Process for converting pyrolysis oils, waxes and / or oligomers to higher value chemicals

Abstract

A process for converting pyrolysis oil, wax and / or oligomer to higher value products is performed in a reactor system that includes a central axis, a feed assembly, and a reactor vessel defining a reaction chamber. A fuel gas feed and an oxidant gas feed are introduced into the inlet assembly in a swirling fluid flow pattern that combust to form a swirling combustion gas. A hydrocarbon gas and a hydrocarbon reactant feed comprising liquid hydrocarbons of pyrolytic oil, wax and / or oligomer are introduced into the inlet assembly. The liquid feed is introduced as a liquid mist or spray in a flow pattern that is not perpendicular to the central axis. A hydrocarbon feed is mixed with the swirling combustion gas to form a swirling heated mixture, which is passed to the reaction chamber to react to form a converted hydrocarbon product.

Description

Cross Reference to Related Applications

[0001] This application claims priority to each of European Patent Application No. 23187528.7, filed July 25, 2023, European Patent Application No. 23187529.5, filed July 25, 2023, European Patent Application No. 23187530.3, filed July 25, 2023, European Patent Application No. 23196604.5, filed September 11, 2023, and Indian Patent Application No. 202341050195, filed July 25, 2023, the entire contents of each of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present disclosure relates to the production of high value chemical products from pyrolysis oil, particularly those from plastic waste, and waxes and / or oligomers. BACKGROUND

[0003] In recent decades, the production of plastics has increased significantly, with an estimated 400 million tons produced each year. Unfortunately, only a small fraction of these plastic waste materials are recycled.

[0004] The problem of plastic waste is complex and multi-faceted and requires a comprehensive solution. While mechanical recycling of plastics has been ongoing, recycling efforts have only had limited success. Only certain types of plastics can be mechanically recycled and even those that can be recycled must be sorted into their different types due to their chemical differences, which requires different processing conditions. Sorting and processing these different plastics can be very expensive. The quality of the mechanically processed is lower than the original plastic formed by polymerization, in which the plastic waste is cleaned and shredded into small pellets or flakes, which are then melted and reformed into a new product. This is due to the degradation of the polymer chains of the reformed plastic. Additionally, residual contaminants can still be present in the reformed plastic, affecting its overall quality.

[0005] One promising solution is to convert plastic waste through chemical processes. This can eliminate the need to sort recycled plastics into their different types. Plastics that are generally not mechanically processable can also be converted using chemical processes. Such mixed plastic waste (MPW) can be converted into valuable chemicals, such as ethylene, propylene, and other olefins and aromatic compounds, using these chemical processes. These chemicals are building blocks for many plastics and other products and can be used as feedstocks for producing new or virgin plastics or other materials.

[0006] This conversion of mixed plastic waste into valuable chemicals provides a promising solution for the manufacture of circular products that can significantly reduce the environmental impact of plastic waste, while also creating value from previously discarded resources.

[0007] A method of processing mixed plastic waste to make it useful for forming more valuable products involves converting the MPW into pyrolysis oil (pyoil) by pyrolysis. Pyrolysis is a thermal decomposition process that involves heating mixed plastic waste in the absence of oxygen, causing the plastics to break down into smaller molecules. The process produces gases and vapors that are then condensed into liquid form to produce pyrolysis oil. Producing pyrolysis oil from plastic waste emits fewer greenhouse gases than incineration.

[0008] In chemical processing, steam cracking is commonly used to convert pyrolysis oil into more valuable products such as ethylene, propylene, and aromatics. However, before the pyrolysis oil can undergo steam cracking, it must first be pre-processed in multiple operating units. This can include distillation, such that only the lighter fractions of the pyrolysis oil are cracked. In addition, pyrolysis oil from MPW typically contains 50% or more unsaturated hydrocarbons. These unsaturated hydrocarbons can cause coking during the steam cracking process, which can decrease process efficiency and cause equipment fouling. As a result, the pyrolysis oil can be hydrogenated in a hydrotreater or undergo other processing steps prior to steam cracking. This requires the addition of hydrogen gas, additional process steps, and additional processing units, increasing the cost and complexity of converting the pyrolysis oil. In addition, even if the pyrolysis oil is hydrogenated, there is still a possibility of coking occurring during steam cracking.

[0009] Accordingly, there is a need for a method of utilizing pyrolysis oil from mixed plastic waste that overcomes these drawbacks to produce more valuable products or chemicals. SUMMARY

[0010] A method of converting pyrolysis oil, wax, and / or oligomers into higher value products is conducted in a reactor system comprising a central axis, a feed assembly, and a reactor vessel defining a reaction chamber. A fuel gas feed and an oxidant gas feed are introduced into the feed assembly to produce a swirling fluid flow pattern about the central axis. The fuel gas feed and the oxidant gas feed are combusted in the feed assembly to form a swirling combustion gas. A hydrocarbon reactant feed comprising at least one of (i) a plastic waste-derived pyrolysis oil, (ii) a wax, and (iii) an oligomer having an average molecular weight (Mn) of 1,000 g / mol to 50,000 g / mol is introduced into the feed assembly. The liquid hydrocarbon has a dynamic viscosity of 0.1 cP to 1000 cP and is introduced into the feed assembly as a liquid spray having a Sauter Mean Diameter (SMD) of 1 pm to 250 pm. The hydrocarbon reactant feed is mixed with the swirling combustion gas to form a swirling heated mixture. The heated mixture is passed into the reaction chamber and reacted within the reaction chamber under reaction conditions suitable for converting hydrocarbons of the hydrocarbon reactant feed into a converted hydrocarbon product. The converted hydrocarbon product is removed from the reaction chamber.

[0011] In certain embodiments, the pyrolysis oil can be a non-hydrogenated pyrolysis oil. The pyrolysis oil can be those derived from pyrolyzing mixed plastic waste materials. In some cases, the pyrolysis oil can have a boiling point range of 75 °C to 650 °C, and in other cases, the pyrolysis oil can be a pyrolysis oil fraction having a boiling point range of 75 °C to 500 °C.

[0012] The oligomers and waxes can be those derived from plastic waste materials and / or byproducts of polymerization processes. The oligomers can have an average molecular weight (Mn) of 2,000 g / mol to 10,000 g / mol.

[0013] The liquid hydrocarbons can comprise 0.5 wt% to 100 wt% of the hydrocarbon reactant feed. The liquid hydrocarbons can be introduced through the liquid feed inlet of the feed assembly in a flow pattern that is not normal to the central axis. In particular embodiments, the liquid spray can be introduced through a two-fluid spray nozzle as a two-fluid spray such that the liquid hydrocarbons are introduced through the two-fluid spray nozzle with a second fluid. The second fluid introduced through the two-fluid spray nozzle can be a gas. The liquid spray can be introduced at a spray angle of 40° or less.

[0014] The hydrocarbon reactant feed can further comprise gaseous hydrocarbons. The converted hydrocarbon product can comprise at least one of olefins, C2to C6olefins, ethylene, propylene, butylene, acetylene, C3to C6acetylenes, butadiene, aromatics, xylene, benzene, toluene, and ethylbenzene. BRIEF DESCRIPTION OF DRAWINGS

[0015] For a more complete understanding of the embodiments described herein, and for further advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which: Figure 1 is an elevation cross-sectional view of a reactor system for converting liquid plastic waste-derived pyrolysis oil, waxes, and oligomers according to various embodiments of the present disclosure; Figure 2 is a perspective view of a feed assembly of the reactor system of Figure 1 Figure 3 is a cross-sectional perspective view of the feed assembly and the upstream end of the reaction chamber of Figure 1 Figure 4 is a plot of vaporization time as a function of droplet size using simplified calculations at approximate conditions in a reactor system such as Figure 1 Figure 5 is a plot of computational fluid dynamics (CFD) calculations showing spray evaporation in a reactor such as Figure 1 the reactor of​​​ Figure 6 FLOWMAX using liquid water and air ® Graph of test results for FM3A dual fluid nozzle showing various droplet sizes under various flow conditions; and Figure 7 Graph of selectivity in weight percent for light olefins and aromatics from full range pyrolysis oil or polybutadiene oligomers in an ANJEVOC reactor. DETAILED DESCRIPTION

[0016] In various embodiments of the present disclosure, pyrolysis oil from mixed plastic waste (MPW), waxes, and / or oligomers is converted to high value chemicals, such as light olefins and aromatics, using unique reactor technology. The pyrolysis oil can be full range pyrolysis oil or various fractions of pyrolysis oil resulting from pyrolysis of MPW. The waxes and / or oligomers can be those obtained from fractionation of plastic waste pyrolysis oil, or can be waxes and / or oligomers obtained from other sources, such as byproducts resulting from polymerization processes. In contrast to conventional steam cracking processing systems for processing pyrolysis oil, which require additional processing steps, conversion of these materials can be accomplished in a single processing step, or with reduced or minimal processing steps and equipment. More specifically, conversion can be achieved by utilizing ANJEVOC (annular jet vortex chamber) reactor technology, which produces an annular, highly swirling jet of feed gas, with hydrogen (or other fuels, such as natural gas, recycled syngas, etc.) and oxygen primarily used to generate the heat needed for hydrocarbon cracking. Examples of such ANJEVOC reactors are described in U.S. Patent Nos. 11,020,719 and 11,123,705; and International Publication Nos. WO2022 / 010821 Al; WO2022 / 010822 Al; and WO2022 / 010823 Al, each of which is incorporated by reference herein in its entirety for all purposes, including the purpose of exemplifying the configuration, construction, and operation of such ANJEVOC reactors and various components thereof.

[0017] The following includes definitions of various terms and phrases used throughout this specification.

[0018] For the purposes of the present disclosure, if a numerical value, concentration, or range is given, each numerical value should be interpreted as being modified by the term "about" once (unless otherwise explicitly indicated) and then interpreted again as not being so modified (unless otherwise explicitly indicated) unless otherwise indicated in context. Moreover, in the description, it is to be understood that the numerical ranges recited are intended to include any and every value within the range, including the end points, unless otherwise indicated. For example, "a range from 1 to 10" should be interpreted to mean each and every possible number along the continuum between the tens, one and ten. Thus, even though a particular number within the range, or an individual number outside the range, can not have been explicitly recited, these are to be interpreted as described above, and the inventors retain the right to set the boundaries of the range.

[0019] The term "about" or "approximately" is defined as nearly about as would be understood by one of ordinary skill in the art. In one non-limiting embodiment, the term is defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0020] For the purposes of the present disclosure, "X, Y, and / or Z" can be interpreted to mean X alone, Y alone, Z alone, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ). Similarly, "at least one of X, Y, and Z" can be interpreted to mean X alone, Y alone, Z alone, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ).

[0021] The use of the words "a" or "an" when used in a claim or specification means "one," but it is also consistent with the meaning of "one or more."

[0022] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0023] ReferenceFigure 1 A front cross-sectional view of a reactor system 10 for converting liquid hydrocarbons is shown. The reactor system 10 is configured for converting liquid hydrocarbons in the form of pyrolysis oil and wax and / or oligomers, which can be produced from the pyrolysis of plastic waste such as MPW or from other sources. The reactor system 10 can also be used to convert gaseous hydrocarbons along with liquid hydrocarbons. The reactor system 10 can constitute an ANJEVOC reactor and includes a reactor vessel 12 having a reactor wall 14 that defines an interior reaction chamber 16. The reactor wall 14 can have a cylindrical configuration with a constant diameter along all or a portion of its length, which can constitute a majority of its length (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%). In most cases, the reactor vessel 12 is oriented vertically so that the cylindrical reactor wall 14 is oriented with an upright orientation with downward flow. However, the reactor can have other orientations (e.g., horizontal, inclined, or upright with upward flow) as the process is governed by centrifugal forces that are orders of magnitude greater than gravity. The reactor vessel 12 can be configured to provide a length to diameter ratio (L / D) of at least 2. In particular applications, the L / D ratio can be in the range of 2 to 10, more particularly 2 to 5.

[0024] The reactor vessel 12 can be formed from steel. In certain embodiments, a cooling jacket can be provided around all or a portion of the reactor vessel 12, with a second steel wall 18 positioned around and spaced apart from the interior reactor wall 14, and a cooling fluid, such as water, can be circulated through the jacket formed between the walls 14, 18. In other embodiments, the reactor wall 14 can be formed from one or more layers of refractory material lined on the interior of the outer steel wall to reduce heat loss and maintain the high temperature of the reactor 10. Due to the unique design and operation of the reactor 10, the reactor wall 14 is cooled internally by high velocity near wall gas flow that is pushed against the reactor wall 14 by centrifugal forces such that an external cooling jacket is not required in some applications. This also allows for refractory material to be used on the interior of the reactor wall 14. Due to the higher temperatures (e.g., 2000°C to 2800°C), refractory materials (without cooling) are generally not used with conventional cracking reactors with pure oxygen. The reaction temperature for converting liquid hydrocarbons, such as crude oil, in the reactor system 10 is generally in the range of 800°C to 2500°C.

[0025] An outlet 20 is provided at the lower or downstream end of the reactor vessel 12 for removing or discharging the cracking products from the reaction chamber 16. The outlet diameter can be the same as the diameter of the reactor wall 14, or the outlet diameter can be reduced to accelerate the flow prior to quenching and downstream collection.

[0026] The reactor 10 includes a reactor inlet assembly 22 coupled or joined to an upper or upstream end of the reactor wall 14 of the reactor vessel 12. Here, the reactor vessel 12 is vertically oriented with the inlet assembly 22 located above the reactor vessel 12. This causes any downstream liquid quench fluid (e.g., water) used to quench the reaction gases within the reaction chamber 16 to be carried by gravity to the outlet 20 rather than toward the upstream end toward the inlet assembly 22.

[0027] The inlet assembly 22 defines a converging-diverging conduit 24 defined by a circumferential wall 26 about a central axis 28 of the reactor 10. The central axis 28 of the reactor 10 can be the same or coincident with the central axis of each of the inlet assembly 22 or conduit 24 and the reactor vessel 12. The circumferential wall 26 extends from opposite upstream and downstream ends of the converging-diverging conduit 24. As used herein, the terms “upstream” and “downstream” or similar expressions in relation to describing various components of the reactor system 10 shall refer to the position of the components relative to the overall direction of fluid flow through the reactor 10 along the central axis 28.

[0028] As can be seen from Figure 1 the width or diameter of the circumferential wall 26 smoothly tapers from the upstream end to define an annular constricted neck portion located between the downstream and upstream ends of the converging-diverging conduit 24. At the annular constricted neck portion, where the circumferential wall 26 of the conduit 24 transitions from converging or narrowing to diverging or widening, the circumferential wall 26 smoothly expands or diverges in width or diameter downstream of the annular constricted neck portion. The interior of the circumferential wall 26 along all or a portion of its length can have a circular perpendicular transverse cross-section relative to the central axis 28. The circumferential wall 26 defines an interior flow path of the feed assembly 32, with the constricted neck portion being part of the smoothly curved and streamlined converging-diverging nozzle of the inlet assembly 22.

[0029] The nozzle geometry of the convergent-divergent conduit 24 is constructed based on theories related to swirling conical jets of viscous, incompressible fluids. This phenomenon is described in the journal article “Novel Annular Jet Vortex Reactor for High-Temperature Thermochemical Conversion of Hydrocarbons to Acetylene” published in ACS Engineering in 2022 (Pannala, S. et al., ACS Engineering, 2022, Vol. 2, No. 5, pp. 406-420). The downstream or divergent portion of the conduit 24 is configured for non-supersonic fluid flow. Conduits or nozzles configured for supersonic flow, such as Laval nozzles, are configured differently from conduit 24 to provide supersonic flow downstream to form a shock wave. In various embodiments, the divergent conduit 24 does not form such supersonic flow or shock waves. Conversely, duct 24 has a geometry that facilitates the recirculation and reflux of gas within the internal reaction chamber 16 near the central axis 28, combined with an annular swirling jet stream adjacent to the internal reactor wall 14. Therefore, duct 24 will have a larger divergence angle than is typically used in Laval nozzles, which have a divergence angle of 15° or less. In some embodiments, the total divergence angle "A" relative to the central axis 28 is... Figure 1 The divergence angle A can be 25° or greater. In certain cases, the divergence angle A of the diverging portion of the conduit 24 discussed herein is 25° to 55°. In some embodiments, the divergence angle A is at least, equal to, and / or between any two of the following: 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, 40°, 41°, 42°, 43°, 44°, 45°, 46°, 47°, 48°, 49°, 50°, 51°, 52°, 53°, 54°, and 55°. Because the upstream swirling flow is connected to the converging-diverging conduit 24, a large divergence angle results in the recirculation of fluid flow at the reactor wall 14.

[0030] The downstream end of the diverging portion of the conduit 24 joins the reactor wall 14 around its periphery at the inlet of the reaction chamber 16, thereby enabling fluid communication between the conduit 24 and the reaction chamber 16 of the reactor vessel 12. The upstream end of the converging portion of the conduit 24 forms the inlet of the reactor vessel 12.

[0031] Reactor system 10 is equipped with reactor feed assembly 32. A perspective view of feed assembly 32 is shown in... Figure 2The reactor feed assembly 32 engages the upstream end of the conduit 24 and is in fluid communication with the conduit 24, with the central axis 28 passing through the reactor feed assembly 32. The feed assembly 32 includes a downstream feed assembly wall 34 that extends circumferentially around and engages the upstream end of the converging portion of the conduit 24. The feed assembly wall 34 or circumferential portion thereof is oriented perpendicular or substantially perpendicular to the central axis 28 (i.e., is within < 5 degrees of perpendicular around its circumference when extending radially from the central axis).

[0032] Axially spaced upstream from the downstream wall 34 along the central axis 28 is an upstream feed assembly wall 36. The upstream wall 36 or circumferential portion thereof is oriented perpendicular or substantially perpendicular to the central axis 28 (i.e., is within < 5 degrees of perpendicular around its circumference when extending radially from the central axis).

[0033] Upstream and downstream gas partition walls 38, 40 are axially spaced between the downstream feed assembly wall 34 and the upstream feed assembly wall 36 and from each other, with the upstream partition wall 38 positioned upstream of the downstream partition wall 40. The partition walls 38, 40 or circumferential portions thereof are also each oriented perpendicular or substantially perpendicular to the central axis 28 (i.e., is within < 5 degrees of perpendicular around its circumference when extending radially from the central axis). Each of the partition walls 38, 40 has a central opening 42, 44, respectively, that surrounds the central axis 28 and is concentric with the converging-diverging conduit 24. The inner ends of the partition walls 38, 40 that define the openings 42, 44 terminate at a location upstream of the converging-diverging conduit 24. The central openings 42, 44 are each of circular configuration. Other continuous curved shapes (e.g., oval) for the central openings 42, 44 can also be used, provided that such configuration facilitates the swirling of the gas to provide the desired swirling flow pattern described herein. The shape can also correspond to the cross-sectional shape of the circumferential wall 26 of the converging-diverging conduit 24. However, in most applications, the central openings 42, 44 will be of circular shape. The central openings 42, 44 can have a diameter or width that is the same as or slightly different (smaller or larger) than the diameter or width of the constriction neck of the converging-diverging conduit 24 at its narrowest point.

[0034] Referring to Figure 1 The upstream partition wall 38 defines an annular gas flow passage 46 between the upstream feed assembly wall 36 and the upstream side of the upstream partition wall 36. In the illustrated embodiment, the flow passage 46 constitutes an upstream annular hydrocarbon reactant feed inlet flow passage for the introduction of gaseous hydrocarbons to be converted into high value chemicals such as light olefins and aromatic compounds. Likewise, an annular gas flow passage 48 is defined by the downstream side of the downstream partition wall 40 and the downstream feed assembly wall 34. In the illustrated embodiment, the flow passage 48 can constitute an annular steam or water inlet flow passage.

[0035] The intermediate dividing wall 50 is axially spaced between the downstream gas dividing wall 40 and the upstream gas dividing wall 38 to define a downstream intermediate annular gas inlet flow passage 52 and an upstream intermediate annular gas inlet flow passage 54. The intermediate dividing wall 50 also has a central opening 56 that surrounds the central axis 28 and is concentric with the converging-diverging conduit 24. The inner end of the dividing wall 50 that defines the opening 56 terminates at a location upstream of the converging-diverging conduit 24. The central opening 56 can have a circular configuration. Other shapes for the central opening 56 (e.g., oval) can also be used provided that such configuration facilitates the swirl of the gas to provide the desired swirl flow pattern described herein.

[0036] The intermediate dividing wall 50 or a circumferential portion thereof is also oriented perpendicular or substantially perpendicular to the central axis 28 (i.e., when it extends radially from the central axis, it is ≤ 5 degrees from perpendicular about its circumference). In the illustrated embodiment, the annular flow passage 52 can constitute an oxygen or oxidizing gas flow passage to facilitate combustion. The annular flow passage 54 can constitute a fuel gas (e.g., H2, CH4, syngas, or a combination of these) flow passage for introducing fuel gas for combustion.

[0037] The region between the downstream and upstream feed assembly walls 34, 36 and radially inwardly spaced from the central openings 42, 44, 56 of the dividing walls 38, 44, 50, respectively, forms a central chamber 58 of the feed assembly 32 about the central axis 28. The central axis 28 also coincides with and forms the central axis of the central chamber 58 and the feed assembly 32.

[0038] This configuration provides flow passages through which the gas feed to be cracked, steam, oxygen, and hydrogen-rich fuel for providing combustion heat can each be introduced separately and pass through flow passages 46, 48, 52, 54, respectively, to pass into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 so that the feed is combusted in the central chamber to form a swirling combustion gas. The feed is introduced into the central chamber in a direction that is not parallel to the central axis 28. To this end, one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38 and 40, the intermediate partition wall 50 (or a circumferential portion thereof) are configured to introduce the feed into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 so that the feed is combusted in the central chamber to form a swirling combustion gas. The feed assembly wall 34, the upstream wall 36, the partition walls 38 and 40, the intermediate partition wall 50 (or a circumferential portion thereof) can be oriented in a direction that is not parallel to the central axis 28. In some embodiments, one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38 and 40, the intermediate partition wall 50 (or a circumferential portion thereof) can be oriented to be less than or equal to 5 degrees, less than or equal to 10 degrees, less than or equal to 20 degrees, less than or equal to 30 degrees, less than or equal to 40 degrees from a direction that is perpendicular to the central axis 28.

[0039] The upstream flow passage 46 can be used as a gaseous hydrocarbon feed inlet flow passage. A fuel gas feed consisting of a hydrogen-rich gas feed (i.e., H2) can be introduced into one of the first and second adjacent annular fuel gas inlet flow passages 52, 54, with an oxidant (i.e., O2) or oxygen-containing gas feed being introduced into the other of the flow passages 52, 54. Typically, the fuel and oxygen feeds will be introduced into flow passages that are immediately adjacent to one another to facilitate rapid combustion. In certain applications, the downstream flow passage 52 can be used to deliver the oxidant or oxygen-containing gas, and the upstream flow passage 54 will be used to deliver the hydrogen-rich fuel gas. A steam feed can be introduced into the downstream annular steam inlet flow passage 48. In other cases, the various feeds can be changed in order within the flow passages 46, 48, 52, 54. For example, any of the flow passages 48, 52, 54 can be used as a gaseous hydrocarbon feed inlet flow passage. In certain applications, the steam feed can be combined with or introduced with one or more of the other feeds. This can include combining the steam feed with the fuel gas feed, the oxygen-containing gas feed, or the hydrocarbon gas feed.

[0040] In certain embodiments, one or more of the flow passages 46, 48, 52, 54 can be left idle or omitted from the feed assembly 32. If a flow passage is omitted, one of the partition walls 38, 40, 50 need not be present, and the number of flow passages will be reduced. In this case, certain feeds can be combined and introduced together, such as the steam feed discussed previously.

[0041] In the illustrated reactor system 10, the flow passages 46, 48, 52, 54 are configured so that the different feeds flow through the flow passages in an inwardly swirling flow pattern perpendicular or substantially perpendicular to the central axis 28, so that the feeds flow around the central axis 28 within the central chamber 58. The swirling fuel gas and oxidant feeds are combusted within the central chamber 58.

[0042] In the illustrated reactor system 10, the walls 34, 36, 38, 40, and 50 forming the different flow passages 46, 48, 52, 54 are parallel to one another. In other cases, however, the walls 34, 36, 38, 40, and 50 can not be parallel to one another. The walls 34, 36, 38, 40, and 50 are axially spaced apart to provide the desired volume and flow characteristics for the gases flowing therethrough. This can be based on the desired flow rate or linear velocity of each of the feed gases and their relative amounts. For example, the relative volume of oxygen required for combustion is typically less than the volume of the hydrogen-rich fuel gas required for combustion. Thus, the dividing wall 50 can be spaced closer to the downstream dividing wall 40 so that the flow passage 54 for the hydrogen fuel is larger and accommodates more of the fuel gas flow. The specific spacing can depend on the combination of fuel gas and oxidant, the desired combustion volume, and the properties of the hydrocarbon feed.

[0043] Annular gas manifolds 60, 62, 64, 66 are disposed around the outer periphery of the flow passages 46, 48, 52, 54, respectively. In an example, the gas manifold 60 can be fluidly coupled to a source of gaseous hydrocarbon feed. The manifold 62 can be fluidly coupled to a source of steam. The manifold 64 can be fluidly coupled to a source of oxygen-containing gas, such as a pure 02feed. And the manifold 66 is fluidly coupled to a source of hydrogen-rich or fuel feed, such as H2. The manifolds 60, 62, 64, 66 are provided with the reactor feed assembly 32 to facilitate the introduction of the feed gases into the flow passages 46, 48, 52, 54. In other embodiments, the different feed sources to each manifold can be varied.

[0044] Generally, the gas inlets from the manifolds 60, 62, 64, 66 are oriented to produce an inwardly swirling flow of gas within the central chamber 58 (e.g., oriented nearly tangentially relative to the outer periphery of the flow passages 46, 48, 52, 54). In other words, the gas inlets direct the incoming flow of gas along a path that extends inwardly from the walls of the central chamber 58, but not directly toward the central axis 28 from the inlets along a radius of the central chamber 58. Incidentally, one or more inlets can be provided for each of the flow passages 46, 48, 52, 54. Moreover, the walls 34, 36, 38, 40, and 50 forming the different flow passages of the feed assembly 32 prevent axial flow of the gas along the direction of the central axis 28 as they are contained within the flow passages 46, 48, 52, 54. The manifolds 60, 62, 64, 66 can be configured as standard manifolds (e.g., snail-like) as can be commonly used in vortex devices.

[0045] Referring to Figure 2 In some embodiments, one or more or all of the flow passages 46, 48, 52, 54 can be provided with a plurality of circumferentially spaced apart guide vanes 68, 70, 72, 74 (e.g., 10 to 60 guide vanes per flow passage). Each guide vane 68, 70, 72, 74 can be a planar member oriented in a plane parallel to the central axis 28 and extending between the walls 34, 36, 38, 40, and 50. The guide vanes 68, 70, 72, 74 can be circumferentially spaced apart from one another by equal distances. In certain embodiments, the guide vanes 68, 70, 72, 74 can be fixed in place with upper and lower side edges of the vanes bonded to the walls 34, 36, 38, 40, and 50 along their length or a portion thereof, such that there is no air gap between the side edges of the vanes 68, 70, 72, 74 and the walls 34, 36, 38, 40, and 50. In other embodiments, however, the guide vanes are movable. In such cases, the upper and lower side edges of the vanes 68, 70, 72, 74 can be closely spaced from the walls 34, 36, 38, 40, and 50 to provide small gaps that allow for movement. The close spacing can minimize the air gap through which gas can pass. Seals can also be used to effectively seal off these spaces or gaps while allowing for movement. In other cases, the vanes 68, 70, 72, 74 can be oriented such that the plane of the vanes is in a non-parallel or tilted orientation relative to the central axis 28. In such cases, the side edges can be fixed to the walls 34, 36, 38, 40, and 50 or remain closely spaced from the walls 34, 36, 38, 40, and 50 to minimize the air gap. In certain applications, the guide vanes 68, 70, 72, 74 can be configured as airfoils, such as described in U.S. Patent No. 11,123,705.

[0046] In the illustrated reactor system 10, the guide vanes 68, 70, 72, 74 are disposed adjacent the outer periphery of the flow passages 46, 48, 52, 54 and are spaced in an annular or circular ring near the manifold inlets. In other reactor systems, they can be disposed in an annular ring at other locations radially inward or further inside the flow passages 46, 48, 52, 54. Alternatively, one or more additional annular sets of guide vanes can be positioned radially inward from those positioned along the outer periphery to promote inwardly swirling fluid flow.

[0047] The feed gas from the manifolds 60, 62, 64, 66 is delivered nearly tangentially to the outer periphery of the central chamber 58, where the guide vanes 68, 70, 72, 74 can direct the gas flow in an inwardly swirling or helical fluid flow pattern within the central chamber 58. In some embodiments, the inlets from the manifolds 60, 62, 64, 66 can be oriented or directed to impart a fully inwardly swirling fluid flow without the use or need of guide vanes. In other embodiments, such as where the gas from the manifold inlets can be directed radially toward the central axis 28 or do not impart a fully desired swirling flow, the guide vanes 68, 70, 72, 74 can impart a full swirling flow to the incoming gas. In such cases, the guide vanes 68, 70, 72, 74 prevent the flow of gas directly toward the central axis 28 and direct the flowing gas nearly tangentially relative to the inner walls of the central chamber 58 to provide an inwardly swirling or helical fluid flow pattern.

[0048] The guide vanes 68, 70, 72, 74 of each flow passage 46, 48, 52, 54 can be mounted on actuators (not shown) so that they can be selectively moved to various positions to provide a selected inwardly helical flow pattern. The guide vanes 68, 70, 72, 74 can be pivoted about an axis parallel to the central axis 28 so that the vanes 68, 70, 72, 74 can be moved to various positions.

[0049] The orientation of the vanes 68, 70, 72, 74 of each flow passage and / or the orientation of the inlets of the manifolds 60, 62, 64, 66 will provide a swirling or helical fluid jet flow in the same rotational direction (i.e., clockwise or counterclockwise) about the central axis 28. Thus, the gas within each of the flow passages will flow clockwise or counterclockwise about the central axis 28. In general, the vanes 68, 70, 72, 74 will all introduce the gas inwardly at the same angle relative to the walls of the central chamber 58 to provide the desired swirling fluid flow characteristics. If the vanes 68, 70, 72, 74 are movable, they will generally be actuated to move in unison or near unison.

[0050] In an example, the oxygen and hydrogen fuel gas from flow passages 52, 54, the gaseous hydrocarbon feed from flow passage 46, and the steam from flow passage 48 can be discharged into the central chamber 58 of the feed assembly 32. This eliminates safety issues that would occur if these gases were pre-mixed prior to being introduced to the feed assembly 32, since the oxygen-containing gas and the hydrogen-rich fuel gas are introduced separately from one another rather than as a mixture. In addition, the combustion reaction occurs rapidly, with the majority of the combustion occurring within a small space within the central chamber 58 in which the two streams of oxygen-containing gas and hydrogen-rich fuel gas from flow passages 52, 54 mix after being discharged from flow passages 52, 54. The combustible mixture can be ignited, for example, using a spark, chemical, or pilot flame that extends through a bottom or side surface of the reactor. The suction from the cyclonic flow can transport heat from the ignition device to the combustion zone 58 to initiate ignition.

[0051] The gaseous hydrocarbon feed from upstream flow passage 46 and the steam from flow passage 48 are discharged into the central chamber 58, such that the gaseous hydrocarbon feed, steam, and heated combustion gas mix together and form a cyclonic gas mixture within the chamber 58. This cyclonic gas mixture then passes through the converging-diverging conduit 24 and into the reaction chamber 16 of the reactor vessel 12.

[0052] A liquid feed inlet 76 is also formed in the upstream feed assembly wall 36 for introducing liquid hydrocarbons to be converted by the reactor system 10 into the feed assembly 32, for example, into all or a portion of the liquid hydrocarbons that are converted into high value chemicals such as light olefins and aromatic compounds. In certain embodiments, there can be more than one or a plurality of liquid feed inlets 76. The liquid feed inlet 76 can be formed as a conduit that joins a length of the feed assembly wall 36. The conduit can include an inlet axis that is aligned and / or parallel to the central axis 28, such that the liquid feed or a substantial portion (i.e., > 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%) of the liquid feed introduced through the inlet 76 can be introduced into the central chamber 58 axially or at a non-perpendicular angle relative to the central axis 28. In other words, the liquid feed introduced through the inlet 76 is not introduced perpendicular to the axis 28. A liquid feed manifold 80 can be used to introduce the liquid feed through the liquid feed inlet 76. The manifold 80 is fluidly coupled to a source of liquid feed containing liquid hydrocarbons to be converted. The manifold 80 includes one or more spray nozzles 78 that can be used to introduce the liquid feed into the central chamber 58 as a liquid spray (i.e., a spray of liquid droplets). In cases where multiple liquid feed inlets 76 are employed, the manifold 80 can include multiple spray nozzles 78 positioned and oriented for introducing the liquid feed through the liquid feed inlets 76 into the central chamber 58 as a plurality of droplet sprays. In some embodiments, the droplets in the liquid feed define a non-swirling spray and / or a radially extending fan pattern such that all or a portion of the droplets are not parallel to the central axis but have both axial and radial velocity components. Furthermore, the droplet pattern can be centered on or near the central axis where the swirling velocity of the swirling fluid flow is lowest. In some embodiments, the one or more spray nozzles 78 introduce the liquid into the central chamber 58 of the feed assembly 32 where the swirling velocity of the swirling fluid flow during operation of the reactor 10 is less than 5 m / s. The one or more spray nozzles can be located within a placement radius (“PR”) defined from a point where the central axis 28 intersects a plane defined by the upstream wall 36 of the feed assembly 32. In one embodiment, the PR is no greater than 30% of the radius of the central chamber 58. In other embodiments, the PR is no greater than 20% of the radius of the central chamber 58. As described below in various embodiments, the use of a nozzle that produces a particular droplet size and placement of the nozzle in a central location (i.e., aligned with or near the central axis) within the feed assembly of the reactor system described below results in hydrocarbon conversion efficiencies not available in conventional reactor systems. As described below, the central location of the nozzle injects the liquid hydrocarbon reactant feed into the region of the reactor at a low swirling velocity (e.g., a swirling velocity less than 5 m / s). This location, along with the droplet size, allows the liquid droplets to vaporize before the droplets enter the region of the feed assembly at higher swirling velocities, thereby preventing rapid coking of the reactor.Thus, the combination of the location of the nozzle and the droplet size produced by the nozzle at that location provides certain unique advantages.

[0053] The combination of the axial and radial flow velocity components define a spray pattern with a low spray angle and maintain that pattern close to the central axis 28. Thus, the droplets are primarily directed axially (e.g., to define a spray angle of 40° or less). Such a spray angle helps ensure that the liquid droplets are vaporized before being captured in the swirling gas flow and forced against the reactor wall by centrifugal force, which can result in coking. In particular embodiments, the spray can have a spray angle of at least, equal to, and / or between any two of: 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 21°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, and 40°. In certain embodiments, the spray pattern can be a solid cone, hollow cone, linear flow, or flat spray pattern. In various embodiments, the liquid feed inlet 76 does not include a guide vane, such as vanes 68, 70, 72, 74, or other structure that can impart a swirling fluid flow to the liquid hydrocarbon prior to entering the central chamber 58.

[0054] By introducing the liquid hydrocarbon axially, the atomized spray with liquid droplets is concentrated near the central axis 28 of the reactor 10, where the swirling velocity is lowest. In fact, the liquid droplets are concentrated at the "eye" of the swirling flow. Away from the central axis 28 or centerline and closer to the wall, higher swirling velocities are encountered. These higher swirling velocities can deposit the atomized droplets on the wall and guide vanes, leading to coking and fouling. The small droplets interact with the counter-current flow of high temperature gas from combustion and strong recycle to vaporize the droplets and follow other hydrocarbon gases to increase the heat and cracking in the reactor 10.

[0055] The spray nozzle 78 can be selected and / or configured to provide a particular droplet size. The spray nozzle can be structured or configured to provide a Sauter Mean Diameter (SMD) or D 32 of 1 pm to 250 pm. As used herein, SMD or D 32SMD is defined as the ratio of the volume of a droplet to the surface area of the droplet in a spray. Droplet measurements can be determined using phase Doppler interferometry (PDI) techniques. In particular embodiments, the nozzle at liquid feed inlet 76 can provide a liquid hydrocarbon feed with an SMD size of at least, equal to, and / or between any two of: 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, and 250 pm.

[0056] The smaller the droplet size, the faster the vaporization and the less likely the droplet is to enter the higher swirl region of the reactor. However, the smaller the droplet size, the higher the pressure drop across the nozzle and there is a limit to the degree of atomization that can be achieved with a nozzle. Thus, droplet size is a compromise between two competing requirements. Figure 4 The graph of Figure 1 shows the vaporization time as a function of droplet size using a simplified calculation under approximate conditions in the reactor. Figure 5 The computational fluid dynamics (CFD) calculation shown in Figure 2 shows the evaporation of a spray in the reactor where all the liquid is vaporized within 5 mm of the injection point. The figure shows the volume fraction of the liquid of the spray, which ranges from approximately 2.5 x 10 -5 to 0 (which indicates that all of the liquid is vaporized).

[0057] Other characteristics of the droplets produced by the spray nozzle 78 can include a weighted average droplet size. The weighted average droplet size can include a mass (volume) median or 50% diameter (DV 0.5), which is the diameter such that 50% of the total volume of the droplets is contained in particles having a smaller diameter. In certain embodiments, the DV 0.5 may be at least, equal to, and / or between any two of: 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, and 250 pm. In other particular embodiments, the spray nozzle is configured to form droplets having a DV 0.5 of 10 pm to 50 pm.

[0058] DV 0.1 is the diameter such that 10% of the total volume of the droplets is found below it. In certain embodiments, the DV 0.1may be at least, equal to, and / or between any two of: 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm. In other particular embodiments, the spray nozzle is configured to form droplets having a DV 0.1 of 5 pm to 25 pm.

[0059] DV 0.9 is the diameter below which 90% of the total volume of droplets is found. In certain cases, the DV 0.9may be at least, equal to, and / or between any two of: 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm, 26 pm, 27 pm, 28 pm, 29 pm, 30 pm, 30 pm, 31 pm, 32 pm, 33 pm, 34 pm, 35 pm, 36 pm, 37 pm, 38 pm, 39 pm, 40 pm, 41 pm, 42 pm, 43 pm, 44 pm, 45 pm, 46 pm, 47 pm, 48 pm, 49 pm, 50 pm, 55 pm, 60 pm, 65 pm, 70 pm, 75 pm, 80 pm, 85 pm, 90 pm, 95 pm, 100 pm, 105 pm, 110 pm, 115 pm, 120 pm, 125 pm, 130 pm, 135 pm, 140 pm, 145 pm, 150 pm, 155 pm, 160 pm, 165 pm, 170 pm, 175 pm, 180 pm, 185 pm, 190 pm, 195 pm, 200 pm, 205 pm, 210 pm, 215 pm, 220 pm, 225 pm, 230 pm, 235 pm, 240 pm, 245 pm, 250 pm, 255 pm, 260 pm, 265 pm, 270 pm, 275 pm, 280 pm, 285 pm, 290 pm, 295 pm, 300 pm, 305 pm, 310 pm, 315 pm, 320 pm, 325 pm, 330 pm, 335 pm, 340 pm, 345 pm, 350 pm, 355 pm, 360 pm, 365 pm, 370 pm, 375 pm, 380 pm, 385 pm, 390 pm, 395 pm, 400 pm, 405 pm, 410 pm, 415 pm, 420 pm, 425 pm, 430 pm, 435 pm, 440 pm, 445 pm, and 450 pm. In one particular embodiment, the spray nozzle is configured to form droplets having a DV 0.9 droplets of 20 pm to 100 pm.

[0060] To facilitate the formation of a suitable fine spray of the liquid hydrocarbon feed having such small droplet size, the liquid hydrocarbon can be modified to have a dynamic viscosity of 0.1 cP to 1000 cP, as measured using ASTM D445, but measured at the operating temperature (i.e., the temperature of the liquid hydrocarbon as it passes through the nozzle) prior to or at the time of introduction. For example, as discussed below, in some cases the liquid hydrocarbon feed can be preheated to a temperature of between 25 °C to 400 °C, and the viscosity is measured at that temperature. Droplet size is approximately proportional to the 0.2 power of dynamic viscosity, so lower dynamic viscosity results in smaller droplet size. Generally, fluids with lower dynamic viscosity also have lower surface tension, and droplet size is approximately related to the 0.5 power of surface tension. In certain embodiments, the liquid hydrocarbon can be modified to have a dynamic viscosity of at least, equal to, and / or between any two of: 0.1 cP, 0.2 cP, 0.3 cP, 0.4 cP, 0.5 cP, 0.6 cP, 0.7 cP, 0.8 cP, 0.9 cP, 1 cP, 2 cP, 3 cP, 4 cP, 5 cP, 6 cP, 7 cP, 8 cP, 9 cP, 10 cP, 15 cP, 20 cP, 30 cP, 40 cP, 50 cP, 60 cP, 70 cP, 80 cP, 90 cP, 100 cP, 150 cP, 200 cP, 250 cP, 300 cP, 350 cP, 400 cP, 450 cP, 500 cP, 550 cP, 600 cP, 650 cP, 700 cP, 750 cP, 800 cP, 850 cP, 900 cP, 950 cP, and 1000 cP. Modification of the hydrocarbon can include heating the hydrocarbon to a sufficient temperature and / or combining the liquid hydrocarbon with a solvent or low viscosity component to reduce the dynamic viscosity. Such solvents can include oligomers, waxes, or other liquids having a lower dynamic viscosity than the hydrocarbon being modified.

[0061] In certain applications, the spray nozzle 78 can be configured or selected as a dual fluid nozzle. Such dual fluid nozzles can allow for the introduction of two different fluids, each having different properties from one another. For example, the liquid can include a liquid phase fluid and a gas phase fluid that are each simultaneously ejected through the nozzle 78. The dual fluid nozzle 78 can have a mixing chamber in which the two fluids mix prior to being discharged as a spray. Such dual fluid nozzles also provide for internal mixing of the two fluids to prevent clogging, as well as provide for a finely atomized spray having the liquid droplet sizes described above. Such dual liquid spray nozzles are described, for example, in U.S. Patent Application Publication No. US2020 / 0147624, the entirety of which is incorporated herein for all purposes, including the description of the construction and use of such nozzles. The dual fluid nozzle can facilitate rapid dispersion of the mixture from the outlet, promote atomization, and form droplets that can be easily transported by the atomizing gas. This can reduce liquid deposition on the outlet of the mixed gas and prevent clogging. Suitable commercially available dual fluid nozzles for use as the spray nozzle 78 can include the dual fluid nozzles sold as FLOWMAX ® X Series or FLOWMAX ® FM3A nozzles.

[0062] The energy input to the spray nozzle is equal to the pressure drop across the nozzle multiplied by the flow rate. To obtain the target droplet size distribution, the selection of the single phase or two phase nozzle depends on the pressure drop of the nozzle. The selection of the single phase or two phase nozzle also depends on various requirements (e.g., (i) spray angle, (ii) hollow versus full spray cone, and (iii) internal and external mixing to address fouling, which can be achieved using a two phase nozzle). Further, for the current application with hydrocarbons, the spray nozzle selection can depend on high temperature operability, coking and fouling characteristics, erosion, ability to detect and pull out the narrow opening of the nozzle, etc. Generally, the dual fluid nozzle provides a wide range of control over the droplet size distribution and self-cleaning ability, as the gas phase can be steam. A disadvantage can be that slight variations in the gas or liquid phase flow rate or pressure can significantly change the droplet and spray characteristics.

[0063] In various embodiments of the present disclosure, a liquid hydrocarbon can be introduced through the dual fluid spray nozzle 78 into the liquid feed inlet 76 with a gaseous hydrocarbon and / or steam (i.e., superheated steam) as the second fluid. The spray nozzle 78 is coupled to one end of a spray manifold 80 that is fluidly coupled to separate upstream sources of the liquid hydrocarbon and gas feed (i.e., steam and / or gaseous hydrocarbon). The pressure range of the liquid feed to the vapor feed depends on the design of the nozzle. For example, Figure 6 The different flow conditions and various droplet sizes (i.e., D 32 , Dv 0.9 , Dv 0.99FLOWMAX using liquid water and air ® Test results for FM3A dual fluid nozzle. Liquid pressure varied from 1 barg to 3 barg at a constant gas pressure of 4.14 barg. The corresponding liquid flow rate ranged from 1 liter / minute to 11 liters / minute, and the air flow rate was between 80 Nm 3 / hr and 100 Nm 3 / hr. For these conditions, the SMD varied from 20 pm to 55 pm. Thus, in this dual fluid nozzle, these parameters can be adjusted depending on any particular hydrocarbon used as the liquid feed and the steam or other gas used as the gas phase.

[0064] If the desired droplet characteristics are not achieved, the droplets can take significantly longer to vaporize. Droplet vaporization time is proportional to the square of the droplet diameter. In addition, the droplets can encounter higher rotational flow velocities, resulting in high centrifugal accelerations (e.g., 100 g to 100,000 g forces), leading to droplet deposition on the walls and coking and fouling of the reactor. This creates a positive feedback loop, where any deposits will destroy the desired fluid dynamics and accelerate additional maldistribution and deposition. This leads to coking and plugging of the reactor. Thus, droplet characteristics in terms of droplet size, spray angle, etc. are important for robust operation of a reactor with a liquid feed.

[0065] In various embodiments of the present disclosure, liquid hydrocarbon feeds that can be converted by the reactor system 10 include those pyrolysis oils derived from plastic waste, including pyrolysis oils from MPW. Plastic waste that can be pyrolyzed to form pyrolysis oils for the liquid feed can include, but is not limited to, polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polylactic acid (PLA), nylon, expanded polystyrene (EPS), also known as Styrofoam®, and the like. These can include those plastic materials formed into microplastics, plastic films and wrapping paper, plastic fibers, fishing equipment, plastic straws and utensils, plastic containers, plastic bottles and caps, and plastic toys and various consumer goods. In addition, these plastics need not be sorted or cleaned, and can be a mixture of all types of plastics prior to pyrolysis, eliminating much of the processing and cost typically associated with mechanical recycling.

[0066] The liquid hydrocarbon feed can include full range pyrolysis oil, which is pyrolysis oil that has not been subjected to any fractionation or distillation. In other embodiments, the plastic waste pyrolysis oil can be a lighter fraction of pyrolysis oil or a portion of pyrolysis oil having a boiling point range less than the final boiling point. The boiling point range of full range pyrolysis oil from MPW is typically 75 °C to about 650 °C. The average molecular weight (Mn) of the pyrolysis oil can be 100 to 400. The lighter fraction of pyrolysis oil can include those with a final boiling point of 600 °C, 550 °C, 500 °C, 450 °C, 400 °C, or lower. In certain applications, the liquid hydrocarbon feed can be a liquid hydrocarbon feed having a boiling point range of at least, equal to, and / or between any two of the following: 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C, 250 °C, 255 °C, 260 °C, 265 °C, 270 °C, 275 °C, 280 °C, 285 °C, 290 °C, 295 °C, 300 °C, 305 °C, 310 °C, 315 °C, 320 °C, 325 °C, 330 °C, 335 °C, 340 °C, 345 °C, 350 °C, 355 °C, 360 °C, 365 °C, 370 °C, 375 °C, 380 °C, 385 °C, 390 °C, 395 °C, 400 °C, 405 °C, 410 °C, 415 °C, 420 °C, 425 °C, 430 °C, 435 °C, 440 °C, 445 °C, 450 °C, 455 °C, 460 °C, 465 °C, 470 °C, 475 °C, 480 °C, 485 °C, 490 °C, 495 °C, 500 °C, 505 °C, 510 °C, 515 °C, 520 °C, 525 °C, 530 °C, 535 °C, 540 °C, 545 °C, 550 °C, 555 °C, 560 °C, 565 °C, 570 °C, 575 °C, 580 °C, 585 °C, 590 °C, 595 °C, 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, and 650 °C.

[0067] The plastic waste pyrolysis oil used as the liquid feed can be non-hydrogenated pyrolysis oil. Such non-hydrogenated pyrolysis oil has not undergone any hydrogenation, such as in a hydrotreater, after pyrolysis. However, hydrogenated pyrolysis oil, as well as mixtures of non-hydrogenated and hydrogenated pyrolysis oil, can also be used as the liquid feed. Because the reactor is capable of converting pyrolysis oil without coking, the pyrolysis oil does not need to be hydrogenated as in a conventional conversion system (e.g., steam cracking). This eliminates the additional processing steps required when processing pyrolysis oil in a conventional steam cracking system. It also allows the use of a full range of plastic waste pyrolysis oil, whereas steam cracking can only utilize the lighter 80-90% fraction of pyrolysis oil, such as those in the C4 to C8 range. The heavier hydrocarbons, such as C9 or higher, require longer residence times in the cracker, which can lead to undesirable coking. In addition, pyrolysis oil cracked in a steam cracker is typically combined with naphtha to improve liquid feedstock quality and increase processing and product yields.

[0068] In contrast, using the reactor system 10 of the present application, there is no need to hydrogenate the pyrolysis oil or oligomers or combine the feed with naphtha or other liquid hydrocarbons. The full range pyrolysis oil, as well as lighter pyrolysis oil fractions, waxes, and oligomers, can be used as the liquid feed. This is due to the extremely short contact or residence times and reactant flow dynamics that occur within the reactor.

[0069] In various embodiments, waxes (i.e., paraffin waxes) and / or oligomers can also be used as the liquid feed and processed in the reactor system 10. These can be waxes and oligomers derived from plastic waste pyrolysis oil, such as by distillation or fractionation. All or a portion of the waxes and oligomers can also be those from other sources, such as byproducts of polymerization processes.

[0070] The waxes can include C 20 to C 50those in the range of 250 g / mol to 1,000 g / mol. In certain embodiments, the average molecular weight (Mn) of the wax can range from at least, equal to, and / or between any two of the following: 250 g / mol, 260 g / mol, 270 g / mol, 280 g / mol, 290 g / mol, 300 g / mol, 310 g / mol, 320 g / mol, 330 g / mol, 340 g / mol, 350 g / mol, 360 g / mol, 370 g / mol, 380 g / mol, 390 g / mol, 400 g / mol, 410 g / mol, 420 g / mol, 430 g / mol, 440 g / mol, 450 g / mol, 460 g / mol, 470 g / mol, 480 g / mol, 490 g / mol, 500 g / mol, 510 g / mol, 520 g / mol, 530 g / mol, 540 g / mol, 550 g / mol, 560 g / mol, 570 g / mol, 580 g / mol, 590 g / mol, 600 g / mol, 610 g / mol, 620 g / mol, 630 g / mol, 640 g / mol, 650 g / mol, 660 g / mol, 670 g / mol, 680 g / mol, 690 g / mol, 700 g / mol, 710 g / mol, 720 g / mol, 730 g / mol, 740 g / mol, 750 g / mol, 760 g / mol, 770 g / mol, 780 g / mol, 790 g / mol, 800 g / mol, 810 g / mol, 820 g / mol, 830 g / mol, 840 g / mol, 850 g / mol, 860 g / mol, 870 g / mol, 880 g / mol, 890 g / mol, 900 g / mol, 910 g / mol, 920 g / mol, 930 g / mol, 940 g / mol, 950 g / mol, 960 g / mol, 970 g / mol, 980 g / mol, 990 g / mol, and 1000 g / mol.

[0071] The oligomers can be those formed from various monomers or combinations of monomers. In the present application, the oligomers can also be those produced from partial or incomplete pyrolysis of a polymer or plastic material. Typically, the monomers will be ethylene or propylene monomers, with ethylene monomers being the primary monomers. The oligomers can include those having an average molecular weight (Mn) of 1,000 to 50,000. In particular embodiments, the average molecular weight (Mn) of the oligomers can be 2,000 to 10,000. In certain instances, the average molecular weight (Mn) of the oligomers can be at least, equal to, and / or between any two of the following: 1,000 g / mol, 1,500 g / mol, 2,000 g / mol, 2,500 g / mol, 3,000 g / mol, 3,500 g / mol, 4,000 g / mol, 4,500 g / mol, 5,000 g / mol, 5,500 g / mol, 6,000 g / mol, 6,500 g / mol, 7,000 g / mol, 7,500 g / mol, 8,000 g / mol, 8,500 g / mol, 9,000 g / mol, 9,500 g / mol, 10,000 g / mol, 11,000 g / mol, 12,000 g / mol, 13,000 g / mol, 14,000 g / mol, 15,000 g / mol, 16,000 g / mol, 17,000 g / mol, 18,000 g / mol, 19,000 g / mol, 20,000 g / mol, 21,000 g / mol, 22,000 g / mol, 23,000 g / mol, 24,000 g / mol, 25,000 g / mol, 26,000 g / mol, 27,000 g / mol, 28,000 g / mol, 29,000 g / mol, 30,000 g / mol, 31,000 g / mol, 32,000 g / mol, 33,000 g / mol, 34,000 g / mol, 35,000 g / mol, 36,000 g / mol, 37,000 g / mol, 38,000 g / mol, 39,000 g / mol, 40,000 g / mol, 41,000 g / mol, 42,000 g / mol, 43,000 g / mol, 44,000 g / mol, 45,000 g / mol, 46,000 g / mol, 47,000 g / mol, 48,000 g / mol, 49,000 g / mol, and 50,000 g / mol.

[0072] The liquid hydrocarbon feed can consist of one or more of the full range pyrolysis oil, pyrolysis oil fractions, waxes and oligomers, and combinations of these. These can all be derived from plastic waste or MPW. The liquid hydrocarbons converted with the reactor system 10 will typically comprise from 0.5 wt% to 100 wt% of the total weight of the hydrocarbon reactant feed (i.e., liquid hydrocarbons and gaseous hydrocarbons). In particular embodiments, the liquid hydrocarbons can comprise at least, equal to, and / or between any two of the following, by total weight of the hydrocarbon reactant feedstock: 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, and 4.0 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt%, 5.0 wt%, 5.1 wt%, 5.2 wt%, 5.3 wt%, 5.4 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5.8 wt%, 5.9 wt%, 6.0 wt%, 6.1 wt%, 6.2 wt%, 6.3 wt%, 6.4 wt%, 6.5 wt%, 6.6 wt%, 6.7 wt%, 6.8 wt%, 6.9 wt%, 7.0 wt%, 7.1 wt%, 7.2 wt%, 7.3 wt%, 7.4 wt%, 7.5 wt%, 7.6 wt%, 7.7 wt%, 7.8 wt%, 7.9 wt%, 8.0 wt%, 8.1 wt%, 8.2 wt%, 8.3 wt%, 8.4 wt%, 8.5 wt%, 8.6 wt%, 8.7 wt%, 8.8 wt%, 8.9 wt%, 9.0 wt%, 9.1 wt%, 9.2 wt%, 9.3 wt%, 9.4 wt%, 9.5 wt%, 9.6 wt%, 9.7 wt%, 9.8 wt%, 9.9 wt%, and 10.0 wt%.0 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, and 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt%, and 100 wt%.

[0073] In various embodiments of the present disclosure, liquid hydrocarbons will be converted in the reactor system 10 along with gaseous hydrocarbons. As used herein, "gaseous hydrocarbons" or similar expressions are intended to include those hydrocarbons under conditions of temperature and pressure such as with or without steam dilution, where the hydrocarbons are in a gaseous or superheated state prior to introduction into the reactor system 10. This can include those hydrocarbons that can be liquids at standard atmospheric conditions but at elevated temperatures and / or reduced pressures such that they are vaporized prior to being introduced into the reactor system 10. For example, the gaseous hydrocarbons can have a boiling point of no greater than 450°C, no greater than 250°C, or no greater than 150°C at one atmosphere. The gaseous hydrocarbons can include, but are not limited to, natural gas liquids (NGLs), natural gas condensate, C4 streams, and gaseous C1 to C4 hydrocarbons. The gaseous hydrocarbons can include methane, ethane, propane, butanes, pentanes, and mixtures thereof. 20 Any one or more of the hydrocarbons or mixtures thereof, and combinations of these.

[0074] In some cases, all or a portion of the gaseous hydrocarbon can be co-fed with the liquid hydrocarbon feed through the liquid feed inlet 76 and the spray nozzle 78. In cases where the liquid hydrocarbon is introduced using a two-fluid spray nozzle 78, the gaseous hydrocarbon can be mixed with the liquid hydrocarbon within the nozzle 78 itself, such as in the mixing chamber of the nozzle, before it is discharged as a spray. In cases where the spray nozzle 78 is not a two-fluid spray nozzle, the liquid and gaseous hydrocarbons can be mixed and combined upstream of the nozzle 78, where they can both be discharged together through the spray nozzle 78. In still other cases, the gaseous hydrocarbon can be introduced separately from the liquid hydrocarbon through the liquid feed inlet 76.

[0075] In many cases, all or a portion of the gaseous hydrocarbon feed to be converted by the reactor system 10 is introduced through one of the annular flow passages 46, 48, 52, 54 of the feed assembly 32. Typically, this will be the upstream flow passage 46 immediately upstream of the liquid feed inlet 76.

[0076] One or both of the liquid and / or gaseous hydrocarbon feeds can be mixed with steam. This is typically superheated steam, which is combined with and co-fed with the hydrocarbon feed prior to the hydrocarbon feed being introduced into the feed assembly 32 or central chamber 58. In cases where the liquid hydrocarbon is introduced using a two-fluid spray nozzle 78, the steam can be mixed with the liquid hydrocarbon within the nozzle 78 itself, before it is discharged as a spray. Steam can also be introduced separately into the feed assembly 32 through one of the annular flow passages, such as the downstream flow passage 48.

[0077] In an example of operation of the reactor system 10, a gaseous hydrocarbon feed, such as one of those previously discussed, is introduced from the manifold 60 through the inlet into the flow passage 46. A hydrogen-containing fuel gas is introduced from the manifold 66 into the flow passage 54. The hydrogen-containing fuel gas can be hydrogen gas (H2), methane (CH4), and / or CO / syngas or a combination of these. Here, CH4is used as the fuel for combustion. In certain embodiments using a combination of hydrogen and methane, the methane can be present in the fuel gas in an amount of 20 mole%, 15 mole%, 10 mole%, 5 mole% or less. Larger amounts of methane can impact the selectivity desired. However, in other embodiments, larger amounts of methane can be used, including 100% methane for the fuel gas. Natural gas can also be used as the fuel gas.

[0078] The hydrogen-containing fuel gas can be a hydrogen-rich stream consisting primarily of hydrogen, which can be a recycle stream from downstream processing, or additional hydrogen. The hydrogen-rich stream can contain other components such as methane, CO, steam, inert gases, and CO2. In certain embodiments and applications, other hydrocarbons can also be used as the fuel gas. Additionally, small amounts of N2may also be present. Sulfur can also be present in the fuel gas or other feed streams. If sulfur is present, additional separation upstream or downstream can be required. The reactor and process are sufficiently robust to accommodate the presence of sulfur, particularly since no catalyst is used. The ratio between the hydrocarbon feed (i.e., the total amount of liquid and gaseous hydrocarbons) and the hydrogen-containing fuel, on a mass basis, is typically in the range of 1 to 15, more particularly 1 to 10.

[0079] An oxidant or oxygen-containing gas as an oxidant feed is introduced through manifold 64 through an inlet into flow passage 52, which can be concentrated or pure oxygen gas such as from an air separation unit (not shown). The introduction of the oxygen-containing gas through downstream flow passage 52 is further spaced apart from the liquid feed inlet 76 and any hydrocarbon gas introduced through flow passage 46 to eliminate or minimize any combustion of the introduced hydrocarbon reactant feed. In certain applications, the molar ratio of H2 / O2may be in the range of 2 to 9, more particularly 2 to 5, and still more particularly 2 to 4. The oxygen feed can provide an oxygen equivalent to fuel molar ratio of 0.2 to 1.0. The excess hydrogen also helps to scavenge the free radicals (e.g., O, OOH, OH) that are formed that would otherwise react with the hydrocarbon feed. In some cases, the molar ratio of H2 / O2may be less than 2 to compensate for other fuel gases, or to have excess O2in the mixing zone to release heat to offset the endothermic cracking reactions. In some cases, the hydrogen is sub-stoichiometric (less than 1) to allow for additional exothermic reactions in the mixing zone. The oxygen feed can provide an oxygen equivalent to fuel molar ratio of 0.125 to 0.50. Further, the ratio between the hydrocarbon feed and the hydrogen fuel, on a mass basis, is typically in the range of 1.0 to 15, depending on the hydrocarbon feed.

[0080] Steam or water can be introduced through manifold 62 and through an inlet into flow passage 48. The steam can be introduced upstream of the other feeds and can be used to cool the converging-diverging duct 24 and the walls of the reactor vessel 12. The introduced steam also lowers the reaction temperature within the reactor 10. The steam can also be pre-mixed with the various feeds, such as with the liquid and gaseous hydrocarbon feeds, the fuel gas, and / or the oxygen-containing feed. In certain applications, the steam can be used in a mass ratio of steam to fuel of greater than 0 to 10.0, more particularly 0 to 2.0.

[0081] In practice, all oxygen and at least a portion of the hydrogen-containing fuel gas are typically burned to form heated combustion products, which are almost completely mixed with the other feed before leaving the convergent-divergent duct 24 and entering the reaction chamber 16. Due to the high centrifugal force of the swirling gas, denser gases (e.g., pyrolysis feed) flow closer to the reactor walls, while the hotter combustion products tend to flow through the center of the reactor. The device geometry and the swirling gas mixture from chamber 58 result in a backflow of the gas mixture within the reaction chamber 16. This mixture flows upstream and radially inward from a thin outer annular layer of mixed gas circulating within the reaction chamber 16. This backflow is caused by the... Figure 3 The high-swirling steam delivered through flow channel 48 may cause internal cooling of the wall. This is achieved through the location... Figure 1 Additional cooling is provided by the water jacket between walls 14 and 18 (if necessary).

[0082] A liquid hydrocarbon feed comprising one or more of pyrolysis oil, plastic waste pyrolysis oil, MPW pyrolysis oil, wax, and oligomers is introduced as a spray from nozzle 78 through inlet 76 and immediately vaporized. The low liquid viscosity and the resulting small droplet size increase the rate at which the liquid feed is heated and vaporized. In various embodiments, it may not be necessary to preheat the liquid hydrocarbons before introducing them into reactor system 10. In some cases, the liquid hydrocarbons may be preheated. This is especially true for oligomers and waxes that are typically solid (or highly viscous) at room temperature. This can reduce the viscosity to the previously discussed viscosity range to facilitate optimal droplet formation. Typical temperatures for preheating the liquid can range from 30°C to 350°C. Other methods of reducing viscosity may include combining the hydrocarbons with a solvent (e.g., oligomers and / or waxes with lower viscosity) and / or using a fraction of the hydrocarbon material with the desired viscosity (i.e., a distillation fraction).

[0083] The operating conditions of reactor 10 can vary depending on the type of hydrocarbon feed. The gas residence time within reactor 10 can range from 50 milliseconds or less, more particularly from 20 milliseconds or less. In a particular embodiment, the residence time range can be 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 milliseconds or less, where 10 microseconds is an approximate minimum residence time. The pressure at the reactor outlet can vary. A suitable pressure at the reactor outlet can range from 0 kPa(g) to 10,000 kPa(g), more particularly from 0 kPa(g) to 1,000 kPa(g).

[0084] The reaction temperature can range from 800°C to 2500°C, with the lowest temperature found at the reactor outlet when all endothermic reactions are complete, and the highest temperature encountered in the combustion zone (flame) of the reactor. The reaction temperature within the reactor and recirculation zone can range from 900°C to 1300°C. In particular embodiments, the temperature within the reactor and recirculation zone can range from 1000°C to 1300°C, more particularly 1200°C to 1250°C. In some embodiments, the reactor temperature is higher than the temperatures reached in conventional cracking reactors, such as tubular furnace reactors, which typically operate at 800°C to 900°C. As previously discussed, this is due to the temperature limitations of the metallic materials used for such conventional reactors. In the reactor, the swirling gas mixture helps to keep the walls of the reactor much cooler than in such conventional cracking reactors. The use of this higher temperature also allows for a shorter residence time or contact time, which results in better selectivity and conversion without forming undesirable products. The operating temperature for the reactor can be selected to avoid excessive production of such undesirable compounds, such as CO and CO2, or to optimize the olefin to acetylene ratio, as acetylene is generally undesirable.

[0085] The gas is introduced and flows through the flow passages 46, 48, 52, 54 such that the axial velocity (i.e., relative to the central axis 28) is zero or near zero before it is discharged into the central chamber 58. The orientation of the inlet (not shown) and / or the guide vanes 68, 70, 72, 74 can be set for each flow passage 46, 48, 52, 54 such that a selected azimuthal to radial velocity ratio is achieved for each of the feed streams flowing through the flow passages 46, 48, 52, 54, where the azimuthal and radial directions are defined in a cross-section perpendicular to the central axis 28 of the reactor 10. In particular, for each inlet, the radial direction is along a line extending from the inlet to the central axis 28. The azimuthal direction is perpendicular to both this radial direction and the axial direction (i.e., the direction of the central axis 28). Turning back to the azimuthal to radial velocity ratio, in particular embodiments, it can range from greater than 0 to 30 or more, more particularly from > 0, 1, or 2 to 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some applications, the azimuthal to radial velocity ratio can range from > 0 to 5, more particularly from 2 to 4. However, the particular azimuthal to radial velocity ratio can vary depending on the particular reactor configuration and the composition of the various streams. This is closely related to the mixing time and the reaction time, depending on the flow rates, composition of the fuel and feedstock used for cracking.

[0086] The converted hydrocarbon products produced in the reactor are removed from the reactor vessel 12 through an outlet 20. The converted hydrocarbon products can be quenched within the quench zone of the reactor 10, or they can be quenched in a quench unit external to the reactor 10, such as a water droplet spray quench vessel or other suitable gas quenching device. The quenched products can be further processed and recovered.

[0087] In variations of the reactor described, additional hydrocarbon feed gas can be introduced as a secondary feed stream at an intermediate location along the length of the reactor vessel 12, such as at an inlet 82 Figure 1 ) to the reactor vessel 12. One or more such inlets 82 can be provided at various locations and in the reactor vessel 12, which can be spaced apart circumferentially and longitudinally. The inlets 82 can be oriented or configured such that the gas is also introduced at an angle to facilitate a rotational flow of fluid, similar to the fluid flow delivered from the inlets of the feed assembly 32. A feed assembly similar to the feed assembly 32 provided on the reactor vessel 12 can be used to introduce such pyrolysis feed gas such that the pyrolysis feed is introduced as a rotational flow of fluid.

[0088] In some embodiments, multiple reactor inlet assemblies and corresponding feed assemblies can be provided in a single reactor while maintaining high performance.

[0089] By utilizing the reactor system 10, plastic waste, including MPW and waste that cannot typically be recovered using mechanical recycling, can be converted into higher value products, such as light olefins and aromatic compounds. Pyrolysis oil from such plastic waste, as well as waxes and oligomers from plastic waste and other sources, can be processed in a single step without the need for hydrogenation or other processing steps typically used to convert these materials. The system is characterized by high conversion of the feed and higher selectivity to olefins. Due to the short residence time, the olefin, unsaturate, and / or aromatic content in the feedstock will not hinder pyrolysis or conversion nor produce excessive coking behavior during the reaction, as these will simply pass through the reactor unchanged.

[0090] The reactor system 10 utilizing a hydrocarbon reactant feed, such as those previously described, can be used to provide various higher value products. These include any one or more of the following: olefins; C2to C6olefins, ethylene, propylene, butylene, acetylene, C3to C6acetylenes, butadiene, aromatic compounds, xylene, benzene, toluene, and ethylbenzene. Further, at least a portion of any one or more of these products in the reactor product stream, such as C2to C6alkanes, xylene, benzene, and toluene, can be separated and recovered from the reactor product stream to form at least a portion of the hydrocarbon reactant feed.

[0091] The following examples are provided to further illustrate various embodiments and applications. Example

[0092] In the following examples, various liquid hydrocarbons were used in different experimental runs with gaseous hydrocarbons in an ANJEVOC reactor system 10 as described herein. Each experimental run is shown as a different data point along the x-axis of Figure 7 Example 1

[0093] Figure 7 Selectivity of light olefins and aromatics in weight percent for full range pyrolysis oil or polybutadiene oligomers with ethane in an ANJEVOC reactor 10 is shown. Ethane gas was introduced through the gas feed 46 of the reactor, while pyrolysis oil and polybutadiene oligomers were each introduced through a single fluid nozzle 78. The pyrolysis oil and polybutadiene oligomers each had a dynamic viscosity of less than 10 cP. The pyrolysis oil and polybutadiene oligomers were each introduced as a spray non-normal and non-tangential to the central axis of the center chamber of the feed assembly of the reactor. The SMD size of the spray during injection was 10 pm to 130 pm. In all experiments, the H2 flow rate was fixed at 4.2 lb / hr and the steam flow rate was fixed at 5 lb / hr. The flow rate of O2 was varied from 14.5 lb / hr to 20 lb / hr. The weight percent of polybutadiene oligomers and full range pyrolysis oil relative to the ethane stream was varied between 25% to 50%. The average molecular weight (Mn) of the full range pyrolysis oil was 280. The average molecular weight (Mn) of the polybutadiene was 1,100. At conversion levels between 83% and 91%, the total selectivity of olefins and aromatics ranged between 62 wt% to 67 wt%.

[0094] While the present disclosure has been shown in some of its forms, it should be apparent to those skilled in the art that it is not thus limited to the forms described, but can be practiced in various changes and modifications that do not part from the scope of the disclosure based on experimental data or other optimizations considering the overall economics of the process. Therefore, it is appropriate that the appended claims be construed broadly and in a manner including equivalences in scope to the range of the present disclosure.​

Claims

1. A method for converting pyrolysis oils, waxes, and / or oligomers into higher-value products in a reactor system, said reactor system comprising a central shaft, a feed assembly, and a reactor vessel defining a reaction chamber, said method comprising: Fuel gas feed and oxidant gas feed are introduced into the feed assembly to generate a swirling fluid flow pattern around the central axis; The fuel gas feed and oxidant gas feed are combusted in the feed assembly to form a swirling combustion gas; A hydrocarbon reactant feed is introduced into the feed assembly, wherein the hydrocarbon reactant feed comprises at least one of (i) pyrolysis oil derived from plastic waste, (ii) wax, and (iii) an oligomer with an average molecular weight (Mn) of 1,000 g / mol to 50,000 g / mol in liquid hydrocarbon, wherein the liquid hydrocarbon has a dynamic viscosity of 0.1 cP to 1000 cP at the temperature at which the liquid hydrocarbon is introduced, and the liquid hydrocarbon is introduced in the form of a droplet spray with a droplet SMD of 10 μm to 250 μm; In the feed assembly, the hydrocarbon reactant feed is mixed with the swirling combustion gas to form a swirling heated mixture; The heated mixture is transferred from the feed assembly to the reaction chamber; The heated mixture is reacted in the reaction chamber under reaction conditions suitable for converting the hydrocarbons fed as hydrocarbon reactants into converted hydrocarbon products; as well as The converted hydrocarbon product is removed from the reaction chamber.

2. The method according to claim 1, wherein the pyrolysis oil is a non-hydrogenated pyrolysis oil.

3. The method according to any one of claims 1 to 2, wherein the pyrolysis oil is derived from the pyrolysis of mixed plastic waste materials.

4. The method according to any one of claims 1 to 3, wherein the pyrolysis oil has a boiling point range of 75°C to 650°C.

5. The method according to any one of claims 1 to 3, wherein the pyrolysis oil is a pyrolysis oil fraction with a boiling point range of 75°C to 500°C.

6. The method according to any one of claims 1 to 5, wherein the oligomer and wax are derived from plastic waste materials and / or byproducts of the polymerization process.

7. The method according to any one of claims 1 to 6, wherein the average molecular weight (Mn) of the oligomer is from 2,000 g / mol to 10,000 g / mol.

8. The method according to any one of claims 1 to 7, wherein the liquid hydrocarbon is 0.5% to 100% by weight of one or more hydrocarbon reactant feeds introduced into the feed assembly.

9. The method according to any one of claims 1 to 8, wherein the liquid hydrocarbon is introduced into the feed assembly in a flow pattern not perpendicular to the central axis.

10. The method according to any one of claims 1 to 9, wherein the liquid spray is introduced as a two-fluid spray through a two-fluid nozzle such that the liquid hydrocarbon is introduced together with a second fluid through the two-fluid nozzle.

11. The method of claim 10, wherein the second fluid introduced through the dual-fluid nozzle is a gas.

12. The method according to any one of claims 1 to 11, wherein the liquid spray is introduced at a spray angle of 40° or less.

13. The method according to any one of claims 1 to 12, wherein the hydrocarbon reactant feed further comprises gaseous hydrocarbons.

14. The method according to any one of claims 1 to 13, wherein the converted hydrocarbon product comprises at least one of olefins, C2 to C6 olefins, ethylene, propylene, butene, acetylene, C3 to C6 alkynes, butadiene, aromatic compounds, xylene, benzene, toluene, and ethylbenzene.

15. The method according to any one of claims 1 to 14, wherein the reactor system is an annular jet vortex reactor chamber (ANJEVOC) reactor system.

16. The method according to any one of the preceding claims, wherein the liquid hydrocarbon is mixed with a second fluid, and the mixture of the liquid hydrocarbon and the second fluid is introduced as a spray through the nozzle.

17. The method according to any one of the preceding claims, wherein the liquid hydrocarbon and the second fluid are mixed upstream of the nozzle.

18. The method according to any one of the preceding claims, wherein the second fluid comprises a gaseous hydrocarbon.

19. The method according to any one of the preceding claims further includes mixing the liquid hydrocarbon with steam.

20. The method according to any one of the preceding claims further includes mixing the gaseous hydrocarbon with steam.

21. The method according to any one of the preceding claims, wherein the steam comprises superheated steam.

22. The method according to any one of the preceding claims further includes preheating the liquid hydrocarbon.

23. The method according to any one of the preceding claims, wherein the liquid hydrocarbon is preheated at a temperature ranging from 30°C to 350°C.

24. The method according to any one of the preceding claims further comprises combining the hydrocarbon with a solvent before introducing the hydrocarbon reactant feed into the feed assembly.

25. The method of claim 1, wherein transferring the heated mixture from the feed assembly to the reaction chamber comprises delivering the heated mixture via a convergent-divergent conduit.

26. The method of claim 25, wherein the convergent-divergent conduit includes a constricted neck portion located between a downstream end and an upstream end of the convergent-divergent conduit.

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