Patent ID: 12239969

REFERENCE NUMERALS

100. . . nozzle110. . . tip/outlet (for liquid feed)115. . . gap120. . . inner tube130. . . annular space140. . . outer tube150. . . first inlet (for liquid feed)160. . . second inlet (for first fluid)170. . . first intermediate tube175. . . third inlet (for third fluid)180. . . second intermediate tube185. . . fourth inlet (for fourth fluid)R100. . . reactorR110. . . reactor wallR120. . . reactor annular spaceR130. . . fluidizing gas inlet (for second fluid)R140. . . catalyst feed lineDR. . . inside diameter of reactorDO. . . inside diameter of outer tubeDI. . . inside diameter of inner tubeDT. . . inside diameter of tipD′ . . . inside diameter of first intermediate tubeWA. . . width of annular space between inner/outer tubesWR. . . width of annular space between reactor/outer tubeWRI. . . width of inner portion of WRWRO. . . width of outer portion of WR

DETAILED DESCRIPTION

The embodiments described herein should not necessarily be construed as limited to addressing any of the particular problems or deficiencies discussed herein. References in the specification to “one embodiment”, “an embodiment”, “an example embodiment”, “some embodiments”, etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.

As used herein the term “substantially” is used to indicate that exact values are not necessarily attainable. By way of example, one of ordinary skill in the art will understand that in some chemical reactions 100% conversion of a reactant is possible, yet unlikely. Most of a reactant may be converted to a product and conversion of the reactant may asymptotically approach 100% conversion. So, although from a practical perspective 100% of the reactant is converted, from a technical perspective, a small and sometimes difficult to define amount remains. For this example of a chemical reactant, that amount may be relatively easily defined by the detection limits of the instrument used to test for it. However, in many cases, this amount may not be easily defined, hence the use of the term “substantially”. In some embodiments of the present invention, the term “substantially” is defined as approaching a specific numeric value or target to within 20%, 15%, 10%, 5%, or within 1% of the value or target. In further embodiments of the present invention, the term “substantially” is defined as approaching a specific numeric value or target to within 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% of the value or target.

As used herein, the term “about” is used to indicate that exact values are not necessarily attainable. Therefore, the term “about” is used to indicate this uncertainty limit. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ±20%, ±15%, ±10%, ±5%, or ±1% of a specific numeric value or target. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ±1%, ±0.9%, ±0.8%, ±0.7%, ±0.6%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, or ±0.1% of a specific numeric value or target.

Among other things, the present disclosure relates to nozzle designs that reduce or eliminate coking/plugging/fouling during high temperature co-processing of bio-oils with petroleum feedstocks to produce biogenic hydrocarbon fuels and/or chemicals. For example, feeding fast-pyrolysis oil (FP oil) and/or catalytic-fast-pyrolysis oil (CFP oil) into a hot reactor (e.g., ˜550° C. and higher) is challenging, because these oils are reactive and break down inside the nozzles that direct them into high temperature environments (e.g., a DCR). The result is often the formation of coke deposits that ultimately block the nozzle, resulting in reactor downtime and lost production. This problem can be exacerbated at small scale (e.g., pilot scale), because of, for example, large surface-to-volume ratios that increase heat transfer to the oil. Small orifices further increase adhesion forces of particles compared to the hydrodynamic forces created by the fluids flowing through the nozzle. The designs described herein apply to laboratory-scale nozzles, pilot-plant scale nozzles, and commercial-scale nozzles.

FIG.1illustrates an example of a DCR system (i.e., a fluid catalytic cracking (FCC) reactor) for cofeeding CFP oil and vacuum gas oil (VGO), a petroleum feedstock, to produce biogenic hydrocarbons, according to some embodiments of the present disclosure. As shown, the two oils can be co-fed into the DCR using a single nozzle. This can provide better cooling than feeding the two liquids through separate nozzles. However, for this exemplary feed, the CFP oil is in physical and thermal contact with the heated VGO (between about 100° C. and about 150° C.), which, when using incumbent nozzle designs, frequently results in the nozzle plugging. In this configuration, without the design changes and modifications described herein, incumbent nozzles often become plugged after only 10 to 20 minutes on-line. AlthoughFIG.1illustrates a specific FCC reactor, a DCR system, this is for exemplary purposes only. The nozzle designs described herein may provide improved performance and longer on-line times in a variety of other high-temperature reactors, where the reactants directed to reactors are prone to coking/plugging/fouling. For simplicity, the coking-prone liquid, e.g., CFP oil/VGO oil mixture, is referred to herein as the “feed liquid”.

FIG.2Aillustrates an exemplary nozzle100designed to mitigate, if not eliminate, plugging issues, according to some embodiments of the present disclosure. The nozzle100includes a concentric-tube (i.e., concentric-pipe) design constructed of an inner tube120placed concentrically within an outer tube140, with both tubes (120and140) placed concentrically within a reactor tube R110(e.g., a portion of a DCR). The placement of the inner tube120within the outer tube140creates an annular space130. Similarly, the placement of the outer tube140within the reactor wall R110creates a second annular space referred to herein as a “reactor annular space” R120. In addition, the exemplary nozzle100illustrated inFIG.2Aincludes a fourth tube positioned between the reactor wall R110and the outer tube140. This fourth tube is referred to herein a “first intermediate tube” (i.e., “heat shield”). The first intermediate tube170further divides the reactor annular space R120into an inner portion and an outer portion, which inFIG.2A, are indicated with reference numerals R120A and R120B, respectively. As shown below, the division of the internal space within the reactor wall R110creates isolated internal volumes, each with its own dedicated purpose, where the combination of the internal volumes achieves, among other things, continuous, plug-free delivery of the feed liquid into the reactor for long periods of time. Each of these volumes will be referred to herein by their respective spaces illustrated inFIG.2A, e.g., annular space130, inner reactor annular space R120A, and outer reactor annular space R120B, and the internal volume of the inner tube120.

Referring again toFIG.2A, each of the inner tube120, the outer tube140, the first intermediate tube170, and the reactor wall R110may be positioned concentrically and in parallel to each other relative to a reference axis, e.g., the y-axis illustrated inFIG.2A. An inlet150(at Level A on the y-axis of the reactor R100) may be configured to receive and direct the feed liquid (not shown) to the proximal end of the inner tube120. In some embodiments of the present disclosure, a feed liquid (e.g., VGO mixed with CFP oil) may contain a gas (e.g., N2and/or steam), which, among other things, may provide higher fluid velocities through the inner tube. Simultaneously, a first fluid (e.g., steam, nitrogen, etc., not shown) may be directed to an inlet160(also at Level A on the y-axis of the reactor R100), which receives and directs the first fluid into the annular space130, at the proximal ends of the inner tube120and the outer tube140. The feed liquid and the first fluid may then flow in parallel, isolated from each other, thereby preventing undesirable reactions from occurring, until the feed liquid reaches the distal end (i.e., Level C) of the inner tube120, at which point the feed liquid exits the distal end of the inner tube120to mix with the first fluid before the resultant mixture exits the nozzle100at the nozzle tip110(at Level C inFIG.2A).

As illustrated inFIG.2A, in some embodiments of the present disclosure, the distal end of the inner tube120may be positioned slightly below the distal end of the outer tube140in the y-axis direction, resulting in a gap115between the distal end of the inner tube120and the distal end of the outer tube140. Further, in some embodiments of the present disclosure, the wall of the outer tube140may be tapered towards the centerline of the inner tube120, thereby narrowing the annular space130. In some embodiments of the present disclosure, this narrowing can result in the inner wall of the outer tube140approaching the outer wall of the inner tube120. Among other things, this narrowing can reduce the cross-sectional area (CSA) of the annular space130available for fluid flow, resulting in the first fluid achieving a relatively high velocity at the point where it mixes with the feed liquid, immediately before the resultant first fluid/feed liquid mixture exits the nozzle100at the tip110, also at a relatively high velocity.

Referring again toFIG.2A, the combined mixture of the liquid feed (e.g., bio-oil, VGO) and the first fluid exiting the tip110of the nozzle100mixes with another mixture of catalyst originating, in this exemplary case, from a catalyst regenerator (seeFIG.1) and a second fluid stream (e.g., nitrogen). As described above, the exemplary nozzle100includes three concentric tubes (inner tube120, outer tube140, first intermediate tube170) positioned concentrically within another tube and/or pipe, in this example, a portion of a reactor R100itself, e.g., a DCR. Solid catalyst returning from the regenerator is directed through a catalyst feed line R140where, in this example, the solid catalyst is combined and mixed with an up-flowing second fluid, for example nitrogen, which enters the reactor R100at inlet R130(at Level A on the y-axis). The nozzle100, in this example, is positioned concentrically within a section of the reactor R100, where the inner surface of the reactor wall R110and the outer surface of the nozzle's outer tube140form the reactor annular space R120, which as described above, is further divided by the first intermediate tube170(i.e., a heat shield) into an inner portion R120A and an outer portion R120B. The second fluid (e.g., N2) may be directed to the outer portion of the reactor annular space R120B at Level A, where it flows upwards, parallel to the flow of the first fluid flowing through the first annular space130and parallel to the flow of the feed liquid flowing through the inner tube120. At Level B, the second fluid mixes with the regenerated solid catalyst entering through the catalyst feed line R140, such that the solid catalyst becomes entrained and is transported through the inner portion of the reactor annular space R120B, where at Level C, the fluidized catalyst mixes with the mixture of the first fluid and feed liquid exiting the tip110of the nozzle100.

Referring again toFIG.2A, the first intermediate tube170(i.e., heat shield) and the resultant inner portion of the reactor annular space R120A, “shield” the first fluid flowing through the annular space130from the relatively hot fluidized solid catalyst stream. Thus, the first intermediate tube170can reduce, minimize, and/or control heat transfer from the solid catalyst to the first fluid. This, as a result, can reduce, minimize, and/or control heat transfer to the feed liquid flowing through the inner tube120. In other words, the inner portion of the reactor annular space R120A and the first intermediate tube170provide resistances to heat transfer from the hot fluidized solid catalyst flowing through the outer portion of the reactor annular space R120B to the temperature-sensitive feed liquid flowing through the inner tube120.

The arrangement illustrated inFIG.2Acan minimize or eliminate plugging at the nozzle tip110because of several factors. First, referring again toFIG.2A, the nozzle tip110at Level C is positioned at a Height H relative to the point where the catalyst is fluidized by the second fluid, at Level B, where the catalyst enters through the catalyst feed line R140. This height H, among other things, allows the fluidized solid catalyst to develop a defined flow in the outer portion of the reactor annular space R120B by the time it reaches Level C to co-mix with the feed liquid/first fluid mixture exiting the nozzle tip110. A defined flow enables even distribution of the fluidized solid catalyst throughout the cross-sectional area available for flow in the outer portion of the reactor annular space R120B, which in turn, ensures uniform mixing of the fluidized solid catalyst with the mixture exiting the nozzle tip110.

In addition, the height H between Levels B and C enables the feed liquid flowing through the inner tube120to preheat (or cool) to a desired target temperature. For example, the first fluid may include steam entering the reactor R100at inlet160at a temperature that is higher than the feed liquid entering at inlet150, flowing in parallel to the first fluid. As a result, the length of the inner tube120corresponding to H may provide sufficient surface area for the steam flowing through the annular space130to sufficiently heat the feed liquid flowing through the inner tube120to some target metric; e.g., exit temperature, liquid viscosity, liquid surface tension, etc. In some embodiments of the present disclosure, dropping the viscosity of a feed liquid below some maximum allowable viscosity may be important to minimize the pressure drop through the inner tube120and/or the pressure drop occurring at the nozzle tip110, and/or to obtain a desired spray profile and/or droplet size of the feed liquid/first fluid mixture exiting the nozzle tip110. Further, in some embodiments of the present disclosure, a shorter Height H may reduce the heating of the second fluid by the catalyst. This in turn can reduce the heating of the feed liquid by the second fluid.

The nozzle design illustrated inFIG.2Aoffers other advantages regarding heat transfer, which can further reduce or eliminate plugging of the nozzle100by coking-prone liquid feed materials. So, in some embodiments, instead of providing heat to the feed liquid, a first intermediate tube170, i.e., heat shield, and the resultant inner portion of the reactor annular space R120A, may “shield” the first fluid flowing through the annular space130from the relatively hot fluidized solid catalyst stream flowing through the outer portion of the reactor annular space R120B. Thus, the first intermediate tube170can reduce, minimize, and/or control heat transfer from the solid catalyst to the first fluid. This, as a result, can reduce, minimize, and/or control heat transfer to the feed liquid flowing through the inner tube120. In other words, the inner portion of the reactor annular space R120A and the first intermediate tube170provide resistances to heat transfer from the hot fluidized solid catalyst flowing through the outer portion of the reactor annular space R120B to the temperature-sensitive feed liquid flowing through the inner tube120.

Referring again toFIG.2A, another control variable for heat transfer from the hot solid catalyst to the liquid feed may be the introduction of a third fluid (not shown) into the inner portion of the reactor annular space R120A. Thus, in some embodiments of the present disclosure, a third fluid may be directed to the annular space R120A between the outer tube140and the first intermediate tube170at an inlet175positioned at about Level A. The third fluid may then flow through the inner portion of the reactor annular space R120A in parallel with the liquid feed (in the inner tube120), the first fluid (in the annular space130), and the second fluid/catalyst (in the outer portion of the reactor annular space R120B). In some embodiments of the present disclosure, a third fluid may be a heat transfer fluid or coolant. For example, water may be directed to the inner portion of the reactor annular space R120A. In some embodiments of the present disclosure, the distal end of a first intermediate tube170may be closed (seeFIGS.2C and2D), thereby preventing the backflow of material into the inner portion of the reactor annular space R120A. In such a nozzle100, the inner portion of the reactor annular space R120A may be evacuated of all mass (e.g., subjected to a vacuum) and/or filled with an insulating material. In addition, sealing the distal end of the inner portion of a reactor annular space R120A may prevent catalyst from entering that space. In some embodiments of the present disclosure, the inner portion of the reactor annular space R120A may contain stagnant gas or may be evacuated (e.g., maintained at a vacuum that is less than 1 atmosphere) to further insulate against heat conduction/convection across R120A. So, the inner portion of the reactor annular space R120A formed by the first intermediate tube170may provide a number of ways to control the heat transfer from the hot catalyst to the feed liquid, both by active heat transfer using a heat transfer fluid and/or passively by the addition of resistance(s) to heat transfer by the use of insulation or vacuum.

FIG.2Billustrates a cross-sectional view of the reactor R100and nozzle100shown inFIG.2Aand calls out a number of inside diameters of the elements described above: DI=inside diameter of the inner tube120; DO=inside diameter of the outer tube140; D′=inside diameter of the first intermediate tube170; and DR=inside diameter of the reactor wall R110. Among other design variables, these diameters may be important for the reliable operation of the nozzles100described herein, especially plug-free operation for extended periods of time; e.g., from days to months. Some of these design variables are summarized in Table 1 for an exemplary pilot-scale reactor and for scale-up to larger reactors in Table 3. Dimensions for the pilot-scale reactor are provided in Table 2. BothFIGS.2A and2Billustrate the various tubes with circular cross-sectional shapes. However, other cross-sectional shapes fall within the scope of the present disclosure; e.g. elliptical, square, triangular, etc.

TABLE 1Pilot-Scale Nozzle Design VariablesDesign VariableUnitsminmaxResidence time in inner tube 120[s]0.020.2Velocity in inner tube 120[m/s]120Reynolds number in inner tube 120[−]103000Heat transfer through inner[W/mm2]0.020.3tube 120Heat transfer to steam/N2[W/mm20.010.12(first gas in 130) and feedouter tubeliquid with N2(in 120)inner area]Residence time in annular[s]0.11space 130Velocity in annular space 130[m/s]0.210(for narrowest portion ofouter tubes havingvarying inside diameter)Reynolds number in annular space[−]103000130 (for widest portionof outer tubes havingvarying inside diameter)CFP Oil in Oil mixture[vol %]120Velocity at tip/outlet (combined[m/s]10100stream/mass exiting at tip 110)Reynolds number at tip/outlet[−]50010000(combined stream/massexiting at tip 110)Ratio of flow rate first fluid (e.g.,[−]110steam) in annular space130/combined flow rate(liquid feed + N2) innertube 120Ratio of outer tube ID/[−]DO/DI1.210inner tube IDRatio of annular space[−]WR/DR0.050.3130 inside risertube R120 (WR)/reactor ID (DR)Ratio of inner tube 120 ID[−]DI/LI1001000DI/Innertube length(level C-level A) (H in FIG. 2A)Ratio of orifice ID DT/[−]DT/DO0.10.5outer tube ID DOIntermediate tube 170 ID/[−]1.051.2outer tube IDOuter portion annulus R120B,[−]WA/WRO0.33WRO/inner portion annulusR120A, WRILength of unshielded section[−]U/H0.11U/nozzle length H

TABLE 2Pilot-Scale Nozzle Dimensions (all in cm)DimensionValueH2.5DT0.1DR0.94DO0.53DI0.11WA0.19WR0.15

TABLE 3Scale-Up Nozzle Design VariablesDesign VariableUnitsminmaxResidence time in inner[s]0.014tube 120Velocity in inner tube 120[m/s]0.1100Reynolds number in inner[−]120000tube 120Heat transfer through inner[W/mm2]0.011tube 120Heat transfer to steam/N2[W/mm2 outer01(first gas in 130) and feedtube inner area]liquid with N2(in 120)Residence time in annular[s]0.0110space 130Velocity in annular space 130[m/s]0.130(for narrowest portion of outertubes having varyinginside diameter)Reynolds number in annular[−]120000space 130 (for widest portionof outer tubes havingvarying inside diameter)CFP Oil in Oil mixture[vol %]0.1100Velocity at tip/outlet[m/s]4200(combined stream/mass exiting at tip 110)Reynolds number at tip/[−]20020000outlet (combinedstream/mass exiting at tip 110)Ratio of flow rate first fluid[−]0.130(e.g., steam) in annular space130/combinedflow rate (liquidfeed + N2) inner tube 120Ratio of outer tube ID/[−]DO/DI1.120inner tube IDRatio of annular space 130[−]WR/DR0.020.5inside riser tube R120(WR)/reactor ID (DR)5Ratio of inner tube 120 ID[−]DI/LI55000DI/Inner tube length (levelC-level A) (H in FIG. 2A)Ratio of orifice ID[−]DT/DO0.011DT/outer tube ID DOIntermediate tube 170[−]1.012D′ ID/outertube IDOuter portion annulus R120B,[−]WA/WRO0.110WRO/inner portionannulus R120A, WRILength of unshielded section[−]U/H0100U/nozzle length H

Referring again toFIG.2B, in some embodiments of the present disclosure, the inner tube120has an inside diameter DIand the outer tube140has an inside diameter DO, such that a ratio of DOto DImay be between about 1.1 and about 20. In some embodiments of the present disclosure, the tip110may have an inside diameter DT(not shown), such that a ratio of DTto DOmay be between about 0.01 and about 1.0. In some embodiments of the present disclosure, the annular space130may be configured so that the first fluid may have a velocity between about 0.1 m/s and about 30 m/s. In some embodiments of the present disclosure, DImay be configured so that the fluid may have a velocity between about 0.1 m/s and about 100 m/s. In some embodiments of the present disclosure, DTmay be configured so that the combination of the liquid feed (e.g., CFP oil/VGO) and the first fluid may have a velocity between about 4 m/s and about 200 m/s. In some embodiments of the present disclosure, the annular space130may be configured so that the first fluid may have a Reynolds number between about 1 and about 20,000. In some embodiments of the present disclosure, a ratio of DIto H (Level C-Level B) may be between about 5 and about 5,000.

Referring toFIGS.2C and2D, these figures illustrate differences in the height of the first intermediate tube170relative to the catalyst feed line R140and the tip110. Referring toFIG.2C, in some embodiments of the present disclosure, a first intermediate tube170may extend from the proximal end (not shown) of the inner tube120to the point where the catalyst is directed into the reactor R100to the level of the catalyst feed line R140(Level B). In this case, the first intermediate tube170does not obstruct the flow path of the catalyst. Referring toFIG.2D, in some embodiments of the present disclosure, a first intermediate tube170may extend from the proximal end (not shown) of the inner tube120to just below the tip110of the nozzle100; e.g., approximately at Level C. This design maximizes the amount of insulation/cooling provided to the nozzle by the first intermediate tube170.

The tips110illustrated inFIGS.2A,2C, and2Deach have a taper in the wall of the outer tube140. Among other things, such a tapered tip design may provide a longer narrow passage for the first gas at the nozzle tip110, which may result in higher pressure drops in the annular space130near the distal end of the inner tube120, which subsequently may prevent backflow of liquid from the nozzle tip to the annular space130. Backflow may result, for example, from fluctuating reactor pressures. Further, referring toFIG.2F, a reduced width of annular space130, near the distal end of the inner tube120, has been introduced, thereby increasing the fluid velocity of the first fluid flowing through the annular space130. This design may provide a larger fluid velocity and pressure drop for a given flow rate, due to the length of the restriction and help with atomization in the nozzle tip. The annular space may further contain a mechanical insert that increases the velocity and/or creates a swirl, such as channels or holes aligned at angles other than 0 degrees with the axis of the inner tube120(FIG.3). Further, the exemplary nozzle tips110shown in each ofFIGS.2A,2C,2D, and2Einclude an inner tube120with a distal end that is cut at about a 90 degree angle relative to the y-axis of the inner tube. As shown inFIG.3, in some embodiments of the present disclosure, the distal end of an inner tube120may be cut at an angle, i.e., cut at an angle other than 90 degrees, for example between 90 degrees and 30 degrees. In some embodiments of the present disclosure, the inner tube120may be narrower in inner diameter at the distal end compared to the remaining length (seeFIG.2F). This will increase the velocity and pressure drop near the tip, but reduce the pressure drop in the remaining section, resulting in an overall lower pressure drop compared to a straight tube. Referring again toFIG.2F, in some embodiments of the present disclosure, an inner portion of the reactor annular space R120A may be utilized to provide a coolant supply and return. For example, a coolant may be provided to the reactor annular space may include water, steam, and glycol-based, organic, inorganic heat transfer fluids, or combinations thereof.

FIG.2Eillustrates another nozzle design, according to some embodiments of the present disclosure. This exemplary nozzle100is similar to the nozzles100illustrated inFIGS.2A,2C, and2D but adds an additional element, a second intermediate tube180positioned in the annular space130between the outer wall of the inner tube120and the inner wall of the outer tube140. A second intermediate tube180, therefore, divides the annular space130into an inner portion130A and an outer portion130B. Among other things, the inner portion of the annular space130A may receive a fourth fluid (not shown) through a fourth inlet185positioned towards the proximal end of the inner tube120. This design may be advantageous when two non-miscible feed liquids are to be used, in which case one liquid may be introduced to the reactor via the inner tube120, while the second liquid may be directed to the reactor through the inner annular space130A. Thus, among other things, the second liquid may provide a heat barrier so that the first liquid may be maintained at a relatively cooler temperature; the inside wall of tube120will be maintained at a colder temperature due to the second intermediate tube180and/or a fourth liquid flowing the inner portion of the annular space130A created by the addition of the second intermediate tube180.

FIG.2Gillustrates an example of a nozzle100having a slightly different tip110. In this example, the taper of the inner wall of the outer tube140is not linear but instead has some curvature. Among other things, such curvature may provide a venturi effect to help sweep the liquid feed, etc., through the nozzle tip110.

Referring again toFIG.2A, in some embodiments of the present disclosure, one or more of the tubes shown (e.g., R110,170,140, and/or120) may include a section that has a thicker wall, such that the cross-sectional area of the corresponding annular space (e.g.,130, R120B) is reduced. Like reducing the nozzle tip110, such a restriction can increase the local fluid velocity, which can in turn, among other things, minimize the back-mixing of streams, provide higher or lower local heat-transfer coefficients, etc.

Experimental:

An “incumbent nozzle” design was compared to a nozzle, referred to below as a “modified nozzle”, according to some embodiments of the present disclosure.FIG.2Cillustrates the basic design used for the modified nozzle, whereas the incumbent nozzle did not include a first intermediate tube170(i.e., heat shield). The incumbent nozzle100was constructed of a 1/16-inch stainless-steel inner tube120positioned within a ¼-inch stainless-steel outer tube140. The inner diameters of the inner and outer tubes were 0.0305 inch and 0.18 inch (RIand RO), respectively. The nozzle tip110was located 8 inches (H) above the catalyst feed line R140. The liquid feed (e.g., oil blend of bio-oil and VGO) and nitrogen were directed to the inner tube120, and steam and nitrogen (i.e., first gas) directed to the annular space130between the inner and outer tubes. The reactor tube was approximately ½ inch in diameter. The horizontal catalyst feed line was approximately ⅜ inch in diameter. In both instances, N2was mainly used as a purge to keep pressure tap lines clean, which are used for example, to differential pressure for estimating flow rates. A small stream of N2prevents either liquid feed or steam from flowing toward the pressure instruments (gauges and transducers). Additionally, as the N2was at a higher pressure than the reactor, the increased pressure may further assist the fluids (liquid feed, steam) to flow towards the reactor.

The modified nozzle was modified to include the following: Length (H): The position of the nozzle tip110relative to the catalyst feed line R140was reduced from 8 inches above the catalyst feed line to 1 inch. This reduced the length of the inner and outer tube and the amount of heat transfer occurring from the hot catalyst to the liquid feed (a mixture of 5 vol % CFP oil/95 vol % VGO). Materials of construction: The original stainless steel of the 1/16-inch inner tube and the ¼-inch outer tube were both replaced with titanium. Titanium has less catalytic activity than stainless steel. Steel can promote unwanted surface reactions of the CFP oil. The inner diameters of the inner and outer tubes were increased to 0.0428 inch and 0.21 inch, respectively.

Referring again toFIG.2C, a modified nozzle100was constructed using a ¼-inch outer diameter tube140with 0.035-inch wall thickness surrounded by a 5/16-inch outer diameter stainless-steel first intermediate tube170with an inner diameter, D′, of 0.281 inch. The distal end of the intermediate tube170was crimped, but not completely plugged, to minimize the backflow of solid catalyst from the second portion of the reactor annular space R120B into the first portion of the reactor annular space R120A. In this exemplary nozzle100, the first intermediate tube170reduced heat transfer from the catalyst to the steam and nitrogen (i.e., first fluid) flowing through the annular space130, which in turn reduced heat transfer to the liquid feed/nitrogen mixture flowing through the inner tube120. Another purpose of the first intermediate tube170was to narrow the reactor annular gap R120A between the first intermediate tube170and the reactor wall R110. This increased the velocity of the fluidizing nitrogen (introduced at the bottom of the outer reactor annular gap R120B), resulting in less of the solid catalyst circulating into the annular gap R120B. This resulted in an oil mixture flowing through a larger section of the inner tube120, i.e., a larger percentage of the nozzle length, H, that was thermally uninsulated by the first intermediate tube170and not actively cooled by the first fluid (e.g., heat transfer fluid) flowing through the inner reactor annular space R120A, and instead being heated by the hot catalyst flowing through the outer reactor annular space R120B. Additional narrowing of the reactor annular space R120B may be achieved by a mechanical insert with channels or holes through which the second fluid is directed, increasing its velocity. The channels or holes may be arranged at angles other than zero with the inner tube120to create a swirling motion of the flow.FIG.5Bshows that this configuration, based on computational fluid dynamic calculations, results in a lower heat transfer to the intermediate tube170(60 W versus 90 W inFIG.5A). Experimentally, this was confirmed by a lower surface temperature of the outside reactor wall (T1=453° C. inFIG.5Bversus T1=488° C. inFIG.5A). As stated above, one reason for exposing the feed liquid flowing through the inner tube120may be to increase its temperature to attain a target fluid viscosity, as long as it does not excessively increase its temperature, which can lead to coking.

Table 4 shows the results of six coprocessing tests (5 vol % CFP oil with 95 vol % VGO). Plugging was measured by feed pressure changes during co-processing: when the feed pressure reached 47 psig, a test was ended. One baseline test was conducted with the incumbent nozzle and five tests were conducted with the modified nozzle (as shown inFIG.2Awith a heat shield). The initial feed pressures were recorded after starting to co-process CFP oil and VGO. In the case of the incumbent nozzle, the initial feed pressure was higher since the inner tube120was longer and had a smaller inner diameter. The reactor pressure downstream of the nozzle tip110was about 25 psig.FIG.4illustrates the results of the feed pressure over time. For the modified nozzle, the data was time-averaged over the five tests. The run times were significantly longer using the modified nozzle compared to the incumbent nozzle, and they approached steady-state operation of the DCR. All tests, both incumbent and modified nozzles, were conducted with a 1/16-inch inner tube120, and the pressures for the incumbent nozzle started to increase after a very short time, but the rate of pressure increase was significantly slower for the modified nozzle relative to the incumbent nozzle.

TABLE 4Results of co-processing CFP oil with VGOusing incumbent and modified nozzlesTime of co-Initialprocessing untilAveragefeed47 psig (frompressurepressureplugging)increaseNozzle type[psig][min][psi/min]Incumbent nozzle3761.67Modified nozzle-run 129260.69Modified nozzle-run 229620.29Modified nozzle-run 329280.64Modified nozzle-run 428580.33Modified nozzle-run 528650.29

Additional nozzle modifications are under development that have not yet been tested. These modifications include: Feeding bio-oil with a 1/16-inch outer diameter (0.010-inch wall thickness) tube120inside a ⅛-inch outer diameter (0.015-inch wall thickness) for VGO (seeFIG.2E). This configuration may, among other things, reduce the temperature of the CFP oil further while preventing direct contact of CFP oil with VGO. In some embodiments of the present disclosure, as described above, vacuum insulation and/or physical insulation (e.g., a ceramic) may be positioned within at least a portion of the outer portion of the reactor annular gap R120A created by the intermediate tube170, as shown inFIG.2A. Among other things, the use of insulation in the inner portion of the reactor annular space R120A may reduce heat transfer to the oil mixture flowing through the inner tube120and may further prevent the entrainment of fluid and dust into the inner portion of the reactor annular space R120A. In some embodiments of the present disclosure, the inner portion of the reactor annular space R120A may be configured to receive a heat-transfer fluid to “actively” cool at least one of the following: the oil mixture flowing through the inner tube120and/or the first fluid flowing through annular space130and/or the solid catalyst and/or second gas flowing through the outer portion of the reactor annular space R120B. In some embodiments of the present disclosure, a heat-transfer fluid may include liquid water, such that at least a portion of the water is vaporized. By feeding water at a precise rate, the evaporation into steam below the nozzle tip may provide extra cooling and prevent heating the oil mixture stream. A pressure feed-back control loop (based on the pressure as well as fluctuation of the pressure, i.e., standard deviation) may be used to determine the required water feed rate.

For longer nozzles, the outside of the outer tube140may be cooled by high-pressure circulating water or oil. Referring toFIG.2F, the inner portion of the reactor annular space R120A may be further divided into a coolant supply line and a coolant return line. In some embodiments of the present disclosure, this type of arrangement may keep the steam cooler, which in turn will keep the liquid feed colder. By adding an additional concentric tube inside the annular gap R120A, water may be guided along the inside gap, cooling the outside of tube140and then flowing back in the outer region of gap R120A. In some embodiments of the present disclosure, generating a micro-emulsion between CFP oil and VGO at the mixing point may prevent the CFP oil from accumulating on the hot surfaces inside the inner tube120. A micro-emulsion may be created by high-shear mixing or the use of ultra-sonic waves.

For long operating times, plugging of the nozzle tip110may be prevented by a metal-alloy rod/wire that is inserted into the inner tube120and that can be mechanically forced through the nozzle tip110for a very short time and immediately retracted thereafter back into the inner tube120. The diameter of the rod/wire must be slightly smaller than the opening of the nozzle tip110, and significantly smaller than the inner diameter of the inner tube120, as not to block the liquid flow in the inner tube120.

The foregoing discussion and examples have been presented for purposes of illustration and description. The foregoing is not intended to limit the aspects, embodiments, or configurations to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the aspects, embodiments, or configurations are grouped together in one or more embodiments, configurations, or aspects for the purpose of streamlining the disclosure. The features of the aspects, embodiments, or configurations, may be combined in alternate aspects, embodiments, or configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the aspects, embodiments, or configurations require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment, configuration, or aspect. While certain aspects of conventional technology have been discussed to facilitate disclosure of some embodiments of the present invention, the Applicants in no way disclaim these technical aspects, and it is contemplated that the claimed invention may encompass one or more of the conventional technical aspects discussed herein. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate aspect, embodiment, or configuration.