OA16337A - Systems and methods for processing nozzle reactor pitch. - Google Patents

Abstract

Methods and systems for cracking hydrocarbon material in a nozzle reactor and processing any un-cracked hydrocarbon material passing through the nozzle reactor. The nozzle reactor used may have a configuration whereby cracking material is injected into the nozzle reactor at a high velocity, including supersonic speed. The hydrocarbon material is injected into the nozzle reactor and intersects with the cracking material to crack hydrocarbon material. Any hydrocarbon material that pass through the nozzle reactor un-cracked can be re- injected into the nozzle reactor. An increase in the concentration and amount of un-cracked hydrocarbons injected into the nozzle reactor may increase the overall conversion of hydrocarbons into lighter hydrocarbons.

Description

Some nozzle reactors operate to cause interaction 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 contrîbute to how the materials interact and what types of alterations are achieved.

One example of a nozzle reactor for altering the physical or chemical composition of materials injected therein is shown in Figure 3 of the U.S. Patent No. 6,989,091. The nozzle reactor discussed in the Ό9Ι patent has two steam injectors and a central feed stock injector, each of which includes a discharge end feeding into a central reactor tube. The two steam injectors are disposed (i) laterally separated from opposing sides of the central feed stock injector and (ii) at an acute angle to the axis of the central feed stock injector. The steam injectors are thus disposed for injection of material into the central reactor tube in the direction of travel of material feed stock injected into the central reactor tube by the central feed stock injector. The central feed stock injector is coaxial with the central reactor tube and has a generally straightthrough bore.

As explained in the ‘091 patent, superheated steam is injected through the two laterally opposed steam injectors into the interior of central reactor tube in order to impact a pre-heated, centrally-located feed stream of certain types of heavy hydrocarbon simultaneously injected into the interior of the central reactor tube via the central feed stock injector. The ‘091 patent states ?

that the object of disclosed nozzle reactor is to crack the feed stream into lighter hydrocarbons through the impact of the steam feeds with the heavy hydrocarbon feed within the reactor tube. According to the ‘091 patent, the types of heavy hydrocarbons processed with the disclosed nozzle reactor are crude oil, atmospherîc residue, and heavy distillâtes. With the nozzle reactor of the *091 patent, a central oil feed stock jet intersects the steam jets at some distance from the éjection of these jets from their respective injectors.

In some embodiments of the nozzle reactor disclosed in the ‘091 patent, a portion of the lighter hydrocarbons produced by cracking heavy hydrocarbon in the nozzle reactor do not meet certain standards for nozzle reactor product. For example, a liquid heavy oil product produced by the nozzle reactor can hâve a molecular weight greater than the desired maximum molecular weight for the hydrocarbon products. Accordingly, the ‘091 patent discloses that a recycle stream may be used in order to recycle these hydrocarbon products back into the nozzle reactor. However, the ‘091 patent appears to only consider such a recycle stream for cracked hydrocarbon products of the nozzle reactor. The ‘091 patent appears to be silent with respect to recycling any un-cracked solid residue (pitch) product produced by the nozzle reactor. In Applicant’s expérience, failure to consider recycle of solid residue is not surprising, as conventional understanding of nozzle reactor technology has generally suggested that solid pitch material exiting a nozzle reactor will not be broken down by recycling it back through a nozzle reactor.

Applicants believe that one disadvantage of the nozzle reactor disclosed in the ‘091 patent is the amount of heavy hydrocarbon that passes through the nozzle reactor un-cracked. Applicants beiieve this is due to the near impossibility of cracking ail material having a boiling température greater than l,050°F (565°C) into material having a boiling température less than l,050°F when the operating température of the nozzle reactor is substantially lower than l,050°F and the reaction time in the nozzle reactor is around a few seconds or less.

The disadvantage of a large quantity of un-cracked material passing through the nozzle reactor in the ‘091 patent is further exacerbated by the apparent failure of the reference to provide any manner în which the nozzle reactor may further process such un-cracked material. If no further nozzle reactor processing is carried out on the un-cracked heavy hydrocarbons, then the efficiency and profitability of the nozzle reactor may be diminished. Even if conventional methods for processing the un-cracked heavy hydrocarbons are relied upon, such as processing the un-cracked heavy hydrocarbon in a coker unit, then the overall cost and complexity of the process may be increased.

SUMMARY

Disclosed below are représentative embodiments that are not intended to be limiting in any way. Instead, the présent dîsclosure is directed toward features, aspects, and équivalents of the embodiments of the method and Systems described below. The disclosed features and aspects of the embodiments can be used alone or in various combinations and sub-combinatîons with one another.

In some embodiments a method of cracking hydrocarbon material in a nozzle reactor and processing pitch produced therefrom is described. The method may include provîding a nozzle reactor. The nozzle reactor may include a reactor body, a first material injector and a second material feed port. The reactor body may include an injection end and an éjection end. The first material injector may include a first material injection passage and may be mounted in the nozzle reactor in material injecting communication with the injection end of the reactor body, The first material injection passage may include an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume éjection section. The first material injection passage may also include a material injection end and a material éjection end in injecting communication with the reactor body passage. The second material feed port may be adjacent to the material éjection end of the first material injection passage. The method may also include injecting a stream of cracking material through the first material injector into the reactor body and injecting hydrocarbon material through the second material feed port into the reactor body. The method may further include collecting the heavy hydrocarbon fraction exiting the nozzle reactor and injecting the heavy hydrocarbon fraction into the reactor body.

In some embodiments, the method may include collecting a first nozzle reactor heavy hydrocarbon fraction exiting a first nozzle reactor. The method may also include providing a second nozzle reactor. The second nozzle reactor may include a reactor body, a first material injector and a second material feed port. The reactor body may include an injection end and an éjection end. The first material injector may include a first material injection passage and may be mounted in the nozzle reactor in material injecting communication with the injection end of the reactor body. The first material injection passage may include an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume éjection section. The first material injection passage may also include a material injection end and a material éjection end in injecting communication with the reactor body passage. The second material feed port may be adjacent to the material éjection end of the first material injection passage. The method may also include injecting a stream of cracking material through the first material injector into the reactor body and injecting the first nozzle reactor heavy hydrocarbon fraction through the second

216337 material feed port into the reactor body. The method may also include collecting a second nozzle reactor heavy hydrocarbon fraction exiting the second nozzle reactor and injecting the second nozzle reactor heavy hydrocarbon fraction into the reactor body.

In some embodiments, a nozzle reactor is described. The nozzle reactor may include a include a reactor body, a first material injector, a second material feed port, and an un-cracked material recycle passage. The reactor body may include an injection end and an éjection end. The first material injector may include a first material injection passage and may be mounted in the nozzle reactor in material injecting communication with the injection end of the reactor body. The first material injection passage may include an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mîd-section intermediate the enlarged volume injection section and enlarged volume éjection section. The first material injection passage may also include a material injection end and a material éjection end in injecting communication with the reactor body passage. The second material feed port may be adjacent to the material éjection end of the first material injection passage. The un-cracked material recycle passage may have a first end and a second end. The first end may be in material receiving communication with the éjection end of the reactor body passage. The second end may be in material injecting communication with the reactor body passage at a location adjacent the material éjection end of the first material injection passage.

The foregoing and other features and advantages of the présent application will become apparent from the following detailed description, which proceeds with reference to the accompanying figures. It îs 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 ail features or advantages recited in this 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 l is a flow diagram of an embodiment of one method described herein;

Figure 2 îs 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 l, showing further construction details for the nozzle reactor;

Figure 4 is a schematic diagram of one embodiment of a system described herein;

Figure 5 is a schematic diagram of one embodiment of a system described herein; and

Figure 6 is a sériés of photographs showing the embodiments of the solid pitch obtained from the nozzle reactor after a first pass, a first recycle and a second recycle.

DETAILED DESCRIPTION

With reference to Figure l, a method for cracking hydrocarbon material and processing any un-cracked heavy hydrocarbon material (also referred to as “pitch”) may generally include a step 100 of providing a nozzle reactor, a step 110 of injecting cracking material into the nozzle reactor, a step 120 of injecting hydrocarbon material into the nozzle reactor, a step 130 of collecting a heavy hydrocarbon fraction exiting the nozzle reactor, and a step 140 of injecting the heavy hydrocarbon fraction into the nozzle reactor. The heavy hydrocarbon fraction may include the highest molecular weight hydrocarbon compounds présent in the original hydrocarbon material that remain un-cracked after passing through the nozzle reactor. Typically, such compounds may constitute a pitch by-product that requires either disposai (resulting in a waste of hydrocarbon material) or processing in supplementary processing equipment, such as a coker (which may increase the overall cost and complexity of the operation). However, in the method

A described herein, the heavy hydrocarbon fraction may be injected back into the nozzle reactor in order to crack the heavy hydrocarbon compounds into lighter hydrocarbon molécules. In some embodiments, recycling the heavy hydrocarbon fraction back into the nozzle reactor (or recycling the heavy hydrocarbon fraction in a second nozzle reactor) may increase the overall conversion of heavy hydrocarbon compounds being passed therethrough into lighter hydrocarbon compounds.

The method may include a step 100 of providing a nozzle reactor. As described above, some nozzle reactors may generally be used to cause interactions between materials and achieve alteration of the physical or chemical composition of one or more of the materials, With reference to Figure 2, a nozzle reactor suitable for use in the method described herein and indicated generally at 10 may hâve a reactor body injection end 12, a reactor body 14 extending from the reactor body injection end I2, and an éjection port 13 in the reactor body 14 opposite its injection end 12. The reactor body injection end 12 may include 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 may be coaxial with the central axis B of the interior reactor chamber 16.

With continuing reference to Figure 2, the injection passage 15 may hâve a circular diametric cross-section and, as shown in the axîally-extending cross-sectional view of Figure 2, opposing înwardly curved side wall portions 17, 19 (i.e., curved înwardly 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 înwardly curved side wall portions 17, 19 of the injection passage 15 may allow for a higher speed of cracking material when passing through the injection passage 15 into the interior reactor chamber I6.

In certain embodiments, the side wall of the injection passage 15 can provide one or more among: (i) unîform axial accélération of cracking material passing through the injection passage; (îi) minimal radial accélération of such cracking 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 I5 substantially isentropic. These latter types of side wall and injection passage features can be, among other things, particularly useful for pilot plant nozzie reactors of minimal size.

A material feed passage I8 may extend from the exterîor of the reactor body 14 toward the interior reactor chamber 16. In the embodiment shown in Figure 2, the material feed passage 18 may be aligned transversely to the axis A of the injection passage 15, although other configurations may be used. The material feed passage 18 may penetrate 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 may include an annular, radially extending reactor chamber feed slot 26 in material-injecting communication with the interior reactor chamber 16. The material feed port 20 may thus be configured to înject feed material: (i) around the entire circumference of a cracking material injected through the injection passage 15; and (i) to impact the entire circumference of the free cracking material stream virtually immediately upon its émission from the injection passage 15 into the interior reactor chamber 16. As noted above, the material feed port 20 may also inject feed material at about a 90° angle to the axis of travel of cracking material injected from the injection passage 15, although other angles greater than or less than 90° may also be used.

The annular material feed port 20 may hâve a U-shaped or C-shaped cross-section among others. In certain embodiments, the annular material feed port 20 may be open to the interior reactor chamber I6, with no arms or barriers în 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 hâve a radiused cross-section.

In alternative embodiments, the material feed passage 18, annular material feed port 20, and/or injection passage 15 may hâve differing orientations and configurations, and there can be more than one material feed passage and associated structure. Similarly, in certain embodiments the injection passage 15 may be located on or in the interior reactor chamber side 23 (and if desired may include an annular cracking material port) rather than at the reactor body injection end 12 of the reactor body 14, and the annular material feed port 20 may be non-annular and located at the reactor body injection end 12 of the reactor body 14.

In the embodiment shown in Figure 2, the interior reactor chamber 16 can be bounded by stepped, telescoping side walls 28, 30, 32 extending along the axial length of the reactor body 14. In certain embodiments, the stepped side walls 28, 30, 32 may be 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 ofthe 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 hydrocarbon material, injected through the annular material feed port 20.

As indicated by the drawing gaps 38, 40 in the embodiment shown în Figure 2, the reactor body 14 may hâve an axial length (along axis B) that is much greater than its width. In the embodiment shown in Figure 2, exemplary length-to-width ratios may typically be in the range of 2 to 4 or more.

The dimensions of the varîous components of the nozzle reactor shown in Figure 2 are not limited, and may generally be adjusted based on the amount of hydrocarbon material to be cracked inside the nozzle reactor. Table l provides exemplary dimensions for the various components of the nozzle reactor based on the hydrocarbon material input in barrels per day (BPD). The dimensions provided in Table l are not exhaustive for the given hydrocarbon input rate, as other dimensions may be used for hydrocarbon inputs of 5,000 BPD, 10,000 BPD and

20,000 BPD.

	Hydrocarbon Input, 000' kg (BPD)
Nozzle Reactor Component (mm)	790 (5,000)	1,580 (10,000)	3,160 (20,000)
Injection Passage, Enlarged Volume Injection Section Diameter	148	207	295
Injection Passage, Reduced Volume Mid-Section Diameter	50	70	101
Injection Passage, Enlarged Volume Ejection Section Diameter	105	147	210
Injection Passage Length	600	840	1,200
Interior Reactor Chamber Injection End Diameter	187	262	375
Interior Reactor Chamber Ejection End Diameter	1,231	1,435	1,821
Interior Reactor Chamber Length	6,400	7,160	8,800
Overall Nozzle Reactor Length	7,000	8,000	10,000
Overall Nozzle Reactor Outside Diameter	1,300	1,600	2,000

Table 1

As can be seen from Table 1, the injection passage may be small relative to the reactor body. The relatîvely small size of the injection passage is bénéficiai in that the injection passage may be part of a replaceable insert that is easily removed from the reactor body. Accordingly,

CM other injection passages having different internai dimensions and providing different types of injection flow properties for the cracking material may be used to increase the versatility of the nozzle reactor as a whole.

With reference now to Figure 3 and the particular embodiment shown therein, the reactor body 44 may include a generally tubular central section 46 and a frustoconical éjection 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 abuttîng the injection nozzle 52. The insert end 50 of the central section 46 may consist of a generally tubular central body 51. The central body 51 may hâve a tubular material feed passage 54 extending from the external periphery 56 of the insert end 50 radially inwardly to injectingly communicate with the annular circumferential feed port dépréssion or channet 58 în the otherwise planar, radially inwardly extending portion 59 of the axially stepped face 61 of the insert end 50. The inwardly extending portion 59 may abut 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 may cooperatively provide an annular feed port 57 disposed generally 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 may be secured within and adjacent to the interior periphery 64 of the reactor body 44. The mechanism for securing the insert end 50 in this position may consist of an axially-extending nut-and-bolt arrangement (not shown) penetrating co-linearly mating passages (not shown) in: (i) an upper radially extending lip 66 on the reactor body 44; (ii) an abuttîng, radially outwardly extending thickened neck section 68 on the insert end 50; and (iii) in tum, the abuttîng injector nozzle 52, Other mechanisms for

Λ securing the insert end 50 within the reactor body 44 may include a press fit (not shown) or mating threads (not shown) on the outer perîphery 62 of the tubular body 51 and on the inner periphery 64 of the reactor body 44. Seals, e.g., 70, may be mounted as desired between, for example, the radîally extending lip 66 and the abutting the neck section 68 and the neck section 68 and the abutting injector nozzle 52.

The non-lînear injection passage 60 may hâve, from an axially-extending cross-sectional perspective, mating, radîally inwardly curved opposing side wall sections 72, 74 extending along the axial length of the non-lînear injection passage 60. The entry end 76 of injection passage 60 may provide a rounded circumferential face abutting an injection feed tube 78, which can be bolted (not shown) to the mating planar, radîally outwardly extending distal face 80 on the injection nozzle 52.

in the embodiment shown in Figure 3, the injection passage 60 may be a DeLaval type of nozzle and hâve an axîally convergent section 82 abutting an intermediate relatively narrower throat section 84, which in turn abuts an axially divergent section 86. The injection passage 60 may also hâve a circular diametric cross-section (i.e., in cross-sectional view perpendicular to the axis of the nozzle passage) ail along its axial length. In certain embodiments, the injection passage 60 may also présent a somewhat roundly curved thick 82, less curved thicker 84, and relatively even less curved and more gently sloped relatively thin 86 axially extending crosssectional 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 présent a substantially isentropic or frictionless configuration for the injection nozzle 52. This configuration may vary, however,

I2

A depending on the application involved in order to yield a substantially isentropic configuration for the application.

The injection passage 60 may be formed in a replaceable injection nozzle insert 90 pressfit or threaded into a matîng injection nozzle mounting passage 92 extending axîally through an injection nozzle body 94 of the injection nozzle 52. The injection nozzle insert 90 may preferably be made of hardened steel alloy, and the balance of the nozzle reactor 100 components other than seals, if any, may preferably be made of steel or stainless steel.

In the particular embodiment shown in Figure 3, the diameter D within the injection passage 60 is 140 mm. The diameter E of the éjection passage opening 96 in the éjection end 48 of the reactor body 44 is 2.2 meters. The axial length of the reactor body 44, from the injection end 88 of the injector passage 60 to the éjection passage opening 96, is 10 meters. These dimensions are not exhaustive, as other dimensions may be used.

The interior périphéries 89, 91 of the insert end 50 and the tubular central section 46, respectively, may 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 may 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 ofthe injection passage 60.

Other embodiments of nozzle reactors suitable for use in the method described herein are set forth in commonly owned, co-pendîng U.S. Application No. 12/245,036, which is hereby incorporated by reference.

The nozzle reactor provided at step 100 may be used to crack hydrocarbon material into lighter hydrocarbons and other components. In order to do so in certain embodiments, a crackîng material and a hydrocarbon material may be injected into the nozzle reactor. The collision of the injected hydrocarbon material with the high speed and high température crackîng material may deliver kinetic and thermal energy to the hydrocarbon material and resuit in the crackîng of the largest hydrocarbon molécules. The applicants believe that this process may continue, but with diminîshed intensity and productivity, through the length of the reactor body 44 as injected hydrocarbon material is forced along the axis of the reactor body 44 and yet constrained from avoiding contact with the crackîng material jet stream by the telescoping interior walls, e.g., 89, 91 101, of the reactor body 44.

In view of the above described mechanism for crackîng hydrocarbon material inside a nozzle reactor, the method may include a step 110 of injecting crackîng material into the nozzle reactor and a step 120 of injecting hydrocarbon material into the nozzle reactor.

Referring first to step 110 and with reference to Figure 2, the crackîng material may be injected into the interior reactor chamber 16 of the nozzle reactor via the injection passage 15. The configuration of the injection passage 15 may provide for the accélération of the crackîng material as it passes through the injection passage 15. With reference to Figure 3, the pressure differentiai from the entry end 76 of the injection passage 60, where the pressure is relatively high, to the éjection end 88 of the injection passage 60, where the pressure is relatively low, may aid in accelerating the crackîng material through the injection passage 60. In certain embodiments having one or more non-linear crackîng material injection passages 60, the pressure differentiai can yield a steady increase in the kinetic energy ofthe crackîng material as it moves along the length of the crackîng material injection passage(s) 60. The crackîng material !4

Y may thereby eject from the éjection 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.

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 may comprise a sériés of conical or toroidal sections (not shown) to provide varying cracking material accélération through the injection passage 60 and, in certain embodiments, supersonic discharge ofthe cracking material from the passage 60.

The cracking material injected into the nozzle reactor at step 110 may be any suitable material for cracking hydrocarbon. In some embodiments, the cracking material is in the form of a gas, such as steam. Other suitable gasses include, but are not limited to, carbon dioxide, and natural gas.

The cracking material entering the injection passage may be pre-treated, such as be preheating the cracking material. In some embodiments, the cracking material may be pre-heated to a température in the range of from about 350°C to about 750°C. The pressure of the cracking material may also be adjusted. In some embodiments, the pressure of the cracking material prior to injection into the injection passage may range from about 5 bar to about 100 bar (gage pressure).

The cracking material exiting the injection passage and entering the reaction chamber may have a température in the range of from about 0°C to about 600°C and may have a pressure în the range of from about 0 bar to about 15 bar (gage pressure). Furthermore, the velocity of the cracking material as it exits the injection passage may range from about Mach l to Mach 5.

The amount of cracking material introduced into the injection passage may vary. In some embodiments, the amount of cracking material introduced into the injection passage may vary from about 0.25 to about 4.0 times the amount (weight basis) of hydrocarbon material injected into the nozzle reactor as described in greater detail below.

Referring now to step 120, hydrocarbon material may also be injected into the nozzle reactor. In some embodiments, the hydrocarbon material may be injected into the interior reactor chamber 16 of the nozzle reactor via the material feed passage I8. With reference to Figure 3, the material feed passage 54 may be oriented in a direction perpendicular to the injection passage 60, although other orientations may be used. In the perpendicular configuration, the hydrocarbon material may thereby travel radially inwardly to impact a transversely (i.e., axially) traveling high speed cracking material virtually immediately upon its éjection from the éjection end 88 of the injection passage 60.

The type of hydrocarbon material injected into the nozzle reactor at step 120 is not limited. In some embodiments, the hydrocarbon material injected into the nozzle reactor has an average molecular weight of greater than about 300 Dalton. In some embodiments, the hydrocarbon material may include bitumen. The hydrocarbon material may also include asphaltene. The hydrocarbon material may also be any mixture of materials that includes various types of hydrocarbons and other materials. In some embodiments, the hydrocarbon material is hydrocarbon material collected from a refinery processing operation. For example, the hydrocarbon material may be residual oit produced by any type of refinery processing operation, such as distillation, coking, hydrocracking, hydrotreating, and solvent deasphalting. Residual oil is described in greater detail in commonly owned, co-pending U.S. Provîsional Application No. 61/169,569.

The hydrocarbon material injected into the nozzle reactor at step 120 may be pretreated prior to injection. In some embodiments, the hydrocarbon material may be pre-heated. In some embodiments, the preheat may provide an injection température of from about 300°C to about 450°C, and more preferably, from about 390°C to about 430° C. Pre-heating may take place at a pressure similar to the pressure inside of the nozzle reactor, fn some embodiments, the preheating may therefore take place at range of from about 2 bar to about 17 bar (which is generally a slightly higher pressure than that in the reactor body 44).

The amount of hydrocarbon material injected into the nozzle reactor is not limited. In some embodiments, the amount of hydrocarbon material injected into the nozzle reactor dépends on the size of the nozzle reactor.

In some embodiments, the amount of hydrocarbon material injected into the nozzle reactor détermines the amount of cracking material injected into the nozzle reactor. In some embodiments, the amount of cracking material injected in the nozzle reactor is from about 0.25 to about 4.0 times the amount (by weight) of hydrocarbon material injected into the nozzle reactor.

The rétention time of the hydrocarbon material in the reactor body zone may be relatively short. In some embodiments, the rétention time is in the range of from about O.l seconds to about 30 seconds. For example, the rétention time of the hydrocarbon material in the reactor body may be about l .0 seconds.

It is generally theorîzed that nozzle reactor as described herein preferentîally cracks molécules having the largest molecular mass over molécules having smaller molecular mass. Applicants belîeve this is due in part to the higher boiling point température of the larger hydrocarbon molécules. The larger hydrocarbon molécules are more likely to be in a liquid state upon injection into the nozzle reactor due to the higher boiling point températures, and consequently, are more likely to be cracked by, e.g., the shockwaves produced by injecting the cracking material into the nozzle reactor at a supersonic speed. Conversely, the molécules having a smaller molecular mass may be présent in the nozzle reactor in a gaseous state, thus making it less likely that the shockwaves will crack the molécules. In some embodiments, the smaller molécules may pass through the nozzle reactor unaltered.

Table 2 shows the approximate percent gain or loss of various hydrocarbon components of a hydrocarbon material that can be achieved in certain embodiments after a single pass through a nozzle reactor as described herein.

Hydrocarbon Molécule	Percent Change
C7 Insoluble Asphaltene	Loss » 75%
C5 Insoluble Asphaltene	Loss > 50%
Resins	Loss > 50%
Aromatics	Gain > 50%
Saturâtes	Gain > 20%

Table 2

As can be seen from Table 2, the largest hydrocarbon molécules (C? asphaltene) of the hydrocarbon material tend to be lost at the greatest rate. The loss of these molécules may be due to the cracking of the large hydrocarbon molécules into smaller aromatics and saturâtes. This may also explain the increase in the amount of aromatics and saturâtes after the hydrocarbon material has been passed through the nozzle reactor.

Ultimately, the material exîting the nozzie reactor may be a combination of cracked and un-cracked hydrocarbon molécules. As noted above, the un-cracked material may include some of the smaller hydrocarbon molécules that passed through the nozzie reactor un-cracked. However, the un-cracked material may also include larger hydrocarbon materials that were not cracked in the nozzie reactor, possibly as a resuit of the short résidence time of the hydrocarbon material in the reactor body. The larger hydrocarbon molécules that exit the nozzie reactor uncracked may constitute a heavy hydrocarbon fraction. Because the molécules of the heavy hydrocarbon fraction are prîmarily un-cracked large hydrocarbon molécules, the heavy hydrocarbon fraction essentially represents unprocessed hydrocarbon material that has limited commercial usefulness. In conventional methods, heavy hydrocarbon fractions may hâve either been discarded or subjected to further processing by additional processing equipment. However, in the method described herein, the heavy hydrocarbon fraction may be re-injected into the nozzie reactor in order to crack the large hydrocarbon molécules into lighter, more useful, hydrocarbon molécules.

Accordingly, the method may further include a step 130 of collecting the heavy hydrocarbon fraction so that the heavy hydrocarbon fraction may be re-injected into a nozzie reactor. Any suitable manner of collecting the heavy hydrocarbon fraction may be used. In some embodiments, ail of the material exiting the nozzie reactor may be collected, and then the heavy hydrocarbon fraction may be separated from the rest of the material exiting the nozzie reactor. The heavy hydrocarbon fraction may be separated according to any method well known to those of ordînary skill in the art, including any séparation method based on the physical properties of the collected hydrocarbon material (e.g., boiling point température).

The exact composition of the heavy hydrocarbon fraction collected in step 130 may vary based on a variety of factors. In some embodiments, the composition of the heavy hydrocarbon fraction will at least partially dépend on the hydrocarbon material. For example, where the hydrocarbon material is bitumen, the heavy hydrocarbon fraction may include un-cracked C₇ or C5 insoluble asphaltene because the C5 and C₇ insoluble asphaltenes are amongst the heaviest hydrocarbon molécules présent in bitumen. In some embodiments, the composition of the heavy fraction will at least partially dépend on a user-defined property for establishing the heavy hydrocarbon fraction. For example, a minimum boiling point température may be selected, above which ail hydrocarbon molécules are included in the heavy hydrocarbon fraction. However, generally speakîng, the heavy hydrocarbon fraction may include hydrocarbon molécules exlting the nozzle reactor having a boîling point température above l,050°F (565°C) or hydrocarbon molécules leaving the nozzle reactor having a molecular weight greater than 500 Daltons.

Once the heavy hydrocarbon fraction has been collected, the method may include a step 140 of injecting the heavy hydrocarbon fraction into the nozzle reactor. In some embodiments, the heavy hydrocarbon fraction may be înjected into the nozzle reactor at a direction transverse to the cracking material entering the nozzle reactor, although other non-transverse injection paths may be used. The heavy hydrocarbon material may be înjected into the nozzle reactor in any suîtable fashion. In some embodiments, the heavy hydrocarbon material may be înjected into the nozzle reactor via the material feed passage I8. A separate injection passage may also exist for injection of the heavy hydrocarbon fraction into the nozzle reactor. Like material feed passage 18, any additional injection passage may inject the heavy hydrocarbon fraction into the nozzle reactor. It is also préférable that any additional injection passage inject the heavy hydrocarbon fraction into the nozzle reactor such that the injected heavy hydrocarbon fraction will intersect with the cracking material at a location approximate injection passage éjection end (i.e., where the cracking material enters the reactor body).

When the heavy hydrocarbon material is injected into the nozzle reactor via the feed material passage 18, the heavy hydrocarbon fraction may be injected into the nozzle reactor together with hydrocarbon material. For example, the heavy hydrocarbon fraction and the hydrocarbon material may be pre-mixed prior to injection into the nozzle reactor. When the hydrocarbon material and the heavy hydrocarbon fraction are injected together, the amount and concentration of the heavy hydrocarbon fraction in the nozzle reactor feed may be increased. An increase in the amount and concentration of heavy hydrocarbon fraction in the nozzle reactor feed may resuit in an overall increase in the cracking of heavy hydrocarbon fraction, For example, when the hydrocarbon material includes bitumen and the heavy hydrocarbon fraction includes C5 and C₇ insoluble asphaltenes, injecting the heavy hydrocarbon fraction with the hydrocarbon material increases the amount and concentration of C5 and C? insoluble asphaltenes in the nozzle reactor feed and may resuit in an increased conversion of C5 and C₇ insoluble asphaltenes into lighter hydrocarbon molécules than if hydrocarbon material alone is injected into the nozzle reactor. Table 3 illustrâtes the approximate increase în conversion of heavy hydrocarbons into lighter hydrocarbons when the concentration and amount of heavy hydrocarbon fraction is increased in the nozzle reactor.

9^

	Percent Change
Hydrocarbon Molécule	Without Heavy Hydrocarbon Fraction Recycle	With Heavy Hydrocarbon Fraction Recycle
C7 insoluble Asphaltene	Loss > 75%	Loss > 95%
C5 Insoluble Asphaltene	Loss > 50%	Loss > 75%
Resins	Loss > 50%	Loss > 75%
Aromatics	Gain > 50%	Gain > 75%
Saturâtes	Gain > 20%	Gain > 35%

Table 3

When the heavy hydrocarbon fraction is injected into the nozzle reactor via an injection passage separate from the material feed passage, the heavy hydrocarbon fraction may still be injected into the nozzle reactor at the same time as hydrocarbon material entering via the material feed passage. In this manner, the amount and concentration of the heavy hydrocarbon fraction may still be increased and result in an increased conversion of heavy hydrocarbon material into lighter hydrocarbon molécules.

Heavy hydrocarbon fraction need not be injected into the nozzle reactor together with additional hydrocarbon material. In some embodiments, the recycled heavy hydrocarbon fraction is the only material injected into the nozzle reactor. In such embodiments, any supply of hydrocarbon material being injected into the nozzle reactor via the material feed passage may be stopped prior to the injection of heavy hydrocarbon fraction back into the nozzle reactor.

In some embodiments, the injection of heavy hydrocarbon fraction into the nozzle reactor may be accomplished via an un-cracked material recycle passage. The un-cracked material recycle passage may be any type of passage capable of transporting the heavy hydrocarbon fraction leavîng the nozzle reactor back into the nozzle reactor, such as tubing or piping. The dimensions and materials of the un-cracked material recycle passage are generally not limited and may be selected according to dimensions and operating conditions of the nozzle reactor. ln some embodiments, the material of the un-cracked material recycle passage is selected so that no material passing therethrough can pass through the walls of the un-cracked material recycle passage,

The un-cracked material recycle passage may hâve a first end and a second end opposite the first end. The first end may be in material receiving communication with the éjection end of the reactor body passage of the nozzle reactor. In some embodiments, the séparation unit for separating the heavy hydrocarbon fraction from the rest of the material exiting the nozzle reactor may be located intermediate of the éjection end of the reactor body passage and the first end of the un-cracked material recycle passage. In such a configuration, the un-cracked material recycle passage may receive predominantly or only the heavy hydrocarbon fraction separated from the remainder of the material exiting the nozzle reactor by the séparation unît. The second end of the un-cracked material recycle passage may be in material injecting communication with the nozzle reactor such that the heavy hydrocarbon fraction passing therethrough may eventually be re-injected into the nozzle reactor. In some embodiments, the second end of the un-cracked material recycle passage is located adjacent the éjection end of the injection passage so that the cracking material may impact the heavy hydrocarbon fraction immediately upon injection into the nozzle reactor. In some embodiments, the second end of the uncracked material recycle passage may be in material injecting communication with the material feed passage. The second end of the uncracked material recycle passage may be aligned with the nozzle reactor such that the heavy hydrocarbon fraction is injected into the nozzle reactor at a direction transverse to the direction the cracking material is injected into he nozzle reactor, although other non-transverse configurations are also possible.

Once heavy hydrocarbon fraction and cracking material hâve been injected into the nozzle reactor and cracking of the hydrocarbon molécules commences, the nozzle reactor will again émit a mixture of cracked and un-cracked material. While the overall cracking rate of the large hydrocarbon molécules that make up the heavy hydrocarbon fraction may increase, an amount of un-cracked large hydrocarbon molécules may still be produced. Accordingly, steps 130 and 140 may be repeated. In a repeat of step 130, the un-cracked large hydrocarbon molécules may be collected as part of a heavy hydrocarbon fraction. In a repeat of step 140, the heavy hydrocarbon fraction may be re-injected into the nozzle reactor to further crack the large hydrocarbon molécules.

Steps 130 and 140 may be repeated any number of times. In some embodiments, the heavy hydrocarbon fraction will disappear altogether after a certain number of recycle steps. Progress towards total cracking of the heavy hydrocarbon molécules may be observed by measuring the hardness of the heavy hydrocarbon fraction collected after each pass through the nozzle reactor. In some embodiments, the first amount of heavy hydrocarbon fraction collected after a first pass of the hydrocarbon material through the nozzle reactor may hâve a crumbly, dusty, and hard consistency. After this material is injected back into the nozzle reactor, the second amount of heavy hydrocarbon fraction collected may hâve a visco-elastic consistency. After the visco-elastic heavy hydrocarbon fraction is injected back into the nozzle reactor, the thîrd amount of heavy hydrocarbon fraction collected may hâve the consistency of a high viscosity fluid. Applicants believe that this continuous change in the consistency of the heavy hydrocarbon fraction from a crumbly solid to an essentially liquid material is evidence of the

AS increased rate of heavy hydrocarbon fraction cracking with every pass and the eventua! élimination of any “pitch” by-product.

The heavy hydrocarbon fraction collected from the nozzle reactor may require pretreatment prior to re-injection into the nozzle reactor. For example, in the case where the heavy hydrocarbon fraction collected has a crumbly, dusty and hard consistency, the heavy hydrocarbon may need to be mixed with another material to put the heavy hydrocarbon fraction in a condition that will allow for transport through the un-cracked material recycle passage and for injection into the nozzle reactor. Any suitable type of material may be used to put the heavy hydrocarbon fraction in a more flowable or injectable condition. In some embodiments, the heavy hydrocarbon material may be mixed with the hydrocarbon material prior to injection into the nozzle reactor. The hydrocarbon material may be in a liquid form at a high température from the séparation process, thereby making the mixture of hydrocarbon material and heavy hydrocarbon fraction flowable and injectable. Other pre-treatment steps, such as pre-heating, may also be preformed on the heavy hydrocarbon fraction where necessary.

In some embodiments, heavy hydrocarbon fraction collected at step 130 may be injected into a second nozzle reactor. The second nozzle reactor may be generally dedicated to processing of the heavy hydrocarbon fraction. The second nozzle reactor may hâve a similar configuration as the nozzle reactor described above, but the second nozzle reactor may be used specifically for receiving the heavy hydrocarbon fraction from the first nozzle reactor and any further heavy hydrocarbon fraction exiting the second nozzle reactor (via the recycle stream). In such embodiments, the collected heavy hydrocarbon fraction may be injected into the second nozzle reactor via a material feed passage or other similar injection passage as described previously with respect to the injection of the heavy hydrocarbon fraction into the first nozzle reactor. In some embodiments, the only hydrocarbon material injected into the second nozzle reactor is heavy hydrocarbon fraction. In other words, no other hydrocarbon material is injected into the second nozzle reactor together with the heavy hydrocarbon fraction.

A cracking material may also be injected into the second nozzle reactor as described in greater detail above with respect to the first nozzle reactor. In some embodiments, the heavy hydrocarbon fraction may be injected into the nozzle reactor at a direction transverse to the direction the cracking material enters the nozzle reactor. The cracking material may be similar or îdentical to the cracking material described above, and in some embodiments, the cracking material includes steam.

The heavy hydrocarbon fraction may be cracked inside of the second nozzle reactor by shockwaves produced by the cracking material injected and expanded into the nozzle reactor. Accordirtgly, the second nozzle reactor may émit cracked hydrocarbons. However, as with the first nozzle reactor, not ail heavy hydrocarbon fractions may be cracked inside of the nozzle reactor. Therefore, the heavy hydrocarbon fraction exiting the nozzle reactor may be collected and re-injected into the second nozzle reactor. Collection of the heavy hydrocarbon fraction exiting the second nozzle reactor may be similar or îdentical to the collection of the heavy hydrocarbon fraction exiting the first nozzle reactor as discussed in greater detail above.

The manner in which the heavy hydrocarbon fraction exiting the second nozzle reactor is re-injected into the second nozzle reactor may be similar to the re-injection of heavy hydrocarbon fraction into the first nozzle reactor as described in greater detail above. For example, the heavy hydrocarbon fraction may be re-injected into the second nozzle reactor via the same material feed passage by which the initial heavy hydrocarbon fraction is injected into the second nozzle reactor or via a separate injection passage provided specifically for re-injection of material that has already been passed through the second nozzle reactor. The heavy hydrocarbon fraction collected from the second nozzle reactor may also be re-injected into the second nozzle reactor together with heavy hydrocarbon fraction collected from the first nozzle reactor, such as by mixing the two heavy hydrocarbon fractions prior to injection into the second nozzle reactor or via sîmultaneous injection through different injection passages.

As with the re-injection of heavy hydrocarbon fraction into the first nozzle reactor, the reinjection of heavy hydrocarbon into the second nozzle reactor may increase the overall concentration and amount of liquid heavy hydrocarbon fraction entering the second nozzle reactor. In this manner, the overall conversion rate of heavy hydrocarbon fraction into lighter hydrocarbon molécules may be increased.

As with heavy hydrocarbon fraction re-injected into the first nozzle reactor, heavy hydrocarbon fraction re-injected into the second nozzle reactor may undergo pretreatment prior to injection into the second nozzle reactor. Such pre-treatment may include heating or cooling the heavy hydrocarbon fraction and mixing the heavy hydrocarbon fraction with a material that may make the heavy hydrocarbon fraction more injectable.

The steps of collecting heavy hydrocarbon fraction exiting the second nozzle reactor and re-injecting the heavy hydrocarbon fraction into the second nozzle reactor may be repeated one or more times în order to reduce or possîbly eliminate the heavy hydrocarbon fraction exiting the second nozzle reactor. In some embodiments, the heavy hydrocarbon fraction exiting the second nozzle reactor may get progressively softer or more liquid-like with each pass through the second nozzle reactor. As described above, applicants believe this to be evidence that the heavy hydrocarbon fraction may eventually be eliminated.

The second nozzle reactor for the recycling of heavy hydrocarbon fraction may be operated at less extreme operatmg conditions than the first nozzle reactor. For example, the second nozzle reactor may be operated at lower températures or a lower steam to oil ratio than the first nozzle reactor. Adjusting the operating conditions of the second nozzle reactor may also maximize the cracking of certain fractions within the solid pitch, such as the resin component of the solid pitch.

With reference to Figure 4, a system 400 for carrying out the method described herein may include a first nozzle reactor 410. The first nozzle reactor 410 may hâve a configuration as shown in Figures 2 and 3 and described in greater detail above. A cracking material stream 420 may be injected into the first nozzle reactor 410 in a direction parallel to the axis of the first nozzle reactor 410. In some embodiments, the cracking material stream 420 includes steam. A hydrocarbon material stream 430 may also be injected into the first nozzle reactor 410. The hydrocarbon material stream 430 may be injected into the first nozzle reactor 410 at a direction transverse to the direction the cracking material stream 420 is injected into the first nozzle reactor, although other directions of injection may be used. In some embodiments, the hydrocarbon material stream 430 may include bitumen. The interaction between the cracking material stream 420 and the hydrocarbon material stream 430 inside the first nozzle reactor 4I0 may resuit in the cracking of some of the hydrocarbon material stream 430 while some of the hydrocarbon material stream 430 may remain un-cracked. Accordingly, a mixture 450 of cracked and un-cracked hydrocarbon material may exit the first nozzle reactor. The mixture 450 may be transported into a séparation unit 460, where the mixture 450 may be separated into a heavy hydrocarbon fraction 470 and a light hydrocarbon product stream 480. The séparation unit 460 may be any suitable séparation unit. The heavy hydrocarbon fraction 470 may include the heaviest hydrocarbon molécules of the hydrocarbon material stream 430 that remain uncracked after passing through the first nozzle reactor. The heavy hydrocarbon fraction 470 may then be recycled back into the first nozzle reactor 410. The heavy hydrocarbon fraction 470 may be re-injected into the first nozzle reactor 410 separate from the hydrocarbon material stream 430 or together with the hydrocarbon material stream 430.

With reference to Figure 5, an alternate embodiment of the system illustrated în Figure 4 may include a first nozzle reactor 4I0 and a second nozzle reactor 510. The heavy hydrocarbon fraction 470 may be injected into the second nozzle reactor 510 rather than re-injecting the heavy hydrocarbon fraction 470 into the first nozzle reactor 4I0. A cracking material stream 520 may also be injected into the second nozzle reactor 510. As with the configuration of first nozzle reactor 4I0, the heavy hydrocarbon fraction 470 may be injected into the second nozzle reactor 510 at a direction transverse to the direction the cracking material stream 520 is injected into the second nozzle reactor 510, although other directions of injection may be used. The mixture 530 of cracked and un-cracked hydrocarbon leavîng the second nozzle reactor 510 may be transported to a séparation unit 540 where the mixture 530 is separated into a heavy hydrocarbon fraction 570 and a light hydrocarbon product stream 580. The heavy hydrocarbon fraction 570 may be recycled back into the second nozzle reactor 510. Re-injection of the heavy hydrocarbon fraction 570 into the second nozzle reactor may be separate from injection of the heavy hydrocarbon fraction 470 into the second nozzle reactor 510 or together with the injection of the heavy hydrocarbon fraction 470 into the second nozzle reactor 510. Additionally, some or ail of the heavy hydrocarbon fraction 570 may be recycled back to and injected into the first nozzle reactor 410.

Examples

Example l

Pure Cold Lake bitumer) having a composition shown in Table 5 below was preheated at rate of 3.1 kg per hour in a sand bath heater to a température of 405°C. The preheated material was then injected into a nozzle reactor as described above and having the dimensions set forth in Table 4. Superheated steam (at a température of 630°C) was also injected into the nozzle reactor at a steam to oil ratio of 1.7. The température at the discharge of the nozzle reactor was 425°C and a reactor rétention time of l .05 seconds was maintained. The nozzle discharge was distilled at about 470°C and resulted in a liquid hydrocarbon product (“distillate, once through”) and solid pitch (“residue, once through”). The solid pitch was reheated at a rate of 3.41 kg per hour at a température of 405° C and re-injected into the nozzle reactor with super heated steam at a steam to oil ratio of 1.7. A reactor température of 430°C and a reaction time 1.02 seconds were maintained. The nozzle discharge was distilled at about 470°C, which resulted in a liquid hydrocarbon product (“distillate, first recycle”) and solid pitch (“residue, first recycle”). The once-recycled pitch was reheated at a rate of 3.64 kg per hour at a température of 409°C, and the reheated once-recycled pitch and superheated steam were injected into the nozzle reactor at a steam to oil ratio of 1.6. The discharge température was 431°C and a reaction time of 1.04 second was maintained. The nozzle discharge was distilled at about 470°C, which resulted in a liquid hydrocarbon product (“distillate, second recycle”) and solid pitch (“residue, second recycle”). Table 6 below summarizes the composition of the various products in terms of the hydrogen-carbon molar ratio.

Nozzle Reactor Component	Size (mm)
Injection Passage, Enlarged Volume Injection Section Diameter	3.0
Injection Passage, Reduced Volume Mid-Section Diameter	1.3
Injection Passage, Enlarged Volume Ejection Section Diameter	2.1
Injection Passage Length	12
Interior Reactor Chamber Injection End Diameter	3.7
Interior Reactor Chamber Ejection End Diameter	24.6
Interior Reactor Chamber Length	128
Overall Nozzle Reactor Length	140
Overall Nozzle Reactor Outside Diameter	260

Table 4

Elemental Composition of Cold Lake Bitumen

C	H	N	O	s	MW (g/mol)
84.0%	10.5%	0.2%	1.0%	4.7%	490

Table 5

	Nozzle Reactor
C	H	S	H/C
Feed		82.6%	10.18%	4.9%	1.43
Residue	Once Through	83.4%	9.8%	4.7%	1.41
	First Recycle	83.9%	9.3%	4.8%	1.33
	Second Recycle	83.4%	9.6%	6.8%	1.38
Distillate	Once Through	83.7%	11.5%	4.2%	1.65
	First Recycle	83.9%	11.8%	3.5%	1.69
	Second Recycle	82.4%	11.3%	3.6%	1.64
Coke	Once Through First Recycle	No coke or other residue produced
	Second Recycle

Table 6

The possible interaction between the steam and the cracked hydrocarbon can illustrated by monitoring the H/C ratios of the reactor feed and reactor products as the recycled pitch

3I r>

continues to be cracked in subséquent passes through the nozzle reactor. The H/C ratios are set forth în Table 7 below.

Parameter	Hydrogen - Carbon Molar Ratio
Once Through	First Recycle	Second Recycle
Feed	l .43	l.4l	1.33
Combined Product	Ï.49	I.45	I.48
% Increase in H/C ratio	4.2%	2.8%	11.3%

Table 7

Table 7 illustrâtes that in ail cases the product has a higher H/C ratio and hence a higher hydrogen content than the corresponding feed. Table 7 also illustrâtes that the hydrogen content could even increases with répétitive recycling.

A small amount of gas was also produced as part of Example l. The gas produced was generally less than a few percent of the feed. If the gas were to be included in the results, the hydrogen pick up in the products will be further demonstrated, since the gas has a much higher hydrogen content than the other two products (liquid and pitch). However, mass balance négative differentials from a 100 wt% will affect hydrogen and carbon overall mass balances driving them to values below 100 wt% for carbon and about 100 wt% for hydrogen.

Example 2

Figures 6A-6C depict the consistency of the pitch collected after each pass through the nozzle reactor in Example I. Figure 6A shows a pitch product that was obtained when only pure

Z'

Coid Lake bitumen was passed through the reactor. At room température the material was a hard and solid product that was readily broken up into small pièces. The pitch obtained after recycling the pitch shown in Figure 6A back through the nozzle reactor according to the process described in Example l is shown in Figure 6B. The pitch product was generally much softer at room température than the pitch shown in Figure 6A. The pitch obtained after recycling the pitch shown in Figure 6B back through the nozzle reactor according to the process described in Example l is shown in Figure 6C. A small amount of pitch was produced. At room température, the pitch shown in Figure 6C had a liquid consistency. Applicants belîeve that one or more recycle steps of the pitch product may have resulted in a total conversion of the hard pitch into liquid product. Other process, such as coking, that is used to reprocess pitch products tend to produce a pitch that becomes very hard and no longer be liquefied (“petroleum coke”).

Example 3

The results obtained in Example l were compared against a staged distillation of Canadian heavy oil through a coking operation as described in a paper by Murray Gray, et al: “Qualîty of Distillâtes from Repeated Recycle of Residue”, Energy & Fuels 2002, 16, 477-484. In the paper the authors présent data on the distillation (coking) at 424°C of Athabasca vacuum residue (+427 deg C material). Details of the coking test procedures and the flow sheet of the experimental plant can be found in this paper.

The results of the staged coking of Athabasca residue as described in the Gray paper are summarized in Table 8 below.

	Coker
C	H	S	H/C
Feed		81.4%	9.6%	5.8%	1.42
Residue	Once Through	83.7%	9.5%	5.0%	1.36
	First Recycle	84.2%	8.2%	5.8%	1.17
	Second Recycle	84.5%	6.6%	6.6%	0.94
Distîllate	Once Through	83,7%	10.6%	4.9%	1.52
	First Recycle	83.3%	9.9%	5.6%	1.43
	Second Recycle	83.9%	9.0%	5.3%	1.29
Coke	Once Through	79.4%	3.1%	6.6%	0.47
	First Recycle	86.9%	3.5%	2.6%	0.48
	Second Recycle	86.4%	3.4%	2.7%	0.47

Table 8

Comparing Table 8 with Table 6 ΐη Example 2, a number of différences between coking and nozzie processing can be identified. It should be noted that while the feed stocks for each process has a different origin, the chemical composition of the two feed materials is substantially similar.

i. The coker distillation step as carried out at 530°C, whereas the nozzie reaction was controlled at a lower température of 430°C.

ii. The results of the once through test for both cases are quite similar if the analyses of both the residue and the distiIlate are compared, although the nozzie reactor produces a somewhat higher quality distîllate.

iii. After the first recycle the coker products are losing hydrogen whereas in the nozzie reactor the presence of steam results in both the residue and the distîllate more or less retaining their hydrogen content relative to the once through case.

iv. The distîllate products from the nozzie reactor hâve a higher H/C ratio than the feed, whereas in the case of coking a significant réduction in the H/C ratio becomes apparent after the second recycle.

v. After the second recycle the residue of the coker tests has little excess hydrogen left and a further recycle is lîkely not possible. The final residue of the nozzle reactor tests has a composition that remains quîte similar to the feed implying that further recycle is very much a possibilîty.

vi. While the coker tests produced a distillate product and a residue for further recycle and a solid residue coke for disposai, the nozzle only produces a liquid product and a recycle residue without any solid disposai material. Furthermore it should be noted that on average a coker converts only up to 65% of its feed into a liquid product. The nozzle reactor on the other hand produces at least 85% liquid product. The remaining 15 % can readily be further processed as the residue will be very liquid as shown in Figure 6C.

Example 4

Example I was carried out several times, and assays were performed on the solid products exîtîng the nozzle reactor to détermine the fraction of the solid product having a boîling point of less than 565°C. The results are summarized below in Table 9.

Process Step	wt-% <5650 in Residue
Distillation	26.7
Once through	34.3
First recycle	42.8
Second recycle	62.8

Table 9

Table 9 illustrâtes that an increase in the amount of material being cracked was achieved by including a nozzle reactor recycle stream for solid pitch. Applicanls believe that this is

ON contrary to the common understanding that recycling solid pitch material will not lead to an increase in the amount of material being cracked.

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 limitîng the scope of the invention. Rather, the scope of the invention is defined by the following ciaims. We therefore claim as our invention all that cornes within the scope and spirit of these ciaims.

Claims (10)

1. What îs claimed is:

   I. A method comprising:

   providing a nozzle reactor, the nozzle reactor comprising:

   a reactor body having a reactor body passage with an injection end and an éjection end;

   a first material injector having a first material injection passage and being mounted in the nozzle reactor in material injecting communication with the injection end of the reactor body, the first material injection passage having (a) an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mîd-section intermediate the enlarged volume injection section and enlarged volume éjection section, (b) a material injection end, and (c) a material éjection end in injecting communication with the reactor body passage; and a second material feed port penetrating the reactor body and being adjacent to the material éjection end of the first material injection passage;

   injecting a stream of cracking material through the first material injector into the reactor body;

   injecting hydrocarbon material through the second material feed port into the reactor body;

   collecting a heavy fraction of hydrocarbons exiting the nozzle reactor; and injecting the heavy fraction of hydrocarbons into the reactor body.

   &
2. 2. The method as recited in claim I, further comprising repeating the steps of collecting a heavy fraction of hydrocarbons exiting the nozzle reactor and injecting the heavy fraction of hydrocarbons into the reactor body one or more fîmes.
3. 3. The method as recited in claim l, wherein the enlarged volume injection section includes a converging central passage section, and the reduced volume mid-section and the enlarged volume éjection section include a diverging central passage section.
4. 4. The method as recited in claim 3, wherein the converging central passage section, the reduced volume mid-section, and the diverging central passage section cooperatively provide a radîally inwardly curved passage side wall intermediate the material injection end and material éjection end in the first material injector.
5. 5. The method as recited in claim l, wherein (a) the reactor body passage has a central rector body axis extending from the injection end to the éjection end of the reactor body passage and (b) the central reactor body axis is coaxial with a first material injection passage axis.
6. 6. The method as recited in claim l, wherein the enlarged volume injection section, reduced volume mid-section, and enlarged volume éjection section in the first material injection passage cooperatively provide a substantially isentropic passage for a first material feed stock through the first material injection passage.
7. 7. The method as recited in claim I, wherein the reactor body passage has a varying cross-sectional area and wherein the cross-sectional area of the reactor body passage either maintains constant or increases between the injection end and the éjection end of the reactor body passage.
8. 8. A method comprising:

   collecting a first nozzle reactor heavy hydrocarbon fraction exiting a first nozzle reactor; providing a second nozzle reactor, the second nozzle reactor comprising:

   a reactor body having a reactor body passage with an injection end and an éjection end;

   a first material injector having a first material injection passage and being mounted in the nozzle reactor in material injecting communication with the injection end of the reactor body, the first material injection passage having (a) an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume éjection section, (b) a material injection end, and (c) a material éjection end in injecting communication with the reactor body passage; and a second material feed port penetrating the reactor body and being adjacent to the material éjection end of the first material injection passage;

   injecting a stream of cracking material through the first material injector into the reactor body;

   injecting the first nozzle reactor heavy hydrocarbon fraction through the second material feed port into the reactor body;

   216337 collecting a second nozzle reactor heavy hydrocarbon fraction exiting the second nozzle reactor; and injecting the second nozzle reactor heavy hydrocarbon fraction into the reactor body.
9. 9. A nozzle reactor comprising:

   a reactor body having a reactor body passage with an injection end and an éjection end;

   a first material înjector having a first material injection passage and being mounted in the nozzle reactor în material injecting communication with the injection end of the reactor body, the first material injection passage having (a) an enlarged volume injection section, an enlarged volume éjection section, and a reduced volume mid-section intermediate the enlarged volume injection section and enlarged volume éjection section, (b) a material injection end, and (c) a material éjection end in injecting communication with the reactor body passage;

   a second material feed port penetrating the reactor body and being adjacent to the material éjection end of the first material injection passage; and an un-cracked material recycle passage having a first end and a second end, wherein the first end is in material receiving communication with the éjection end of the reactor body passage and wherein the second end is in material injecting communication with the reactor body passage at a location adjacent the material éjection end of the first material injection passage.
10. 10, The nozzle reactor as recited in claim 9, wherein the second material feed port penetrating the reactor body is aligned transverse to a first material injection passage axis extending from the material injection end and material éjection end in the first material injection passage în the first material injector.