WO2025021902A1 - Procédé de conversion d'huiles de pyrolyse, de cires et/ou d'oligomères en produits chimiques de valeur supérieure - Google Patents

Procédé de conversion d'huiles de pyrolyse, de cires et/ou d'oligomères en produits chimiques de valeur supérieure Download PDF

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Publication number
WO2025021902A1
WO2025021902A1 PCT/EP2024/071072 EP2024071072W WO2025021902A1 WO 2025021902 A1 WO2025021902 A1 WO 2025021902A1 EP 2024071072 W EP2024071072 W EP 2024071072W WO 2025021902 A1 WO2025021902 A1 WO 2025021902A1
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Prior art keywords
hydrocarbon
feed
mol
liquid
reactor
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English (en)
Inventor
Sreekanth Pannala
Li Chen
Balamurali Krishna Nair
Retheesh Madhusudanan VANCHIYIL
Byeongjin BAEK
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Priority to CN202480048535.8A priority Critical patent/CN121586758A/zh
Publication of WO2025021902A1 publication Critical patent/WO2025021902A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/008—Pyrolysis reactions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/002—Cooling of cracked gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C10G9/38—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours produced by partial combustion of the material to be cracked or by combustion of another hydrocarbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the present disclosure is directed to the production of high value chemical products from pyrolysis oils, particularly those from plastic waste, and waxes and/or oligomers.
  • Plastic waste through chemical processes. This may eliminate the need to sort the recycled plastic into their different types. Plastics that typically cannot be mechanically processed may also be converted using chemical processes. Such mixed plastic wastes (MPW) can be converted into valuable chemicals, such as ethylene, propylene and other olefins and aromatics using these chemical processes. These chemicals are the building blocks of many plastics and other products and can be used as a feedstock for the production of new or virgin plastics or other materials.
  • MPW mixed plastic wastes
  • One method of processing mixed plastic waste so that it can be used to form more valuable products involves converting the MPW to pyoil through pyrolysis.
  • Pyrolysis is a thermal decomposition process that involves heating the mixed plastic waste in the absence of oxygen, leading to the breakdown of the plastic into smaller molecules. The process produces gases and vapors, which are then condensed into liquid form to create pyoil. The production of pyoil from plastic waste emits fewer greenhouse gases than incineration.
  • steam cracking is typically used to convert pyoil into more valuable products, such as ethylene, propylene and aromatics.
  • pyoil Before the pyoil can undergo steam cracking, however, it must first be pretreated in multiple operation units. This can include distillation, so that only the lighter fraction of the pyoil is cracked.
  • pyoil from MPW typically contains 50% or more unsaturated hydrocarbons. During the steam cracking process, these unsaturated hydrocarbons can cause coking, which can reduce the efficiency of the process and lead to equipment fouling.
  • the pyoil may therefore be hydrogenated in a hydrotreater or undergo other processing steps before steam cracking. This requires added hydrogen, additional process steps, and additional processing units, increasing the cost and complexity of converting the pyoil.
  • even with the hydrogenation of the pyrolysis oil there is still potential for coking to occur during steam cracking.
  • a method of converting pyrolysis oils, waxes, and/or oligomers to higher value products is carried out in a reactor system comprising a central axis, a feed assembly, and a reactor vessel that defines a reaction chamber.
  • a fuel gas feed and an oxidizer gas feed are introduced into the feed assembly to produce a swirling fluid flow pattern about the central axis.
  • the fuel gas feed and oxidizer gas feed are combusted in the feed assembly to form swirling combustion gases.
  • a hydrocarbon reactant feed comprising a liquid hydrocarbon of at least one of (i) plastic-waste-derived pyrolysis oils, (ii) waxes, and (iii) oligomers having an average molecular weight (Mn) of from 1,000 g/mol to 50,000 g/mol is introduced into the feed assembly.
  • the liquid hydrocarbon has a dynamic viscosity from 0.1 cP to 1000 cP and is introduced as a liquid spray having a Sauter Mean Diameter (SMD) of droplets from 1 pm to 250 pm into the feed assembly.
  • the hydrocarbon reactant feed is mixed with the swirling combustion gases 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 to convert the hydrocarbons of the hydrocarbon reactant feed into a converted hydrocarbon product.
  • the converted hydrocarbon product is removed from the reaction chamber.
  • the pyrolysis oils may be non-hydrogenated pyrolysis oils.
  • the pyrolysis oils may be those derived from pyrolyzing mixed plastic waste materials.
  • the pyrolysis oils may have a boiling point range of from 75 °C to 650 °C in some instances and in others the pyrolysis oils may be that fraction of pyrolysis oils having a boiling point range of from 75 °C to 500 °C.
  • the oligomers and waxes may be those derived from plastic waste materials and/or byproducts of the polymerization process.
  • the oligomers may have an average molecular weight (Mn) of from 2,000 g/mol to 10,000 g/mol.
  • the liquid hydrocarbon may make up from 0.5 wt% to 100 wt% of the hydrocarbon reactant feeds.
  • the liquid hydrocarbon may be introduced through a liquid feed inlet of the feed assembly in a flow pattern that is non-perpendicular to the central axis.
  • the liquid spray may be introduced as a two-fluid spray through a two-fluid nozzle so that the liquid hydrocarbon is introduced through the two-fluid nozzle with a second fluid.
  • the second fluid introduced through the two-fluid nozzle may be a gas.
  • the liquid spray may be introduced in a spray angle of 40° or less.
  • the hydrocarbon reactant feed may further comprise a gaseous hydrocarbon.
  • the converted hydrocarbon product may comprise at least one of an olefin, a C2 to Ce olefin, ethylene, a propylene, a butene, acetylene, a C3 to Ce alkyne, a butadiene, an aromatic compound, a xylene, benzene, toluene, and ethyl benzene.
  • FIG. 3 is cross-sectional perspective view of the feed assembly and upstream end of a reaction chamber of the reactor system of FIG. 1;
  • FIG. 4 is a plot of the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in a reactor systems, such as that of FIG. 1;
  • FIG. 5 is a plot showing the Computational Fluid Dynamics (CFD) calculations of spray evaporation in a reactor, such as that of FIG. 1, wherein all the liquid was vaporized within 5 mm from the injection point;
  • CFD Computational Fluid Dynamics
  • FIG. 6 is a plot of the results of testing of a FLOWMAX® FM3A two-fluid nozzle using liquid water and air showing the various droplet sizes under various flow conditions; and [0021]
  • FIG. 7 is a plot of selectivity in weight percent of light olefins and aromatics for either full range pyoil or poly butadiene oligomer in an ANJEVOC reactor.
  • unique reactor technology is utilized to convert pyoil from mixed plastic wastes (MPW), waxes and/or oligomers to produce high value chemicals, such as light olefins and aromatics.
  • the pyoil may be whole-range pyoil or various fractions of pyoil produced from pyrolysis of the MPW.
  • the waxes and/or oligomers may be those obtained from fractional distillation of plastic waste pyoil and/or waxes or oligomers obtained from other sources, such as byproducts from the polymerization process.
  • the conversion of these materials may be accomplished in single step of processing or with reduced or minimal processing steps and equipment, as compared to conventional steam cracking processing systems utilized to process pyoil, which requires additional processing steps. More specifically, the conversion may be achieved by utilizing ANJEVOC (ANnular JEt VOrtex Chamber) reactor technology that produces annular highly swirled jets of feed gases where hydrogen (or other fuels such as natural gas, recycled syngas, etc.) and oxygen gases are mainly used to generate the heat required for cracking of hydrocarbons. Examples of such ANJEVOC reactors are described in U.S. Patent Nos. 11,020,719 and 11,123,705; and International Publication Nos. W02022/010821A1; W02022/010822A1, and
  • FIG. 1 an elevational cross-sectional representation of a reactor system 10 for the conversion of liquid hydrocarbons is shown.
  • the reactor system 10 is configured for the conversion of liquid hydrocarbons in the form of pyoil and waxes and/or oligomers, which may 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 in conjunction with the liquid hydrocarbons.
  • the reactor system 10 may 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 may have a cylindrical configuration with a constant diameter along all or a portion of its length, which may constitute a majority (i.e.
  • the reactor vessel 12 is oriented vertically so that the cylindrical reactor wall 14 is oriented in an upright orientation with downward flow.
  • the reactor can have other orientations (e.g., horizontal, sloped, or upright with upward flow), however, because the process is controlled by the centrifugal force, which exceeds the gravitational force by several orders of magnitude.
  • the reactor vessel 12 may be configured to provide a length to diameter ratio (L/D) of at least 2. In particular applications, the L/D ratio may range from 2-10, more particularly from 2-5.
  • the reactor vessel 12 may be formed from steel.
  • a cooling jacket can be provided around all or portions of the reactor vessel 12, wherein a second steel wall 18 is positioned around and spaced from the inner reactor wall 14 and a cooling fluid, such as water, may be circulated through the jacket formed between the walls 14, 18.
  • the reactor wall 14 may be formed from one or more layers of refractory material that line the interior of an outer steel wall to reduce heat loss and sustain the high temperatures of the reactor 10. Because of the unique design and operation of the reactor 10, the reactor wall 14 is cooled internally by the high-velocity near-wall gas flow pushed by centrifugal forces against the reactor wall 14 so that in some applications no exterior cooling jacket is required.
  • Refractory materials typically cannot be used with conventional cracking reactors with pure oxygen due to the higher temperatures (e.g., from 2000 °C to 2800 °C).
  • Reaction temperature for the conversion of liquid hydrocarbons, such as crude oil, in the reactor system 10 will typically range from 800 °C to 2500 °C.
  • An outlet 20 is provided at a lower or downstream end of the reactor vessel 12 for removing or discharging cracked products from the reaction chamber 16.
  • the outlet diameter can be same as the diameter of the reactor wall 14 or the outlet diameter may be reduced to accelerate the flow before quenching and collection downstream.
  • the inlet assembly 22 defines a converging-diverging conduit 24 defined by a circumferential wall 26 that surrounds a central axis 28 of the reactor 10. is the central axis 28 of the reactor 10 may be the same or coincide with the central axis of each of the inlet assembly 22 or conduit 24 and reactor vessel 12.
  • the circumferential wall 26 extends from opposite upstream and downstream ends of the converging-diverging conduit 24.
  • upstream and downstream or similar expressions with respect to describing various components of the reactor system 10 shall refer to the position of the component with respect to the direction of overall fluid flow through the reactor 10 along the central axis 28.
  • the circumferential wall 26 smoothly tapers in width or diameter from the upstream ends to define an annular constricted neck portion located between the downstream and upstream ends of the converging-diverging conduit 24.
  • the circumferential wall 26 smoothly expands or diverges in width or diameter downstream from the annular constricted neck portion.
  • the interior of the circumferential wall 26 may have a circular perpendicular transverse cross section with respect to the central axis 28 along all or a portion of its length.
  • 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 convergingdiverging nozzle of the inlet assembly 22.
  • the nozzle geometry of the converging-diverging conduit 24 is configured based upon the theory relating to swirling conical jets of a viscous incompressible fluid. This phenomenon is described in the journal article by Pannala et al., entitled “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, 2(5), 406-420). The downstream or diverging portion of the conduit 24 is configured for non-supersonic fluid flow.
  • Conduits or nozzles configured for supersonic flow are configured differently from the conduit 24 to provide supersonic flow downstream to form a shockwave.
  • the diverging conduit 24 does not form such supersonic flow or shockwave.
  • the conduit 24 has a geometry that facilitates a recirculation and backflow of gases within the interior reaction chamber 16 near the central axis 28 in combination with annular swirling jet gas flow adjacent to the inner reactor wall 14.
  • the conduit 24 will have a greater angle of divergence than the angle of divergence typically utilized in de Laval nozzles, which have an angle of divergence of 15° or less.
  • the overall angle of divergence “A” (FIG.
  • the angle of divergence A for the diverging portion of the conduit 24 discussed herein is from 25° to 55°.
  • the angle of divergence A is from at least, equal to, and/or between any two of 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°.
  • the large divergence angle leads to recirculation of fluid flow at the reactor wall 14, as a result of the upstream swirling flow coupled with the convergent divergent conduit 24.
  • the downstream end of the diverging portion of conduit 24 joins the reactor wall 14 at an inlet of the reaction chamber 16 around its perimeter so that the conduit 24 is in fluid communication with the reaction chamber 16 of the reactor vessel 12.
  • the upstream end of the converging portion of conduit 24 forms an inlet for the reactor vessel 12.
  • upstream feed assembly wall 36 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 portions thereof are oriented perpendicular to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
  • An upstream gas partition wall 38 and a downstream gas partition wall 40 are axially spaced between the downstream and upstream feed assembly walls 34, 36 and are axially spaced from one another, with the upstream partition wall 38 being positioned upstream from the downstream partition wall 40.
  • the partition walls 38, 40 or circumferential portions thereof are also each oriented perpendicularly to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
  • 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 defining the openings 42, 44 terminate at a position upstream of the converging-diverging conduit 24.
  • the central openings 42, 44 each have a circular configuration.
  • Other continuously-curved shapes for the central openings 42, 44 e.g., oval
  • This shape may also correspond to the cross-sectional shape of the circumferential wall 26 of the converging-diverging conduit 24.
  • the central openings 42, 44 will be circular in shape.
  • the central openings 42, 44 may have a diameter or width that is the same or slightly different (smaller or larger) than the diameter or width of the constricted neck of the converging-diverging conduit 24 at its narrowest point.
  • the upstream partition wall 38 defines an annular gas flow passage 46 located between the upstream feed assembly wall 36 and the upstream side of the upstream partition wall 36.
  • the flow passage 46 constitutes an upstream annular hydrocarbon reactant feed inlet flow passage for introducing a gaseous hydrocarbon to be converted, e.g., into high value chemicals such as light olefins and aromatics.
  • 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.
  • the flow passage 48 may constitute an annular steam or water inlet flow passage.
  • An intermediate partition wall 50 is axially spaced between the downstream gas partition wall 40 and the upstream gas partition wall 38 to define downstream and upstream intermediate annular gas inlet flow passages 52, 54.
  • the intermediate partition 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 ends of the partition wall 50 defining the opening 56 terminate at a position upstream of the converging-diverging conduit 24.
  • the central opening 56 may have a circular configuration. Other shapes for the central opening 56 (e.g., oval) may also be used provided such configuration facilitates the swirling of gases to provide the required swirling flow patterns described herein.
  • the intermediate partition wall 50 is also oriented perpendicularly to or substantially perpendicularly (i.e., ⁇ 5 degrees from perpendicular about its circumference as it extends radially from the central axis) to the central axis 28.
  • the annular flow passage 52 may constitute an oxygen or oxidizing gas flow passage to facilitate combustion.
  • the annular flow passage 54 may constitute a fuel gas (e.g., H2, CH 4 , syngas or a combination of these) flow passage for introducing a fuel gas for combustion.
  • the central axis 28 also coincides with and forms a central axis of the central chamber 58 and feed assembly 32.
  • This configuration provides flow passages through which gas feeds to be cracked, steam, oxygen gas, and hydrogen-rich fuel for providing combustion heat can each be separately introduced and passed through the flow passages 46, 48, 52, 54, respectively, into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases.
  • the feeds are introduced into the central chamber in a direction that is non-parallel to the central axis 28.
  • one or more of the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 are configured to introduce the feeds into the central chamber 58 of the feed assembly 32 in a swirling fluid flow pattern about the central axis 28 such that the feeds combust in the central chamber to form swirling combustion gases.
  • the feed assembly wall 34, the upstream wall 36, the partition walls 38, and 40 the intermediate partition wall 50 (or circumferential portions thereof) may be oriented in a direction that is non-parallel to the central axis 28.
  • 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 circumferential portions thereof) may be oriented 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 perpendicular the central axis 28.
  • the upstream flow passage 46 can act as a gaseous hydrocarbon feed inlet flow passage.
  • a fuel gas feed comprised of an hydrogen-rich gas feed i.e., H2
  • an oxidizer i.e., O2
  • oxy gen-containing gas feed may be introduced into the other of the flow passages 52, 54.
  • the fuel and oxygen gas feeds will be introduced into flow passages that are immediately adjacent to one another to facilitate rapid combustion.
  • the downstream flow passage 52 may be used for delivering the oxidizer or oxygen-containing gas and the upstream flow passage 54 will be used for delivering the hydrogen-rich fuel gas.
  • the steam feed may be introduced into the downstream annular steam inlet flow passage 48.
  • the various feeds may be altered in sequences within the flow passages 46, 48, 52, 54.
  • any of flow passages 48, 52, 54 can act as a gaseous hydrocarbon feed inlet flow passage.
  • the steam feed may be combined or introduced with one or more of the other feeds. This may include combining the steam feed with the fuel-gas feed, the oxy gen-containing gas feed, or the hydrocarbon gas feed.
  • the flow passages 46, 48, 52, 54 are configured so that the different feeds pass through flow passages perpendicularly or substantially perpendicularly to the central axis 28 in an inwardly swirling fluid flow pattern within said flow passages so that the feeds flow about the central axis 28 within the central chamber 58.
  • the swirling fuel gas and oxidizer feeds combust within the central chamber 58.
  • the walls 34, 36, 38, 40, and 50 forming the different flow passages 46, 48, 52, 54 are parallel to one another. However, in other cases, walls 34, 36, 38, 40, and 50 may be non-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 through them. This may be based upon the desired flow rates or linear velocities of each of the feed gases and their relative amounts. For instance, the relative volume of oxygen gas needed for the combustion is typically smaller than the volume of the hydrogen-rich fuel gas needed for the combustion.
  • the partition wall 50 may be spaced closer to the downstream partition wall 40 so that the flow passage 54 for the hydrogen fuel is larger and accommodates the greater flow of fuel gas.
  • the particular spacing may depend on fuel gas and oxidizer combination, the desired volume for combustion, and nature of the hydrocarbon feeds.
  • Annular gas manifolds 60, 62, 64, 66 are provided around the outer periphery of the flow passages 46, 48, 52, 54, respectively.
  • the gas manifold 60 may be fluidly coupled to a gaseous hydrocarbon feed source.
  • the manifold 62 may be fluidly coupled to a steam source.
  • the manifold 64 may be fluidly coupled to an oxygen-containing-gas source, such as a pure O2 feed.
  • the manifold 66 is fluidly coupled to a hydrogen-rich or fuel feed source, such as H2.
  • the manifolds 60, 62, 64, 66 are provided with the reactor feed assembly 32 to facilitate introduction of feed gases into the flow passages 46, 48, 52, 54. In other embodiments, the different feed sources to each manifold may be varied.
  • the gas inlets from the manifolds 60, 62, 64, 66 are oriented to generate an inwardly swirling flow of gases within central chamber 58 (e.g., oriented nearly tangentially with respect to an outer perimeter of the flow passages 46, 48, 52, 54).
  • the gas inlets direct the incoming flow of gases along paths that extend inwardly from the walls of central chamber 58 but not along a radius of central chamber 58 directly toward the central axis 28 from the inlets.
  • one or more inlets may be provided for each flow passage 46, 48, 52, 54.
  • the walls 34, 36, 38, 40, and 50 that form the different flow passages of the feed assembly 32 prevent the gases from flowing axially along the direction of central axis 28 while 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 may be typically used in vortex devices.
  • one or more or all of the flow passages 46, 48, 52, 54 may be provided with a plurality of circumferentially spaced guide vanes 68, 70, 72, 74 (e.g., 10 to 60 guide vanes for each flow passage).
  • Each guide vane 68, 70, 72, 74 may be a planar member that is oriented in a plane that is parallel to the central axis 28 and extends between the walls 34, 36, 38, 40, and 50.
  • the guide vanes 68, 70, 72, 74 may be circumferentially spaced an equal distance from one another.
  • the guide vanes 68, 70, 72, 74 may be fixed in place, with the upper and lower side edges of the guide vanes being joined along their lengths or a portion of their lengths to the walls 34, 36, 38, 40, and 50 so that there are no air gaps between the side edges of the vanes 68, 70, 72, 74 and the walls 34, 36, 38, 40, and 50.
  • the guide vanes are movable. In such cases, the upper and lower side edges of the vanes 68, 70, 72, 74 may be closely spaced from the walls 34, 36, 38, 40, and 50 to provide a small clearance to allow movement. The close spacing may minimize air gaps through which gases may pass.
  • the vanes 68, 70, 72, 74 may be oriented so that the plane of the vane is in a non-parallel or slanted orientation relative to the central axis 28. In such cases, the side edges may be fixed to the walls 34, 36, 38, 40, and 50 or remain closely spaced from walls 34, 36, 38, 40, and 50 to minimize air gaps.
  • the guide vanes 68, 70, 72, 74 may be configured as airfoils, such as described in U.S. Patent No. 11,123,705.
  • the guide vanes 68, 70, 72, 74 are provided adjacent to the outer perimeter of the flow passages 46, 48, 52, 54 and are spaced in an annular or circular ring pattern near the manifold inlets. In other reactor systems, they may be provided in an annular pattern at other positions located radially inward or further within the interior of the flow passages 46, 48, 52, 54. Alternatively, one or more additional annular sets of guide vanes may be located radially inward from those located along the outer periphery to facilitate inwardly swirling fluid flow.
  • Feed gases from the manifolds 60, 62, 64, 66 are delivered nearly tangentially to the outer perimeter of the central chamber 58, where the guide vanes 68, 70, 72, 74 may direct the gas flow in an inwardly swirling or spiraling fluid flow pattern within the central chamber 58.
  • the inlets from the manifolds 60, 62, 64, 66 may be oriented or directed to impart the full inwardly swirling fluid flow without the use of or need for guide vanes.
  • the guide vanes 68, 70, 72, 74 may impart the full swirling flow of the introduced gases, such as in instances where the gas from the manifold inlets may be directed radially toward the central axis 28 or do not impart the full desired swirling flow. In such cases the guide vanes 68, 70, 72, 74 prevent flow directly toward the central axis 28 and direct the flowing gases nearly tangentially with respect to the inner walls of central chamber 58 to provide the inwardly swirling or spiraling fluid flow pattern.
  • the guide vanes 68, 70, 72, 74 of each flow passage 46, 48, 52, 54 may be mounted on actuators (not shown) so that they can be selectively movable to various positions to provide a selected inwardly spiraling flow pattern.
  • the guide vanes 68, 70, 72, 74 may be pivotal about an axis that is parallel to the central axis 28 so that the vanes 68, 70, 72, 74 may be moved to various positions.
  • the orientation of the vanes 68, 70, 72, 74 and/or the orientation of the inlets of the manifolds 60, 62, 64, 66 of each flow passage will provide swirling or spiraling fluid jet flow that is in the same rotational direction about the central axis 28, i.e., clockwise or counterclockwise.
  • gases within each of the flow passages will flow clockwise or counterclockwise about the central axis 28.
  • the vanes 68, 70, 72, 74 will all introduce gases at the same angle inner relative to the walls of central chamber 58 to provide the desired swirling fluid flow characteristics. If the vanes 68, 70, 72, 74 are movable, then they will typically be actuated to move in unison or close to unison.
  • oxygen and hydrogen fuel gases from flow passages 52, 54, gaseous hydrocarbon feed from flow passage 46, and steam from flow passage 48 may be discharged into the central chamber 58 of the feed assembly 32. Because the oxy gen-containing gas and hydrogen-rich fuel gas are introduced separately from one another and not as mixture, this eliminates safety issues that would otherwise occur if these gases were premixed prior to their introduction into the feed assembly 32. Furthermore, the combustion reaction takes place rapidly, with most of the combustion occurring within a small space within the central chamber 58 where the two streams of oxy gen-containing gas and hydrogen-rich fuel gas from the flow passages 52, 54 are mixed after being discharged from the flow passages 52, 54.
  • the combustible mixture can be ignited, e.g., using a spark, chemicals or pilot flame that extends through the bottom surface or side surfaces of the reactor. Suction from the swirling flow can transport heat from an ignition device to the combustion zone 58 to initiate the ignition.
  • a liquid feed inlet 76 is also formed in the upstream feed assembly wall 36 for introducing, into the feed assembly 32, all or a portion of the liquid hydrocarbons to be converted by the reactor system 10 into, e.g., high value chemicals such as light olefins and aromatics.
  • the liquid feed inlet 76 may be formed as a length of conduit that joins the feed assembly wall 36.
  • the conduit may include an inlet axis that is aligned with and/or parallel to the central axis 28 so that the liquid feeds or a majority (i.e.
  • liquid feeds introduced through the inlet 76 may be introduced axially or at a non-perpendicular angle with respect to the central axis 28 into the central chamber 58. In other words, the liquid feeds introduced through the inlet 76 are not introduced perpendicularly to axis 28.
  • a liquid feed manifold 80 may be used to introduce liquid feeds through the liquid feed inlet 76.
  • the manifold 80 is fluidly coupled to a liquid feed source comprising the liquid hydrocarbon to be converted.
  • the manifold 80 comprises one or more spray nozzles 78 that may be used to introduce the liquid feed as a liquid spray (i.e., a spray of liquid droplets) into the central chamber 58.
  • the manifold 80 may comprise multiple spray nozzles 78 positioned and oriented for introducing, into the central chamber 58 through the liquid feed inlets 76, the liquid feed as multiple sprays of droplets.
  • the droplets in the liquid feed define anon- swirling spray and/or a radially-extending fanned pattern so that all or a portion of the droplets are not parallel to the central axis, but will have axial and radial flow velocity components.
  • the droplet pattern may be centered on or close to the central axis where the swirl velocities are lowest.
  • one or more spray nozzles 78 introduce liquid into the central chamber 58 of the feed assembly 32 where the swirl velocity of the swirling fluid flow is less than 5 m/s during operation of the reactor 10.
  • One or more spray nozzles may be located within a certain 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.
  • PR placement radius
  • 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.
  • the central location of the nozzle injects the liquid hydrocarbon reactant feed into an area of a reactor with a low swirl velocity (e.g., swirl velocity of less than 5 m/s).
  • the location along with the droplet size allows the liquid droplets to vaporize before the droplets enter an area of the feed assembly with higher swirl velocities, thereby preventing rapid coking of the reactor.
  • the combination of a location for the nozzle and a droplet size generated by the nozzle at that location thus provides certain unique advantages.
  • the combination of axial and radial flow velocity components defines a spray pattern that has a low spray angle and keeps the pattern close to the central axis 28.
  • the droplets are directed primarily axially (e.g., to define a spray angle of 40° or less). Such a spray angle helps ensure that liquid droplets are vaporized before being caught in the swirling gas flow and forced by centrifugal forces against the reactor wall, which can lead to coking.
  • the spray pattern may 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°.
  • the spray pattern may be a solid conical, hollow-conical, linear stream, or flat spray pattern.
  • the liquid feed inlet 76 is does not include guide vanes, such as the vanes 68, 70, 72, 74, or other structures that may impart a swirling fluid flow to the liquid hydrocarbon before it enters the central chamber 58.
  • the atomized spray with liquid droplets is primarily concentrated close to the central axis 28 of the reactor 10 where the swirl velocity is lowest. In effect, the liquid droplets are concentrated at the “eye” of the swirling flow. Higher swirl velocities are encountered away from the central axis 28 or centerline and closer to the walls. These higher swirl velocities could deposit the atomized droplets on the walls and guide vanes causing coking and fouling.
  • the small droplets interact with the counter current flow of the high temperature gases from the combustion and strong recirculation to vaporize the droplets and follow the other hydrocarbon gases to increase heat and crack in the reactor 10.
  • the spray nozzle(s) at the liquid feed inlet 76 may provide a SMD size for the liquid hydrocarbon feed of from 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
  • FIG. 4 shows the vaporization times as a function of droplet size using a simplified calculation with approximate conditions in the reactor.
  • FIG. 5 shows the Computational Fluid Dynamics (CFD) calculations of spray evaporation in the reactor, wherein all the liquid was vaporized within 5 mm from the injection point.
  • the plot shows the volume fraction of liquid of the spray that ranges from approximately 2.5 xlO' 5 at its introduction and goes to 0 (which indicates that all the liquid was vaporized).
  • Weighted average droplet size may include a mass (volume) median or 50% diameter (Dvo.s), which is the diameter at which 50% of the total volume of droplets are contained in particles with smaller diameters.
  • the Dvo.s of the droplets may be from 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 m, 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
  • the Dvo.i is the diameter below which 10% of the total volume of droplets are found.
  • the Dvo.i of the spray may be from 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
  • the Dvo.9 is the diameter below which 90% of the total volume of droplets are found.
  • the Dvo.9 of the spray may be from 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,
  • the spray nozzle is configured to form droplets with a Dvo.9 from 20 pm to 100 pm.
  • the liquid hydrocarbon may be modified to have a dynamic viscosity from 0.1 cP to 1000 cP prior to or at its introduction, as measured using ASTM D445, but at the temperature of operation (i.e., the temperature of the liquid hydrocarbon when passed through the nozzle(s)).
  • the liquid hydrocarbon feed may in some cases be preheated to a temperature between 25 °C to 400°C and viscosity measured at this temperature.
  • the droplet size is approximately proportional to dynamic viscosity to the power of 0.2 and thus lower dynamic viscosity leads to smaller droplet size.
  • fluids with lower dynamic viscosity also have lower surface tension and the droplet size is approximately correlated to surface tension to the power of 0.5.
  • the liquid hydrocarbon may be modified to have a dynamic viscosity from 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
  • Modification of the hydrocarbon may include heating the hydrocarbon to a sufficient temperature and/or combining the liquid hydrocarbon with a solvent or low viscosity component to lower the dynamic viscosity.
  • solvents may include an oligomer, wax or other liquid have a lower dynamic viscosity than the hydrocarbon being modified.
  • the spray nozzle(s) 78 may be configured or selected as a two- fluid nozzle.
  • Such two-fluid nozzles may allow for the introduction of two different fluids, each having different properties from the other.
  • the liquids could include a liquid phase fluid and vapor phase fluid that are each sprayed simultaneously through the nozzle 78.
  • the two-fluid nozzle 78 may have a mixing chamber where the two fluids are mixed prior to being discharged as a spray.
  • Such two-fluid nozzles also provide internal mixing of the two fluids to prevent clogging, as well as providing a fine atomized spray having the above-stated droplet size.
  • Such two-liquid spray nozzles are described, for example, in U.S. Pat. App.
  • Two-fluid nozzles may facilitate rapidly diffusing the mixture from the outlet, promoting atomization, and forming droplets, which can be conveyed easily by the atomization gas. This can reduce liquid deposition on the mixed gas outlet and prevent clogging.
  • a suitable commercially available two-fluid nozzle for use as the spray nozzle(s) 78 may include that marketed as the FLOWMAX® X-Series or FLOWMAX® FM3 A nozzle, available from Spraying Systems Co., Tokyo, Japan.
  • two-fluid nozzles provide a broad range of control over the droplet size distribution and ability to self-clean as the vapor phase can be steam.
  • a disadvantage may be that slight variations in vapor phase or liquid phase flow rates or pressures can dramatically vary the droplet and spray characteristics.
  • the liquid hydrocarbon may be introduced into the liquid feed inlet 76 through the two-fluid spray nozzle 78 along 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 the spray manifold 80 that is fluidly coupled to separate upstream liquid hydrocarbon and gas feed (i.e., steam and/or gaseous hydrocarbons) sources.
  • the range of pressures for the liquid feed versus vapor feed depend on the design of the nozzle. For example, FIG.
  • FIG. 6 shows the results of testing of a FLOWMAX® FM3A two-fluid nozzle using liquid water and air under different flow conditions and the various droplet sizes (i.e., D32, DVO.9, Dvo.99).
  • the liquid pressure was varied in the range of 1-3 barg at a constant gas pressure of 4.14 barg.
  • the corresponding liquid flow was in the range of 1 - 11 liters per minute and air flow rate was between 80-100 Nm 3 /hr.
  • the SMD varied between 20 pm to 55 pm.
  • these parameters may be tuned for any particular hydrocarbon used as liquid feed and paired with steam or other gas as the vapor phase in such two-fluid nozzles.
  • Droplet vaporization time is proportional to square of the droplet diameter.
  • the droplets may encounter higher swirl velocities leading to high centrifugal acceleration (e.g., 100 g to 100,000 g forces), resulting in deposition of the droplets on the walls and coking and fouling of the reactor. This creates a positive feedback loop where any deposits will disrupt desirable hydrodynamics and accelerate additional maldistribution and deposition. This leads to coking and plugging of the reactor.
  • the droplet characteristics in terms of droplet size, spray angle, etc. are thus important.
  • the liquid hydrocarbon feed that can be converted by the reactor system 10 includes those pyrolysis oils derived from plastic wastes, including pyrolysis oils from MPW.
  • Plastic wastes that may be pyrolyzed to form pyrolysis oils used for the liquid feed may include, but are 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, etc.
  • PET polyethylene terephthalate
  • HDPE high-density polyethylene
  • PVC polyvinyl chloride
  • LDPE low-density polyethylene
  • PP polypropylene
  • PS polystyrene
  • ABS acrylon
  • plastic materials formed as microplastics, plastic films and wrappers, plastic fibers, fishing gear, plastic straws and utensils, plastic containers, plastic bottles and caps, and plastic toys and various consumer goods. Furthermore, these plastics do not need to be sorted or cleaned and can be a mixture of all types of plastics before they are pyrolyzed, eliminating a significant amount of the processing and costs that are typically associated with mechanical recycling.
  • the liquid hydrocarbon feed may include whole-range pyoil, which is that pyoil that has not undergone any fractionation or distillation.
  • the plastic waste pyoil may be a lighter fraction of pyoil or that portion of pyoil having a boiling point range of less than the final boiling point.
  • Whole-range pyoil from MPW typically has a boiling point range from 75 °C to around 650 °C.
  • the pyoils may have an average molecular weight (Mn) from 100 to 400.
  • Lighter fractions of the pyoil may include those with a final boiling point from 600 °C, 550 °C, 500 °C, 450 °C, 400 °C or less.
  • the liquid hydrocarbon feed may be that having boiling point range from at least, equal to, and/or between any two of 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,
  • the plastic waste pyoils for the liquid feed may be non-hydrogenated pyrolysis oils.
  • Such non-hydrogenated pyoils have not undergone any hydrogenation, such as in a hydrotreater, after pyrolysis.
  • Hydrogenated pyoils can also be used for the liquid feed, however, as well as a mixture of non-hydrogenated and hydrogenated pyoils.
  • the pyrolysis oils do not need to be hydrogenated, as in conventional conversion systems (e.g., steam cracking), because of the reactor’s ability to convert the pyoils without coking. This eliminates the additional processing steps required when processing pyoils in conventional steam cracking systems.
  • waxes i.e., paraffins
  • oligomers may also be used as the liquid feed and processed in the reactor system 10. These may be waxes and oligomers derived from plastic waste pyoils, such as through distillation or fractionation. All or a portion of the waxes and oligomers may be those from other sources, as well, such as byproducts of the polymerization process.
  • the waxes may include those paraffins in the C20 to C50 range or higher.
  • the waxes used for the liquid feed may have an average molecular weight (Mn) from 250 g/mol to 1,000 g/mol.
  • the waxes may have an average molecular weight (Mn) range from at least, equal to, and/or between any two of 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/
  • the oligomers may be those formed from various monomers or combinations of monomers. In the present application, the oligomers may also be those produced from the partial or incomplete pyrolysis of the polymers or plastic materials. Typically, the monomers will be ethylene or propylene monomers, with ethylene monomers being the predominant monomers.
  • the oligomers may include those having an average molecular weight (Mn) from 1,000 to 50,000. In particular embodiments, the oligomers may have an average molecular weight (Mn) of from 2,000 to 10,000.
  • the oligomers may have an average molecular weight (Mn) from at least, equal to, and/or between any two of 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, 2
  • the liquid hydrocarbon feed may be comprised of one or more of whole-range pyoil, a pyoil fraction, waxes, and oligomers, and combinations of these. These may all be derived from plastic waste or MPW.
  • the liquid hydrocarbon converted with the reactor system 10 will typically make up from 0.5 wt% to 100 wt% of the total weight of the hydrocarbon reactant feeds (i.e., both liquid and gas hydrocarbons).
  • the liquid hydrocarbon may make up from at least, equal to, and/or between any two of 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%,
  • the liquid hydrocarbon will be converted in the reactor system 10 along with a gaseous hydrocarbon.
  • gaseous hydrocarbon or similar expressions is meant to include those hydrocarbons that are at conditions, such as temperature and pressure with or without addition of steam dilution, where the hydrocarbon is in a gaseous or superheated state prior to its introduction into the reactor system 10. This may include those hydrocarbons that may be liquids at standard atmospheric conditions but are at elevated temperatures and/or reduced pressures, such that they are vaporized prior to their introduction into the reactor system 10.
  • the gaseous hydrocarbon may have a boiling point at one atmosphere no greater than 450 °C, no greater than 250°C, or no greater than 150°C.
  • the gaseous hydrocarbon may include, but is not limited to, natural gas liquids (NGL), a natural gas condensate, a C4 stream, and any one or more of a gaseous Ci to C20 hydrocarbon or mixtures thereof, and combinations of these.
  • NNL natural gas liquids
  • C4 stream a natural gas condensate
  • Ci to C20 hydrocarbon a gaseous Ci to C20 hydrocarbon or mixtures thereof, and combinations of these.
  • all or a portion of the gaseous hydrocarbon can be cofed with the liquid hydrocarbon feed through the liquid feed inlet 76 and spray nozzle 78.
  • the gaseous hydrocarbon may be mixed with the liquid hydrocarbon within the nozzle 78 itself, such as in a mixing chamber of the nozzle, prior to it being discharged as a spray.
  • the spray nozzle 78 is not a two-fluid nozzle, the liquid and gaseous hydrocarbons may be mixed and combined upstream of the nozzle 78, where they both may be discharged together through the spray nozzle(s) 78.
  • the gaseous hydrocarbon may be introduced separately from the liquid hydrocarbon through the liquid feed inlet 76.
  • all or a portion of the gaseous hydrocarbon feed to be converted by the reactor system 10 is introduced through one of the annular gas flow passages 46, 48, 52, 54 of the feed assembly 32. Typically, this will be the upstream flow passage 46, which is immediately adjacent to the liquid feed inlet 76.
  • One or both of the liquid hydrocarbon feed and/or gaseous hydrocarbon feed may be mixed with steam. This is typically superheated steam that is combined with and fed with the hydrocarbon feed prior to its introduction into the feed assembly 32 or central chamber 58.
  • the steam may be mixed with the liquid hydrocarbon within the nozzle 78 itself prior to it being discharged as a spray. Steam may also be separately introduced into the feed assembly 32 through one of the annular flow passages, such as the downstream flow passage 48.
  • a gaseous hydrocarbon feed such as those discussed previously, is introduced from manifold 60 through an inlet into flow passage 46.
  • a hydrogen-containing fuel gas is introduced from manifold 66 into flow passage 54.
  • the hydrogen-containing fuel gas may be hydrogen gas (H2), methane (CH4), and/or CO/syngas or a combination of these.
  • the CH4 is used as fuel for combustion.
  • the methane may be present in the fuel gas in an amount from 20 mol%, 15 mol%, 10 mol%, 5 mol% or less. Greater amounts of methane may impact the desired selectivity. In other embodiments, however, greater amounts of methane may be used, including 100% methane for the fuel gas. Natural gas may also be used as fuel gas.
  • the hydrogen-containing fuel gas may be a hydrogen-gas-rich stream composed primarily of hydrogen gas, which may be a recycled stream from downstream processing, or additional hydrogen gas.
  • the hydrogen-gas-rich stream may contain other components such as methane, CO, steam, inert gases, and CO2.
  • Other hydrocarbons can also be used as the fuel gas in certain embodiments and applications. Additionally, small amounts of N2 can 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 may 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 of liquid and gaseous hydrocarbons) to hydrogen-containing fuel will typically range from 1 to 15, more particularly from 1 to 10, based on mass.
  • An oxidizer or oxygen-containing gas which may be a concentrated or pure oxygen gas, such as from an air separation unit (not shown), is introduced as the oxidizer feed through manifold 64 through inlets into the flow passage 52. Having the oxygen-containing gas introduced through the downstream flow passage 52 spaces it further from liquid feed inlet 76 and any hydrocarbons gas introduced through flow passage 46 to eliminate or minimize any combustion of the introduced hydrocarbon reactant feeds.
  • the mole ratio of H2/O2 may range from 2 to 9, more particularly from 2 to 5, and still more particularly from 2 to 4.
  • the oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.2 to 1.0.
  • An excess of hydrogen also helps to scavenge free radicals (e.g., O, OOH, OH) formed that would otherwise react with the hydrocarbon feeds.
  • a mole ratio of H2/O2 may be less than 2 to compensate for other fuel gases or to have excess O2 in the mixing region to release heat to counter endothermic cracking reactions.
  • hydrogen is sub- stoichiometric (below 1) to allow for additional exothermic reactions in the mixing zone.
  • the oxygen feed may provide an oxygen equivalent-to-fuel mole ratio from 0.125 to 0.50.
  • the ratio between the hydrocarbon feeds to hydrogen fuel will typically range from 1.0 to 15 based on mass depending on the hydrocarbon feed.
  • Steam or water may be introduced through manifold 62 and through inlets into the flow passage 48. Steam may be introduced upstream of the other feeds and may be used to cool the walls of the converging-diverging conduit 24 and reactor vessel 12. The introduced steam also reduces the reaction temperatures within the reactor 10. Steam may also be pre-mixed with the various feeds, such as with the liquid and gaseous hydrocarbon feeds, fuel gas, and/or oxygen- containing feed. Steam may be used in a mass ratio of steam-to-fuel from greater than 0 to 10.0, more particularly from 0 to 2.0, in certain applications.
  • the liquid hydrocarbon feed comprising one or more of pyoil, plastic waste pyoil, MPW pyoil, waxes, and oligomers is introduced through the inlet 76 from nozzle 78 as a spray is immediately vaporized.
  • the low liquid viscosity and resulting small droplet size increase the speed with which the liquid feed is heated and vaporized.
  • the liquid hydrocarbon may be preheated. This may be particularly true for oligomers and waxes, which are typically solid (or highly viscous) at room temperature.
  • Typical temperatures for the preheated liquid may range from 30 °C to 350 °C.
  • Other methods of reducing the viscosity may include combining the hydrocarbon with a solvent (e.g., oligomers and/or waxes with lower viscosities) and/or using that fraction (i.e., distillation fraction) of the hydrocarbon material having the desired viscosity.
  • a solvent e.g., oligomers and/or waxes with lower viscosities
  • fraction i.e., distillation fraction
  • the operational conditions of the reactor 10 may vary.
  • the gas residence time within the reactor 10 may range from 50 milliseconds or less, more particularly from 20 milliseconds or less.
  • the residence time may range from20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 millisecond or less, with 10 microseconds being the approximate lowest residence time.
  • the pressure at the reactor outlet may vary.
  • a suitable pressure at the reactor outlet may range from 0 kPa (g) to 10,000 kPa (g), more particularly from 0 kPa (g) to 1,000 kPa (g).
  • Reaction temperatures may range from 800 °C to 2500 °C where the lowest temperatures are found at the reactor exit when all the endothermic reactions are completed and the highest temperatures are encountered in the combustion regions of the reactor (flame).
  • the reaction temperature within the reactor and recirculation zone may range from 900 °C to 1300 °C.
  • the temperature within the reactor and recirculation zone may range from 1000 °C to 1300 °C, more particularly from 1200 °C to 1250 °C.
  • the reactor temperature is higher than what is achieved in conventional cracking reactors, such as tube furnace reactors, which typically operate at 800 °C to 900 °C.
  • the swirling gas mixture facilitates keeping the walls of the reactor much cooler than in such conventional cracking reactors.
  • the use of such higher temperatures also allows a shorter residence or contact times shorter contact times resulting in better selectivity and conversion without formation of unwanted products.
  • Operating temperatures for the reactor may be selected to avoid excess production of such unwanted compounds, such as CO and CO2, or optimize the olefin-to-acetylene ratio, as acetylene is typically not desired.
  • the gases are introduced and flow through the flow passages 46, 48, 52, 54 so that the axial velocity (i.e., relative to the central axis 28) is zero or nearly zero prior to being discharged into the central chamber 58.
  • the inlets (not shown) and/or the orientation of the guide vanes 68, 70, 72, 74 may be set for each flow passage 46, 48, 52, 54 so that a selected azimuthal-to- radial velocity ratio for each of the feed streams that flow through the flow passages 46, 48, 52, 54 is achieved, wherein the azimuthal and radial directions are defined in a cross-section perpendicular to the central axis 28 of the reactor 10.
  • the radial direction is along a line that extends 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).
  • the azimuthal-to-radial velocity ratio may 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.
  • the azimuthal-to-radial velocity ratio may range from > 0 to 5, more particularly from 2 to 4.
  • the particular azimuthal-to-radial velocity ratio may vary depending upon the particular reactor configuration and composition of the various streams, however. This is more intimately related to the mixing times and reaction times depending on the flow rates, composition of the fuel and feedstocks used for cracking.
  • Converted hydrocarbon products produced in the reactor are removed from the reactor vessel 12 through outlet 20.
  • the converted hydrocarbon products may be quenched within a quench zone of the reactor 10 or they may be quenched exterior to the reactor 10 in a quenching unit, such as a water-droplet-spray quench vessel, or other suitable gas quench device.
  • the quenched products may be further processed and recycled.
  • additional hydrocarbon feed gas can be introduced as a secondary feed stream at an intermediate position along the length of reactor vessel 12, such as at inlet 82 (FIG. 1).
  • inlet 82 (FIG. 1).
  • One or more such inlets 82 may be provided at various locations and in the reactor vessel 12, which may be circumferentially and longitudinally spaced apart.
  • the inlets 82 may be oriented or configured so that gases are introduced at an angle, as well, to facilitate swirling fluid flow, similar to that delivered from the inlets of the feed assembly 32.
  • Feed assemblies provided on the reactor vessel 12 similar to the feed assembly 32 may be used for the introduction of such cracking feed gas so that the cracking feed is introduced as a swirling fluid flow.
  • a plurality of reactor inlet assemblies and corresponding feed assemblies can be provided in a single reactor while maintaining the high performance.
  • the plastic wastes including MPW and wastes that typically cannot be recycled using mechanical recycling, can be converted into higher value products, such as light olefins and aromatics.
  • the pyoil from such plastic wastes, and waxes and oligomers, both from plastic waste and from other sources, can be processed in a single step process, without hydrogenation or other processing steps that are typically employed in converting these materials.
  • the system features high conversion of the feed and higher selectivity for olefins. Due to the short residence time, olefins, unsaturates and/or aromatic content in the feedstock will not hinder cracking or conversion nor create excessive coking behaviors during the reaction, as these will merely pass through the reactor unchanged.
  • the reactor system 10 utilizing the hydrocarbon reactant feeds can be used to provide a variety of higher value products. These include any one or more of olefins, C2 to Ce olefins, ethylene, propylenes, butenes, acetylene, C3 to Ce alkynes, butadienes, aromatic compounds, xylenes, benzene, toluene, and ethyl benzene.
  • any one or more of these products, such as C2 to Ce alkanes, xylenes, benzene, and toluene, in the reactor product stream may be separated from the reactor product stream and recycled to form at least a portion of the hydrocarbon reactant feeds.
  • FIG. 7 shows selectivity in weight percent of light olefins and aromatics for either full range pyoil or polybutadiene oligomer with ethane in the ANJEVOC reactor 10,.
  • the ethane gas was introduced through the gas feed 46 of the reactor, while the pyoil and polybutadiene oligomer were each introduced through a single-fluid nozzle 78.
  • the pyoil and polybutadiene oligomer each had a dynamic viscosity of less than 10 cP.
  • the pyoil and polybutadiene oligomer were each introduced as a spray non-perpendicularly and non- tangentially to the central axis of the central chamber of the feed assembly of the reactor.
  • the spray had a SMD size from 10 pm to 130 pm during injection.
  • the H2 flow rate was fixed at 4.2 Ib/hr and the steam flow rate was fixed at 5 Ib/hr.
  • the flow rate of O2 varied from 14.5 to 20 Ib/hr.
  • the weight percentage of polybutadiene oligomer and full range pyoil varied between 25 to 50% with respect to the ethane flow.
  • the average molecular weight (Mn) of the full range pyoil was 280.
  • the average molecular weight (Mn) for polybutadiene was 1,100.
  • the overall selectivity for olefins and aromatics ranged between 62 - 67 wt% at a conversion level between 83 and 91%.

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Abstract

Un procédé de conversion d'huiles de pyrolyse, de cires et/ou d'oligomères en produits de valeur supérieure est mis en œuvre dans un système de réacteur comprenant un axe central, un ensemble d'alimentation et une cuve de réacteur qui délimite une chambre de réaction. Une charge de gaz combustible et une charge de gaz oxydant sont introduites dans l'ensemble d'entrée selon un motif d'écoulement de fluide tourbillonnant et brûlent pour former des gaz de combustion tourbillonnants. Des charges de réactifs hydrocarbonés formées d'un gaz hydrocarboné et d'un hydrocarbure liquide comprenant des huiles de pyrolyse, des cires et/ou des oligomères sont introduites dans l'ensemble d'entrée. La charge liquide est introduite sous la forme d'un brouillard ou d'une pulvérisation de liquide selon un motif d'écoulement qui est non perpendiculaire à l'axe central. La charge d'hydrocarbures se mélange avec les gaz de combustion tourbillonnants pour former un mélange chauffé tourbillonnant qui rejoint la chambre de réaction pour réagir et former des produits hydrocarbonés convertis.
PCT/EP2024/071072 2023-07-25 2024-07-24 Procédé de conversion d'huiles de pyrolyse, de cires et/ou d'oligomères en produits chimiques de valeur supérieure Pending WO2025021902A1 (fr)

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PCT/EP2024/071069 Pending WO2025021899A1 (fr) 2023-07-25 2024-07-24 Procédé et réacteur de conversion d'hydrocarbures liquides en produits chimiques à valeur supérieure
PCT/EP2024/071071 Pending WO2025021901A1 (fr) 2023-07-25 2024-07-24 Procédé de conversion d'hydrocarbures liquides et gazeux en produits chimiques de valeur supérieure
PCT/EP2024/071072 Pending WO2025021902A1 (fr) 2023-07-25 2024-07-24 Procédé de conversion d'huiles de pyrolyse, de cires et/ou d'oligomères en produits chimiques de valeur supérieure
PCT/EP2024/071219 Pending WO2025021962A1 (fr) 2023-07-25 2024-07-25 Réacteur à hydrocarbures avec partie de col rétrécie et buse de pulvérisation

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PCT/EP2024/071069 Pending WO2025021899A1 (fr) 2023-07-25 2024-07-24 Procédé et réacteur de conversion d'hydrocarbures liquides en produits chimiques à valeur supérieure
PCT/EP2024/071071 Pending WO2025021901A1 (fr) 2023-07-25 2024-07-24 Procédé de conversion d'hydrocarbures liquides et gazeux en produits chimiques de valeur supérieure

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CN121568782A (zh) 2026-02-24
WO2025021962A1 (fr) 2025-01-30
CN121586758A (zh) 2026-02-27
CN121569007A (zh) 2026-02-24
WO2025021899A1 (fr) 2025-01-30
WO2025021901A1 (fr) 2025-01-30
WO2025021900A1 (fr) 2025-01-30
CN121569009A (zh) 2026-02-24

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