Water-washed recycled pyrolysis oil for feeding cracking equipment

Abstract

Various methods and systems are disclosed that include water washing of recycled pyrolysis oil for feed to a cracking unit, and in one embodiment includes a method that includes contacting the recycled pyrolysis oil with water to produce a refined pyrolysis oil, and cracking the refined pyrolysis oil to produce products.

Description

[Technical field]

[0001] The present application relates to the cracking of hydrocarbons, and more particularly, in one or more embodiments, to methods and systems involving water washing of recycled pyrolysis oil for feed to a cracking unit. [Background technology]

[0002] The rate of plastic production has increased steadily over the past century, with a global value of about 400 million tons (400 MT) in 2016, with a corresponding increase in plastic waste. Several waste abatement methods have been proposed over the years, from direct recycling to energy generation from plastic waste. One route for recycling plastic waste is to combine it with conventional petroleum feedstocks for co-processing in conventional refining processes, such as thermal conversion processes (e.g., coking, visbreaking, or other pyrolysis) and / or catalytic conversion processes (such as fluid catalytic cracking). In one example, a pyrolysis process can be used to convert plastic waste to oil (e.g., recycled pyrolysis oil) by thermal decomposition of the polymers contained in the plastic waste. Recycled pyrolysis oil (and other recycled pyrolysis oils) typically contains a mixture of hydrocarbons that could be co-processed with conventional petroleum feedstocks.

[0003] Cracking of hydrocarbons is a widely used process to produce olefins and aromatics. Steam cracking is one technique to produce olefins and aromatics by thermal cracking of petroleum feedstocks in the presence of steam at high temperatures. Typically, feedstocks for steam cracking may include gaseous or liquid hydrocarbons such as naphtha, vacuum gas oil, crude oil, and natural gas liquids (e.g., liquefied petroleum gas, condensates, ethane, propane, butane, etc.), among others. Although recycled pyrolysis oils contain a mixture of hydrocarbons, their use in cracking processes may have drawbacks. For example, plastic waste may contain various contaminants (e.g., chlorides, fluorides, bromides, phosphorus-containing compounds, nitrogen, oxygenates, etc.), which may make their use in cracking difficult, as recycled pyrolysis oils may also contain similar contaminants. Conventional cracking processes may be sensitive to many of the contaminants contained in recycled pyrolysis oil. For example, these contaminants can cause metal contamination, catalyst poisoning, and / or other problems in cracking furnaces or other downstream units that would result in expensive and time-consuming remedial work if these recycled pyrolysis oils were used in cracking processes. Summary of the Invention [Means for solving the problem]

[0004] Exemplary methods are disclosed herein that may include contacting recycled pyrolysis oil with water to produce refined pyrolysis oil, which may further include cracking the refined pyrolysis oil to produce products.

[0005] Further disclosed herein is an exemplary method that may include reducing the total acid number of the recycled pyrolysis oil to obtain a refined pyrolysis oil having a TAN of about 1.5 mg KOH / g or less as determined by ASTM D664. The method may further include cracking the refined pyrolysis oil to produce products.

[0006] Further disclosed herein are examples that may include removing nitrogen from the recycled pyrolysis oil to obtain a refined pyrolysis oil having a total nitrogen content of about 850 wppm or less. The method may further include cracking the refined pyrolysis oil to produce products.

[0007] Further disclosed herein are examples that may include removing chlorides from the recycled pyrolysis oil to obtain a refined pyrolysis oil having a total chloride content of about 150 wppm or less. The method may further include cracking the refined pyrolysis oil to produce products. [Brief description of the drawings]

[0008] These drawings illustrate certain aspects of the disclosure and should not be used to limit or define the disclosure.

[0009] [Figure 1] FIG. 1 is a block diagram illustrating an exemplary process including water washing of recycled pyrolysis oil for feed to a cracker. [Diagram 2] FIG. 2 is a schematic diagram illustrating an exemplary embodiment for water washing recycled pyrolysis oil. [Diagram 3] FIG. 3 is a schematic diagram illustrating an exemplary embodiment for water washing recycled pyrolysis oil. [Figure 4] FIG. 4 is a schematic diagram illustrating an exemplary embodiment of a feed apparatus to a steam cracking furnace. [Diagram 5] FIG. 5 is a schematic diagram illustrating another exemplary embodiment of a feed apparatus to a steam cracking furnace. [Figure 6]FIG. 6 is a schematic diagram illustrating another exemplary embodiment of a feed apparatus to a steam cracking furnace. [Figure 7] FIG. 7 is a schematic diagram illustrating an exemplary embodiment of a multiple steam cracking furnace feeder. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] This application relates to the cracking of hydrocarbons, and more particularly, in one or more embodiments, to a method and system that includes water washing of recycled pyrolysis oil for feeding to a cracker. Advantageously, water washing of recycled pyrolysis oil should reduce contaminants therein and result in a suitable feed for subsequent cracking. Without washing, recycled pyrolysis oil contains several contaminants that make its use in cracking problematic. Contaminants in recycled pyrolysis oil include, but are not limited to, chlorides, nitrogen, and oxygenates. As used herein, the term "oxygenates" refers to any compound that contains oxygen as part of its chemical structure. Some oxygenates may include, but are not limited to, alcohols, aldehydes, ketones, and ethers, for example. Pretreatments such as hydrotreating and thermal dechlorination can be used to reduce contaminants, but can add undesirable complexity and cost to economically use recycled pyrolysis oil in subsequent cracking operations.

[0011] FIG. 1 is a simplified block diagram illustrating a system 10 for recycling waste materials according to some embodiments. As shown, the system 10 may include the following units: (i) a pyrolysis unit 12 in which a waste-containing pyrolysis feed 14 is pyrolyzed to form recycled pyrolysis oil; (ii) a water wash unit 16 for washing a water wash feed 18 containing recycled pyrolysis oil to remove contaminants; and (iii) a cracking unit 20 for cracking at least the purified pyrolysis oil in the cracker feed 22 from the water wash unit 16. Although the recycled pyrolysis oil from the water wash unit 16 is referred to as refined, it is not intended to imply that the water wash unit 16 removes all contaminants from the recycled pyrolysis oil, but rather that the water wash unit 16 refines the recycled pyrolysis oil by reducing the content of one or more contaminants. In addition, FIG. 1 is not intended to imply that direct fluid connections between the pyrolysis unit 12 and the water wash unit 16 and between the water wash unit 16 and the cracking unit 20 are required. Rather, the pyrolysis derived plastics may be produced at one location and then shipped to another location for water washing. Similarly, refined pyrolysis oil may be produced at one location and shipped to another location for cracking.

[0012] The waste material fed to the pyrolysis unit 12 may include plastic waste material obtained from any source, including, but not limited to, municipal, industrial, commercial, or consumer sources. In some embodiments, the plastic waste material may include post-consumer plastics. The plastic waste material may further be obtained from a common source or from mixed sources, including mixed plastic waste material obtained from municipal or regional sources and / or waste streams of polyethylene terephthalate (PET), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene, and / or polystyrene. Additionally, the waste material may include thermoplastic elastomers and thermoset rubbers, such as from tires and other articles made from natural rubber, polybutadiene, styrene-butadiene, butyl rubber, and ethylene propylene diene monomer rubber (EPDM). The waste material to be treated may also include, but is not limited to, any of a variety of used polymeric and non-polymeric articles. Some examples of the many types of polymeric articles include films (including cast, blown, etc.), sheets, fibers, woven and nonwoven fabrics, furniture (e.g., garden furniture), sports equipment, bottles, food and / or liquid storage containers, transparent and translucent articles, toys, tubes and pipes, sheets, packaging, bags, sacks, coatings, caps, closures, crates, pallets, cups, non-food containers, pails, insulation, and / or medical devices. Further examples include automobile, aircraft, boat and / or marine components (e.g., bumpers, grills, trim parts, dashboards, instrument panels, etc.), wire and cable jackets, agricultural films, geomembranes, play equipment, and other such articles, whether blow molded, rotationally molded, injection molded, etc. Any of the above may include mixtures of polymeric and non-polymeric items (e.g., packaging articles or other articles may include inks, paperboard, paper, metal deposits, etc.).Those skilled in the art will appreciate that such polymeric articles may be made from any of a variety of polymeric and / or non-polymeric materials, and that the polymeric materials may range widely (e.g., ethylene-based, propylene-based, butyl-based polymers, and / or any C2-C6. 40 or higher olefin-based polymers, and further comprising any one or more monomers, such as C2 to C 40 It will be recognized that polymers based on monomers such as α-olefins, diolefins, cyclic olefins, etc. Common examples include ethylene, propylene, butylene, pentene, hexene, heptene, and octene, as well as multi-olefin (including cyclic olefin) monomers such as ethylidene norbornene (ENB) and vinylidene norbornene (VNB) (including, for example, when such cyclic olefins are used as comonomers with, for example, ethylene monomer).

[0013] In some embodiments, the waste may include one or more plastics classified by the Society of the Plastics Industry as plastic identification codes (PIC) 1-7. For example, the waste may include one or more of the following plastics: polyethylene terephthalate, classified as PIC 1; high density polyethylene, classified as PIC 2; polyvinyl chloride, classified as PIC 3; low density polyethylene, classified as PIC 4; polypropylene, classified as PIC 5; polystyrene, classified as PIC 6; and polycarbonate and other plastics, classified as PIC 7. Combinations of various plastics classified as PIC 1-7 may also be used in some embodiments.

[0014] In the pyrolysis unit 12, the waste-containing pyrolysis feed 14 may be pyrolyzed to form recycled pyrolysis oil. Pyrolysis is a chemical recycling technique that involves the thermal decomposition of waste to produce gaseous and liquid products called recycled pyrolysis oil and recycled pyrolysis gas. As used herein, "recycled pyrolysis oil" refers to a composition of matter that is liquid when measured at 25° C. and 1 atmosphere, at least a portion of which is obtained from the pyrolysis of recycled waste (e.g., recycled plastic waste). As used herein, "recycled pyrolysis gas" refers to a composition of matter that is gaseous at 25° C. and 1 atmosphere, at least a portion of which is obtained from the pyrolysis of recycled waste. In some embodiments, the waste may be heated in an environment that is free (or substantially free) of oxygen. For example, pyrolysis may occur in an environment that includes 5 weight percent or less of oxygen, 3 weight percent or less of oxygen, 1 weight percent or less of oxygen, or 0.5 weight percent or less of oxygen. The pyrolysis products may depend on several factors, including, but not limited to, pyrolysis reactor temperature, pyrolysis reactor pressure, reactor residence time, and process configuration. Exemplary pyrolysis techniques for producing recycled pyrolysis oil are described in U.S. Patent No. 10,131,847, the entire disclosure of which is incorporated herein by reference. Pyrolysis unit 12 can include a variety of different equipment suitable for the pyrolysis of waste materials, including, but not limited to, reactors, extruders, tanks, vessels, valves, sensors, hoppers, conveying systems, and piping, among others.

[0015] Specific pyrolysis techniques will now be described in more detail. In an exemplary embodiment, waste material (e.g., plastic waste material) may be provided, for example, in the form of granules, flakes, or pellets and fed to the pyrolysis unit 12. In the pyrolysis unit 12, the waste material may be melted to generate a molten liquid (e.g., molten plastic). For example, the waste material may be melted in an extruder to a temperature of 300°C to 320°C. The molten liquid may then be pyrolyzed in an oxygen-free (or substantially oxygen-free) environment to generate pyrolysis gases. For example, the molten liquid may be heated to a higher temperature, such as 390°C to about 410°C, while stirring, in a pyrolysis chamber. Long-chain hydrocarbons (e.g., about 30 carbon atoms or longer) in the generated pyrolysis gases may then be condensed and further pyrolyzed for further thermal cracking, while shorter-chain hydrocarbons may exit in gaseous form. For example, the generated pyrolysis gases may be directed to a contactor to contact a bank of condenser elements (e.g., plates) where the long-chain hydrocarbons may condense. The long chain hydrocarbons may flow back from the condenser to the pyrolysis chamber. The pyrolysis gas containing the short chain hydrocarbons may be distilled in a distillation column to provide recycled pyrolysis gas and recycled pyrolysis oil.

[0016] As described above, the pyrolysis unit 12 produces recycled pyrolysis oil. The specific composition and properties of the recycled pyrolysis oil vary based on several factors, including pyrolysis conditions, pyrolysis technology, and initial waste. The recycled pyrolysis oil may include hydrocarbons such as paraffins, aromatics, naphthalenes, and olefins. In some embodiments, the recycled pyrolysis oil may include 90% or more hydrocarbons having at least 5 carbon atoms. For example, the recycled pyrolysis oil may include 90%, 95%, 98%, 99% or more by weight of hydrocarbons having at least 5 carbon atoms. In some embodiments, the recycled pyrolysis oil may include 50% or less by weight of olefins. For example, the recycled pyrolysis oil may contain olefins in an amount of 0.1 wt% to 50 wt%, 0.1 wt% to 40 wt%, 0.1 wt% to 25 wt%, 0.1 wt% to 10 wt%, or 10 wt% to 20 wt%, 20 wt% to 30 wt%, 30 wt% to 40 wt%, or 30 wt% to 50 wt%. In some embodiments, the recycled pyrolysis oil may contain aromatic compounds in an amount of 25 wt% or less. For example, the recycled pyrolysis oil may contain aromatic compounds in an amount of 0.1 wt% to 25 wt%, 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt%, or 10 wt% to 20 wt%, 20 wt% to 25 wt%. However, it should be understood that a particular recycled pyrolysis oil may have a concentration of components outside these disclosed ranges.

[0017] The recycled pyrolysis oil may have any suitable API degree desired for a particular application. As used herein, the term "API degree" is a measure of how heavy or light an oil is compared to water, measured according to ASTM D4052. In some embodiments, the recycled pyrolysis oil may have an API degree of 25-75, 25-65, 25-50, 30-70, 50-75, or 30-65.

[0018] In some embodiments, the recycled pyrolysis oil may have a final boiling point of 600° C. or less. As used herein, the final boiling point is the temperature at which the highest boiling compound vaporizes, as determined according to ASTM 2887. In some embodiments, the recycled pyrolysis oil may have a final boiling point of 400° C. to 600° C., 450° C. to 600° C., 500° C. to 600° C., 550° C. to 600° C., 400° C. to 550° C., 450° C. to 550° C., 450° C. to 500° C., or 500° C. to 550° C.

[0019] In some embodiments, the recycled pyrolysis oil may have a kinematic viscosity at 40° C. ("KV40") of 2 centistokes (cSt) or less. As used herein, the term "kinematic viscosity at 40° C." or "KV40" of an oil refers to the kinematic viscosity at 40° C. measured according to ASTM D445.

[0020] The recycled pyrolysis oil may contain high levels of some contaminants that make the recycled pyrolysis oil unsuitable for further processing (e.g., cracking) to produce more valuable products. For example, the recycled pyrolysis oil may contain nitrogen, chlorides, fluorine and fluorine-containing compounds, bromine and bromine-containing compounds, phosphorus and phosphorus-containing compounds, and oxygenates, including but not limited to alcohols, aldehydes, ketones, and ethers, at levels that make further processing difficult. In some embodiments, the recycled pyrolysis oil may have a total nitrogen content of 860 weight parts per million (wppm) or more. For example, the recycled pyrolysis oil (wppm) may have a total nitrogen content of 860 wppm to 3000 wppm, 900 wppm to 2000 wppm, 900 wppm to 1500 wppm, or 900 wppm to 1400 wppm. As used herein, total nitrogen content is the sum of measurements of all nitrogen species in the recycled pyrolysis oil, as determined according to ASTM D5762. The recycled pyrolysis oil may have a total chloride content of 160 wppm or more. For example, the recycled pyrolysis oil may have a total chloride content of 170 wppm to 300 wppm, 170 wppm to 275 wppm, 170 wppm to 250 wppm, 200 wppm to 300 wppm, or 200 wppm to 250 wppm. As used herein, the total chloride content is the sum of the measured values ​​of all chlorides (organic and inorganic) in the recycled pyrolysis oil, as determined according to ASTM D7359. The recycled pyrolysis oil may contain fluorine and / or fluorine-containing compounds in an amount of 1 wppm to 1000 wppm or more. Alternatively, the recycled pyrolysis oil may contain fluorine and / or fluorine-containing compounds in an amount of 1 wppm to 10 wppm, 10 wppm to 100 wppm, 100 wppm to 500 wppm, 500 wppm to 1000 wppm, or any range therebetween. The recycled pyrolysis oil may contain bromine and / or bromine-containing compounds in an amount of 1 wppm to 1000 wppm or more.Alternatively, the recycled pyrolysis oil may contain bromine and / or bromine-containing compounds in an amount of 1 wppm to 10 wppm, 10 wppm to 100 wppm, 100 wppm to 500 wppm, 500 wppm to 1000 wppm, or any range therebetween. The recycled pyrolysis oil may contain phosphorus and / or phosphorus-containing compounds in an amount of 1 wppm to 1000 wppm or more. Alternatively, the recycled pyrolysis oil may contain phosphorus and / or phosphorus-containing compounds in an amount of 1 wppm to 10 wppm, 10 wppm to 100 wppm, 100 wppm to 500 wppm, 500 wppm to 1000 wppm, or any range therebetween. Oxygenates (e.g., alcohols, ethers, and other species containing oxygen) in recycled pyrolysis oil can be difficult to precisely quantify, but their presence can be problematic in downstream processing, for example, increasing carbon monoxide and carbon dioxide products in downstream cracking operations. In some embodiments, recycled pyrolysis oil may contain oxygenates in an amount between 1 wppm and 10 wppm, in an amount between 10 wppm and 100 wppm, in an amount between 100 wppm and 500 wppm, in an amount between 500 wppm and 1000 wppm, or any range therebetween.

[0021] In addition to certain concentrations of contaminants, certain contaminants can result in high acidity in the recycled pyrolysis oil that can be problematic for further processing. The total acid number, determined according to ASTM D664, is a measurement that can be used to quantify the acidity of the recycled pyrolysis oil. The recycled pyrolysis oil may have a total acid number of 1.7 mgKOH / g or more. In some embodiments, the recycled pyrolysis oil may have a total acid number of 1.7 mgKOH / g to 4 mgKOH / g, 1.7 mgKOH / g to 3 mgKOH / g, 1.7 mgKOH / g to 2.5 mgKOH / g, 2 mgKOH / g to 4 mgKOH / g, 2 mgKOH / g to 3 mgKOH / g, or 2 mgKOH / g to 2.5 mgKOH / g.

[0022] Continuing to refer to FIG. 1, the system 10 further includes a water wash unit 16 for reducing contaminants in the recycled pyrolysis oil. The water wash unit 16 receives a water wash feed 18 from the pyrolysis unit 12, the water wash feed 18 including recycled pyrolysis oil. In the water wash unit 16, the recycled pyrolysis oil is contacted with water to produce refined pyrolysis oil. For example, the water wash unit 18 may include mixing the recycled pyrolysis oil with water to selectively transfer certain solutes from the recycled pyrolysis oil to the water, thus extracting contaminants from the recycled pyrolysis oil to be produced. The recycled pyrolysis oil and the water may then be separated to produce a water phase and a refined pyrolysis oil phase.

[0023] The contacting of the recycled pyrolysis oil and water in the water wash unit 16 can occur under any of a variety of suitable conditions to achieve the desired level of contaminant reduction. For example, the contacting can occur at a weight ratio of recycled pyrolysis oil to water of from 0.1:1 to 3:1. By way of further example, the contacting can occur at a temperature of from 10° C. to 100° C. By way of further example, the contacting can occur at a pressure of from ambient to 2100 kPA.

[0024] The water used in the water wash unit 16 may be any suitable water for removing contaminants from the recycled pyrolysis oil, including, but not limited to, fresh water, deionized water, and demineralized water, among others. In some embodiments, the water may have a neutral or basic pH. For example, the water may have a pH of 7-13, 7-12, 7-10, 7-9, or any range therebetween. In certain embodiments, the water may be neutral at pH 7. In embodiments, the water may be acidic. For example, the water may have a pH of 4-7, a pH of 4-6, a pH of 4-5, or any range therebetween. In embodiments where the recycled pyrolysis oil contains acidic contaminants, the water used may be neutral to basic. In embodiments where the recycled pyrolysis oil contains basic contaminants, the water used may be neutral to acidic.

[0025] The water wash unit 16 may have any of a variety of configurations suitable for liquid-liquid extraction. For example, the water wash unit 16 may utilize a mixer-settler, a column, or a centrifugal contactor. The water wash unit 16 may include any of a variety of different equipment to facilitate contact between the water and the recycled pyrolysis oil, including, but not limited to, mixers, tanks, centrifugal contactors, vessels, columns, valves, sensors, and piping, among others.

[0026] FIG. 2 illustrates an exemplary embodiment of a water wash unit 16 for washing recycled pyrolysis oil, according to an exemplary embodiment. As illustrated, the water wash unit 16 may receive a water wash feed 18. Water 22 from a water supply at a rate regulated by a valve 24 may be combined with the recycled pyrolysis oil in the water wash feed 18, and the combined water wash feed then passes through a mixing device 28 before entering a washing drum 26. Although the water and recycled pyrolysis oil are shown as joining together prior to being fed to the mixing device 28, the water and recycled pyrolysis oil may be fed to the mixing device 28 differently, for example, they may be fed separately to the mixing device 28. Additionally, although the mixing device 28 is shown as a separate component, it may be configured differently, for example, the mixing device 28 may be incorporated into the washing drum 26 with the washing drum 26 having a mixing section (not shown) and a settling section (not shown). Any suitable mixing device 28 may be used to facilitate contact between the water and the recycled pyrolysis oil, including, but not limited to, paddle mixers and in-line mixers, among others. In the washing drum 26, a two-phase separation occurs between the water and the recycled pyrolysis oil, producing refined pyrolysis oil and water containing the contaminants extracted from the recycled pyrolysis oil. The refined pyrolysis oil may be removed from the washing drum 26 via line 30 at a rate controlled by valve 32. Water containing the extracted contaminants may be removed from the washing drum 26 via line 34 at a rate controlled by valve 36. Although FIG. 2 shows a single stage separation, it should be understood that the exemplary embodiment may use multiple extraction stages, for example, by placing multiple mixing devices 28 and washing drums 26 in series.

[0027] FIG. 3 illustrates another exemplary embodiment of a water wash unit 16 for washing recycled pyrolysis oil, according to an exemplary embodiment. As illustrated, the water wash unit 16 may receive a water wash feed 18. The water wash feed 18 containing recycled pyrolysis oil may be fed to a wash tower 38 at a rate controlled by a valve 40. Water 22 from a water supply may be introduced to the wash tower 38 at a rate controlled by a valve 42 to contact the recycled pyrolysis oil. By contacting the recycled pyrolysis oil in the wash tower 38, the water should remove contaminants from the recycled pyrolysis oil. The wash tower 38 may include a working section 44, which may include, for example, packing or trays to facilitate contact of the water and recycled pyrolysis oil. The water and recycled pyrolysis oil may flow countercurrently through the wash tower to produce refined pyrolysis oil, which may be removed from the wash tower 38 via line 46 at a rate controlled by a valve 48. Water containing the extracted contaminants may be removed from scrubber 38 via line 50 at a rate controlled by valve 52 .

[0028] As mentioned above, the water washing unit 16 should remove contaminants from the recycled pyrolysis oil to produce a refined pyrolysis oil suitable for further processing. For example, the refined pyrolysis oil may have a total nitrogen content of 850 wppm or less. In some embodiments, the refined pyrolysis oil may have a total nitrogen content of 200 wppm to 850 wppm, 400 wppm to 850 wppm, 500 wppm to 850 wppm, 600 wppm to 850 wppm, 200 wppm to 800 wppm, 200 wppm to 600 wppm, 400 wppm to 850 wppm, 400 wppm to 800 wppm, or 400 wppm to 600 wppm. In some embodiments, the total nitrogen content in the recycled pyrolysis oil may be reduced by the water washing in an amount of at least 15%, at least 30%, at least 40%, at least 50%, or at least 60%. As a further example, the refined pyrolysis oil may have a total chloride content of 150 wppm or less. In some embodiments, the refined pyrolysis oil may have a total chloride content of 50 wppm to 150 wppm, 75 wppm to 150 wppm, 100 wppm to 150 wppm, 50 wppm to 140 wppm, 75 wppm to 140 wppm, or 100 wppm to 140 wppm.

[0029] In some embodiments, the refined pyrolysis oil may have a total fluorine and / or fluorine-containing compound content of 850 wppm or less. In some embodiments, the refined pyrolysis oil may have a total fluorine and / or fluorine-containing compound content of 200 wppm to 850 wppm, 400 wppm to 850 wppm, 500 wppm to 850 wppm, 600 wppm to 850 wppm, 200 wppm to 800 wppm, 200 wppm to 600 wppm, 400 wppm to 850 wppm, 400 wppm to 800 wppm, or 400 wppm to 600 wppm. In some embodiments, the total fluorine and / or fluorine-containing compounds in the recycled pyrolysis oil may be reduced by water washing in an amount of at least 15%, at least 30%, at least 40%, at least 50%, or at least 60%.

[0030] In some embodiments, the refined pyrolysis oil may have a total bromine and / or bromine-containing compound content of 850 wppm or less. In some embodiments, the refined pyrolysis oil may have a total bromine and / or bromine-containing compound content of 200 wppm to 850 wppm, 400 wppm to 850 wppm, 500 wppm to 850 wppm, 600 wppm to 850 wppm, 200 wppm to 800 wppm, 200 wppm to 600 wppm, 400 wppm to 850 wppm, 400 wppm to 800 wppm, or 400 wppm to 600 wppm. In some embodiments, the total bromine and / or bromine-containing compound content in the recycled pyrolysis oil may be reduced by at least 15%, at least 30%, at least 40%, at least 50%, or at least 60% by the water wash.

[0031] In some embodiments, the refined pyrolysis oil may have a total phosphorus and / or phosphorus-containing compound content of 850 wppm or less. In some embodiments, the refined pyrolysis oil may have a total phosphorus and / or phosphorus-containing compound content of 200 wppm to 850 wppm, 400 wppm to 850 wppm, 500 wppm to 850 wppm, 600 wppm to 850 wppm, 200 wppm to 800 wppm, 200 wppm to 600 wppm, 400 wppm to 850 wppm, 400 wppm to 800 wppm, or 400 wppm to 600 wppm. In some embodiments, the total phosphorus and / or phosphorus-containing compound content in the recycled pyrolysis oil may be reduced by at least 15%, at least 30%, at least 40%, at least 50%, or at least 60% by the water wash.

[0032] In some embodiments, the total chloride content in the recycled pyrolysis oil may be reduced by the water wash in an amount of at least 20%, at least 30%, at least 40%, at least 50%, or at least 60%. By way of further example, the refined pyrolysis oil may have a total acid number of 1.5 mg KOH / g or less. In some embodiments, the refined pyrolysis oil may have a total acid number of 0.5 mg KOH / g to 1.5 mg KOH / g, 0.75 mg KOH / g to 1.5 mg KOH / g, 1 mg KOH / g to 1.5 mg KOH / g, 0.5 mg KOH / g to 1.4 mg KOH / g, 0.75 mg KOH / g to 1.4 mg KOH / g, or 1 mg KOH / g to 1.4 mg KOH / g. In some embodiments, the total acid number of the recycled pyrolysis oil may be reduced by the water wash in an amount of 20% or more, 30% or more, 40% or more, 50% or more, or 50% or more. In addition, although the removal of oxygenates can be difficult to directly quantitate, their removal can be indicated by a reduction in carbon monoxide and carbon dioxide production in subsequent cracking when the recycle pyrolysis is water washed.

[0033] Referring to FIG. 1, the system 10 further includes a cracking unit 20 that receives a cracker feed 22 containing refined pyrolysis oil from the waste cleaning unit 16. In the cracking unit 20, the long chain hydrocarbons in the refined pyrolysis oil are cracked into smaller hydrocarbons, including but not limited to olefins (e.g., ethylene, propylene, butylene), aromatics (e.g., benzene, toluene, xylene), and molecular hydrogen (H2), or any combination thereof. Any suitable technique for cracking the refined pyrolysis oil can be used. Examples of suitable techniques may include, but are not limited to, thermal cracking, steam cracking, flexicoking, delayed coking, and fluid catalytic cracking. The cracking unit 20 may include any of a variety of different equipment to facilitate cracking and subsequent separation and purification, including, but not limited to, furnaces, columns, vessels, sensors, and piping, among others.

[0034] In some embodiments, steam cracking may be used in the cracking unit 20 to convert the refined pyrolysis oil to olefins. Steam cracking is a technique that can be used to thermally crack a variety of hydrocarbons into lighter hydrocarbons, such as olefins and aromatics. Conventional steam cracking techniques utilize a steam cracking furnace that includes two sections, a convection section and a radiant (or pyrolysis) section. According to an exemplary embodiment, the refined pyrolysis oil enters the convection section of the steam cracking furnace, where it is heated by indirect contact with hot flue gas from the radiant section and by direct contact with steam. In the convection section, the refined pyrolysis oil may be heated to a temperature of 100° C. or higher. For example, the refined pyrolysis oil may be heated to a temperature of 100° C. to 650° C., 100° C. to 500° C., 100° C. to 450° C., 100° C. to 400° C., 200° C. to 650° C., 300° C. to 650° C., 400° C. to 650° C., 500° C. to 650° C., 400° C. to 600° C., 400° C. to 500° C., or 300° C. to 500° C. The refined pyrolysis oil and steam may be supplied to the steam cracking furnace at any suitable refined pyrolysis oil to steam weight ratio, including refined pyrolysis oil to steam weight ratios of 1:0.1 to 1:2 (e.g., 1:0.1 to 1:0.5, 1:0.75 to 1:0.5, or 1:1 to 1:0.5).

[0035] The mixture of hydrocarbons and steam is then introduced into the radiant section of the steam cracking furnace where thermal cracking occurs. In the radiant section, the mixture can be heated to a temperature of, for example, 400°C to 950°C, 400°C to 900°C, 400°C to 750°C, 700°C to 900°C, or 950°C to 9000°C, including temperatures of. The radiant section may have any suitable pressure for cracking, including but not limited to pressures of 0.1 bar absolute to 5 bar absolute, 1 bar absolute to 5 bar absolute, or 2 bar absolute to 5 bar absolute. The radiant section may have any suitable residence time for cracking, including but not limited to residence times of 0.1 seconds to 2 seconds, 0.5 to 1 second, or 1 second to 2 seconds. The cracker effluent exits the steam cracking furnace for further downstream processing, including quenching. Quenching may be desirable to cool the cracking effluent and prevent further reaction. Cooling can occur, for example, in a transfer line exchanger for steam production or in a quench point or quench pipe for receiving the cracker effluent.

[0036] In some embodiments, the refined pyrolysis oil can be cracked in the cracking unit 20 in the presence of a hydrocarbon co-feed. Any residual contaminants in the refined pyrolysis oil can be further diluted by blending with the hydrocarbon co-feed. For example, the refined pyrolysis oil can be steam cracked in the presence of a hydrocarbon co-feed in a steam cracking furnace. The refined pyrolysis oil can be mixed before or after being introduced into the steam cracking furnace to obtain a mixed feed that is then cracked. Suitable hydrocarbon co-feeds can include any of a variety of hydrocarbon steam cracker feeds that can be cracked in a steam cracker. Examples of suitable hydrocarbon co-feeds can include, but are not limited to, ethane, propane, butane, asphaltenes, petroleum resids (e.g., atmospheric resids, vacuum resids), pitch, crude oil, naphtha, gas oils (e.g., vacuum gas oil, heavy gas oil), liquefied petroleum gas, condensates, one or more other hydrocarbons, or combinations thereof. In some embodiments, there may be multiple hydrocarbon co-feeds, for example, a first hydrocarbon co-feed may be combined with the refined pyrolysis oil for cracking, and a second hydrocarbon co-feed may be simultaneously cracked in the same (or different) steam cracking furnace while being separated from the refined pyrolysis oil. The second hydrocarbon co-feed separated may be the same or different from the first hydrocarbon co-feed combined with the refined pyrolysis oil. For example, the first hydrocarbon co-feed combined with the refined pyrolysis oil may be a heavier hydrocarbon liquid (e.g., gas oil) than the second hydrocarbon co-feed separated (e.g., butane, naphtha).

[0037] The refined pyrolysis oil and the hydrocarbon co-feed can be combined in any suitable ratio. For example, the refined pyrolysis oil and the hydrocarbon co-feed can be combined in a refined pyrolysis oil to hydrocarbon co-feed weight ratio of 1:100 to 1:1.5, such as, but not limited to, 1:50 to 1:1.5, 1:25 to 1:1.5, 1:20 to 1:1.5, 1:100 to 1:5, 1:100 to 1:4, 1:100 to 1:10, 1:50 to about 1:5, or 1:20 to 1:5. Additionally, when combined with a co-feed, the mixture of refined pyrolysis oil and hydrocarbon co-feed may be fed to a steam cracker furnace with steam in any suitable ratio, including a weight ratio of the mixture to steam of 1:0.1 to 1:2 (e.g., 1:0.1 to 1:0.5, 1:0.75 to 1:0.5, or 1:1 to 1:0.5). The co-feed may include refined pyrolysis oil in an amount of 0.1% to 50% by weight. Alternatively, the co-feed may comprise refined pyrolysis oil in an amount of 0.1 wt% to 1 wt%, 1 wt% to 5 wt%, 5 wt% to 10 wt%, 10 wt% to 15 wt%, 15 wt% to 20 wt%, 20 wt% to 25 wt%, 25 wt% to 30 wt%, 30 wt% to 35 wt%, 35 wt% to 40 wt%, 40 wt% to 45 wt%, 45 wt% to 50 wt%, or any range therebetween. The co-feed may comprise a hydrocarbon co-feed in an amount of 0.1 wt% to 50 wt%. Alternatively, the co-feed may comprise the hydrocarbon co-feed in an amount of 0.1 wt% to 1 wt%, in an amount of 1 wt% to 5 wt%, in an amount of 5 wt% to 10 wt%, in an amount of 10 wt% to 15 wt%, in an amount of 15 wt% to 20 wt%, in an amount of 20 wt% to 25 wt%, in an amount of 25 wt% to 30 wt%, in an amount of 30 wt% to 35 wt%, in an amount of 35 wt% to 40 wt%, in an amount of 40 wt% to 45 wt%, in an amount of 45 wt% to 50 wt%, or any range therebetween.

[0038] FIG. 4 is a schematic diagram illustrating an exemplary embodiment of a feed to a steam cracking furnace 54. The steam cracking furnace 54 may include a convection section 56 and a radiant section 58. As shown, the cracker feed 22 containing refined pyrolysis oil may be fed to the convection section 56. In the illustrated embodiment, the refined pyrolysis oil in the cracker feed 22 may be mixed with a hydrocarbon co-feed from line 60 to form a mixed feed. In some embodiments, the refined pyrolysis oil and the hydrocarbon co-feed may be mixed before entering the convection section 56, and the mixed feed then enters the convection section 56 of the steam cracking furnace 54. This mixed feed of refined pyrolysis oil and hydrocarbon co-feed may pass through a series of tubes 62 through the convection section 56. The flue gas from the radiant section 58 travels upward through the convection section 56, heating the tubes 62 and their contents, thus preheating the mixed feed. The mixed feed of refined pyrolysis oil and hydrocarbons co-fed in the convection section 56 may be diluted with steam fed by line 64 to the convection section tubes 62. This diluted mixture is then fed in tubes 62 to the radiant section 58 where it is cracked, and a cracker effluent is removed from the radiant section 58 by effluent line 66. As mentioned above, the cracker effluent may include cracker products, including, but not limited to, olefins and / or aromatics.

[0039] FIG. 5 is a schematic diagram showing another exemplary embodiment of a feed to a steam cracking furnace 54. Similar to the embodiment of FIG. 4, the illustrated embodiment of FIG. 5 includes a steam cracking furnace 54 that receives a cracker feed 22 containing refined pyrolysis oil in a convection section 56. As shown, the refined pyrolysis oil may be mixed with a hydrocarbon co-feed from a line 60 such that the mixed feed passes through the convection section 56 via a tube 62 to a radiant section 58. Prior to the radiant section 58, the mixed feed of refined pyrolysis oil and hydrocarbon co-feed is diluted with steam from a line 64, and then the diluted mixture is cracked in the radiant section 58, and the cracker effluent is removed from the radiant section 58 by an effluent line 66. However, in addition to the refined pyrolysis oil and the hydrocarbon co-feed, a second hydrocarbon co-feed may also be fed to the convection section 56. As shown, a second cracker feed 67 including a second hydrocarbon co-feed may be introduced into the convection section 56 where the second cracker feed 67 passes through the convection section 56 through a series of second tubes 68 to the radiant section 58. In the illustrated embodiment, the second hydrocarbon co-feed in the second tubes 68 may be separated from the refined pyrolysis oil as it passes through the steam cracking furnace 54. Flue gas from the radiant section 58 travels upward through the convection section 56, heating the tubes 68 and their contents, thus preheating the second hydrocarbon co-feed. The second hydrocarbon co-feed in the convection section 56 may be diluted with additional steam provided by line 70 into the tubes 68 in the convection section. This diluted second co-feed may then be provided in the tubes 68 to the radiant section 58 where it is cracked and additional cracker effluent is removed from the radiant section 58 by a second effluent line 72. This additional cracker effluent may include cracker products including, but not limited to, olefins and / or aromatics.

[0040] FIG. 6 is a schematic diagram showing another exemplary embodiment of a feed system to a steam cracking furnace 54. Similar to the embodiment of FIG. 4, the illustrated embodiment of FIG. 5 includes a steam cracking furnace 54 having a cracker feed 22 containing refined pyrolysis oil. As shown, the cracker feed 22 containing refined pyrolysis oil passes through a tube 62 to a radiant section 58 of the steam cracking furnace 54. In addition, a hydrocarbon co-feed is also introduced to the steam cracking furnace 54. However, instead of being mixed before being fed to the steam cracking furnace 54, the hydrocarbon co-feed and the refined pyrolysis oil are mixed in the tube 62 of the steam cracking furnace 54. As shown, the hydrocarbon co-feed may be fed to the convection section 56 of the steam cracking furnace 54 via a line 60. The refined pyrolysis oil may be fed to the steam cracking furnace 54 via the cracker feed 22. In the illustrated embodiment, there are multiple potential feed locations for the cracker feed 22 to the steam cracking furnace 54, illustrated in FIG. 5 as cracker feed 22a, cracker feed 22b, cracker feed 22c, and cracker feed 22d. Each of the different potential feed locations is downstream of the feed location of line 60, with the hydrocarbon co-feed and cracker feed 22a and cracker feed 22b being upstream of the steam feed location, and cracker feed 22c and cracker feed 22d being downstream of the steam feed location. Flue gas from the radiant section 58 travels upward through the convection section 56, heating tubes 62 and their contents, thus preheating the refined pyrolysis oil and the hydrocarbon co-feed. The refined pyrolysis oil and the hydrocarbon co-feed in the convection section 56 may be diluted with steam fed by line 64 into the tubes 62 in the convection section. The dilute mixture of steam, refined pyrolysis oil, and hydrocarbon co-feed may be fed to radiant section 58 in tube 62 where it is cracked, and the cracker effluent is removed from radiant section 58 by effluent line 66. As mentioned above, the cracker effluent may include cracker products including, but not limited to, olefins and / or aromatics.

[0041] FIG. 7 is a schematic diagram showing an exemplary embodiment of a feed system for multiple steam cracking furnaces. In the illustrated embodiment, three steam cracking furnaces are shown, identified as a first steam cracking furnace 74, a second steam cracking furnace 76, and a third steam cracking furnace 78. As shown, a cracker feed 22 containing refined pyrolysis oil is provided and may be combined with a hydrocarbon co-feed from line 60 to obtain a mixed co-feed. The cracker feed 22 may then be split into a first cracker feed 80 and a second cracker feed 82. The first cracker feed 80 containing the mixed co-feed may be fed to the first steam cracking furnace 74, where it is diluted with steam from a first cracker steam line 84 and then cracked, and the first cracker effluent is removed from the first steam cracking furnace 74 via a first cracker effluent line 86. The second cracker feed 82 containing the mixed co-feed may be fed to the second steam cracking furnace 76 where it is diluted with steam from the second cracker steam line 88 and then cracked, with the second cracker effluent being removed from the second steam cracking furnace 76 via the second cracker effluent line 90. A separate hydrocarbon feed stream may also be provided and fed to the third steam cracking furnace 78 via line 92. This separate hydrocarbon feed stream may include any of the co-feeds described above and may be the same or different from the hydrocarbon co-feed mixed with the refined pyrolysis oil. In the third steam cracking furnace 78, the second hydrocarbon feed stream from line 92 may be diluted with steam from a third cracker steam line 94 and then cracked, with a third cracker effluent being removed from the third steam cracking furnace 78 via a third cracker effluent line 96. In each of the steam cracking furnaces, the products in the effluent may include, but are not limited to, olefins and aromatics.

[0042] Thus, the present disclosure may provide methods and systems that include water washing of recycled pyrolysis oil for feed to a cracker. The following are non-limiting exemplary embodiments according to the present disclosure.

[0043] An exemplary embodiment of the method includes contacting recycled pyrolysis oil with water to produce a refined pyrolysis oil and cracking the refined pyrolysis oil to produce a product. This exemplary embodiment may include one or more of the following: Element 1: contacting recycled pyrolysis oil with water to produce a refined pyrolysis oil; Element 2: cracking the refined pyrolysis oil to produce a product includes steam cracking the refined pyrolysis oil in the presence of steam; Element 3: cracking the refined pyrolysis oil is performed in the presence of a hydrocarbon co-feed; Element 4: mixing the refined pyrolysis oil with the co-feed to produce a mixed feed; and cracking the mixed feed; Element 5: cracking the mixed feed is performed in a steam cracking furnace, the method including cracking a second hydrocarbon feed in the steam cracking furnace, the second hydrocarbon feed being separated from the refined pyrolysis oil in the steam cracking furnace; Element 6: the hydrocarbon co-feed is mixed with the second hydrocarbon feed to be separated; element 7: cracking the refined pyrolysis oil is performed in a steam cracking furnace, and the refined pyrolysis oil and the hydrocarbon co-feed are separately fed to the steam cracking furnace; element 8: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the hydrocarbon co-feed; element 9: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the steam; element 10: the hydrocarbon co-feed and the refined pyrolysis oil are present in a weight ratio of refined pyrolysis oil to hydrocarbon co-feed of about 1:100 to about 1:2; element 11: mixing the refined pyrolysis oil with the hydrocarbon co-feed to obtain a mixed feed; cracking the mixed feed in at least first and second steam cracker furnaces to obtain a first product; and cracking a separate hydrocarbon feed stream to obtain a second product.Element 12: the hydrocarbon co-feed comprises at least one hydrocarbon selected from the group consisting of ethane, propane, butane, asphaltenes, residual oil, pitch, crude oil, naphtha, gas oil, liquefied petroleum gas, condensate, and combinations thereof; Element 13: removing oxygen-containing compounds from the recycled pyrolysis oil; Element 14: removing methanol from the recycled pyrolysis oil; Element 15: the product comprises at least one hydrocarbon selected from the group consisting of olefins, aromatics, and combinations thereof; Element 16: the recycled pyrolysis oil comprises about 95% or more by weight of hydrocarbons having at least 5 carbon atoms, the recycled pyrolysis oil comprises about 50% or less by weight of olefins, the recycled pyrolysis oil comprises about 20% or less by weight of aromatics, and the recycled pyrolysis oil has a final boiling point of about 400° C. to about 600° C.; Element 17: the water has a pH of about 7 to about 10; Element 18: the TAN of the refined pyrolysis oil is in accordance with ASTM The total nitrogen content of the refined pyrolysis oil is from about 400 wppm to about 850 wppm, and the total chloride content of the refined pyrolysis oil is from about 75 wppm to about 150 wppm;Element 19: The recycled pyrolysis oil is derived at least in part from plastic waste;Element 20: The recycled pyrolysis oil is derived at least in part from post-consumer plastic.Element 21: The recycled pyrolysis oil further comprises at least one additional contaminant selected from the group consisting of fluorine, fluorine-containing compounds, bromine, bromine-containing compounds, phosphorus, phosphorus-containing compounds, and combinations thereof, and the method further comprises removing at least a portion of the at least one additional contaminant from the pyrolysis oil.

[0044] Another exemplary embodiment of the present disclosure is a method comprising reducing the total acid number of recycled pyrolysis oil to obtain a refined pyrolysis oil having a TAN of about 1.5 mg KOH / g or less as determined by ASTM D664, and cracking the refined pyrolysis oil to produce products. This exemplary embodiment may include one or more of the following: Element 1: contacting the recycled pyrolysis oil with water to obtain a refined pyrolysis oil; Element 2: cracking the refined pyrolysis oil to produce products comprises steam cracking the refined pyrolysis oil in the presence of steam; Element 3: cracking the refined pyrolysis oil is performed in the presence of a hydrocarbon co-feed; Element 4: mixing the refined pyrolysis oil with the co-feed to obtain a mixed feed; and cracking the mixed feed; Element 5: cracking the mixed feed is performed in a steam cracking furnace, the method comprising cracking a second hydrocarbon feed in the steam cracking furnace, the second hydrocarbon feed being separated from the refined pyrolysis oil in the steam cracking furnace; Element 6: the hydrocarbon co-feed is mixed with the second hydrocarbon feed to be separated; element 7: cracking the refined pyrolysis oil is performed in a steam cracking furnace, and the refined pyrolysis oil and the hydrocarbon co-feed are separately fed to the steam cracking furnace; element 8: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the hydrocarbon co-feed; element 9: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the steam; element 10: the hydrocarbon co-feed and the refined pyrolysis oil are present in a weight ratio of refined pyrolysis oil to hydrocarbon co-feed of about 1:100 to about 1:2; element 11: mixing the refined pyrolysis oil with the hydrocarbon co-feed to obtain a mixed feed; cracking the mixed feed in at least first and second steam cracker furnaces to obtain a first product; and cracking a separate hydrocarbon feed stream to obtain a second product.Element 12: the hydrocarbon co-feed comprises at least one hydrocarbon selected from the group consisting of ethane, propane, butane, asphaltenes, residual oil, pitch, crude oil, naphtha, gas oil, liquefied petroleum gas, condensate, and combinations thereof; Element 13: removing oxygen-containing compounds from the recycled pyrolysis oil; Element 14: removing methanol from the recycled pyrolysis oil; Element 15: the product comprises at least one hydrocarbon selected from the group consisting of olefins, aromatics, and combinations thereof; Element 16: the recycled pyrolysis oil comprises about 95% or more by weight of hydrocarbons having at least 5 carbon atoms, the recycled pyrolysis oil comprises olefins in an amount of about 50% or less by weight, the recycled pyrolysis oil comprises aromatics in an amount of about 20% or less by weight, and the recycled pyrolysis oil has a final boiling point of about 400° C. to about 600° C.; Element 17: the water has a pH of about 7 to about 9; Element 18: the TAN of the refined pyrolysis oil is in accordance with ASTM The total nitrogen content of the refined pyrolysis oil is from about 400 wppm to about 850 wppm, and the total chloride content of the refined pyrolysis oil is from about 75 wppm to about 150 wppm;Element 19: The recycled pyrolysis oil is derived at least in part from plastic waste;Element 20: The recycled pyrolysis oil is derived at least in part from post-consumer plastic.Element 21: The recycled pyrolysis oil further comprises at least one additional contaminant selected from the group consisting of fluorine, fluorine-containing compounds, bromine, bromine-containing compounds, phosphorus, phosphorus-containing compounds, and combinations thereof, and the method further comprises removing at least a portion of the at least one additional contaminant from the pyrolysis oil.

[0045] Another exemplary embodiment of the present disclosure is a method including removing nitrogen from recycled pyrolysis oil to obtain a refined pyrolysis oil having a total nitrogen content of about 850 wppm or less, and cracking the refined pyrolysis oil to produce products. This exemplary embodiment may include one or more of the following: Element 1: contacting the recycled pyrolysis oil with water to obtain a refined pyrolysis oil; Element 2: cracking the refined pyrolysis oil to produce products includes steam cracking the refined pyrolysis oil in the presence of water vapor; Element 3: cracking the refined pyrolysis oil is performed in the presence of a hydrocarbon co-feed; Element 4: mixing the refined pyrolysis oil with the co-feed to obtain a mixed feed; and cracking the mixed feed; Element 5: cracking the mixed feed is performed in a steam cracking furnace, the method including cracking a second hydrocarbon feed in the steam cracking furnace, the second hydrocarbon feed being separated from the refined pyrolysis oil in the steam cracking furnace; Element 6: the hydrocarbon co-feed is mixed with the second hydrocarbon feed to be separated; element 7: cracking the refined pyrolysis oil is performed in a steam cracking furnace, and the refined pyrolysis oil and the hydrocarbon co-feed are separately fed to the steam cracking furnace; element 8: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the hydrocarbon co-feed; element 9: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the steam; element 10: the hydrocarbon co-feed and the refined pyrolysis oil are present in a weight ratio of refined pyrolysis oil to hydrocarbon co-feed of about 1:100 to about 1:2; element 11: mixing the refined pyrolysis oil with the hydrocarbon co-feed to obtain a mixed feed; cracking the mixed feed in at least first and second steam cracker furnaces to obtain a first product; and cracking a separate hydrocarbon feed stream to obtain a second product.Element 12: the hydrocarbon co-feed comprises at least one hydrocarbon selected from the group consisting of ethane, propane, butane, asphaltenes, residual oil, pitch, crude oil, naphtha, gas oil, liquefied petroleum gas, condensate, and combinations thereof; Element 13: removing oxygen-containing compounds from the recycled pyrolysis oil; Element 14: removing methanol from the recycled pyrolysis oil; Element 15: the product comprises at least one hydrocarbon selected from the group consisting of olefins, aromatics, and combinations thereof; Element 16: the recycled pyrolysis oil comprises about 95% or more by weight of hydrocarbons having at least 5 carbon atoms, the recycled pyrolysis oil comprises olefins in an amount of about 50% or less by weight, the recycled pyrolysis oil comprises aromatics in an amount of about 20% or less by weight, and the recycled pyrolysis oil has a final boiling point of about 400° C. to about 600° C.; Element 17: the water has a pH of about 7 to about 9; Element 18: the TAN of the refined pyrolysis oil is in accordance with ASTM The total nitrogen content of the refined pyrolysis oil is from about 400 wppm to about 850 wppm, and the total chloride content of the refined pyrolysis oil is from about 75 wppm to about 150 wppm;Element 19: The recycled pyrolysis oil is derived at least in part from plastic waste;Element 20: The recycled pyrolysis oil is derived at least in part from post-consumer plastic.Element 21: The recycled pyrolysis oil further comprises at least one additional contaminant selected from the group consisting of fluorine, fluorine-containing compounds, bromine, bromine-containing compounds, phosphorus, phosphorus-containing compounds, and combinations thereof, and the method further comprises removing at least a portion of the at least one additional contaminant from the pyrolysis oil.

[0046] Another exemplary embodiment of the present disclosure is a method comprising removing chlorides from recycled pyrolysis oil to obtain a refined pyrolysis oil having a total chloride content of about 150 wppm or less. The method may further comprise cracking the refined pyrolysis oil to produce products. This exemplary embodiment may include one or more of the following: Element 1: contacting the recycled pyrolysis oil with water to obtain a refined pyrolysis oil; Element 2: cracking the refined pyrolysis oil to produce products comprises steam cracking the refined pyrolysis oil in the presence of water vapor; Element 3: cracking the refined pyrolysis oil is performed in the presence of a hydrocarbon co-feed; Element 4: mixing the refined pyrolysis oil with the co-feed to obtain a mixed feed; and cracking the mixed feed; Element 5: cracking the mixed feed is performed in a steam cracking furnace, the method comprising cracking a second hydrocarbon feed in the steam cracking furnace, the second hydrocarbon feed being separated from the refined pyrolysis oil in the steam cracking furnace; Element 6: the hydrocarbon co-feed is mixed with the second hydrocarbon feed to be separated; element 7: cracking the refined pyrolysis oil is performed in a steam cracking furnace, and the refined pyrolysis oil and the hydrocarbon co-feed are separately fed to the steam cracking furnace; element 8: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the hydrocarbon co-feed; element 9: the refined pyrolysis oil is fed to the steam cracking furnace downstream of the steam; element 10: the hydrocarbon co-feed and the refined pyrolysis oil are present in a weight ratio of refined pyrolysis oil to hydrocarbon co-feed of about 1:100 to about 1:2; element 11: mixing the refined pyrolysis oil with the hydrocarbon co-feed to obtain a mixed feed; cracking the mixed feed in at least first and second steam cracker furnaces to obtain a first product; and cracking a separate hydrocarbon feed stream to obtain a second product.Element 12: the hydrocarbon co-feed comprises at least one hydrocarbon selected from the group consisting of ethane, propane, butane, asphaltenes, residual oil, pitch, crude oil, naphtha, gas oil, liquefied petroleum gas, condensate, and combinations thereof; Element 13: removing oxygen-containing compounds from the recycled pyrolysis oil; Element 14: removing methanol from the recycled pyrolysis oil; Element 15: the product comprises at least one hydrocarbon selected from the group consisting of olefins, aromatics, and combinations thereof; Element 16: the recycled pyrolysis oil comprises about 95% or more by weight of hydrocarbons having at least 5 carbon atoms, the recycled pyrolysis oil comprises olefins in an amount of about 50% or less by weight, the recycled pyrolysis oil comprises aromatics in an amount of about 20% or less by weight, and the recycled pyrolysis oil has a final boiling point of about 400° C. to about 600° C.; Element 17: the water has a pH of about 7 to about 9; Element 18: the TAN of the refined pyrolysis oil is in accordance with ASTM The total nitrogen content of the refined pyrolysis oil is from about 400 wppm to about 850 wppm, and the total chloride content of the refined pyrolysis oil is from about 75 wppm to about 150 wppm;Element 19: The recycled pyrolysis oil is derived at least in part from plastic waste;Element 20: The recycled pyrolysis oil is derived at least in part from post-consumer plastic.Element 21: The recycled pyrolysis oil further comprises at least one additional contaminant selected from the group consisting of fluorine, fluorine-containing compounds, bromine, bromine-containing compounds, phosphorus, phosphorus-containing compounds, and combinations thereof, and the method further comprises removing at least a portion of the at least one additional contaminant from the pyrolysis oil. EXAMPLES

[0047] In order to facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. The following examples should in no way be read to limit or define the entire scope of the present disclosure.

[0048] Example 1 This example is provided to illustrate the removal of contaminants from recycled pyrolysis oil by water washing. The water used in this example was deionized water. The recycled pyrolysis oil was derived at least in part from plastic waste and had the following properties: specific gravity of 0.78-0.8, kinematic viscosity of 1.2 cSt-2 cSt, and boiling point range of about 90°F (about 32.2°C) to about 875°F (about 468.3°C) (determined according to ASTM 2887). The recycled pyrolysis oil and water were used in a 50:50 volume ratio. Each washing cycle involved combining the recycled pyrolysis oil and water in a shaker, followed by stirring for 5-10 minutes, and then centrifuging. This was repeated with fresh deionized water for a total of four washing cycles, and the total nitrogen content and total acid number (TAN) of the recycled pyrolysis oil were recorded initially and then after each washing cycle. The results of this example are shown in the table below.

[0049] [Table 1]

[0050] Example 2 This example is provided to further illustrate the removal of contaminants from recycled pyrolysis oil by water washing. The water used in this example was deionized water. The pH of the water was adjusted to 9 and 12 for samples 6 and 7, respectively, using sodium hydroxide. The recycled pyrolysis oil was derived at least in part from plastic waste and had the following properties: specific gravity of 0.78-0.8, kinematic viscosity of 1.2 cSt-2 cSt, and boiling point range of about 90°F (about 32.2°C) to about 875°F (about 468.3°C) (determined according to ASTM 2887). The recycled pyrolysis oil and water were used in a volume ratio of 50:50. One washing cycle was performed that included combining the recycled pyrolysis oil and water in a shaker, followed by stirring for 5-10 minutes, and then centrifuging. The total nitrogen, basic nitrogen, non-basic nitrogen, and total chloride content were determined for the recycled pyrolysis oil both before and after washing. Total nitrogen was determined according to ASTM D5762. Basic nitrogen was determined according to UOP269. Non-basic nitrogen was determined by the difference between total nitrogen and basic nitrogen. Total chloride was determined according to ASTM7359.

[0051] The results of this example are shown in the table below.

[0052] [Table 2]

[0053] Example 3 The following example is provided to further illustrate the removal of contaminants from recycled pyrolysis oil by water washing. The water used in this example was deionized. The recycled pyrolysis oil was derived at least in part from plastic waste and had the following properties: specific gravity of 0.78-0.8, kinematic viscosity of 1.2 cSt-2 cSt, and boiling point range of about 90°F (about 32.2°C) to about 875°F (about 468.3°C) (determined according to ASTM 2887). The recycled pyrolysis oil and water were used in a 50:50 volume ratio. Each washing cycle involved combining the recycled pyrolysis oil and water in a shaker, followed by stirring for 5-10 minutes, and then centrifuging. Samples 8-10 were not washed. Sample 11 was also tested without washing and with 6 washing cycles. Sample 12 was tested without washing and with 3 washing cycles. The samples (with or without washing) were then fed separately to a pilot-scale steam cracking furnace unit. A gas chromatography system and method was used to measure the steam cracker furnace effluent to identify and quantify the carbon monoxide (CO) and carbon dioxide (CO2) peaks. The CO and CO2 peak areas were then calculated to convert to mass percent in the base feed. The carbon monoxide and carbon dioxide yields were reduced for the washed samples, indicating that oxygenates were removed from the recycled pyrolysis oil from the washing process.

[0054] [Table 3]

[0055] While the present disclosure has been described with respect to certain embodiments and examples, those skilled in the art having the benefit of this disclosure will appreciate that other embodiments may be devised that do not depart from the scope and spirit of the present disclosure as disclosed herein. Although individual embodiments are discussed, the present disclosure encompasses all combinations of all such embodiments.

[0056] Although compositions, methods, and processes are described herein in terms of "comprising," "containing," "having," or "including" various components or steps, the compositions and methods may also "consists essentially of" or "consists of" the various components and steps. Unless otherwise specified, the phrases "consists essentially of" and "consists essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned herein, unless such steps, elements, or materials affect the basic and novel characteristics of the disclosure. In addition, they do not exclude impurities and deviations normally associated with the elements and materials used.

[0057] All numerical values ​​within the detailed description and claims herein that are modified by "about" or "approximately" with respect to a stated value are intended to account for experimental error and variations that would be expected by one of ordinary skill in the art.

[0058] For the sake of brevity, only certain ranges are expressly disclosed herein. However, a range from any lower limit may be combined with any upper limit to recite a range that is not expressly recited, and a range from any lower limit may be combined with any other lower limit to recite a range that is not expressly recited, and similarly, a range from any upper limit may be combined with any other upper limit to recite a range that is not expressly recited.

Claims

1. contacting the recycled pyrolysis oil with water to produce a refined pyrolysis oil; cracking the refined pyrolysis oil to produce products; A method comprising:

2. reducing the total acid number of the recycled pyrolysis oil to obtain a refined pyrolysis oil having a TAN of about 1.5 mg KOH / g or less as determined by ASTM D664; cracking the refined pyrolysis oil to produce products; A method comprising:

3. removing nitrogen from the recycled pyrolysis oil to obtain a refined pyrolysis oil having a total nitrogen content of about 850 wppm or less; cracking the refined pyrolysis oil to produce products; A method comprising:

4. removing chlorides from the recycled pyrolysis oil to obtain a refined pyrolysis oil having a total chloride content of about 150 wppm or less; cracking the refined pyrolysis oil to produce products; A method comprising:

5. The method of any one of claims 2 to 4, comprising contacting the recycled pyrolysis oil with water to obtain the refined pyrolysis oil.

6. 6. The method of claim 5, wherein the step of cracking the refined pyrolysis oil to produce products comprises steam cracking the refined pyrolysis oil in the presence of steam.

7. 6. The method of claim 5, wherein cracking the refined pyrolysis oil is carried out in the presence of a hydrocarbon co-feed.

8. blending the refined pyrolysis oil with the hydrocarbon co-feed to obtain a blended feed; cracking the mixed feed; The method of claim 7 further comprising:

9. 9. The method of claim 8, wherein the step of cracking the mixed feed is carried out in a steam cracking furnace, the method including cracking a second hydrocarbon feed in the steam cracking furnace, the second hydrocarbon feed being separated from the refined pyrolysis oil in the steam cracking furnace.

10. 10. The method of claim 9, wherein the hydrocarbon co-feed is heavier than the second hydrocarbon feed being separated.

11. 8. The method of claim 7, wherein cracking the refined pyrolysis oil is carried out in a steam cracking furnace, and the refined pyrolysis oil and the hydrocarbon co-feed are fed separately to the steam cracking furnace.

12. 12. The method of claim 11, wherein the refined pyrolysis oil is fed to the steam cracking furnace downstream of the hydrocarbon co-feed.

13. 12. The method of claim 11, wherein the refined pyrolysis oil is fed downstream of the steam to the steam cracking furnace.

14. 8. The method of claim 7, wherein the hydrocarbon co-feed and the refined pyrolysis oil are present in a weight ratio of refined pyrolysis oil to hydrocarbon co-feed of from about 1:100 to about 1:

2.

15. blending the refined pyrolysis oil with the hydrocarbon co-feed to obtain a blended feed; cracking the mixed feed in at least first and second steam cracker furnaces to obtain a first product; cracking a separate hydrocarbon feed stream to obtain a second product; The method of claim 7 further comprising:

16. 8. The method of claim 7, wherein the hydrocarbon co-feed comprises at least one hydrocarbon selected from the group consisting of ethane, propane, butane, asphaltenes, resid, pitch, crude oil, naphtha, gas oil, liquefied petroleum gas, condensates, and combinations thereof.

17. 6. The method of claim 5, further comprising removing oxygen-containing compounds from the recycled pyrolysis oil.

18. 6. The method of claim 5, further comprising removing methanol from the recycled pyrolysis oil.

19. 6. The method of claim 5, wherein the recycled pyrolysis oil further comprises at least one additional contaminant selected from the group consisting of fluorine, fluorine-containing compounds, bromine, bromine-containing compounds, phosphorus, phosphorus-containing compounds, and combinations thereof, and the method further comprises removing at least a portion of the at least one additional contaminant from the recycled pyrolysis oil.

20. 6. The method of claim 5, wherein the product comprises at least one hydrocarbon selected from the group consisting of olefins, aromatics, and combinations thereof.

21. 6. The method of claim 5, wherein the recycled pyrolysis oil comprises about 95% by weight or more of hydrocarbons having at least 5 carbon atoms, the recycled pyrolysis oil comprises about 50% by weight or less of olefins, the recycled pyrolysis oil comprises about 20% by weight or less of aromatics, and the recycled pyrolysis oil has a final boiling point of about 400°C to about 600°C.

22. The method of claim 5, wherein the water has a pH of about 7 to about 10.

23. 6. The method of claim 5, wherein the TAN of the refined pyrolysis oil is from about 0.5 to about 1.5 mg KOG / g as determined by ASTM D664, the total nitrogen content of the refined pyrolysis oil is from about 400 wppm to about 850 wppm, and the total chloride content of the refined pyrolysis oil is from about 75 wppm to about 150 wppm.

24. 6. The method of claim 5, wherein the recycled pyrolysis oil is derived at least in part from plastic waste.

25. 6. The method of claim 5, wherein the recycled pyrolysis oil is derived at least in part from post-consumer plastics.

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