vacuum distillation unit. The residual oil can also be a combination of different bottoms, such as a combination of atmospheric bottoms and vacuum bottoms. In some embodiments, the residual oil includes the asphaltenes and asphalt residue that are obtained from a deasphalting process. Deasphalting processes include processes for precipitating asphaltenes and solvent deasphlating processes, such as a residual oil supercritical extraction (or ROSE™) process. Where the residual oil is asphaltenes and asphalt residue, the material may require some form of pretreatment and/or conditioning prior to being injected into the nozzle reactor.

In some embodiments, the pretreatment or conditioning of asphaltenes includes mixing the asphaltenes with a solvent in order to form a liquid composition that may be injected into the nozzle reactor. The asphaltene can be mixed with any solvent capable of dissolving the asphaltenes and keeping them in solution until the mixture is fed into the nozzle reactor. In some embodiments, the solvent can be an aromatic solvent, such as toluene, Aromatic 100, Aromatic 150, or vacuum gas oil (VGO). Mixing the asphaltene and solvent can be accomplished by any suitable method, including through the use of a powered mixing unit. The amount of solvent added to the asphaltene is also not limited. In some embodiments, the asphaltene: solvent ratio is from about 1 :2 to about 2:1.

In some embodiments, the asphaltene and solvent mixture is preheated prior to injection into the nozzle reactor. In some embodiments, the mixture of solvent and asphaltene is preheated to an incipient cracking temperature of from about 350 °C to about 450°C prior to entering the nozzle reactor.

Where the asphaltene is pretreated with a solvent as described above, the cracked product can undergo a separation process to separate the various components of the cracked product, including removing any remaining solvent from the cracked product. Additionally, distillates from the cracked products can be separated and recycled back into the system and used as solvent. The separation process can be any suitable process, such as a heating step that causes the solvent to evaporate from the cracked products.

The residual oil can also include bottoms from a hydrocracking operation or a coking operation. Residue from a coker is typically referred to as coke, and the coke is typically difficult to dispose of. One possible use of the inert coke has been to utilize the coke in high cost gasifiers for the production of CO and H ₂ as feed to an expensive Fischer-Tropsch plant.

However, when utilizing a nozzle reactor as disclosed herein, the coke from a coker can be fed into the nozzle reactor for upgrading of the high molecular weight coke. The coke may require some form of pretreatment and/or conditioning prior to injection. In some embodiments, the pretreatment or conditioning of coke includes fine grinding the coke and mixing it with in an organic solvent. The coke may be ground into pieces having a size less than 250 microns. Such grinding can be accomplished by any grinding method known to those or ordinary skill in the art. In one example, the grinding may be performed by hand. In another example, the coke may be ground in an industrial grinding mill. The ground coke can then be mixed with an organic solvent. In some embodiments, the organic solvent can be selected from Aromatic 100, Aromatic 150, and VGO. The ground coke may be mixed with the organic solvent while being ground into smaller particles or after the coke has been ground into smaller particles. Where solvent is added to the coke after grinding, the pretreatment process may also include a mixing or agitation step to form a solvent/coke slurry. Any method for mixing the materials may be used, including manual mixing and powered mixing. The organic solvent may be added to the ground up coke in any suitable amount for creating a mixture of the two materials. In some embodiments, solvent is added to ground coke at a weight ratio of from 2: 1 to 1: 1.

In some embodiments, the finely ground coke can be mixed with a gaseous carrier material prior to being injected into the nozzle reactor. Any carrier gas suitable for transporting the coke into the nozzle reactor can be used. In some embodiments, the carrier gas is natural gas, nitrogen, or refinery fuel gas. The mechanism of transporting the mixture of ground coke and carrier gas towards and into the nozzle reactor can generally be via dense phase pneumatic conveying. Any suitable ratio of coke to carrier gas can be used. In some embodiments, the ratio of coke to carrier gas ranges from 30: 1 to 50: 1 on a weight basis.

In some embodiments, the mixture of ground coke and solvent can be preheated prior to injection into the nozzle reactor. The mixture of ground coke and solvent can be heated to a temperature below the solvent boiling point in order to avoid coking of pipes and furnaces.

Where the coke is pretreated with solvent as described above, the cracked product can undergo a separation process to separate the various components of the cracked product, including removing any remaining organic solvent from the cracked product. The separation process can include any suitable process, including any process for removing the product distillates from coke conversion. The unreacted coke material and the VGO can be recycled back to the initial stages of the process and blended with additional fresh mixtures of solvent and ground coke. In some embodiments, the residual oil includes the stripped remainder of a vacuum stripping unit. Vacuum stripping units are stripper units operated at reduced pressure to facilitate the transfer of less volatile components into the stripping gas. Vacuum stripping units generally include a feed inlet at the top of the unit where feed material is dispersed over a packed column. The vacuum stripping unit also includes a stripping gas inlet at the bottom of the unit. In operation, the stripping gas rises through the packed column as the feed material trickles down through the packed column. The packed column increases the surface area of the feed material. In operation, volatile components of the feed material transfer into the stripping gas as it rises up and past the feed material. The reduction of pressure inside the packed column facilitates the transfer of less volatile components (i.e., components that would not transfer into the stripping gas at atmospheric conditions). Thus, stripping gas leaving the top of the unit includes volatile components stripped from the feed material. Conversely, the feed material leaving the bottom of the unit is stripped of the volatile components and includes only the least volatile components of the feed material. Where the feed material is a hydrocarbon source, the lighter hydrocarbon fractions of the feed material will be stripped away from the feed material in the stripping gas, while the heavy hydrocarbons will remain in the stripped material that trickles to the bottom of the packed column. This material can be collected at the bottom of the packed column as residual oil and injected into the nozzle reactor. As can be understood from the above description, residual oil can include hydrocarbon material where the lighter fractions of a hydrocarbon source are not part of the residual oil. Removing the light hydrocarbon fractions of a hydrocarbon material prior to injection of the hydrocarbon material into the nozzle reactor (such as in the case of vacuum stripping as described above) can provide several benefits. Firstly, steam utilization in the nozzle reactor can be reduced. The lighter fractions of the hydrocarbon material will typically be in a gaseous state when entering the nozzle reactor, which tends to dilute the steam after it is injected into the nozzle reactor. Additional superheated steam is typically required to make up for this dilution. By reducing or eliminating the gaseous light hydrocarbon fractions, less steam consumption can occur, in some embodiments, because the steam is more concentrated inside the nozzle reactor.

The conversion rate of the hydrocarbon material injected into the nozzle reactor can also be improved by the absence of the lighter hydrocarbon material, which tends to only interfere with the cracking of the heavier hydrocarbon material. Finally, a more compact system can be used.

The nozzle reactor provided in step 1000 generally operates on the principle that the fractions of the residual oil having the largest molecular mass will be cracked (most likely by Shockwaves) first inside the nozzle reactor. Introducing at least a fraction of the residual oil into the nozzle reactor in a liquid phase can thereby ensure that the liquid fraction will be cracked before any gaseous fraction of the residual oil introduced into the nozzle reactor. Accordingly, the temperature of residual oil can be adjusted such that at least a fraction of the residual oil is injected into the nozzle reactor in a liquid phase. The temperature to which the residual oil is adjusted is not limited, and can vary based on the properties of the residual oil, including the various boiling points of the different fractions of the residual oil. In some embodiments, the method can further include a recycle step. More specifically, any residual oil that exits the nozzle reactor uncracked can be recycled back to the second material feed port. In this manner, the uncracked residual oil undergoes an additional pass through the nozzle reactor, thereby possibly increasing the overall efficiency of the nozzle reactor with respect to cracking of the residual oil. The uncracked residual oil can be passed back to the second material feed port in any suitable manner, such as by piping, and can include a pump to help transport the uncracked residual oil back to the second material feed port.

The small amount of pitch that may be produced by the nozzle reactor can also be transported to other processing equipment located upstream of the nozzle reactor in the refining process. For example, where the nozzle reactor is located downstream of a hydrocracker or a coker and generally receives the residues from these processing units, the small amount of pitch material produced by the nozzle reactor can be recycled back to the hydrocracker or the coker. The coke precursor carbon, also known as Conradson Carbon, disappears when hydrocarbon material is fed through a nozzle reactor, thus resulting in an absence of coke precursor carbon in the small amount of pitch produced by the nozzle reactor. As such, this material can be recycled back to a hydrocracker or coker, and processing of this material in the hydrocracker or coker is less likely to produce waste coke products. The recycle stream from a nozzle reactor can also blend back with the initial material fed into the refinery process. That is to say, the recycle stream can blend with material that has not yet undergone any refinery processing. The blend of the recycle stream and the initial material then undergoes refinery processing steps.

The recycle stream can be pre-heated prior to injecting the recycle stream into the nozzle reactor or upstream processing units as discussed in greater detail above. More specifically, if the recycle stream is blended with material that has not been at least partially preheated, then the combined stream can be preheated prior to being introduced into the nozzle reactor or upstream processing units. The temperature to which the blended material is pre-heated can generally be any suitable temperature for facilitating cracking of the blended material inside the nozzle reactor or processing the blended material in upstream processing units. In some embodiments, the blended material is pre-heated to a range of from 300°C to 440°C. If the recycle stream is injected directly into the nozzle reactor or upstream processing unit without blending, then the recycle stream may not need to be pre-heated. This is because the recycle stream will already be at the temperature to which material fed into the nozzle reactor or upstream processing unit is pre-heated. In some embodiments, a method of modifying a refinery plant including at least one of a coker, a hydrocracker, and a deasphalting unit is disclosed. The method generally includes replacing a coker, a hydrocracker, and/or a deasphalting unit with a nozzle reactor as disclosed herein. Substituting a coker, a hydrocracker, and/or a deasphalting unit with a nozzle reactor can beneficially improve the conversion of the residual oil into light hydrocarbons. For example, cokers generally convert up to 60 wt-% of residual oil and hydrocrackers generally convert 75 wt-% of residual oil, while a nozzle reactor may convert as much as 95 wt-% of the residual oil.

Substituting the nozzle reactor for at least one of a coker, a hydrocracker, and a deasphalting unit can be carried out by any suitable procedure for disconnecting at least one the coker, hydrocracker, and deasphalting unit from the refinery process and connecting the nozzle reactor to the refinery process. Generally speaking, substitution may only require diverting the stream normally fed to at least one of the coker, hydrocracker, and/or deasphalting unit to, for example, the material feed passage of a nozzle reactor. In this manner, the feed stream for at least one of a coker, hydrocracker, and/or deasphalting unit can be fed into the reactor body of the nozzle reactor where a cracking material will work to crack the heavy hydrocarbons in the feed stream.

The nozzle reactor generally includes a nozzle reactor according to any embodiment of the nozzle reactors described in greater detail above. The nozzle reactor can replace any type of coker, hydrocracker, or deasphalting unit. For example, the nozzle reactor can replace a delayed coker, a fluid, coker or a flexicoker. The nozzle reactor can also replace a ROSE™ deasphalting unit (or be used in conjunction with it to treat asphaltenes).

The nozzle reactor used in place of at least one of the coker, hydrocracker and/or deasphalting unit may produce a small quantity of pitch by-product. The pitch by-product can be recycled back into the nozzle reactor via, for example, the material feed passage. Such a recycle stream is not possible in, for example, a coker, since it is difficult for a coker to process the very stable coke.

In some embodiments, the small amount of pitch by-product that may be produced by the nozzle reactor can be recycled back to any of the at least one coker, hydrocracker or solvent deasphalting unit that has not been replaced in the system by a nozzle reactor. For example, in a refining process having a coker and a hydrocracker and where only the hydrocracker is replaced with a nozzle reactor, the pitch by-product that may be produced by the nozzle reactor can be recycled back to the coker. If such a pitch by-product is not recycled back into the nozzle reactor or a remaining coker, hydrocracker or deasphalting unit, the pitch by-product can still be used for steam generation, such as the steam can be used as a cracking material in the nozzle reactor. Unrecycled pitch by-product can also be further processed to generate asphalt product that can be used for road surfacing, roof shingle production, and other products utilizing asphalt.

With respect to replacing cokers, the use of a nozzle reactor can include the added benefit of producing a stable product. Generally speaking, cokers produce highly olefinic and hence very unstable products. These materials generally need an immediate hydrotreating step to produce a more stable product. To the contrary, the nozzle reactor produces products that are stable and do not require any further processing before transport to a final product production facility. Furthermore, the gas produced in the nozzle can be less than 10% of what a coker produces, which results in environmental advantages. Also, as noted above, cokers generally do not allow for the recycle of stable coke produced by the coker, which thereby drastically reduces the total liquid product yield possible in a coker.

With respect to replacing hydrocrackers, the use of a nozzle reactor can include the added benefit of being less expensive and less complex than a traditional hydrocracker. Moreover, unlike the hydrocrackers, no hydrogen is necessary in operation of the nozzle reactor while still producing a stable product.

With respect to replacing deasphalting units, the use of a nozzle reactor can include the added benefit of limiting or eliminating the need to dispose of asphaltene waste. Refineries using deasphalting units typically have to pay to dispose of these hydrocarbon wastes, but this material can readily be further processed through the nozzle reactor. Replacing a deasphalting unit with a nozzle reactor can also increase the versatility of a refinery plant normally employing a deasphalting unit. Typically, deasphalting units are used in light oil refineries. These light oil refineries are not capable of processing heavy oil due to the heavy waste components found therein. However, when a nozzle reactor is used to replace a deasphalting unit, the light oil refinery obtains the ability to process the heavy oil it previously could not. Deasphalting units such as those performing the ROSE™ process may be eliminated from the refinery by substituting a nozzle reactor and a vacuum distillation tower while also expanding the ability of the refinery to handle different types of material. In a refinery plant including any combination of a coker, a hydrocracker, and a deasphalting unit, the method of modifying the refinery plant can include replacing any combination of the units with one or more nozzle reactors. The units (i.e., the coker, hydrocracker, and deasphalting unit) can be replaced with a nozzle reactor at a 1:1 ratio (i.e., one nozzle reactor for each unit replaced). Furthermore, one coker, one hydrocracker, and/or one deasphalting unit can be replaced with multiple nozzle reactors.

In some embodiments, one or more nozzle reactors are used in conjunction with existing cokers, hydrocrackers, or deasphalting units. For example, where the capacities of the existing cokers, hydrocrackers, or deasphalting units are limited, nozzle reactors can be added to increase the overall capacity of the refinery. In some embodiments, a refinery plant utilizing the nozzle reactors described herein is disclosed. The refinery plant generally utilizes a refinery residue-producing processing unit having a refinery residue outlet and a nozzle reactor. The refinery residue outlet of the refinery residue-producing processing unit is fluidly connected to the nozzle reactor such that refinery residue leaving the refinery residue-producing processing unit can be fed into the reactor body of the nozzle reactor for cracking with cracking material.

The refinery plant can generally be any type of refinery plant used for processing of heavy hydrocarbon material, such as heavy oil, bitumen and crude oil, into useful, lighter hydrocarbon materials. The refinery plant can therefore also include any additional units needed for the processing of heavy hydrocarbon material. The refinery plant can include at least one of a coker, a hydrocracker, and a deasphalting unit, although in some embodiments, the refinery plant excludes these units. In their place, the refinery plant utilizes one or more nozzle reactors to crack feeds typically sent to a coker, hydrocracker, or deasphalting unit. The refinery residue-producing processing unit of the refinery plant can be any type of refinery residue-producing processing unit used in heavy hydrocarbon processing. Examples of refinery residue-producing processing unit that can be included in the refinery plant include, but are not limited to, distillation units, vacuum stripping units, hydrocrackers, cokers, and deasphalting units. The refinery plant can include more than one refinery residue-producing processing unit and can include more than one type of refinery residue-producing processing unit. As noted above, the refinery residue-producing processing unit can include a refinery residue outlet. The refinery residue outlet can be the outlet for the residue portion of the feed stream fed to the refinery residue-producing processing unit The refinery residue can be as described above in the previous embodiment, and therefore generally includes the remainder of any stream of material fed to a unit of a refinement process after removal of a part or parts of the stream of material.

The nozzle reactor used in the refinery plant can generally be a nozzle reactor according to any embodiments described in greater detail above.

As noted above, the refinery residue-producing processing unit can include a refinery residue outlet and the refinery residue outlet can be in fluid communication with nozzle reactor such that refinery residue leaving the refinery residue-producing processing unit via the refinery residue outlet is injected into the reactor body of the nozzle reactor for cracking with cracking material. In some embodiments, the refinery residue outlet is in fluid communication with the material feed passage of the nozzle reactor. In some embodiments, the refinery residue outlet is in fluid communication with the injection passage. Fluid communication between the refinery residue-producing processing unit and the nozzle reactor can be achieved by any suitable means. For example, the fluid communication can be achieved via a pipe running between the two units. As with other embodiments described above, the nozzle reactor can also include a recycle stream so that any material leaving the nozzle reactor can be fed back to the nozzle reactor. The material that can be recycled back into the nozzle reactor can include cracked material, uncracked material, or pitch by-product. The recycle stream can connect with the refinery residue stream being fed to the nozzle reactor or can recycle back to a different inlet near the injection end of the reactor body of the nozzle reactor. A recycle stream of material leaving the nozzle reactor can also be recycled back to an upstream processing unit in the refinery plant. In some embodiments, a light product stream of the nozzle reactor is recycled all the way back to the feed stream initially entering the refinery system, such as prior to being introduced into a distillation unit. In some embodiments, pitch by-product produced by the nozzle reactor is recycled back to a coker, hydrocracker or other processing unit.

The refinery residue need not be pre-heated prior to being injected into the nozzle reactor. The refinery residue leaving the refinery residue-producing processing unit can already be at a temperature suitable of injection into the nozzle reactor. For example, refinery residue such as distillation tower bottoms leave the distillation towers at a high temperature, and therefore can be injected into the nozzle reactor without a pre-heating step. In some cases, the refinery residue is cooled before introduction into the nozzle reactor. For example, LC Finer bottoms can be cooled when valuable syncrude or virgin oil is blended into the bottoms to make transportation feasible. The discharge temperature of the hydrocracker furnace (-525 °C) is higher than the feed for the nozzle reactor (-425 °C).

In some embodiments, a method of assembling a refinery plant is disclosed, with reference to Figure 9, the method generally includes a step 2000 of providing a refinery residue- producing processing unit, a step 2100 of providing a nozzle reactor, and a step 2200 of providing refinery residue fluid communication between the refinery residue outlet of the refinery residue-producing processing unit and the second material feed port of the nozzle reactor. More specifically, the refinery residue-producing processing unit has a refinery residue outlet and the nozzle reactor has a material feed passage. The fluid communication between the refinery residue-producing processing unit and the nozzle reactor is provided by connecting the refinery residue outlet of the refinery residue-producing processing unit with the material feed passage of the nozzle reactor.

The refinery plant to be assembled can generally be any type of refinery plant used for processing of heavy hydrocarbon material, such as heavy oil, bitumen and crude oil, into useful, lighter hydrocarbon materials. The refinery plant being assembled can therefore also include any additional units needed for the processing of heavy hydrocarbon material.

The refinery residue-producing processing unit provided in step 2000 can be any type of refinery residue-producing processing unit used in hydrocarbon processing. Examples of refinery residue-producing processing unit include distillation units and deasphalting units. The distillation units that can be included in the refinery plant include, but are not limited to, atmospheric distillation units and vacuum distillation units. The refinery plant can include more than one refinery residue-producing processing unit and can include more than one type of refinery residue-producing processing unit. As noted above, the refinery residue-producing processing unit can include a refinery residue outlet. The refinery residue outlet can be the outlet for the residue portion of the feed stream fed to the refinery residue-producing processing unit that is not separated from the feed stream.

The step 2000 of providing a refinery residue-producing processing unit can include, but is not limited to, partially or wholly constructing the refinery residue-producing processing unit or obtaining the refinery residue-producing processing unit from a third party, such as via a sale, donation or lease of the equipment.

The nozzle reactor provided in step 2100 can generally be a nozzle reactor according to any embodiment described in greater detail above. The step 2100 of providing a nozzle reactor can include partially of wholly constructing the nozzle reactor or obtaining the nozzle reactor from a third party, such as via a sale, donation or lease of the equipment.

The step 2200 of providing refinery residue fluid communication between the refinery residue outlet of the refinery residue-producing processing unit and the material feed passage of the nozzle reactor can be accomplished by any suitable means for allowing refinery residue from the refinery residue-producing processing unit to travel into the reactor body of the nozzle. An example of providing such a fluid communication includes providing piping between the refinery residue outlet of the refinery residue-producing processing unit and the material feed passage of the nozzle reactor. Such fluid communication can include allowing the refinery residue to travel through the pipe via gravity or through the use of a pump.

Providing refinery residue fluid communication between the refinery residue outlet and the material feed passage can also allow for the addition of other streams to the fluid communication provided between the refinery residue-producing processing unit and the nozzle reactor. For example, where piping is used to provide the fluid communication, the piping between the refinery residue-producing processing unit and the nozzle reactor can receive other piping that delivers additional components to the refinery residue stream traveling to the nozzle reactor. Such components can include, but are not limited to, a solvent to decrease the viscosity of the refinery residue or a recycle stream returning uncracked refinery residue that has passed through the nozzle reactor back to the second material feed port. Other chemicals, reagents and or hydrocarbons can also be added to enhance the uptake of hydrogen from the first material into the second material.

In some embodiments, fluid communication is provided between two or more refinery residue-producing processing units and a nozzle reactor or between a refinery residue-producing processing unit and two or more nozzle reactors. For example, providing the fluid communication can include piping that branches in order to either split the refinery residue stream so that it can be injected into multiple nozzle reactors or by joining together several refinery residue streams from different refinery residue-producing processing unit to travel to one nozzle reactor. As such, the nozzle reactor can receive a refinery residue stream comprising refinery residue from both a different types of refinery residue-producing processing unit, such as from a vacuum distillation column and an atmospheric distillation column.

In several of the embodiments described above, a recycle stream is contemplated, whereby material leaving the nozzle reactor is recycled back through the nozzle reactor in an attempt to further crack the material or, in the case of material that passes through the nozzle reactor uncracked, crack the material for the first time. In addition to the recycle stream or alternative to the recycle stream, further nozzle reactors may be used to crack this material. Method utilizing multiple nozzle reactors can be used to increase the overall conversion of material feed into lighter components via cracking. The nozzle reactor system described herein can 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 uncracked or not sufficiently cracked material.

With reference to Figure 10, the nozzle reactor system 300 generally includes a first nozzle reactor 310 and a second nozzle reactor 320. Nozzle reactor system 300 also includes a first separation unit 330. First separation unit 330 generally separate the material leaving first nozzle reactor 310 into a light stream and a heavy stream. Accordingly, first separation unit 330 include a light stream outlet 332 and a heavy stream outlet 334. Heavy stream outlet 334 is in fluid communication with the material feed passage of second nozzle reactor 320 so that the heavy components of heavy stream outlet 334 are transported to second nozzle reactor 320 for cracking.

First and second nozzle reactors 310, 320 can generally be a nozzle reactor according to any embodiments described herein.

First and second nozzle reactors 310, 320 can be identical or first and second nozzle reactors 310, 320 can be different. In some embodiments, 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 can be 1/3 or less the interior reactor chamber volume of first nozzle reactor 310. Additionally, nozzle reactor system 300 en include more than two nozzle reactors. Other features of the nozzle reactor are described in greater detail above. First separation unit 330 can 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 is generally 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 can 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 can be used between first nozzle reactor 310 and first separation unit 330. In one example, the fluid communication can be piping extending between the ejection end of first nozzle reactor 310 and first separation unit 330.

As noted above, first separation unit 330 can generally include light stream outlet 332 and heavy stream outlet 334. Light stream outlet 332 generally includes 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 can 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 can include 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 generally includes any materials not having the predetermined property or properties. As such, heavy stream outlet 334 can 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, e.g., 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 can 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 can be used to classify the material leaving first nozzle reactor 310 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 below 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 can 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 can 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 is established between heavy stream outlet 334 and second nozzle reactor 320. More specifically, a fluid communication is established between heavy stream outlet 334 and the material feed passage of second nozzle reactor 320. However, fluid communication can also be established between heavy stream outlet 334 and any portion of second nozzle reactor 320. Any manner of fluid communication can be used between second nozzle reactor 320 and heavy stream outlet 334. In one example, the fluid communication is piping extending between the heavy stream outlet 334 and second nozzle reactor 320. A pump can also be used in connection with the fluid communication to assist the flow of material through the fluid communication.

Second nozzle reactor 320 can 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. As discussed in greater detail above, 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 can 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 can pass through the reaction chamber without being cracked. These gaseous fractions can 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 can 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 can 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 can be achieved by reducing the ratio of cracking material mass to material feed mass or by reducing the superheat in the cracking material while maintaining the ratio of cracking material mass to material feed mass.

In some embodiments, nozzle reactor system 300 further includes a second separation unit 340. Second separation unit 340 can be in fluid communication with the ejection 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 can generally include a light stream outlet 342 and a heavy stream outlet 344.

Like first separation unit 330, second separation unit 340 generally includes 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 can 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 can be used between second nozzle reactor 320 and second separation unit 340. In one example, the fluid communication is piping extending between the ejection end of second nozzle reactor 320 and second separation unit 340.

As noted above, second separation unit 340 generally includes light stream outlet 342 and heavy stream outlet 344. Light stream outlet 342 generally includes material that has a predetermined property or properties when leaving second nozzle reactor 320. Correspondingly, heavy stream outlet 344 generally includes material that 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. Alternatively, the same predetermined property or properties can 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 can be selected as the parameter for separating light and heavy streams.

In some embodiments, light stream outlet 342 is 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 material 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 can 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 can be used between light stream output 342 and first nozzle reactor 310 and/or second nozzle reactor 320. In one example, the fluid communication is 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 can 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 can 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 can also be provided between light stream outlet 332 and first nozzle reactor 310. Additionally, a portion of heavy stream outlet 334 can 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 can 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 can be used. Each nozzle reactor can 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 uncracked or not sufficiently cracked.

Furthermore, the nozzle reactors can be arranged in parallel in addition to a series arrangement. For example, a first nozzle reactor can 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 some embodiments, a material feed cracking method is disclosed. The material feed cracking method generally allows 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 are selected so that the second nozzle reactor is more likely to break down material that passes through the first nozzle reactor uncracked or not sufficiently cracked.

The material feed cracking method generally includes a first step of injecting a first stream of cracking material through an injection passage of a first nozzle reactor into an interior reactor chamber of a first nozzle reactor. Material feed is then 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 material are produced. The method then includes 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 is 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 interior 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 are produced.

The first and second nozzle reactors referred to above can generally include a nozzle reactor according to any embodiment described herein.

The first and second streams of cracking material can be any suitable cracking material for cracking the material feed. In some embodiments, the cracking material is a cracking gas, such as steam. The first and second streams of cracking material can be introduced into the injection passages at any suitable temperature and pressure. In some embodiments, 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 can be 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 can be any residual portion of a separated hydrocarbon stream, such as the bottoms fraction from a distillation unit. The high asphaltene content can 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 and first heavy stream can be introduced into the material feed passages at any suitable temperature and pressure. In some embodiments, the material 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 can range from about 2 bar to about 15 bar. The ratio of cracking material to material feed can range from about 0.5:1.0 to about 4: 1. The ratio of cracking material to first heavy material can range from about 0.1 : 1.0 to about 0.8: 1.0. As noted above, the injection of the material feed and the first stream of cracking material can result in the production of first light material 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 can pass through the nozzle reactor without being cracked. These gaseous fractions can be considered non-participating in that they will not be cracked by the shock waves. Where such material feed passing through the nozzle uncracked includes large molecules, further work may need to be done to accomplish cracking of the material into useful material.

In some embodiments, the operating conditions of the first nozzle reactor can 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 can be achieved by, for example, pre-heating the material feed prior to injection into the nozzle reactor. In an example where the material feed includes bitumen, the bitumen can comprise a fraction having a boiling point higher than 200°C. The pre-heating temperature can 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 can pass through the first nozzle reactor uncracked, at which point they can be fed to a second nozzle reactor. The temperature of the gaseous material leaving the first nozzle reactor can 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 can be injected into the second nozzle reactor to undergo another attempt at cracking the material in the nozzle reactor. The second nozzle reactor cab be identical in size and dimension to the first nozzle reactor, or may be different than the first nozzle reactor. In some embodiments, 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 can 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 some embodiments, the first light material and the first heavy material leaving the first nozzle reactor are 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 can be separated for consumption or recycle while the heavy and large components that make up the first heavy material can be sent to the second nozzle reactor. Sending only the first heavy material to the second nozzle reactor can 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 can be accomplished by any suitable means for separation of the components. Properties such as density and boiling point can be used to effect separation. Separation can 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 can also be separated. Any suitable means for separation, such as those mentioned above, can be used to effect the separation.

The method can 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 can further comprise a step of injecting the first light material or second light material into the reaction chamber of the first nozzle reactor. EXAMPLES Background Example

A conventional refinery includes four separate hydrocarbon processing units:

1. A Distillation Unit (DU)

2. A Fluid Catalytic Cracker (FCC)

3. A Hydrotreater

4. Coker

Cold Lake bitumen is fed to the Distillation Unit where the bitumen feed is fractionated as follows:

20.8% light fraction (boiling point < 700 deg F)

24.2% mid-distillate fraction (boiling point between 700 and 1050 deg F) 54.9% bottoms fraction (boiling point > 1050 deg F).

100% Total The bottoms fraction (54.9%) is fed to a coker, which converts the bottoms as follows:

18.4% petroleum cokes for disposal 11.7% heavy coker oil (HCO) 19.9% light gas oil 4 .9% gas

54.9% Total

The HCO (11.7%) from the coker is joined with the mid-distillate fraction (24.2%) from the distillation unit, and the mixture (35.9% total) is fed to the Fluid Catalytic Cracker. In the FCC, the mixture is cracked into the following products:

5.0% marketable fuel oil

7.8% combined gas (5.6%) and FCC cokes (2.2%) 23.1% liquid product 35.9% Total

The FCC liquid product (23.1%) joins the coker light gas oil (19.9%) and Distillation

Unit light fraction (20.8%) as feed (total 63.8%) to the hydrotreater, where all feed is converted into light products. The following overall balance is the result:

Bitumen Feed 100.0% Hydrotreater Light Product 63.8%

FCC Marketable Fuel Oil 5.0% Cokes: 20.6%

Gases: 10.5%

100% Example A

A modified refinery can have four separate hydrocarbon processing units, where a Nozzle Reactor System replaces the traditional coker:

1. A Distillation Unit (DU)

2. A Fluid Catalytic Cracker (FCC) 3. A Hydrotreater, and

4. A Nozzle Reactor System (NRS)

Cold Lake bitumen is fed to the Distillation Unit where the bitumen feed is fractionated as follows: 20.8% light fraction (boiling point < 700 deg F)

24.2% mid-distillate fraction (boiling point between 700 and 1050 deg F) 54.9% bottoms fraction (boiling point > 1050 deg F). 100% Total

The DU bottoms fraction (54.9%) is fed to a Nozzle Reactor System and is converted into the following products:

7.4% NRS liquid pitch for further processing or disposal 22.8 NRS mid-distillate 24.7% liquid pitch stream (recycled back to DU)

54.9% Total

The NRS mid-distillate (30.9%) joins the DU mid-distillate (24.2%) as feed stock (55.1% total) for the Fluid Catalytic Cracker. In the FCC, the feed stock is cracked into the following products: 6.0% fuel oil (recycled back to the NRS for further cracking)

9.8% combined gas (7.8%) and FCC cokes (2.0%) 39.2% liquid product 55.1% Total The FCC liquid product (39.2%) joins the NRS mid-distillate product (22.8%) and Distillation Units light fraction (20.8%) as feed (total 82.8%) to the hydrotreater where all is converted into light products. The following overall balance is the result:

Bitumen Feed 100.0%

Hydrotreater Light Product 82.8%

FCC Cokes: 2.0% Gases: 7.8%

NRS Liquid Pitch 7.4%

Comparing Background Example (coking) with Example A (nozzle reactor), a nozzle reactor system will produce 29.6% more valuable product than a coker unit operation will generate. Furthermore the nozzle reactor system also produces less gas and a liquid pitch product that can be further processed if needed. The reduction in the amount of cokes can be an advantage to the system described in Example A, as it is well known that the disposal of solid petroleum coke can present an environmental problem. Example B

Distillation bottoms comprising hydrocarbons having predominantly molecular weights in the range of -300 to -4,000 are adjusted to a temperature of 425 deg C. The distillation bottoms are injected into a nozzle reactor via the second material feed port of the nozzle reactor. Simultaneously, superheated steam at a temperature of about 1250 deg F is injected into the converging section of the nozzle of the nozzle reactor at a flow rate of about 1.5 times the flow rate of the distillation bottoms into the nozzle reactor. The distillation bottoms and steam are retained inside the nozzle reactor for a period of time around 0.6 seconds. Shockwaves produced inside the nozzle convert approximately 45% of the distillation bottoms having a boiling point above 1050 deg F into lighter hydrocarbons having a boiling point less than 1050 deg F. The nozzle reactor emits a mixture of steam, cracked, and uncracked hydrocarbons at a temperature ofabout 400 deg C. Example C

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 T (400 °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 ⁰ F (680°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 produced inside the nozzle convert approximately 45% per pass of the hydrocarbon source that has a boiling point of greater than 1050 ⁰ F (566 °C) into lighter hydrocarbons with a boiling point of less than 1050 °F (566 °C). The nozzle reactor emits a mixture of steam, cracked hydrocarbons, and uncracked hydrocarbons at a temperature of about 788 ⁰ F (420 °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 Daltons 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 including about 75% of the total VDU bottoms stream is recycled back to the first nozzle reactor, while a second stream including 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 T (371 °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 °F (680 °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 rate 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 65% 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 ⁰ 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 ⁰ F (371 °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 invention all that comes within the scope and spirit of these claims.