Catalytic upcycling of waste plastics to sustainable aviation fuels
Patent Information
- Authority / Receiving Office
- US · United States
- Patent Type
- Applications(United States)
- Current Assignee / Owner
- JOHNS HOPKINS UNIVERSITY
- Filing Date
- 2026-03-31
- Publication Date
- 2026-08-06
Smart Images
Figure US20260226352A1-D00000_ABST
Abstract
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application claiming priority to International Patent Application No. PCT / US2024 / 047359 filed on 19 Sep. 2024, which claims the benefit of U.S. Provisional Application No. 63 / 588,100, filed Oct. 5, 2023, the contents of which are incorporated herein by reference in their entirety.BACKGROUND
[0002] Polymers are irreplaceable in the global economy, with a myriad of uses in packaging, construction, transportation, electronics, and health-care industries. Many of these applications rely on plastics as inexpensive disposable materials and are often precisely constructed to confer desired properties essential for the targeted function. Their massive-scale manufacture, single-use function, long lifetimes, slow decomposition rates, and disruption of sensitive ecosystems, however, have created a crisis of plastic waste.
[0003] In light of both the large drain on global resources and the massive amount of waste material generated, plastics represent a tremendous and as-yet-untapped domestic resource for the production of chemicals and new materials. Efficient technologies for extracting this value from discarded polymers would be equivalent to recovering about 3.5 billion barrels of oil each year and could create entirely new industries. Currently, most of the stored energy in plastics is irreversibly lost into landfills that are overflowing throughout our planet, resulting in environmental and health hazards caused by microplastic pollution on land and in the ocean. While physical recycling is desirable and widespread in many areas for a wide range of materials, recycling requires intense human labor under harsh working conditions and sophisticated machinery with huge energy inputs, and has proven most effective for recovering glass, paper, and metals such as aluminum. Recycling, to date, has not been able to efficiently and cleanly recoup the inherent value in plastics, especially low-density polyethylene (plastic bags), polypropylene, and polystyrene. The syntheses of many virgin plastics are currently less expensive than creating quality recycled materials, because plastics are made on a large scale in centralized plants, from inexpensive monomers such as ethylene, in processes that are tightly integrated into commodity chemical production. As a result, many plastics are just burned as fuel or inefficiently reprocessed to manufacture lower-value materials (known as downcycling), resulting in minimal economic incentives for waste recovery, sorting, and processing.
[0004] Unfortunately, many plastics end up in the oceans. Some reports state that between 75 and 199 million tons of plastic is polluting our oceans. Rather than evenly dispersing in the oceans, plastics tend to concentrate in one of five gyres. Current estimates of the total size of the northern pacific gyre, the largest gyre, is that it covers more than 15,000,000 square kilometers. In addition, these plastics are broken down into small pieces by ultraviolet light and fluid power. These plastics and microplastics, which are tens of microns to several millimeters in size, are accidentally introduced into the body of fish and other aquatic organisms as food. It has been reported that some marine organisms die as a result. In addition, microplastics may have harmful substances attached to them, and there are concerns that eating fish that contain such microplastics may have an enormous impact on human health.
[0005] Chemical upcycling, an emerging alternative to the classical recycling approach, would use plastic waste as a feedstock for the synthesis of value-added chemicals and materials. Disadvantageously, most plastic collected today is not deemed suitable for upcycling due, in part, to the variability of the incoming plastic stream. The sources of the variability include the mixing of different types of plastics, the degree of degradation associated with reprocessing plastics, and the presence of low molecular weight compounds.
[0006] To address the imminent plastic waste management challenges, the present inventors developed an effective strategy to upcycle waste plastics, including marine waste plastics, into sustainable aviation fuels using halloysite-based catalysts. The demand for aviation fuels is increasing each year at an enormous pace and the large amount of plastic waste, e.g., marine plastic waste, can be treated as valuable chemical feedstock to produce sustainable aviation fuels. Furthermore, producing sustainable aviation fuels (SAF) from waste plastics can improve the environment and may boost aircraft performance.SUMMARY
[0007] In some aspects, the present disclosure relates to a system for upcycling plastic waste to produce sustainable aviation fuels (SAF), said system comprising:
[0008] a plug-flow reactor (PFR) with catalytic hydrocracking functionality, wherein the PFR comprises a reactor tube comprising a catalytic material;
[0009] a tubular furnace that can accommodate the reactor tube;
[0010] a source of inert gas;
[0011] a source of hydrogen gas; and
[0012] a cold trap.
[0013] In other aspects, the present disclosure relates to a process of upcycling plastic waste to produce sustainable aviation fuels (SAF), said process comprising:
[0014] introducing the plastic waste to the reactor tube of a plug-flow reactor (PFR), wherein the PFR comprises a catalytic material;
[0015] positioning the reactor tube of the PFR in a furnace;
[0016] removing air from the reactor tube using at least one inert gas;
[0017] heating the reactor tube to a target temperature;
[0018] introducing a feeding gas to the reactor tube once the target temperature is achieved; and
[0019] collecting the SAFs through solvent extraction in a cold trap.
[0020] In another aspect, a process of upcycling plastic waste to produce sustainable aviation fuels (SAF), said process comprising:
[0021] positioning a reactor tube of a plug-flow reactor (PFR) in a furnace, wherein the PFR comprises a catalytic material;
[0022] removing air from the reactor tube using at least one inert gas;
[0023] heating the reactor tube to a target temperature;
[0024] introducing a feeding gas to the reactor tube once the target temperature is achieved; and
[0025] collecting the SAFs through solvent extraction in a cold trap.
[0026] Other aspects, features and advantages of the invention will be more fully apparent from the ensuing disclosure and appended claims.BRIEF DESCRIPTION OF THE FIGURES
[0027] FIG. 1. A schematic of the upcycling system described herein.
[0028] FIG. 2. Upcycling performance results obtained using the system described herein. The “recondensed” fraction is long-chain olefins greater than C18.
[0029] FIG. 3. An illustration of the halloysite structure.DETAILED DESCRIPTION OF THE DISCLOSURE
[0030] Although the claimed subject matter will be described in terms of certain embodiments, other embodiments, including embodiments that do not provide all of the benefits and features set forth herein, are within the scope of this disclosure as well. Various structural and parameter changes may be made without departing from the scope of this disclosure.Definitions
[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.
[0032] “About” and “approximately” are used to provide flexibility to a numerical range endpoint by providing that a given value may be “slightly above” or “slightly below” the endpoint without affecting the desired result, for example, + / −5%.
[0033] The phrase “in one embodiment” or “in some embodiments” as used herein does not necessarily refer to the same embodiment, though it may. Furthermore, the phrase “in another embodiment” as used herein does not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments of the invention may be readily combined, without departing from the scope or spirit of the invention.
[0034] The terms “comprise(s),”“include(s),”“having,”“has,”“can,”“contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms “a,”“and” and “the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,”“consisting of” and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not.
[0035] For the recitation of numeric ranges herein, each intervening number there between with the same degree of precision is explicitly contemplated. For example, for the range of 6-9, the numbers 7 and 8 are contemplated in addition to 6 and 9, and for the range 6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, and 7.0 are explicitly contemplated.
[0036] As used herein, a “system” refers to a plurality of real and / or abstract elements operating together for a common purpose. In some embodiments, a “system” is an integrated assemblage of hardware and / or software elements. In some embodiments, each component of the system interacts with one or more other elements and / or is related to one or more other elements. In some embodiments, a system refers to a combination of components and software for controlling and directing methods.
[0037] The terms “plastics” and “polymers” are used interchangeably herein. A polymer is a carbon-based (at least 50 mass % C) material chiefly made up of repeating units and having a number average molecular weight of at least 100, typically greater than 1000 or greater than 10,000.
[0038] As used herein, “halloysite” corresponds to the aluminosilicate clay mineral with a hollow nanotubular structure and having the formula Al2(Si2O5)(OH)4. Halloysite is a layered structure comprising siloxane layers and gibbsite-like layers containing aluminum ions and OH groups. Halloysite has two different polymorphs; a hydrated one and a dehydrated one (metahalloysite), wherein the latter is characterized by having reduced interlayer spacing relative to the former. An illustrative depiction of a halloysite structure is shown in FIG. 3, showing an external siloxane surface, an internal aluminal surface, and the layers. It should be appreciated that the term “halloysite” includes aluminosilicate clay minerals that are “substantially halloysitic,” for example, wherein ionic substitution has occurred wherein at least one ion of the halloysite crystal lattice has been replaced by a different ion having the same charge and approximately the same size. It should be appreciated that the substantially halloysitic material is also a layered structure comprising siloxane layers and gibbsite-like layers containing aluminum ions and OH groups and can be used as the catalytic material in the system and method described herein. It should be appreciated that the ionic substitution to yield a substantially halloysitic material is not the same as intercalation, as described herein.
[0039] As used herein, the “sustainable aviation fuels (SAFs)” comprise n-alkanes, iso-alkanes, aromatics, and cycloalkanes. In some embodiments, the SAFs comprise: iso-alkanes, which have high specific energy, good thermal stability, and low freezing points; and cycloalkanes, which have the required density and nitrile seal-swelling capacity typical of aromatics present in aviation fuels.
[0040] For the purposes of this description, the “n-alkanes” include C7-C18 hydrocarbons. In some embodiments, the n-alkanes comprise at least one substitution, e.g., a methyl group, to improve the low temperature fluidity of the n-alkane.
[0041] For the purposes of the present description, the “iso-alkanes” include C7-C17 hydrocarbons having, at least, a methyl group located on the second carbon of a carbon chain. The iso-alkanes may be lightly branched, e.g., with additional methyl or ethyl group, or heavily branched, e.g., isopropyl groups, or a combination of both lightly and heavily branched.
[0042] For the purposes of the present description, the “cycloalkanes” include C7-C16 monocycloalkanes and / or C10-C14 dicycloalkanes. In some embodiments, the monocycloalkanes have alkyl chains and branches stemming from the central ring, wherein the central ring comprises 3-10 carbon atoms, preferably 5-7 carbon atoms. In some embodiments, the dicycloalkanes comprise fused cyclic rings and can further comprise alkyl chains and branching. In some embodiments, the dicycloalkanes comprise at least one of cis-decalin, trans-decalin, endo-tetrahydrodicyclopentadiene, exo-tetrahydrodicyclopentadiene, adamantine, trimethyl adamantine, carane, camphane, pinane, and sabinane.
[0043] As used herein, the terms “aromatics” or “aromatic compound” are used to refer to a hydrocarbon compound or compounds comprising one or more aromatic groups such as, for example, single aromatic ring systems (e.g., benzyl, phenyl, etc.) and fused polycyclic aromatic ring systems (e.g. naphthyl, 1,2,3,4-tetrahydronaphthyl, etc.). Examples of aromatic compounds include, but are not limited to, benzene, toluene, indane, indene, 2-ethyl toluene, 3-ethyl toluene, 4-ethyl toluene, trimethyl benzene (e.g., 1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, 1,2,3-trimethyl benzene, etc.), ethylbenzene, styrene, cumene, methylbenzene, propylbenzene, xylenes (e.g., p-xylene, m-xylene, o-xylene, etc.), naphthalene, methyl-naphthalene (e.g., 1-methyl naphthalene, anthracene, 9.10-dimethylanthracene, pyrene, phenanthrene, dimethyl-naphthalene (e.g., 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene, 2,5-dimethylnaphthalene, etc.), ethyl-naphthalene, hydrindene, methyl-hydrindene, and dymethyl-hydrindene. Single-ring and / or higher ring aromatics may also be produced in some embodiments.
[0044] The term “plug flow reactor,” also known as tubular reactors or continuous tubular reactors, is used to refer to reactors wherein reactants continuously flow through a tube or pipe as if they were a “plug” of fluid, with no back-mixing between different portions of the fluid, and products exit the reactor. The reactor contents are not continuously stirred but instead as the plug of fluid flows through the tube or pipe, reactants are converted to products.
[0045] The terms “olefin” or “olefin compound” (a.k.a. “alkenes”) are given their ordinary meaning in the art and are used to refer to any unsaturated hydrocarbon containing one or more pairs of carbon atoms linked by a double bond. Olefins include both cyclic and acyclic (aliphatic) olefins, in which the double bond is located between carbon atoms forming part of a cyclic (closed-ring) or of an open-chain grouping, respectively. In addition, olefins may include any suitable number of double bonds (e.g., monoolefins, diolefins, triolefins, etc.). Examples of olefin compounds include, but are not limited to, ethene, propene, allene (propadiene), 1-butene, 2-butene, isobutene (2 methyl propene), butadiene, and isoprene, among others. Examples of cyclic olefins include cyclopentene, cyclohexane, cycloheptene, among others. Aromatic compounds such as toluene are not considered olefins; however, olefins that include aromatic moieties are considered olefins, for example, benzyl acrylate or styrene.
[0046] As used herein, an “inert gas” includes, but is not limited to, nitrogen, helium, argon, neon, xenon, krypton, and radon.
[0047] The term “yield” is used herein to refer to the amount of a product flowing out of a reactor divided by the amount of reactant flowing into the reactor, usually expressed as a percentage or fraction. Yields are often calculated on a mass basis or on the basis of a particular feed component. Mass yield is the mass of a particular product divided by the weight of feed used to prepare that product. For example, if 500 grams of polymer is fed to a reactor and 45 grams of benzene is produced, the mass yield of benzene would be 45 / 500=9% benzene.
[0048] The term “plastic waste,” as used herein, includes at least one of the major thermoplastic resins such as polyethylene (low density, linear low density, and high density), polypropylene, polyethylene terephthalate, polystyrene, and polyvinyl chloride. It should be appreciated that the plastic waste can include terrestrial plastic waste, for example as collected by recycling facilities, or marine plastic waste, for example, floating marine plastic waste or plastic waste collected from the bottom of a body of water. Methods of collection of marine plastic waste are known in the art.
[0049] As defined herein, “intercalated” describes the insertion of an organic or inorganic species between layers in a crystal lattice or other structure, resulting in interlayer spacing between the layers.
[0050] Broadly, the present invention provides a robust upcycling system designated for plastic waste including, but not limited to, marine plastic waste. This system comprises a plug-flow reactor (PFR) with catalytic reforming functionality. The system further comprises halloysite-based catalysts to convert plastic waste, e.g., marine plastic waste, into sustainable aviation fuels (SAFs), as defined herein. Using the system described herein, SAF yields of greater than 28% have been obtained. In some embodiments, the upcycling system is portable.
[0051] Referring to FIG. 1, an embodiment of the system is illustrated. Plastic waste, e.g., marine plastic waste, is introduced to a plug-flow reactor maintained substantially at atmospheric pressure. In some embodiments, the plastic waste is in the gaseous phase and is flown into the PFR. In some embodiments, the plastic waste is in the solid phase. The PFR comprises a reactor tube, wherein the reactor tube comprises a catalyst material capable of hydrocracking the components of the plastic waste into value-added products. In some embodiments, the catalyst material comprises a halloysite. In some embodiments, the plastic waste is introduced to the reactor tube comprising the catalyst material. Thereafter, the reactor tube of the PFR is positioned in a furnace, e.g., a tubular furnace. Inert gas is introduced to the reactor tube to remove any remaining air and maintain an inert gas atmosphere therein. Once an inert gas atmosphere is achieved in the reactor tube, the reactor tube is heated to a target reaction temperature. In some embodiments, the target reaction temperature is in a range from about 400° C. to about 500° C., or about 420° C. to about 480° C., or about 430° C. to about 470° C., or about 440° C. to about 460° C., or about 450° C. In some embodiments, the target reaction temperature is in a range from about 450° C. to about 500° C., or about 450° C. to about 480° C. As soon as the target reaction temperature is reached, a feeding gas can be introduced. In some embodiments, the feeding gas comprises hydrogen gas and at least one inert gas. In some embodiments, the feeding gas comprises about 1 vol % to about 10 vol % hydrogen gas, balance being the at least one inert gas. In some embodiments, the feeding gas comprises about 1 vol % to about 10 vol % hydrogen gas, gaseous plastic waste, and at least one inert gas. In some other embodiments, the plastic waste is introduced as a solid into the PFR. The target liquid products are collected after the reaction is complete through solvent extraction in a cold trap. In some embodiments, the solvent extraction uses methanol, ethanol, or acetone. In some embodiments, the solvent extraction uses ethanol. In some embodiments, the target liquid products include SAFs selected from n-alkanes, iso-alkanes, aromatics, and cycloalkanes. In some embodiments, the target liquid products include iso-alkanes, as defined herein. In some embodiments, the target liquid products include cycloalkanes, as defined herein.
[0052] Advantageously, PFRs can be easily tuned for various parameters including, but not limited to, temperature, gas flow, and pressure. In some embodiments, catalyst regeneration is achievable using the process of calcination, wherein the catalyst materials is heated to a high temperature in the presence of air to remove volatile substances, as understood in the art. In some embodiments, catalyst regeneration is achievable in the PFR needing only about two hours of air flow. In some embodiments, catalyst regeneration is achievable in a normal furnace, with or without air flow. For example, the calcination of a spent catalyst can be achieved after about one hour in a normal furnace without air flow.
[0053] Halloysite and substantially halloysitic materials are particularly advantageous for catalytic hydrocracking because of the nanotubular nature of the material, while also being highly stable, resistant against most organic solvents, and abundantly, and inexpensively, available. In some embodiments, the hollow interior of the nanotubes of halloysite are about 10 nm to 20 nm in diameter, preferably about 12 nm to 18 nm in diameter, and even more preferably about 13 nm to 17 nm in diameter. In some embodiments, the halloysite is not substantially intercalated, although some natural intercalation is expected. In some embodiments, the halloysite is intercalated to some extent, whether naturally and / or intentionally. In some embodiments, the layered halloysite is intentionally intercalated with organic or inorganic species to increase the performance of the catalyst, wherein the organic or inorganic species include, but are not limited to, precious metals (e.g., ruthenium, iridium, palladium), fatty acids (e.g., stearic acid), salts (e.g., NH4Cl, H2PtCl6, IrCl3, Pt(acac)2, Pd(acac)2) and carbon or graphitic carbon nanotubes. In some embodiments, the halloysite acts as support for metal nanoparticles (e.g., Fe, Co, Ni, Pd, Ag, Cu, Ce, Cd, Zn, Ti, Au, La, Mo, Pt, Mn), whether adsorbed to the surface and / or located inside the tubes. In some embodiments, metal is impregnated on the outside (i.e., on or in the external siloxane surface) or inside (i.e., on or in the internal aluminal surface) of the halloysite using a metal precursor to increase the performance of the catalyst. In some embodiments, the inner diameter of the halloysite structure can be enlarged using an acid treatment to increase the performance of the catalyst.
[0054] In some embodiments, the catalyst material is regenerated for further catalytic reactions. In some embodiments, the catalyst material comprises a halloysite or a substantially halloysitic material, and it is regenerated through calcination in air for reuse.
[0055] It should be appreciated by the person skilled in the art that by controlling the makeup of at least one of the plastic waste, the temperature of the catalytic hydrocracking, and the nature of the halloysite catalyst, the makeup of the SAFs produced can be controlled including, but not limited to, carbon length, branching level, degree of unsaturation, degree of cyclization / aromatization, presence of functional groups, thermal stability, and energy density.
[0056] In some embodiments, the hydrogen gas is generated in proximity to the upcycling system. For example, in some embodiments, hydrogen gas is generated from the electrolysis of seawater. In other words, a portable system can be located on a coastline of, or within, a body of seawater comprising salt and can be a source of marine plastic waste and seawater for the generation of hydrogen gas using electrolysis. It should be appreciated by the person skilled in the art that the hydrogen gas can be generated using other methods including, but not limited to, steam methane reforming, partial oxidation of heavier hydrocarbons, coal gasification, biogas gasification, and methane pyrolysis. In some embodiments, hydrogen gas is used in the feeding gas. In some embodiments, hydrogen gas is used in the feeding gas and is used to provide energy to other parts of the upcycling system.
[0057] It should be appreciated by the person skilled in the art that the upcycling system described herein can be portable, but it is not required. Further, the upcycling system described herein can be located in or near seawater, but it is not required.
[0058] There are different ways to collect plastic waste from harbors, water reservoirs (lakes, ponds), rivers (rivers, canals) and coastal areas. In some embodiments, manual collection is used wherein workers maneuver motorized boats and collect the waste with a dip net or other collection means. In some embodiments, mechanized collection is used, wherein vehicles specifically designed to perform clean-up operations, maneuvered by on-board human operators, are able to collect floating wastes by a grid bucket. In some embodiments, robotic collection is used, including wire-guided waste collection modules. Robotic collection can also include aquatic drones that collect floating waste in aquatic areas. Another robot collector accumulates the waste between two hulls. To collect floating plastic waste from the ocean, floating net barriers having a large U shape can be pulled behind two ships.
[0059] Accordingly, in a first aspect, a system for upcycling plastic waste to produce sustainable aviation fuels (SAF) is described, said system comprising:
[0060] a plug-flow reactor (PFR) with catalytic hydrocracking functionality, wherein the PFR comprises a reactor tube comprising a catalytic material;
[0061] a tubular furnace that can accommodate the reactor tube;
[0062] a source of inert gas;
[0063] a source of hydrogen gas; and
[0064] a cold trap.
[0065] In some embodiments, the catalytic material comprises halloysite or a substantially halloysitic material. In some embodiments, the system further comprises a source of gaseous plastic waste. In some embodiments, the source of gaseous plastic waste is premixed with the source of the inert gas and the source of hydrogen gas.
[0066] In a second aspect, a process of upcycling plastic waste to produce sustainable aviation fuels (SAF), said process comprising:
[0067] introducing the plastic waste to the reactor tube of a plug-flow reactor (PFR), wherein the PFR comprises a catalytic material;
[0068] positioning the reactor tube of the PFR in a furnace;
[0069] removing air from the reactor tube using at least one inert gas;
[0070] heating the reactor tube to a target temperature;
[0071] introducing a feeding gas to the reactor tube once the target temperature is achieved; and
[0072] collecting the SAFs through solvent extraction in a cold trap.
[0073] In some embodiments, the catalytic material comprises halloysite or a substantially halloysitic material. In some embodiments, the target temperature is in a range from about 400° C. to about 500° C. In some embodiment, the feeding gas comprises hydrogen gas. In some embodiments, the SAFs comprise iso-alkanes. In some embodiments, the SAFs comprise cycloalkanes.
[0074] In a third aspect, a process of upcycling plastic waste to produce sustainable aviation fuels (SAF), said process comprising:
[0075] positioning a reactor tube of a plug-flow reactor (PFR) in a furnace, wherein the PFR comprises a catalytic material;
[0076] removing air from the reactor tube using at least one inert gas;
[0077] heating the reactor tube to a target temperature;
[0078] introducing a feeding gas to the reactor tube once the target temperature is achieved; and
[0079] collecting the SAFs through solvent extraction in a cold trap.
[0080] In some embodiments, the catalytic material comprises halloysite or a substantially halloysitic material. In some embodiments, the target temperature is in a range from about 400° C. to about 500° C. In some embodiment, the feeding gas comprises gaseous plastic waste, hydrogen gas, and an inert gas. In some embodiments, the SAFs comprise iso-alkanes. In some embodiments, the SAFs comprise cycloalkanes.Computer Program Product
[0081] The present subject matter described in the first, second, or third aspects may be a system, a method, and / or a computer program product. In some embodiments, the computer program product may include a computer readable storage medium (or media) having computer readable program instructions thereon for causing a processor to carry out aspects of the present subject matter.
[0082] In some embodiments, the computer readable storage medium can be a tangible device that can retain and store instructions for use by an instruction execution device. The computer readable storage medium may be, for example, but is not limited to, an electronic storage device, a magnetic storage device, an optical storage device, an electromagnetic storage device, a semiconductor storage device, or any suitable combination of the foregoing. A non-exhaustive list of more specific examples of the computer readable storage medium includes the following: a portable computer diskette, a hard disk, a RAM, a ROM, an erasable programmable read-only memory (EPROM or Flash memory), a static random access memory (SRAM), a portable compact disc read-only memory (CD-ROM), a digital versatile disk (DVD), a memory stick, a floppy disk, a mechanically encoded device such as punch-cards or raised structures in a groove having instructions recorded thereon, and any suitable combination of the foregoing. A computer readable storage medium, as used herein, is not to be construed as being transitory signals per se, such as radio waves or other freely propagating electromagnetic waves, electromagnetic waves propagating through a waveguide or other transmission media (e.g., light pulses passing through a fiber-optic cable), or electrical signals transmitted through a wire.
[0083] In some embodiments, computer readable program instructions described herein can be downloaded to respective computing / processing devices from a computer readable storage medium or to an external computer or external storage device via a network, for example, the Internet, a local area network, a wide area network and / or a wireless network, or Near Field Communication. The network may comprise copper transmission cables, optical transmission fibers, wireless transmission, routers, firewalls, switches, gateway computers and / or edge servers. A network adapter card or network interface in each computing / processing device receives computer readable program instructions from the network and forwards the computer readable program instructions for storage in a computer readable storage medium within the respective computing / processing device.
[0084] In some embodiments, computer readable program instructions for carrying out operations of the present subject matter may be assembler instructions, instruction-set-architecture (ISA) instructions, machine instructions, machine dependent instructions, microcode, firmware instructions, state-setting data, or either source code or object code written in any combination of one or more programming languages, including an object oriented programming language such as Java, Smalltalk, C++, Javascript or the like, and conventional procedural programming languages, such as the “C” programming language or similar programming languages. The computer readable program instructions may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server. In the latter scenario, the remote computer may be connected to the user's computer through any type of network, including a local area network (LAN) or a wide area network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet Service Provider). In some embodiments, electronic circuitry including, for example, programmable logic circuitry, field-programmable gate arrays (FPGA), or programmable logic arrays (PLA) may execute the computer readable program instructions by utilizing state information of the computer readable program instructions to personalize the electronic circuitry, in order to perform aspects of the present subject matter.
[0085] In some embodiments, the computer readable program instructions may be provided to a processor of a computer, special purpose computer, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions / acts specified in the flowchart and / or block diagram block or blocks. In some embodiments, the computer readable program instructions may also be stored in a computer readable storage medium that can direct a computer, a programmable data processing apparatus, and / or other devices to function in a particular manner, such that the computer readable storage medium having instructions stored therein comprises an article of manufacture including instructions which implement aspects of the function / act specified in the flowchart and / or block diagram block or blocks.
[0086] In some embodiments, the computer readable program instructions may also be loaded onto a computer, other programmable data processing apparatus, or other device to cause a series of operational steps to be performed on the computer, other programmable apparatus or other device to produce a computer implemented process, such that the instructions which execute on the computer, other programmable apparatus, or other device implement the functions / acts specified in the flowchart and / or block diagram block or blocks.
[0087] In light of the present disclosure and the general level of skill in the art, those of skill can appreciate that the following examples are intended to be exemplary only and that numerous changes, modifications, and alterations can be employed without departing from the scope of the presently disclosed subject matter. The synthetic descriptions and specific examples that follow are only intended for the purposes of illustration, and are not to be construed as limiting in any manner to make compounds of the disclosure by other methods.EXAMPLE
[0088] Referring to FIG. 1, the marine plastic waste upcycling to SAFs was conducted in a plug-flow reactor at atmospheric pressure. The reactor tube was loaded with 50 mg of halloysite and 200 mg HDPE was loaded on top the halloysite, with a layer of quartz wool or some other material that serves as a support for the HDPE on the catalyst therebetween. The reactor tube was put in a tubular furnace. An inert gas flow was introduced to the reactor to remove any remaining air and maintain an inert gas atmosphere therein. Once the air was completely removed from the reactor tube, as readily determined by the skilled artisan, the reactor tube was heated to a target reaction temperature (e.g., 450° C.). As soon as the reaction temperature was reached, a feeding gas was introduced, wherein the feeding gas comprised 5 vol % H2 with the balance inert gas. The gas products were measured through online and continuous gas chromatography injections. The liquid products (e.g., n-alkanes, iso-alkanes, cycloalkanes, aromatics) were collected after the reaction was complete through solvent (e.g., ethanol) extraction in a cold trap. The recovered halloysite catalyst was washed with organic solvent (e.g., using ethanol or methanol) and dried to separate generated coke and any remaining recondensed heavy olefin products for chromatography analysis of same. The halloysite catalyst was regenerated through calcination in air.
[0089] The results are shown in FIG. 2, where it can be seen that the highest SAF yield obtained was 29.25% at 450° C. As the temperature increases, the SAF yield decreases. In all performance tests, >80% of HDPE can be converted into gaseous hydrocarbons, C5-C6 hydrocarbons and SAFs.
Claims
1. A system for upcycling plastic waste to produce sustainable aviation fuels (SAF), said system comprising:a plug-flow reactor (PFR) with catalytic hydrocracking functionality, wherein the PFR comprises a reactor tube comprising a catalytic material;a tubular furnace that can accommodate the reactor tube;a source of inert gas;a source of hydrogen gas; anda cold trap.
2. The system of claim 1, wherein the catalytic material comprises a halloysite or a substantially halloysitic material.
3. The system of claim 1, wherein the tubular furnace can be heated to temperatures in a range from about 400° C. to about 500° C.
4. The system of claim 1, wherein the source of hydrogen gas is an electrolysis system.
5. The system of claim 1, wherein the source of hydrogen gas is a seawater electrolysis system.
6. The system of claim 1, wherein the cold trap is used for solvent extraction of the SAFs.
7. A process of upcycling plastic waste to produce sustainable aviation fuels (SAF), said process comprising:positioning a reactor tube of a plug-flow reactor (PFR) in a furnace, wherein the PFR comprises a catalytic material;removing air from the reactor tube using at least one inert gas;heating the reactor tube to a target temperature;introducing a feeding gas to the reactor tube once the target temperature is achieved; andcollecting the SAFs through solvent extraction in a cold trap.
8. The process of claim 7, wherein the catalytic material comprises a halloysite or a substantially halloysitic material.
9. The process of claim 7, wherein the plastic waste comprises at least one of low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polyethylene terephthalate, polystyrene, and polyvinyl chloride.
10. The process of claim 7, wherein the at least one inert gas is selected from the group consisting of nitrogen, helium, argon, neon, and xenon.
11. The process of claim 7, wherein the target temperature is in a range from about 400° C. to about 500° C.
12. The process of claim 7, further comprising introducing plastic waste to the reactor tube before positioning the reactor tube of the PFR in the furnace, wherein the feeding gas comprises hydrogen gas and at least one inert gas.
13. The process of claim 7, wherein the feeding gas comprises gaseous plastic waste, hydrogen gas and at least one inert gas.
14. The process of claim 7, wherein the feeding gas comprises about 1 vol % to about 10 vol % hydrogen.
15. The process of claim 14, wherein the hydrogen gas is generated using an electrolysis system.
16. The process of claim 14, wherein the hydrogen gas is generated using a seawater electrolysis system.
17. The process of claim 7, wherein the SAFs are selected from the group consisting of n-alkanes, iso-alkanes, cycloalkanes, aromatics, and combinations thereof.
18. The process of claim 7, further comprising regenerating the catalytic material for reuse.