Compositions of plastic materials and methods for treating plastic materials to form said compositions

Abstract

This patent application relates to a plastic composition comprising: - a plastic material that is free of halogenated components or has a halogen content of less than or equal to 0.5% by mass relative to the plastic material; - an oligomer derived from the plastic contained in the plastic material; - a halide salt; and - a hydrocarbon.

Description

Technical Field

[0001] This invention belongs to the field of chemical recycling processes for plastics, and its purpose is to enhance plastic materials that were originally intended for landfill or waste-to-energy disposal.

[0002] In particular, this patent application relates to a composition of plastic material and a method for preparing the same, wherein the plastic material in the composition is halogen-free or has a reduced halogen content, and the preparation method is capable of chemically treating plastic materials containing halogenated components and mixtures of different plastic materials, or even recycled plastic materials.

[0003] Furthermore, this patent application relates to a method capable of simultaneously processing distillation residues, particularly vacuum residues, and plastic materials as defined herein, to produce a halogen-free or halogen-containing plastic material composition with a halogen content of less than or equal to 0.5% by weight relative to the plastic material, which can then be enhanced by appropriate refining processes for light hydrocarbon products such as naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO), and heavy vacuum gas oil (HVGO). Background Technology

[0004] The main objective of this invention is to reduce the halogen (preferably chlorine) content of the starting plastic material to form a plastic composition wherein the plastic material is free of halogenated components or the halogen content is less than or equal to 0.5% by weight relative to the plastic material.

[0005] The pyrolysis process of plastics can follow molecular or chemical methods.

[0006] According to molecular methods, polymers are processed to obtain monomers used initially. Conversely, according to chemical methods, synthetic building blocks for the petrochemical industry can be obtained starting from plastic materials.

[0007] The proposed solution makes it possible to incorporate plastic materials into the circular economy loop, where they would otherwise be intended for landfill or waste-to-energy disposal, thus positively impacting the reduction of raw material consumption from both fossil-derived (petroleum-derived polymer materials) and plant-derived (bio-based polymer materials) sources.

[0008] In this patent application, plastic material refers to a solid composition of one or more plastics containing halogenated components and possibly other compounds of organic or inorganic origin.

[0009] In this patent application, "plastic" refers to the IUPAC definition of "polymer material that may contain other substances to improve performance or reduce cost".

[0010] Typically, plastics are polymer materials or mixtures of polymer materials.

[0011] In this patent application, PLASMIX refers to a mixture of sorted wastes from separate collections of post-consumer plastic packaging. At the sorting center, certain polymers are initially selected, particularly polyethylene, polypropylene, and PET (polyethylene terephthalate). All unselected items are named PLASMIX.

[0012] Plasmix can be washable, meaning it has been washed to remove the wet parts contained within, or, for that matter, unwashed.

[0013] In this patent application, "inerting agent" refers to a chemical compound that can react with halogens present in plastic materials.

[0014] In this patent application, when measured in a composition of plastic materials, "halogen content in plastic materials by mass" refers to a measurement performed according to the method described below.

[0015] Two samples of the plastic material composition were taken. In the first sample, halogens were determined by ion chromatography after mineralization by a bomb calorimeter. The second sample was treated at 550°C for 4 hours under an inert atmosphere (nitrogen) and atmospheric pressure. In the second sample treated in this way, halogens were determined by ion chromatography after mineralization by a bomb calorimeter. The difference in halogen content between the first and second samples was evaluated. The difference was attributed to organic halogens, and therefore, for the purposes of this invention, it was defined as the amount of organic halogens. Such an amount is "halogen content in the plastic material, by mass".

[0016] In this manner, when the final composition obtained by the described and claimed methods is fed to a downstream refining process, it is observed that no hydrogen halides are found in the produced gas, or in the light and heavy fractions. Furthermore, it is observed that alkyl or aryl halides are not present in the gas, light fraction, or heavy fraction of the refining process.

[0017] In this manner, starting from an inert mixture prepared according to the described and required methods, the hydrocarbon products obtained through a refining process (described in detail below) are substantially halogen-free.

[0018] In this patent application, the gaseous product or gas is detected and measured by the ASTM D7833 standard refinery gas analysis and is a product (gas) containing 1 to 4 carbon atoms, defined as GASES.

[0019] In this patent application, light fractions are defined as gaseous products containing more than 5 carbon atoms as detected by refinery gas analysis according to ASTM D7833 standard, and liquid products with a boiling point range of 36°C to 170°C as measured by ASTM D2887 and ASTM D6352.

[0020] In this patent application, the heavy fraction is defined as a liquid product with a boiling point range of 170°C to 500°C as measured by ASTM D2887 and ASTM D6352.

[0021] The bottom is determined by other products, namely liquid or solid products with a boiling point greater than 500℃ (500+℃).

[0022] Gaseous or liquid products are tested and measured according to the ASTM D7833 standard for refinery gas analysis.

[0023] In this patent application, the slurry phase refers to a mixture of liquid and solid.

[0024] In this patent application, the term "solid" refers to the insoluble tetrahydrofuran fraction, which is referred to herein as the acronym THF-i.

[0025] In this patent application, the term "asphaltite" refers to an organic fraction that is soluble in tetrahydrofuran but insoluble in n-pentane.

[0026] Asphaltenes are classified according to their insolubility in n-alkanes (typically having 5-7 carbon atoms, C5-C7). Such compounds are usually composed of a core of various branched aromatic condensate polymers linked together by straight chains. The interior of such compounds may contain heteroatoms (S, N), which gives them polarity.

[0027] In this patent application, unless otherwise specified, all quantities are expressed in weight (mass) and percentages are weight percentages.

[0028] In this patent application, all weight percentages are calculated relative to the total mass of the stated and claimed product, compound, mixture, or composition.

[0029] In this patent application, the term “substantially free of X” (where “X” is a general compound or component, such as halogen) means that the amount of X is absent or less than or equal to 5 ppm relative to the weight of a compound, composition or mixture containing X, where ppm refers to parts per million by weight.

[0030] Gaseous products obtained using the methods described herein are tested and measured according to the ASTM D7833 standard refinery gas analysis and are products (gases) containing 1 to 4 carbon atoms, defined as GASES.

[0031] The light fractions obtained by the methods described herein are defined as gaseous products containing more than 5 carbon atoms as detected by refinery gas analysis according to ASTM D7833 standard, and liquid products with a boiling point change of 36°C to 170°C as measured by ASTM D2887 and ASTM D6352.

[0032] The heavy fraction obtained by the method described herein is defined as a liquid product with a boiling point change of 170°C to 500°C as measured by ASTM D2887 and ASTM D6352.

[0033] The distillation residue used in the methods described herein is determined by a liquid product with a boiling point greater than or equal to 500°C (500+°C), or it may be a solid.

[0034] The gaseous or liquid products obtained using the methods described herein are tested and measured using ASTM D7833 standard refinery gas analysis.

[0035] In this patent application, yield is defined as the ratio between the amount of product obtained in a method and the amount of product supplied.

[0036] In this patent application, a significant change in the yield of 'X' ('X' is a compound or component) means that the yield of X does not change or changes by at most 10%, preferably 5%, wherein the percentage is the difference (in mass) between the maximum yield of X and the minimum yield of X divided by the total material supplied to the method (still in mass).

[0037] In this patent application, all operating conditions reported herein must be understood as preferred conditions, even if not explicitly stated otherwise.

[0038] For the purposes of this discussion, the terms “comprising” or “including” also include the terms “consisting of” or “substantially consisting of”.

[0039] For the purposes of this discussion, unless otherwise specified, the definition of an interval always includes extreme values.

[0040] WO 2008 / 141830 describes a process for the hydroconversion of heavy oil, wherein the reaction is carried out at a concentration capable of accumulating at least 50 kg / m³. 3 The process is carried out in a solid-state bubbling reactor, using hydrogen or a mixture of hydrogen and sulfuric acid as fuel, wherein the weight ratio of hydrogen to the charge is at least 0.3. The concentration of molybdenum used as a catalyst is at least 5 kg / m³. 3 Loading.

[0041] WO 2008 / 141831 describes a system for heavy oil hydroconversion, comprising a solids accumulation reactor and a stripping section, either external or internal to the reactor. When the stripping section is internal, the reactor can be fully or partially filled, and the stripping section can be located at the top of the reactor or downstream of piping within the reactor. When the stripping section is external, the reactor (fully filled) provides a forced recirculation loop of the liquid phase to itself. A liquid-vapor separator may also be present downstream of the reactor.

[0042] WO 2016 / 103199 describes a system for heavy oil hydroconversion, comprising a reactor, a liquid-vapor separator, and a stripping section for the conversion products outside the reactor. Stripping gas is introduced directly into the reaction effluent through a stripping gas injection pipe located at a point on a connecting pipe between the reactor head and the liquid-vapor separator, the connecting pipe being inclined upwards at least from the injection point at a slope of 2% to 20% relative to the horizontal plane. The stripping gas injection pipe is inclined at an angle of 20° to 65° relative to the axis of the connecting pipe between the reactor head and the separator. The stripping gas flow introduced into the connecting pipe between the reactor head and the separator flows from top to bottom. After stripping, the effluent is sent to an HP / HT phase separator to separate the liquid phase (which is recycled back to the reactor) still containing small amounts of solids (solids formed during the reaction and dispersed catalyst) and the vapor phase containing the reaction products.

[0043] WO 2018 / 078555 describes a process for the hydroconversion of heavy petroleum products, wherein the heavy petroleum products are reacted in a hydroconversion reactor together with a recycle containing hydrogenated gas in the presence of a suitable catalyst to produce a two-phase effluent.

[0044] The reaction effluent is fed into a high-pressure, high-temperature stripping step, which is operated at the reaction pressure using a stripping gas stream with the same composition as the gas fed into the reactor; this produces a vapor phase stream and a slurry phase stream containing heavy products and solids. This slurry is partially recycled to the hydroconversion section and partially extracted to continuously form a purge stream.

[0045] CN 108587668 describes a process for improving the production of light gas oil from waste plastics and heavy oil through pyrolysis, desulfurization, and viscosity-reducing cracking of heavy oil and plastic waste. The process is characterized by the use of an FCC catalyst for pyrolysis, desulfurization, and viscosity-reducing cracking.

[0046] WO 2011 / 08247 describes a method for reducing the viscosity of heavy oil by viscosity-reducing cracking, the method comprising the following steps:

[0047] - Mix heavy oil with at least one of flue gas, CO2 and steam to produce blended heavy oil;

[0048] - Heating the mixed heavy oils to produce heated heavy oil; and

[0049] - High-pressure pulses are generated in heated heavy oil to break it down and produce cracked oil with a lower viscosity than heavy oil.

[0050] WO 97 / 08266 describes a viscosity-reducing cracking process for the co-processing of polyolefin plastic materials and the production of fuel oil. Under viscosity-reducing cracking conditions, a feed stream containing 0.01% to 5% by weight of plastic material and heavy oil is co-fed into the viscosity-reducing cracking zone. Under these conditions, the product contains a gas oil fraction that increases yield and a carbonaceous deposit and bottom fraction that decrease yield.

[0051] In the prior art, many processes for pyrolyzing heavy oil are known, which produce lighter hydrocarbons and typically generate solid residues. For example, US 3,957,620 describes a method for processing heavy oil by mixing it with an alkali metal carbonate at a temperature of 450-650°C, thereby cracking the heavy oil in the presence of steam or oxygen vapor and recovering low-sulfur hydrocarbons and light hydrocarbon gases.

[0052] For specific purposes, the treatment of bituminous materials with certain salts, including sodium carbonate, is also known. For example, US 3,440,073 discloses the use of sodium carbonate in bituminous materials to reduce odor. Other materials suitable for this purpose include sodium hydroxide, sodium borate, potassium hydroxide, potassium carbonate, lithium hydroxide, and barium hydroxide. Sodium carbonate in aqueous solution form is particularly effective.

[0053] Finally, many waste treatment processes are known, such as fuels made from non-recyclable industrial waste (RDF), to reduce the chlorine content present. In fact, chlorine is an undesirable component because burning it produces dioxins (highly toxic) or hydrogen chloride (a gas that is highly corrosive to mucous membranes or in contact with water-containing materials).

[0054] WO 2018 / 025103 discloses a dechlorination process for a hydrocarbon stream or its precursor (plastic waste), the process comprising introducing a zeolite catalyst and optional stripping gas together with plastic containing more than 10 ppm chlorine into a volatilization extruder to reduce the chlorine content.

[0055] Zeolites may contain catalysts for fluid catalytic cracking (FCC), hydrophobic zeolites, ZSM-5 zeolites, or combinations thereof.

[0056] The devolatile extruder operates at temperatures ranging from 150°C to 450°C.

[0057] In the degassing step, the pressure can be 10 Torr to atmospheric pressure, and the residence time can be 6 seconds to 1 hour.

[0058] Optional "chlorine absorbent" additives may include palygorskite, activated carbon, dolomite, bentonite, iron oxide, goethite, hematite, magnetite, alumina, silicon dioxide and aluminosilicates, sodium oxide, calcium oxide or magnesium oxide.

[0059] JP-H 1119617A describes a process for removing chlorine from solid fuel (RDF) by supplying RDF and a chlorine removal agent into an apparatus for mixing and pulverizing RDF, followed by heat treatment and washing to remove sodium chloride. The chlorine removal agent is an alkali metal compound, particularly hydroxides or carbonates, especially sodium and potassium hydroxides and carbonates.

[0060] US 6,372,807 describes a method for converting a mixture of plastic waste in the presence of mineral oil for thermal and mechanical treatment of the waste, the method comprising grinding the plastic waste at a temperature of 150 to 250°C in the presence of at least 20% low-density polyethylene (LDPE) with a softening point of less than 150°C.

[0061] JP-H 10,235,186A discloses a process for gas dechlorination that uses carbonates to reduce the chlorine present in the gas. Contact can be carried out, for example, with a solution, suspension, or powder.

[0062] JP-H 10,235,309A discloses a method for preventing the formation of hydrochloric acid during the processing of plastics at a certain temperature. The method envisions, for example, using sodium bicarbonate, which reacts with hydrogen chloride to form sodium chloride, water, and carbon dioxide, thereby preventing the formation of dioxins.

[0063] JP-H 11199703A discloses a method for treating waste plastics to almost completely remove chlorine. The method envisions heating the plastic to 250-300°C to remove hydrogen chloride. The plastic is then ground and treated in a second reactor, where sodium hydroxide, sodium carbonate, or a mixture of both are used as reactants to remove the remaining chlorine in the form of sodium chloride at a temperature of 300-330°C.

[0064] JP-H 1121573° discloses a dechlorination process for RDF, which envisions treating RDF at a temperature of 200°C to 1000°C and contacting it with a dechlorinating agent (e.g., sodium bicarbonate).

[0065] CN 1353005A and CN 1219581C describe a dechlorination method using a solid reagent, such as powdered or paste-like calcium oxide or calcium hydroxide, or precipitated calcium carbonate, at high temperature. The dechlorination agent and method enable the removal of chlorine from natural gas, naphtha, syngas used in ammonia production, and hydrogen.

[0066] JP 2001 270962 teaches a dechlorination method by mechanical action. The chlorinated resin is ground and mixed with an alkali metal hydroxide or carbonate. The dechlorination resin is characterized by the fact that the mixture is transformed into a mixture of dechlorination resin and alkali metal chloride by applying mechanical energy, such as compression, shearing, impact, or friction. For example, a grinding mill can be used.

[0067] The mixture was washed with water to remove alkali metal chlorides.

[0068] Preferably, the chlorine-containing resin is PVC, and the alkali metal is sodium or potassium, such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Removal can be carried out by washing with water, because during mechanical processing, the chlorine is converted into inorganic powder.

[0069] The mechanical energy is applied for 15 to 3000 minutes.

[0070] WO 2014 / 033733 describes a method for removing chlorides from heavy hydrocarbon streams by steam. Such heavy hydrocarbon streams are naphtha, diesel, light gas oil, light coking gas oil, atmospheric distillation residues, or vacuum distillation residues.

[0071] Existing methods envision using a degassing section to remove light chlorine compounds (e.g., HCl) generated during the heating and recycling of plastic materials.

[0072] The drawback of such a solution is that a system must be designed to handle highly corrosive and toxic gaseous effluents, which is typically expensive.

[0073] In other processes, it is recommended to use metal-based salts to react with hydrogen chloride produced from the decomposition of polyvinyl chloride (PVC) contained in recycled plastic materials.

[0074] However, such salts are generally unstable, especially in processes where water is also present in trace amounts and at high temperatures (such as above 300°C) (which are often necessary for processing heavy hydrocarbon streams).

[0075] In fact, even if the metal salt added at the inlet of the process is in excess relative to the chlorine it contains, the hydrocarbon stream generated in the process in gaseous state (and therefore cannot contain solid salt) still contains chlorine (mainly hydrogen chloride).

[0076] The presence of hydrogen chloride in the hydrocarbon feed stream is undesirable because it necessitates the use of expensive acid-resistant metal alloys to limit the formation of organochlorines in subsequent processes, or because the hydrocarbon products intended for sale have strict limitations on the residual acidity and / or dioxin generation when the hydrocarbons are burned.

[0077] There is also a desire to increase the distillation residues in oil plants and produce light hydrocarbon blends with higher added value relative to the distillation residues.

[0078] Plastic materials, including recycled plastic materials, may further include salts and oxides of metals belonging to the alkaline earth metal group, such as calcium carbonate. The presence of these generally does not pose a problem for the processes described in the prior art; in fact, as noted in some patent applications cited in the prior art, they may be intentionally added to remove or prevent the formation of chlorine.

[0079] However, the presence of these compounds is undesirable in the treatment of distillation residues because they remain in the light fractions unless removed. This is especially true for chlorine. Furthermore, recycled plastic materials containing calcium, primarily in the form of salts, are not treated in processes according to existing technologies.

[0080] The applicant has discovered that, according to the teachings of the present invention, if plastic materials (including recycled plastic materials) are not properly treated, the release of halogens, and in particular the release of chlorine as hydrochloric acid, is observed in downstream refining processes. Summary of the Invention

[0081] The applicant has prepared a composition of a plastic material mixed with hydrocarbons, oligomers derived from the plastic material, and halide salts, the properties of which enable the plastic material (including recycled material) to be enhanced into high-value-added hydrocarbons, such as naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO), and heavy vacuum gas oil (HVGO), through refining processes.

[0082] Therefore, the subject of this patent application is a composition of a plastic material comprising:

[0083] - Plastic materials that are free of halogenated components or have a halogen content of less than or equal to 0.5% by mass relative to the plastic material.

[0084] -Oligomers derived from the plastic contained in the plastic material,

[0085] -Hydrochlores,

[0086] -hydrocarbon.

[0087] In addition, the applicant has discovered a method for processing plastic materials containing halogenated components (including recycled plastic materials) to obtain a composition of the plastic material mixed with hydrocarbons, oligomers derived from the plastic material and halide salts, preferably the composition described and claimed in this patent application.

[0088] Another subject of this patent application is a method for producing a composition of a plastic material mixed with hydrocarbons, oligomers derived from said plastic material, and a halide salt, said method being capable of processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, said method comprising the following steps:

[0089] - In one or more devices including heating and mixing devices, plastic materials (including recycled plastic materials), inert reagents and hydrocarbon streams containing halogenated components are heated and mixed simultaneously or in separate stages to form a composition, said composition is subjected to a temperature of 150°C to 450°C, and the composition thus obtained is held in said temperature range for 10 seconds to 30 minutes to form a final composition;

[0090] The method is characterized in that the amount of inert reagent added in the method is such that the ratio of the sum of the moles of alkali metals belonging to Group IA to the sum of the moles of halogens contained in the plastic material is at most 20:1.

[0091] According to the preferred embodiment, in the described and claimed method, the amount of inert reagent added is such that:

[0092] - The ratio of the sum of the molar numbers of alkali metals belonging to Group IA to the sum of the molar numbers of halogens contained in the plastic material is at most 20:1, preferably varying between 10:1 and 1:1, and even more preferably varying between 3:1 and 3:2; and

[0093] - The ratio of the mass of the alkali metal belonging to Group IA to the mass of the plastic material is at least 1:1000, preferably 1:500 to 1:10, and even more preferably 1:100 to 5:100.

[0094] Another subject of this patent application is a composition of a plastic material mixed with a hydrocarbon, an oligomer derived from said plastic material, and a halide salt, comprising:

[0095] - Plastic materials that are free of halogenated components or have a halogen content of less than or equal to 0.5% by mass relative to the plastic material.

[0096] -Oligomers derived from the plastic contained in the plastic material,

[0097] -Hydrochlores,

[0098] -hydrocarbon.

[0099] The composition can be obtained by a method capable of processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method comprising the following steps:

[0100] - In one or more devices including heating and mixing devices, plastic materials (including recycled plastic materials), inert reagents and hydrocarbon streams containing halogenated components are heated and mixed simultaneously or in separate stages to form a composition, said composition is subjected to a temperature of 150°C to 450°C, and the composition thus obtained is held in said temperature range for 10 seconds to 30 minutes to form a final composition;

[0101] The method is characterized in that the amount of inert reagent added in the method is such that the ratio of the sum of the moles of alkali metals belonging to Group IA to the sum of the moles of halogens contained in the plastic material is at most 20:1.

[0102] The final composition obtained by the methods described and claimed can then be processed in a refining process to produce hydrocarbon products, preferably light fractions, heavy fractions and gases; more preferably selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO).

[0103] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising the step of converting the final composition of the plastic material through a refining process.

[0104] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by a thermal or catalytic conversion process, optionally in the presence of an inert agent, said hydrocarbon product preferably light fractions, heavy fractions and gases; more preferably products selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO) and heavy vacuum crude diesel oil (HVGO).

[0105] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising the step of converting the final composition of the plastic material into hydrocarbon products by a viscous cracking method, optionally in the presence of an inert agent, said hydrocarbon products preferably light fractions, heavy fractions and gases; more preferably products selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO).

[0106] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising the step of converting the final composition of the plastic material into hydrocarbon products by cracking or hydrocracking processes, optionally in the presence of an inert agent, said hydrocarbon products preferably light fractions, heavy fractions and gases; more preferably products selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO).

[0107] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising, optionally in the presence of an inert reagent, a step of converting the inert final mixture into a hydrocarbon product by a catalytic or non-catalytic hydrogenation conversion process, said hydrocarbon product preferably being a light fraction, a heavy fraction, and a gas; more preferably a product selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO), and heavy vacuum gas oil (HVGO).

[0108] Another embodiment of the invention is the described and claimed method for processing plastic materials or mixtures of plastic materials (including recycled plastic materials) containing halogenated components, the method further comprising the step of converting the final composition of the plastic material into a hydrocarbon product, optionally in the presence of an inert agent, via a catalytic hydroconversion process using Eni slurry technology (EST), the hydrocarbon product preferably being a light fraction, a heavy fraction, and a gas; more preferably a product selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO), and heavy vacuum gas oil (HVGO).

[0109] The first advantage of this invention is that it provides a method for processing plastic materials (preferably recycled plastic materials) and hydrocarbons that is simple and flexible in terms of the composition of the plastic material to be recycled. A flexible method means that compositional changes within the aforementioned limits do not cause any significant changes in the yield of the light fraction.

[0110] A second advantage of the present invention is that it provides a method for treating plastic materials that does not produce hydrogen halides even when the halogen content in the plastic material is high, i.e., up to 10% by weight, preferably up to 6% by weight. In fact, the inert reagent can react with the halogenated components present in the plastic material. In this manner, when the plastic material treated with the inert reagent is fed to a refining process downstream of the described and claimed method, it is observed that the resulting light and heavy fractions, as well as the gas, do not contain hydrogen halides. It is also observed that the product obtained by the refining process does not contain alkyl or aryl halides.

[0111] A third advantage of the invention is that it provides a method for processing plastic materials that can generate a substantially halogen-free gaseous stream at the outlet, even when the halogen content in the plastic material to be recycled is high, i.e., up to 10% by weight, preferably up to 6% by weight.

[0112] A fourth advantage of the present invention is that it provides a method for processing plastic materials that can produce substantially halogen-free light hydrocarbon mixtures, even when the halogen content in the plastic material to be recycled is high, i.e., up to 10% by weight, preferably up to 6% by weight.

[0113] A fifth advantage of the present invention is that it provides a method for processing plastic materials that does not require the use of a catalyst in the pretreatment step.

[0114] Another advantage of this invention is the ability to identify inert agents used in processes for recycling plastic materials. Attached Figure Description

[0115] Further advantages of the invention will become more apparent from the following description and accompanying drawings, which are given by way of non-limiting example only and represent preferred embodiments of the invention.

[0116] Figure 1 A preferred embodiment of the invention is shown, in particular, the method is carried out by extrusion in an apparatus comprising portions (4) and (5). Figure 1 In this context, parts (4) and (5) are hydrodynamically connected to each other. (See reference...) Figure 1 (1) is the feed of depressurized residue; (2) is the feed of plastic material including recycled plastic; (3) is the feed of inert reagent. Part (4) is the first part of the extrusion unit, in which the plastic material (2) including recycled plastic is melted and mixed with inert reagent (3); in this part, dehalogenation is partial. Part (5) is the second part of the extrusion unit, in which depressurized residue is supplied; in this part, at least partially dehalogenated plastic material is mixed with depressurized residue, and the resulting composition can undergo further possible degradation.

[0117] Figure 2 A fluorescence micrograph of the sample from Comparative Example 1 is shown.

[0118] Figure 3 A fluorescence micrograph of the sample of Example 3 (according to an embodiment of the invention) at the extruder exit is shown.

[0119] Figure 4 It shows the Figure 2 Image analysis of micrographs was performed to assess the minimum mixing area; the figure shows the analysis of the normalized coefficient of variation (H) of the product in Comparative Example 1 as a function of the mixing area. Figure 2 Image analysis).

[0120] Figure 5 It shows the Figure 3 Image analysis of micrographs was performed to assess the minimum mixing area; the figure illustrates the analysis of the normalized coefficient of variation (H) of the product at the extruder exit as a function of the mixing area in Example 3. Figure 3 Image analysis). Detailed Implementation

[0121] Now also refer to Figure 1-5 All embodiments of the present invention are described in detail.

[0122] A first embodiment of the present invention is a composition of a plastic material mixed with a hydrocarbon, an oligomer derived from the plastic material, and a halide salt. The composition comprises:

[0123] - Plastic materials that are free of halogenated components or have a halogen content of less than or equal to 0.5% by mass relative to the plastic material.

[0124] -Oligomers derived from the plastic contained in the plastic material,

[0125] -Hydrochlores,

[0126] -hydrocarbon.

[0127] The halide salt can be selected from Group IA alkali metal salts; preferably, it is selected from Group IA alkali metal chlorides, Group IA alkali metal fluorides, Group IA alkali metal bromides, and Group IA alkali metal iodides. More preferably, the halide salt is a Group IA alkali metal chloride. Even more preferably, it is a halide salt selected from lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, and potassium bromide.

[0128] In hydrocarbons, heavy fractions or vacuum residues are preferred.

[0129] The oligomers derived from the plastic material can be considered according to the definition in the IUPAC Gold Book. Preferably, the oligomers have a molecular weight of 100 to 10 kDa. Preferably, the mass of the oligomers derived from the plastic material is at least three times greater than the amount (by mass) of the oligomers already present as impurities in the plastic constituting the plastic material.

[0130] The oligomers derived from the plastic material are oligomers produced from the thermal degradation of the plastic material.

[0131] As mentioned above, plastic materials include any combination of one or more virgin or recycled plastics.

[0132] For example, virgin plastic may be substandard or second-choice plastic, or, for another reason, partially or wholly undesirable.

[0133] For example, recycled plastic can be plastic waste or plastic derived from waste through a recycling process.

[0134] When a plastic material also includes recycled plastic, it is called recycled.

[0135] As previously mentioned, like plastics, the plastic material may also contain organic or inorganic compounds; for example, metallic materials, ceramic materials, building materials (including wood, bricks, and cement); insulating materials (such as glass wool and asbestos); paper and paper scraps; food scraps; and materials derived from soil (such as clay, stone, and compost). Plastics may also include expanded, semi-expanded, or expandable foams.

[0136] Preferably, the plastic material comprises at least 60% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, and particularly 100% by weight of plastic, to calculate the percentage relative to the total weight of the plastic material.

[0137] Preferably, the recycled plastic material is PLASMIX.

[0138] According to a preferred embodiment, the recycled plastic material is in the form of a sheet and has a median size (D) greater than 0.2 cm. 50 (That is, 50% of the material is trapped in a filter with a vertical mesh size of 0.2 cm). More preferably, it has a median size (D) greater than 0.2 cm. 50 ).

[0139] Preferably, the recycled plastic material in sheet form is characterized by an apparent density greater than 50 kg / m³ as measured according to ASTM D1895-17 (Method C, "Pre-Loading" Density Measurement). 3 More preferably greater than 100 kg / m 3 .

[0140] According to another preferred embodiment, the recycled plastic material is compacted in granular form, which is obtained by extruding sheets through a template having holes with a diameter of 2 to 20 mm, preferably 3 to 8 mm.

[0141] Preferably, the recycled plastic material in granular form is characterized by an apparent density greater than 200 kg / m³ as measured according to ASTM D1895-17 (Method B). 3 Even more preferred is greater than 300 kg / m 3 .

[0142] The plastic composition of the plastic material preferably includes at least one component selected from the following, wherein the percentage is expressed by weight relative to the total weight of the plastic (unless otherwise stated):

[0143] Polyethylene: 10-100%

[0144] Polypropylene: 0-50%

[0145] Polystyrene: 0-50%

[0146] Polyester: 0-20%

[0147] • Total of cellulose, urethane, and polyamide polymers: 0-20%

[0148] Inorganic fillers, such as talc and calcium carbonate: 0-30%

[0149] • Chlorinated polymer, wherein the weight (mass) of chlorine is 0.05 to 15%, more preferably 0.1 to 10%, more preferably 0.3 to 8%, and more preferably 1.5 to 6% of the total weight (mass) of the plastic material contained in the recycled plastic material.

[0150] The halogenated component is present in the plastic mixture in an amount of no more than 10%, preferably no more than 6%, and even more preferably 0.2% to 5%, based on the mass of halogen atoms relative to the mass of the plastic material.

[0151] The halogenated component can be the halogen itself, a halogen-containing organic molecule, or a halogen-containing inorganic molecule. Examples of organic molecules are polymers, particularly polyvinyl chloride or chloroprene; or hexabromocyclododecane; or decabromodiphenyl ether. Examples of inorganic molecules are magnesium chloride or titanium chloride.

[0152] The halogen present in the molecule or contained therein can be chlorine, fluorine, bromine, or iodine. Different halogenated components can coexist; for example, among those mentioned in this patent application, a combination of hexabromocyclododecane, decabromodiphenyl ether, and polyvinyl chloride can be present.

[0153] Other organic or inorganic compounds may also be present in plastic mixtures, which function as, for example, antioxidants, heat stabilizers, acid stabilizers, nucleating agents, UV stabilizers, antiblocking agents, slip agents, antislip agents, plasticizers, external lubricants, mold release agents, flame retardants, polymer processing aids, dyes (organic and inorganic), antistatic agents, crosslinking agents, crosslinking aids, extender oils, vulcanization accelerators, antiozone agents, and mixtures thereof.

[0154] Other bromine-containing organic and inorganic additives may also be present in the plastic mixture. These additives are generally used to impart flame retardant properties to the plastic, and are present in amounts such that the bromine content (by weight) is up to 5% relative to the total amount of plastic contained in the recycled plastic material, preferably 0.01 to 3%, and even more preferably 0.2 to 2%.

[0155] Polyethylene refers to polymers or copolymers of ethylene, or mixtures thereof; preferably selected from high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), metallocene-catalyzed polyethylene (m-PE), ethylene-vinyl acetate polymer (EVA), and mixtures thereof.

[0156] Polypropylene refers to polymers or copolymers of propylene, or mixtures thereof; preferably selected from polypropylene (PP) or ethylene propylene diene monomer (EPDM) and mixtures thereof.

[0157] Polystyrene refers to polymers or copolymers of styrene, and mixtures thereof; preferably selected from polystyrene (PS), expandable polystyrene (EPS), high-impact polystyrene (HIPS), acrylonitrile butadiene styrene (ABS), styrene-acrylonitrile copolymer (SAN), acrylonitrile ethylene styrene (AES), styrene (meth)acrylate copolymer (SMMA), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butene-styrene block copolymer (SEBS), and mixtures thereof, as well as mixtures with polycarbonate (PC), PC / HIPS, and PC / ABS.

[0158] Chlorinated polymers refer to polymers or copolymers of vinyl chloride, or copolymers of vinylidene chloride, or mixtures thereof; preferably selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and copolymers thereof and mixtures thereof.

[0159] Polyesters refer to polycarbonate (PC), polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(D-lactic acid) (PDLA), poly(D,L-lactic acid) (PDLLA), polyhydroxyalkanoates (PHA), and mixtures thereof.

[0160] Polyamides are polymers characterized by amide groups CO-NH, synthesized through the condensation polymerization of dicarboxylic acids and diamines or the ring-opening polymerization of lactams. Preferred polyamides are nylon 6 (PA6), nylon 66 (PA66), nylon 46 (PA46), and nylon 12 (PA12).

[0161] The urethane polymer is preferably selected from polyurethane (PU), which contains aliphatic, aromatic, ester, ether, or urea groups and mixtures thereof.

[0162] Cellulose polymers refer to polymers derived from cellulose, preferably selected from nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate, ethylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, benzyl cellulose, and regenerated cellulose and mixtures thereof.

[0163] In the method according to the invention, a plastic material (including recycled plastic material), an inert reagent, and a hydrocarbon stream containing a halogenated component are heated and mixed simultaneously or in a separate stage in one or more apparatuses including heating and mixing devices to form a composition. The composition is then heated to a temperature of 150°C to 450°C and maintained within this temperature range for 10 seconds to 30 minutes to form the final composition.

[0164] The amount of inert reagent added must be such that the ratio of the sum of the moles of alkali metals belonging to Group IA to the sum of the moles of halogens contained in the plastic material is at most 20:1, preferably varying between 10:1 and 1:1, and even more preferably varying between 3:1 and 3:2.

[0165] According to the preferred method, the amount of inert reagent added is such that:

[0166] - The ratio of the sum of the molar numbers of alkali metals belonging to Group IA to the sum of the molar numbers of halogens contained in the plastic material is at most 20:1, preferably varying between 10:1 and 1:1, and even more preferably varying between 3:1 and 3:2; and

[0167] - The ratio of the mass of the alkali metal belonging to Group IA to the mass of the plastic material is at least 1:1000, preferably from 1:500 to 1:10, and even more preferably from 1:100 to 5:100.

[0168] Preferably, the final composition obtained therefrom is that described and claimed in this patent application.

[0169] Inert reagents can be in elemental form, usually in metallic form, or in organic or inorganic compound form.

[0170] The inert reagent in elemental form can be an alkali metal belonging to Group IA of the periodic table, with periods 2 (lithium) to 6 (cesium), i.e., selected from lithium, sodium, potassium, rubidium, and cesium, more preferably from lithium, sodium, and potassium; even more preferably from lithium or sodium; and related combinations thereof. Among the combinations, a combination of metallic lithium and sodium is preferred. More preferably, the inert reagent is metallic lithium. More preferably, the inert reagent is metallic sodium. More preferably, the inert reagent is a combination of lithium and sodium. In a preferred form, the inert reagent is a sodium compound. Among sodium compounds, carbonates, bicarbonates, carboxylates, biphenyls, cyclopentadiene, butyl, butyryl, oxides, hydroxides, alkyl sulfonates, and alkylbenzene sulfonates are preferred. Among sodium carboxylate compounds, stearates, palmitates, neopentanoates, and octanoates are preferred. Among sodium stearates, sodium 12-hydroxystearate is preferred. Among lithium compounds, methyl, butyl, aspartate, acetate, carbonate, bicarbonate, stearate, oxides, and hydroxides are preferred. In lithium stearate, lithium 12-hydroxystearate is preferred. A dehydrating inert reagent is preferred, i.e., a material that can react with water to form a chemical species that no longer contains water, such as elemental lithium, elemental sodium, sodium biphenyl, and sodium cyclopentadienyl.

[0171] According to a preferred embodiment of the invention, the preferred sodium compounds are carbonates and carboxylates.

[0172] Advantageously, the inert reagent may also include ketones, particularly 2,2-dimethoxypropane, which is up to 10% by weight relative to the total weight of the inert reagent.

[0173] Preferred hydrocarbons include heavy fractions, distillation residues, and vacuum residues.

[0174] The vacuum residue is a mixture of heavy hydrocarbons, characterized by having 15 or more carbon atoms and a boiling point of at least 300°C. The vacuum residue is a residual stream from an industrial distillation column, remaining after vacuum distillation of crude oil. The vacuum residue is characterized by an asphaltenes content of at least 3%, more preferably 4% to 50%, and even more preferably 5% to 25%, as measured by standard ASTM D6560 or equivalent. The aromatic content of the asphaltenes, as measured by ASTM D2007 or equivalent, is at least 3%, preferably 4% to 60%, and more preferably 5% to 45%. The asphaltenes have a boiling point distribution (ASTM D7169 or equivalent) of the different compounds constituting the vacuum residue, characterized by a maximum amount of 25% (preferably 1% to 20%) with a boiling point below 500°C and a maximum amount of 35% (preferably 1% to 30%) with a boiling point below 530°C.

[0175] Preferably, the amount of plastic material (by mass) varies between 2% and 300% relative to the amount of hydrocarbon (by mass) or relative to the amount of vacuum residue (by mass); more preferably between 5% and 100%, even more preferably between 10% and 70%, even more preferably between 30% and 60%.

[0176] In a preferred form, the described and claimed method is carried out by simultaneously or separately extruding, heating, and mixing the plastic material, inert reagent, and hydrocarbon.

[0177] As previously stated, the described and claimed methods can be carried out in one or more devices including heating and mixing devices.

[0178] Preferably, the equipment can be selected from static mixers, dynamic mixers, mixing containers, mixing systems integrated into heating devices, extruders, single-screw extruders, twin-screw extruders, twin-screw co-rotating extruders, internal mixers, and BUSS mixing extruders.

[0179] Examples of static mixers, dynamic mixers, and mixing containers are described below.

[0180] According to a preferred embodiment of the invention, in an extruder, the rotary motion of the screw and the alternating piston motion can be combined in the direction of fluid movement, thereby making mixing more efficient. In the case of an extruder, kneading and / or gear-driven mixing elements, or even screw elements that remain floating relative to the rotating body of the screw, can also be used.

[0181] In a preferred embodiment, the described and claimed method occurs in a single stage. In this manner, the plastic material, inert reagent, and hydrocarbon are supplied directly to one or more devices including heating and mixing equipment.

[0182] According to the preferred two-stage approach, the described and claimed methods include:

[0183] - In the first stage, plastic materials and inert reagents are mixed to form a first composition, which is subsequently supplied only to one or more devices including heating and mixing apparatus, in which the mixture is heated; and

[0184] -In the second stage, the first composition is mixed with a hydrocarbon stream to form the final composition of the plastic material.

[0185] Similarly, according to the two-stage method, the composition is heated to a temperature of 150°C to 450°C and held within the temperature range for 10 seconds to 30 minutes to form the final composition.

[0186] Similarly, according to this two-stage approach, the amount of inert reagent added must be such that the ratio of the sum of the moles of alkali metals belonging to Group IA to the sum of the moles of halogens contained in the plastic material is at most 20:1, preferably varying between 10:1 and 1:1, and even more preferably varying between 3:1 and 3:2.

[0187] Similarly, in this two-stage approach, all the preferred conditions specified in this patent application are valid.

[0188] In the two-stage approach, among all the devices listed in this patent application, these devices can be different or the same, and are therefore the preferred technical solution.

[0189] In the preferred two-stage approach, the plastic material can preferably be preheated to a temperature of at least 150°C; preferably, the temperature is between 170°C and 280°C, and even more preferably, between 180°C and 240°C. Preferably, the temperature causes the polymer to enter a molten state.

[0190] In the described and claimed methods, the heating of the plastic material, the inert reagent, and the hydrocarbon stream can preferably reach a temperature of 220°C to 450°C, more preferably 300°C to 430°C, and even more preferably 350°C to 420°C.

[0191] Heating and preheating can be performed using suitable direct or indirect heat exchange devices known in the prior art.

[0192] The composition thus prepared can be subjected to pressures greater than atmospheric pressure, preferably 1 to 200 bar (absolute pressure), and even more preferably 5 to 100 bar (absolute pressure).

[0193] In the preferred two-stage method described and claimed, the addition of the hydrocarbon stream can be carried out at a pressure greater than atmospheric pressure, preferably from 1 bar (absolute) to 50 bar (absolute), and even more preferably from 2 bar (absolute) to 20 bar (absolute).

[0194] In the described and claimed method, heating is controlled, i.e., the temperature of the composition is monitored and the heating supply is adjusted so that the temperature of the composition and / or the temperature of the device in which the composition flows is maintained within a predetermined temperature range for a predetermined time.

[0195] The predetermined time is 10 seconds to 30 minutes, preferably 15 to 600 seconds, or even more preferably 25 to 250 seconds.

[0196] In the two-stage approach, the predetermined time refers to the total time for performing both stages.

[0197] Advantageously, the described and claimed methods can be carried out in a single device or in two or more separate devices.

[0198] Preferably, in the two-stage method, the equipment is an extruder.

[0199] All of the aforementioned extruders are applicable to this preferred embodiment.

[0200] Feeding the plastic material, inert reagent, and hydrocarbon stream into the device described in this patent application can be performed using any apparatus known in the art. Alternatively, the plastic material, inert reagent, and hydrocarbon stream can be supplied to the device separately.

[0201] Suitable apparatus for preparing inert reagents, plastic materials, and hydrocarbon streams can be selected from mixing vessels that allow for coarse mixing; or systems capable of preparing fine mixtures of the components, such as dynamic mixers (i.e., mixers with stationary and rotating or oscillating motion sections) and static mixers (where the components are mixed by motion induced when interacting with the geometry of the mixer). Among dynamic mixers, turbine mixers are preferred. Combinations of static and dynamic mixers can be used. For example, retracted open impeller pumps (capable of pumping liquids also containing large solids) are used in conjunction with mixing heads (see Silverson Verso Vessel Package mixer). In static mixers, mixers such as SMX, SMXI, and their derivatives can be used. Preferred static mixers are those that provide very large channels for fluid flow, which is useful in the presence of solids (to prevent blockages). Statiflo DSM can be mentioned among these. In dynamic mixers, marine propellers, propellers, airfoils, ribbon mixers, and anchors can be used, for example.

[0202] To assess the mixing quality in the described and claimed methods, in addition to photomicrographing the inert mixture sample leaving the mixing apparatus and qualitatively assessing the degree of mixing, a quantitative assessment was performed by analyzing the coefficient of variation (CoV) of the plastic material in the inert mixture at the outlet, and by numerical analysis of the microscopic images, as shown below.

[0203] The coefficient of variation (CoV) is a dimensionless ratio, obtained by dividing the standard deviation of the measurement by its mean:

[0204]

[0205]

[0206] Where N is the number of samples and x is the measurement quantity. The average of the measured quantities.

[0207] References on CoV computation can be found in patents US 5,795,364 and US 6,897,014.

[0208] The measured quantity x is the average grayscale value (corresponding to the fraction of plastic material in the inert mixture at the outlet), obtained by digitizing the aforementioned microscopic image. The digitized image has a pixel resolution of approximately 5 micrometers and an area A of approximately 22 mm². 2 .

[0209] The sample is obtained by dividing such a region into equal areas (equal to A). N =AN) N regions of numbers, and calculate the average value x of each region. i To obtain.

[0210] For low N values ​​(tending towards 2), the calculated CoV is close to 0 because the effect of poor dispersion of the dispersed material over large areas is reduced, and the average value of x is similar for each region if its distribution is good enough. Conversely, as N tends to a large value, the area used to calculate x is small, and therefore CoV decreases. For images with only two gray levels, it can be shown that when the area is reduced to just one square pixel, the corresponding CoV is the largest and depends entirely on the average concentration or the average gray level, according to the following formula:

[0211]

[0212] Expressing the degree of mixing as a CoV ratio is advantageous (see, for example, patent USA 5,597,236 or “LaminarFlow in Static Mixers with Helical Element”, A. Bakker, RD LaRoche, EM Marshall, The Online CFM Book, 1998):

[0213]

[0214] This limits H(N) to between 0 (completely homogeneous) and 1 (completely separated), regardless of the amount of recycled plastic material in the sample being analyzed.

[0215] To highlight the area of ​​the recycled plastic material, the image was converted to grayscale ranging from 0 to 255.

[0216] By tracking H(N) as the area A of the region N The mixed image obtained by the function (N) provides useful information about the aggregate morphology of recycled plastic materials.

[0217] Specifically, H(N) was obtained. C The area A of the region is 2 / 3.N The value of (N) A C =A N (N C This indicates the degree of dispersion of the recycled plastic material. In fact, the area greater than the stated value A... C The collected samples statistically exhibit a variance in the content of recycled plastic materials that is less than or equal to a fixed value. Below, we obtain H(N) C The parameter A is 2 / 3. C =A N (N C This will be referred to by the term "minimum mixing area" (MMA).

[0218] Methodologically speaking, the minimum mixing area is determined by... Figure 4 and Figure 5 The area A of the region shown as a function of H(N) N (N) data is calculated using linear interpolation.

[0219] According to the teachings of the present invention, the minimum mixing area measured on the produced composition sample can preferably be less than or equal to 0.03 mm. 2 More preferably 0.001mm 2 Up to 0.02mm 2 Even more preferably, 0.005mm 2 Up to 0.015mm 2 .

[0220] To achieve such a degree of mixing, those skilled in the art can improve the mixing equipment or modify its process parameters.

[0221] For example, if an extruder is used, the screw profile can be changed (e.g., by increasing the number of mixing elements), i.e., by acting on process parameters (e.g., by lowering the temperature to promote an increase in viscosity and thus mixing, or by increasing the screw speed).

[0222] In a preferred embodiment, the final composition can be filtered.

[0223] In a preferred embodiment, plastic materials, inert reagents, and hydrocarbon streams can be filtered.

[0224] In the preferred embodiment, both of the aforementioned filtering operations are present in the described and claimed method.

[0225] For this purpose, any system known in the prior art for this purpose can be used, such as fixed or movable filters, and filter replacement systems that may implement management modes that consider online filter replacement modes without interrupting operation, continuous or intermittent cleaning, or when pressure loss exceeds a certain threshold.

[0226] In one embodiment of the invention, any vapors that have formed, particularly water vapor and light organic compounds, are removed during heating.

[0227] In one embodiment of the invention, no vapors formed are removed during heating.

[0228] In a preferred embodiment of the invention, no catalyst is used, specifically neither as a fixed component contained in the device, for example, fixed to the walls of the device, nor as a component of the supplied composition. In fact, the method of the invention also operates without a catalyst, and catalytic processes are generally more complex and expensive to manage.

[0229] When using an extruder, such removal can be achieved by providing an opening in the extruder barrel through which vapors are removed, but not by removing the processed composition that can be conveyed by the screw. The pressure at the opening point is selected to enable gas removal; that is, the pressure can be atmospheric pressure, below atmospheric pressure, or even higher.

[0230] Another embodiment of the invention is a composition comprising a plastic material mixed with a hydrocarbon, an oligomer derived from the plastic material, and a halide salt, comprising:

[0231] - Plastic materials that are free of halogenated components or have a halogen content of less than or equal to 0.5% by mass relative to the plastic material.

[0232] -Oligomers derived from the plastic contained in the plastic material,

[0233] -Hydrochlores,

[0234] -hydrocarbon.

[0235] The composition can be obtained by a method capable of processing plastic materials containing halogenated components (including recycled plastic materials), the method comprising the following steps:

[0236] - In one or more devices including heating and mixing devices, plastic materials (including recycled plastic materials), inert reagents and hydrocarbon streams containing halogenated components are heated and mixed simultaneously or in separate stages to form a composition, said composition is subjected to a temperature of 150°C to 450°C, and the resulting composition is held within said temperature range for 10 seconds to 30 minutes to form a final composition;

[0237] The method is characterized in that the amount of inert reagent added in the method is such that the ratio of the sum of the moles of alkali metals belonging to Group IA to the sum of the moles of halogens contained in the plastic material is at most 20:1.

[0238] Furthermore, all preferred and example conditions are valid for this implementation scheme, and all definitions described herein are valid.

[0239] Once the final composition is formed using the described and claimed methods, it can optionally be fed to a refining process in the presence of an inert agent as described in this patent application to improve hydrocarbon products, preferably selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LVGO), and heavy vacuum gas oil (HVGO).

[0240] Preferred refining processes may be selected from one or more of the following technologies:

[0241] - Thermal or catalytic conversion processes; viscosity-reducing cracking processes;

[0242] - Coking process;

[0243] - Cracking or hydrocracking process;

[0244] - Catalytic or non-catalytic hydrogenation conversion processes;

[0245] - Catalytic hydroconversion process using Eni slurry technology (EST).

[0246] Even more preferred refining processes are viscous cracking, coking, and catalytic hydroconversion. Even more preferred is the catalytic hydroconversion process.

[0247] The inert reagents optionally used in the refining process described herein are selected from the group described and claimed in this patent application. This means that the inert reagent in elemental form can be an alkali metal belonging to Group IA of the periodic table, with periods 2 (lithium) to 6 (cesium), i.e., selected from lithium, sodium, potassium, rubidium, cesium, more preferably from lithium, sodium, potassium; even more preferably from lithium or sodium; and related combinations thereof. Among the combinations, a combination of metallic lithium and sodium is preferred. More preferably, the inert reagent is metallic lithium. More preferably, the inert reagent is metallic sodium. More preferably, the inert reagent is a combination of lithium and sodium. In a preferred form, the inert reagent is a sodium compound. Among sodium compounds, carbonates, bicarbonates, carboxylates, biphenyls, cyclopentadiene, butyl, butyryl, oxides, hydroxides, alkyl sulfonates, and alkylbenzene sulfonates are preferred. Among sodium carboxylate compounds, stearates, palmitates, neopentanoates, and octanoates are preferred. Among sodium stearate, sodium 12-hydroxystearate is preferred. Among lithium compounds, methyl, butyl, aspartate, acetate, carbonate, bicarbonate, stearate, oxide, and hydroxide are preferred. Among lithium stearate, 12-hydroxystearate is preferred. A dehydrating inert agent is preferred, i.e., a material capable of reacting with water to form a chemical substance that no longer contains water, such as elemental lithium, elemental sodium, sodium biphenyl, and sodium cyclopentadienyl. According to a preferred embodiment of the invention, preferred sodium compounds are carbonates and carboxylates. Advantageously, the inert agent may also include ketones, particularly 2,2-dimethoxypropane, which accounts for up to 10% by weight of the total inert agent. Preferably, in the refining process and its preferred processes, the inert agent may differ in amount and / or type from those used in the foregoing steps, i.e., those used in the process of treating plastic materials according to this patent application.

[0248] The refining process described in this patent application is preferably operated at a process temperature of 350-700°C, more preferably 390-500°C, even more preferably 400-480°C, and even more preferably 420-450°C.

[0249] The refining process described in this patent application is preferably operated at a pressure of 2-1000 atm, more preferably 5-500 atm, even more preferably 10-300 atm, and even more preferably 80-200 atm, where atm refers to the relative pressure in atmospheric pressure.

[0250] The final composition may preferably be mixed with additional depressurization residue. In this case, the weight ratio of the final inert mixture to the depressurization residue is 0.01-2, preferably 0.03-1.5, and even more preferably 0.1-1.

[0251] The methods and refining processes for processing plastic materials described and claimed in this patent application can be carried out in different equipment, or even in different production locations, or even geographically separate.

[0252] In fact, the final composition described in this patent application can be easily transported, even though it can solidify unless kept at a certain temperature.

[0253] In this case, it may be necessary to melt the final composition in order to feed it. Any method known in the art can be used for this purpose. For example, the final compound can be mechanically stirred at 200°C for 2 hours using a steel stirrer with a two-bladed propeller.

[0254] According to a preferred alternative, the method for processing plastic materials described and claimed in this patent application is carried out within the same equipment used for the described and claimed refining process. In this case, intermediate operations are unnecessary. The final composition can be supplied directly to the described and claimed refining process or placed in a buffer container to handle any equipment malfunctions.

[0255] Eni slurry technology is a catalytic hydrogenation conversion process that includes the following steps:

[0256] • The raw materials are mixed with hydrocarbons to form a reaction mixture, wherein the hydrocarbons are preferably heavy fractions, more preferably distillation residues, and even more preferably vacuum residues, and may be preheated;

[0257] ● The slurry-phase reactant mixture, the molybdenum-containing catalyst precursor, and the hydrogen-containing feed stream are fed into the hydroconversion section, where the hydroconversion reaction takes place, producing reaction effluent;

[0258] ● The reaction effluent is separated into gas and slurry phases into at least one high-pressure, high-temperature separator.

[0259] ● The separated gas phase is then sent to a gas processing section, which has the function of separating liquid fractions from a gas containing hydrogen and hydrocarbon gases having 1-4 carbon atoms; the liquid fractions include naphtha, atmospheric gas oil (AGO), and vacuum gas oil (VGO).

[0260] • The slurry layer is then fed to a separation section, which is equipped to separate vacuum gas oil (VGO), heavy vacuum gas oil (HVGO), light vacuum gas oil (LVGO), and atmospheric gas oil (AGO) from a heavy organic product stream containing asphaltenes, unconverted feed, catalyst, and solids formed during the hydroconversion reaction.

[0261] • A portion of the heavy organic product is recycled to the hydroconversion section, or it is mixed with the load before being supplied to the hydroconversion section and mixed with the remaining product to form a washing stream.

[0262] Preferably, the raw materials used in the Eni slurry conversion process are the final composition obtained by the method for treating plastic materials described and claimed in this patent application.

[0263] In the method, the catalytic hydrogenation conversion reaction under high pressure and high temperature and the separation of the reaction effluent are carried out in a temperature range of 420°C to 440°C and a pressure of 155 atm to 160 atm.

[0264] The efficiency of the final inert mixture hydroconversion process is considered to be the mass fraction of light distillate produced relative to the mass of the plastic material and the vacuum residue supplied during the plastic material processing, which is equal to at least 5%, preferably 10-70%, and even more preferably 20-50%.

[0265] Surprisingly, it has been found that the yield of the light fraction as defined above is higher, i.e., equal to at least 15%, or even more preferably 20-80%, if the ratio of the plastic material to the total amount of the supplied vacuum residue is at least 0.1.

[0266] To better understand the present invention and its scope of application, some embodiments are given below, although these embodiments do not in any way constitute a limitation on the scope of the present invention.

[0267] Comparative Example 1

[0268] The method for processing recycled plastic materials involves grinding the recycled plastic material, which comprises approximately 65% ​​polyolefin, 5% polyamide, 14% high-impact polystyrene, 6% polyethylene terephthalate, 2% polyvinyl chloride, and smaller amounts of other materials. The grinding process is as follows: recycled plastic material in the form of a film with an average size of 3cm × 3cm is fed into a Retsch ZM200 rotor ultracentrifugal mill with an annular screen, a current absorption of 1300W, and a rotation speed of 6000-18000rpm.

[0269] The total chlorine content is approximately 1.14% by weight of chlorine relative to the total weight of the plastic material.

[0270] Low-temperature grinding of recycled plastic materials was performed under the following operating conditions:

[0271] • Quantitative feeding at a sliding speed of 5 using a Retsch DR100 sampler.

[0272] ·RPM=10000

[0273] Grinding time = 60 minutes per 15-20 grams of product

[0274] · 0.12mm annular screen

[0275] • Dry ice is added to the rotor for cooling to prevent any material buildup during the grinding process.

[0276] • Suction-type cyclone collection tank

[0277] The low-temperature grinding of recycled plastic materials produces a product characterized by D 50 Particle size distribution ≤0.2mm.

[0278] Take 10 g of the cryogenically ground recycled plastic material at room temperature and add it to 90 g of the depressurized residue preheated to 200 °C. In a 500 mL beaker equipped with a steel mechanical stirrer with a two-bladed propeller, heat the mixture at 200 °C for 2 hours with mechanical stirring at 60 rpm.

[0279] According to embodiments 2 to 5 of the present invention

[0280] Methods for treating recycled plastic materials by... Figure 1 The following components are added to the twin-screw co-rotating extruder described in the article to carry out the process:

[0281] The first component is a recycled plastic material, which consists of approximately 65% ​​polyolefin, 5% polyamide, 14% high-impact polystyrene, 6% polyethylene terephthalate, 2% polyvinyl chloride, and smaller amounts of other materials.

[0282] Recycled plastic materials contain 1.14% chlorine, calculated as the weight of chlorine (in atoms) relative to the total weight of the recycled plastic material.

[0283] Recycled plastic materials contain 2% calcium, which is calculated as calcium (in atoms) relative to the total weight of the recycled plastic material.

[0284] Recycled plastic materials are selected to remove inert materials such as stones and large metals. The recycled material is thickened in the form of granules approximately 2 cm in length and 5 mm in diameter, and then fed into the extruder hopper through a loss-in-weight feeder with flow control.

[0285] The second component is light sodium carbonate from Brenntag, whose D 50 It is equal to 0.063 mm. The sodium carbonate, as powder, is supplied to the same extruder hopper via a loss-in-weight feeder that also has flow control.

[0286] The third component consists of industrial-derived vacuum residues, as shown in Table 1.

[0287] Table 1

[0288] nature Unit of measurement value How to use Density at 15℃ kg / m 3 ]]> 1004 ASTM-D1298 S (sulfur) weight% 4.33 ASTM-D1552 CCR weight% 18.5 D-4530ASTM Asphalt weight% 14.6 ASTM 6560 Aromatic weight% 29.2 D2007 ASTM 500℃- weight% 15 ASTM 7169 530℃- weight% 23 ASTM 7169

[0289] in:

[0290] "S" represents the sulfur content.

[0291] "CCR" stands for Comstock Carbon Residue.

[0292] "500℃-" indicates the percentage of materials with a boiling point below 500℃.

[0293] "530℃-" represents the percentage of materials with a boiling point below 530℃.

[0294] Twin-screw co-rotating extruders are appropriately equipped to enable the feeding of both solids and liquids.

[0295] Reference Figure 1 (1) Represents the depressurized residue feeding system. The depressurized residue is melted in a tank heated to 160°C and placed on a scale, and then supplied to the extruder via a volumetric pump. The flow rate is adjusted by changing the pump speed and stroke based on the weight loss of the scale. The depressurized residue stream is injected into the extruder, splitting the total flow into three streams, and then injected into the total flow at three different points in the extruder, all downstream of the melting, dehalogenation, and inerting sections of the polymer mixture. The flow rate at each injection point is locally regulated by a manual valve (placed on the feed line of each of the three streams) to ensure that the upstream pressure at each injection point is the same (and therefore the flow rates are similar).

[0296] (2) A feeding system for recycled plastic material to the hopper of a twin-screw co-rotating extruder is shown. The recycled plastic material is fed via a loss-in-weight feeder with flow control.

[0297] (3) A feeding system for inert additives to the hopper of a twin-screw co-rotating extruder is shown. The inert additives are fed via a loss-in-weight feeder with flow control.

[0298] The twin-screw co-rotating extruder used in embodiments of the present invention for melting, dehalogenation, inerting, and mixing is characterized by a screw diameter of D = 30 mm and a characteristic length defined by the ratio L / D = 76. The screw rotation speed is set to 900 rpm. The extruder is heated using resistance heating within the barrel and cooled by a water circuit. Each part of the barrel has independent control, so the temperature can be set as needed and adjusted via feedback.

[0299] The extruder is made of Figure 1 The first part shown in (4) is dedicated to the melting, dehalogenation and stabilization of halogenated compounds in the downstream process.

[0300] Recycled plastic materials and inert additives are fed into this first part through a dedicated feed hopper.

[0301] The first section of the extruder has a characteristic length of 24 times its diameter and operates according to the following barrel temperature profiles, which are divided into three distinct zones:

[0302] In the first zone, dedicated to the transfer of recycled plastic at the inlet (characteristic length 4 times the diameter), the temperature is set to 50°C.

[0303] In the second zone, dedicated to melting recycled plastics (characteristic length 4 times the diameter), the temperature is set to 250°C.

[0304] In the third zone, dedicated to the dehalogenation and inertization of recycled plastics (characteristic length 16 times diameter), the temperature is set at 390°C.

[0305] The third zone of the first part of the extruder is equipped with a degassing zone to remove the generated gases, mainly carbon dioxide (CO2) and water vapor (H2O), which is operated at 0.2 bar (absolute pressure) by a dedicated pressure reducing pump.

[0306] Figure 1 The second section of the extruder shown in (5) is dedicated to the close mixing of the material stream leaving the first section. This second section has a characteristic length of 52 times the diameter and operates as follows.

[0307] The first portion of depressurized residue is injected eight times its diameter downstream of the first section of the extruder; the barrel temperature is set to 240°C. Immediately after the depressurized residue inlet, the screw is equipped with a mixing element eight times its diameter in length. Next is a transfer element four times its diameter in length; then, the second portion of depressurized residue is injected. The barrel temperature is set to 220°C. Immediately after the second portion of depressurized residue inlet, the screw is equipped with a mixing element twelve times its diameter in length. Next is a transfer element four times its diameter in length. Then, the third portion of depressurized residue is injected. The barrel temperature is set to 180°C. Immediately after the third portion of depressurized residue inlet, the screw is equipped with a mixing element twelve times its diameter in length.

[0308] The last four times the diameter of the section is dedicated to cooling the mixture and is operated by setting the cylinder temperature to 160°C.

[0309] The extruder uses a starvation feed management system, which adjusts the extruder speed (screw speed) to make its flow rate greater than the flow rate from the feed hopper. In this way, there is no material accumulation in the hopper, but the uniformity of the feed is not well controlled.

[0310] Various experiments were conducted, varying the ratios between the supplied material streams (recycled plastic material, sodium carbonate, and vacuum residue). The experimental compositions and process conditions used are summarized in Table 2.

[0311] Table 2

[0312] Example 2 Example 3 Example 4 Example 5 Recycled plastic materials 9.7% w / w 19.4% w / w 29.1% w / w 19.5% w / w Sodium carbonate 0.3% w / w 0.6% w / w 0.9% w / w 0.5% w / w decompression residue 90.0% w / w 80% w / w 70.0% w / w 80.00% w / w Flow rate kg / h 60 60 60 60 Sodium / plastic material mass ratio 1.5％ 1.5％ 1.5％ 1.1％ Na / Cl (mol / mol) 2 2 2 1.5

[0313] In Examples 2 to 4, the Na / Cl molar ratio was approximately 2, while in Example 5, the Na / Cl molar ratio was approximately 1.5. The Na / Cl molar ratio refers to the ratio of the number of moles of sodium contained in the inert reagent to the number of moles of chlorine contained in the plastic material.

[0314] In Examples 2 to 4, the sodium / plastic material feed mass ratio was approximately 1.5%, while in Example 5, the sodium / plastic material feed mass ratio was approximately 1.1%. The sodium / plastic material mass ratio refers to the ratio of the mass of sodium contained in the inert reagent to the mass of the plastic material.

[0315] The products from Examples 2 to 5 were sampled twice at the extruder exit.

[0316] The only halogen detected in the samples was chlorine. In the first sample, chlorine was determined by ion chromatography after the sample was mineralized by a calorimetric bomb.

[0317] The second sample was treated at 550°C for 4 hours under an inert atmosphere (nitrogen) and atmospheric pressure. In this second sample, chlorine was determined by ion chromatography after the treated sample was mineralized by a calorimetric bombardment.

[0318] The difference in the amount of chlorine between the first and second samples was assessed. This difference was attributed to organic chlorine, and therefore, for the purposes of this invention, it was defined as the amount of organic chlorine.

[0319] Therefore, the mass ratio of the amount of the organochlorine to the amount of the supplied plastic material is calculated.

[0320] For all four examples 2, 3, 4 and 5, the ratio was less than 2000 ppm (0.2%).

[0321] The products of Examples 2 to 5 at the outlet of the extruder are supplied to a stirred autoclave for hydrogenation conversion of the composition obtained at the outlet of the extruder.

[0322] A molybdenum 2-ethylhexanoate solution was added to the autoclave in such an amount that the molybdenum content was approximately 3000 wppm by weight (mass) relative to the total mass of the product obtained at the bottom of the extruder.

[0323] The autoclave is then pressurized and heated through various pressurization and heating steps. Specifically, in these embodiments, compressed hydrogen is first injected to 90 bar (gauge pressure), and then the autoclave is heated to 160°C. In the second step, the pressure is increased to 120 bar (gauge pressure) by injecting hydrogen, and then heated to 430°C. Finally, compressed hydrogen is injected again to bring the pressure to 160 bar (gauge pressure).

[0324] After reaching the desired temperature (430°C) for 4 hours, the autoclave was cooled to 250°C and completely depressurized. Head vapor was extracted and condensed in a cold trap at 0°C (analyzed by ASTM D2887). Non-condensable gases were collected in a gas sampler (analyzed by ASTM D7833). After extracting the light product, the autoclave was cooled to room temperature. Finally, the residual material contained in the autoclave was extracted. The residue contained in the autoclave was treated with tetrahydrofuran (THF) to obtain a solution of 2% by mass of the residue relative to THF. This addition determines the precipitation of substances insoluble in THF, such as metal sulfides or carbonaceous materials produced during the test. Therefore, the tetrahydrofuran-insoluble fraction was filtered, dried, and weighed. THF was evaporated from the tetrahydrofuran-soluble fraction, and the sample was analyzed by ASTM D6352.

[0325] The reaction products were quantified and characterized, as shown in Table 3.

[0326] Yields are calculated as the mass of each of the fractions (head gas, light fraction, heavy fraction, bottom fraction) relative to the mass obtained at the extruder outlet and the initial load.

[0327] Gaseous products are tested and measured using the ASTM D7833 standard refinery gas analysis and produce contents (gases) of 1 to 4 carbon atoms, which are defined as GASES.

[0328] Light fractions are defined as gaseous products containing more than five carbon atoms as determined by refinery gas analysis according to ASTM D7833, and liquid products with a boiling point range of 36°C to 170°C as measured by ASTM D2887 and ASTM 6352. Heavy fractions are defined as liquid products with a boiling point range of 170°C to 500°C as measured by ASTM D2887 and ASTM D6352. The bottom fraction is determined by other products, i.e., liquid products with a boiling point greater than 500°C (500+°C), or solid properties (insoluble in THF).

[0329] Table 3

[0330]

[0331] Comparative Examples 6 and 7

[0332] Comparative Examples 6 and 7 were carried out using the same operating method as Examples 2-5 of the present invention, except that the concentration of the inert reagent was changed: 0% for Comparative Example 6 and 0.1% for Comparative Example 7, wherein the percentage is expressed relative to the total amount supplied to the extruder, and the concentration of the depressurized residue was maintained at 80% relative to the total amount supplied to the extruder.

[0333] The compositions used in the experiments and the process conditions used are summarized in Table 4.

[0334] Table 4

[0335] Example 6 Example 7 Recycled plastic materials 20.0% w / w 19.9% ​​w / w Sodium carbonate 0% w / w 0.1% w / w decompression residue 80.0% w / w 80.0% w / w flow 60kg / h 60kg / h Sodium / plastic material mass ratio 0％ 0.2％ Na / Cl (mol / mol) 0 0.3

[0336] In Example 7, the molar ratio of Na / Cl supplied was approximately 0.3. In Example 7, the mass ratio of sodium to plastic material supplied was approximately 0.2%.

[0337] The products from Examples 6 and 7 at the outlet of the extruder are supplied to a stirred autoclave for hydrogenation conversion of the depressurization residue.

[0338] The experiment was conducted in the same manner as experiments 2 to 5 above, and the results are shown in Table 5.

[0339]

[0340]

[0341] Comparative Example 8

[0342] Repeat Embodiment 3 of the present invention, by Figure 1 The inert reagent (2) feed hopper will feed commercial calcium carbonate masterbatch based on polyethylene “POLYBATCH LCC 70” produced by “A. Schulman”. The masterbatch contains 70% by weight of calcium carbonate.

[0343] The compositions used in the experiments and the process conditions used are summarized in Table 6.

[0344] Table 6

[0345]

[0346] The experiments in the high-pressure reactor using the hydrogenation conversion reaction were conducted in the same manner as the previous experiments 2-5, and the results are shown in Table 7.

[0347]

[0348] According to embodiments 9, 10, and 11 of the present invention

[0349] Repeating Embodiment 3 of the invention, a recycled plastic material having the composition shown in Table 8 is fed into... Figure 1 In the aforementioned twin-screw co-rotating extruder.

[0350] Table 8

[0351] Example 9 Example 10 Example 11 polyethylene %w / w 44 63 13 polypropylene %w / w 24 24 54 polystyrene %w / w 15 0 16 Polyethylene terephthalate %w / w 6 0 5 polyamide %w / w 5 0 0 Polyvinyl chloride %w / w 2 2 2

[0352] The results of the hydrogenation conversion reaction in the autoclave are shown in Table 9.

[0353] Table 9

[0354] Example 9 Example 10 Example 11 gas wt / wt 进料 ]] 10％ 10％ 10％ Light fractions wt / wt 进料 ]] 20％ 16％ 21％ Heavy fraction wt / wt 进料 ]] 43％ 50％ 50％ bottom wt / wt 进料 ]] 27％ 24％ 19％

[0355] According to Embodiment 12 of the present invention

[0356] Repeat Example 3, feeding the following components into... Figure 1 In the aforementioned twin-screw co-rotating extruder:

[0357] - The recycled plastic material comprises 42% polyethylene, 21% polypropylene, 2% polyamide, 10% high-impact polystyrene (HIPS), 6% polyethylene terephthalate, 10% polyvinyl chloride, and small amounts of other materials. Recycled plastic material is selected to remove inert materials such as stones and large metals. The recycled material is thickened into granules approximately 2 cm in length and 5 mm in diameter, and then fed into the extruder hopper through a loss-in-weight feeder with flow control.

[0358] -Brenntag "Light Sodium Carbonate" sodium carbonate with a d50 of 0.063 mm. Sodium carbonate is supplied in powder form to the same extruder hopper via a loss-in-weight feeder that also has flow control.

[0359] Table 10 summarizes the tested mixtures (as a percentage of the total weight of material supplied to the extruder) and flow rates.

[0360] Table 10

[0361]

[0362]

[0363] In Example 12, the molar ratio of Na / Cl supplied was approximately 1.5. In Example 12, the mass ratio of sodium to plastic material supplied was approximately 5.5%.

[0364] The results of the hydrogenation conversion reaction in the autoclave are shown in Table 11.

[0365] Table 11

[0366] Example 12 gas wt / wt 进料 ]] 9％ Light fractions wt / wt 进料 ]] 16％ Heavy fraction <![CDATA[wt / wt 进料 ]]> 49％ bottom <![CDATA[wt / wt 进料 ]]> 26％

[0367] Analysis of chlorine content in comparative examples and in examples 2-8 and 12 according to the present invention

[0368] Tables 12 and 13 show the chlorine content in each part of Examples and Comparative Examples 2-8 and 12, i.e., the number of parts by weight of chlorine (in atomic weight) relative to the total weight of the analytical portion.

[0369] It is believed that chlorine exists only as hydrogen chloride (HCl) in the gaseous phase. Hydrogen chloride in the gaseous phase was determined using a Dräger tube.

[0370] Chlorine in the light fraction is determined using the method shown in D4929. Chlorine in the heavy fraction is determined using the method shown in D7536.

[0371] After the bottom sample was mineralized by a calorimetric bomb, the chlorine in the bottom was determined by distillation titration.

[0372] Table 12: Total Chlorine Analysis

[0373] Example 2 Example 3 Example 4 Example 5 Example 12 gas ppm <1 <1 <1 <1 1 Light fraction ppm <5 <5 <5 <5 <5 Heavy fraction ppm <5 <5 <5 <5 <5 Bottom %wt / wt >0.4 >0.8 >1.2 >0.8 >3.9

[0374] Table 13: Total Chlorine Analysis

[0375]

[0376]

[0377] Comments on the experimental results

[0378] Although the inert feed stream and the recycled plastic material stream are supplied separately, it is surprising that the supplied inert reagent is available. In fact, even at a dosage slightly above stoichiometry (Examples 5 and 12: Na:Cl ratio = 1.5), the inert reagent prevents chlorine from being released into the gas and distillate.

[0379] This is even more surprising, because calcium is already present and tightly dispersed within the polymer matrix. In fact, calcium salts typically have a size of no more than 1 micrometer and are tightly mixed with the plastic material during extrusion during their production; in contrast, the sodium salt used in the examples has a particle size of approximately 100 micrometers and is not present in the plastic material but is added during processing.

[0380] In Examples 2, 3, and 4 (with different concentrations of depressurization residue of 90%, 80%, and 70%), the feed stream from the extruder outlet was supplied to an autoclave for the hydroconversion reaction. The chlorine concentration of the light hydrocarbon stream and the gas stream at the equipment outlet was <5 ppm. This demonstrates the effectiveness of the method when the concentration of recycled plastic material varies.

[0381] This was also verified in the feed stream at the outlet of the equipment operated according to the description of Example 5, although in this case the amount of inert reagent added to the extruder was less than the amount of inert reagent used to prepare the mixtures for the aforementioned Examples 2, 3, and 4. In particular, in Examples 2, 3, and 4, the addition of inert reagent was operated to maintain a stoichiometric ratio of Na / Cl equal to 2, which is the opposite of Example 5 of the invention, in which the inert reagent was operated such that the ratio was equal to about 1.5.

[0382] The results of Example 12 were particularly surprising. In fact, the chlorine supply was very high in this case – approximately 5.7% of the weight of the recycled plastic material. Nevertheless, and despite a Na / Cl ratio of approximately 1.5, no chlorine was recorded in either the liquid effluent (fraction) or the gaseous effluent.

[0383] Conversely, in Comparative Example 6, chlorine was detected in both the gaseous and light hydrocarbon streams at the equipment outlet. No inert reagent was added in this example. This comparative example also demonstrates a particularly important aspect of the invention: calcium is not so effective, being actually excessive relative to chlorine and clearly in close contact with the recycled plastic material.

[0384] The presence of chlorine in the gas and light fraction can still be found in Example 7. In this case, the feed of the sodium-based inert reagent is adjusted so that the inert reagent is added in a lower amount relative to the stoichiometric ratio of sodium present in the inert reagent to chlorine contained in the recycled plastic material entering the extruder is 1:1.

[0385] The presence of chlorine was also detected in the gaseous effluent and light fraction of Comparative Example 8. In this case, the preparation steps were performed so that an equal amount (in stoichiometry of calcium ions for the preparation of CaCl2 relative to sodium ions for the preparation of NaCl) of calcium carbonate masterbatch was used instead of the inert reagent sodium calcium carbonate.

[0386] This means that even when calcium is supplied as an inert reagent according to the method of the invention, it is surprisingly ineffective.

[0387] Similarly, the comparative analysis of the sulfur content at the bottom of Example 5 highlights the presence of a significantly lower sulfur content compared to the bottom of Comparative Example 8. Therefore, it is surprisingly inferred that calcium is more effective at fixing sulfur than sodium.

[0388] It was observed that in the presence of alkaline earth metal salts, particularly calcium salts, but in the absence of alkali metal salts, such as sodium salts (e.g., Comparative Example 8), the bottom contained sulfides of the alkaline earth metals, particularly calcium sulfide.

[0389] The presence of calcium sulfide is undesirable because:

[0390] a) The sulfides at the outlet of the autoclave are mainly in the form of hydrogen sulfide (H2S); hydrogen sulfide is a useful gas in various refining processes (e.g., catalytic hydroconversion according to the already mentioned WO 2008 / 141830), and its consumption is therefore undesirable.

[0391] b) Sulfates, such as calcium sulfide, are generally toxic and harmful, and give materials containing such sulfates (e.g., bottoms) an unpleasant, distinctive odor.

[0392] The applicant observed that, surprisingly, the sulfur content at the bottom of the autoclave was lower when an alkaline inert reagent, such as sodium, was used instead, also in the presence of alkaline earth elements such as calcium.

[0393] Without requiring proof, it can be assumed that the alkali metal in the inert reagent that has not reacted with hydrogen halides (such as hydrogen chloride, HCl) can react with sulfur to form the corresponding sulfide (e.g., Na₂S), or can prevent the formation of alkaline earth metal salts (e.g., CaS). Under the conditions described in this invention, the alkali metal sulfide (e.g., Na₂S) may react with hydrogen halides (e.g., HCl) to form alkali metal halides (e.g., NaCl) and hydrogen sulfide (H₂S). Alternatively, the alkali metal in the inert reagent, as well as the alkali metal that has not yet reacted with hydrogen halides (e.g., Na₂CO₃), can react with sulfur and hydrogen halides present as alkaline earth metal sulfides (e.g., CaS and organic sulfur) to form alkali metal halides (NaCl) and hydrogen sulfide (H₂S). Furthermore, alkali metal sulfides (such as Na2S) are generally effective nucleophiles and therefore have the further advantage of being able to dechlorinate alkyl and aromatic chlorides formed by reacting hydrochloric acid produced during the process with alkenes and / or aromatic compounds already present in the vacuum residue to form sodium chloride, and help reduce the formation of chlorinated products in the reaction gases during distillation and hydrogenation treatment.

[0394] High sulfur content in solid residues is undesirable: besides the treatment issues, the increase in solids produced is also undesirable because it reduces the yield of valuable products such as fractions. Conversely, it is desirable for sulfur to be present in the form of hydrogen sulfide (which is used in refineries for different treatments).

[0395] Examples 9, 10, and 11 demonstrate that the methods identified in this invention are also applicable to a very wide range of variations in the polymer composition of recycled plastic materials.

[0396] Furthermore, compared to the wide range of compositional variations, the changes in light fraction yields were very limited. For example, between Example 11 and Example 10, polyethylene decreased from 63% to 13%, a reduction of almost 5 times, while the light fraction yield changed by only 4% (from 18% to 24%).

[0397] Figure 2 and 3 Microscopic images of Comparative Example 1 and Embodiment 3 of the Invention are shown respectively. Bright areas in the images correspond to localized enrichment areas of the recycled plastic material, and dark areas correspond to RV-rich areas. Visual evaluation of the images supports the statement that the mixture prepared according to the method described herein ( Figure 2 The characteristic of this is the tight mixing between the recycled plastic material and the decompression residue. In contrast, the sample prepared according to the method of Comparative Example 1... Figure 3A worse degree of mixing was observed. This was confirmed by a quantitative assessment using the method of calculating the minimum mixing area. Quantitatively, the non-uniform distribution of recycled plastic material in the decompression residue prepared according to Example 1 was confirmed by the value of the minimum mixing area, which did not reach the value obtained for the mixtures compared according to the method described in the present invention. In fact, for H = 2 / 3 (= ca. 0.67), the mixing area (i.e., the minimum mixing area) of Comparative Example 1 was approximately 0.032 square millimeters (see...). Figure 4 Conversely, the mixing area of ​​Example 3, which was still evaluated for H=2 / 3, was only 0.0095 square millimeters (see...). Figure 5 ).

Claims

1. A composition of plastic material mixed with a hydrocarbon, an oligomer derived from the plastic material and a halogenated salt, the composition comprising: • a plastic material free of halogenated components or having a halogen content lower than or equal to 0.5% by mass with respect to the plastic material, • an oligomer derived from the plastic contained in the plastic material, • a halogenated salt selected from the group consisting of chlorides of alkali metals of group IA, fluorides of alkali metals of group IA, bromides of alkali metals of group IA, iodides of alkali metals of group IA, • a hydrocarbon selected from the group consisting of heavy fractions, distillation residues; wherein the mass content of plastic material is comprised between 2% and 300% with respect to the mass content of hydrocarbon.

2. The composition according to claim 1, wherein the hydrocarbon is a vacuum residue.

3. The composition according to claim 1, wherein the chlorides of alkali metals of group IA are selected from the group consisting of lithium chloride, sodium chloride, potassium chloride.

4. The composition according to claim 1, wherein the bromides of alkali metals of group IA are selected from the group consisting of lithium bromide, sodium bromide, potassium bromide.

5. The composition of any one of claims 1-4, wherein the minimum mixing area is less than or equal to 0.03 mm 2 .

6. The composition of claim 5, wherein the minimum mixing area is 0.001 mm 2 to 0.02 mm 2 .

7. A process for the production of a composition as defined in any one of the preceding claims, the process comprising the following steps: - heating and mixing, in one or more apparatuses comprising heating and mixing means, simultaneously or in separate phases, a plastic material containing halogenated components, an inert agent and a hydrocarbon stream selected from the group consisting of heavy fractions, distillation residues, so as to form a composition, said composition being brought to a temperature comprised between 150°C and 450°C and the composition thus obtained is kept in said temperature range for a time comprised between 10 seconds and 30 minutes, so as to form a final composition which is a composition as defined in any one of the preceding claims; the process being characterized in that the amount of inert agent added during the process is such that the ratio between the sum of the moles of alkali metals belonging to group IA and the sum of the moles of halogen contained in the plastic material containing halogenated components is comprised between 1:1 and 20:

1.

8. The process according to claim 7, wherein the plastic material containing halogenated components comprises a recycled plastic material containing halogenated components.

9. The process according to claim 7, wherein the plastic material containing halogenated components contains organic or inorganic compounds.

10. The process according to any one of claims 7 to 9, wherein the plastic material containing halogenated components comprises at least 60% by weight of plastic, said % being calculated with respect to the total weight of the plastic material containing halogenated components.

11. The process according to claim 10, wherein the plastic material containing halogenated components comprises at least 80% by weight of plastic, said % being calculated with respect to the total weight of the plastic material containing halogenated components.

12. The process according to claim 11, wherein the plastic material containing halogenated components comprises 100% by weight of plastic, said % being calculated with respect to the total weight of the plastic material containing halogenated components.

13. The process according to claim 7, wherein the plastic material containing halogenated components is PLASMIX.

14. The method of claim 7, wherein the plastic material containing halogenated components is in the form of flakes and has a median particle size (D50) greater than 0.2 cm. 50 ) or wherein the plastic material containing halogenated components is compacted in the form of granules, the granules being obtained by extruding flakes through a die having a hole with a diameter of 2 to 20 mm.

15. The method according to claim 14, wherein the plastic material containing a halogenated component in the form of a flake is characterized by an apparent density greater than 50 kg / m3 as measured according to ASTM D1895-17 Method C "Pre-loaded" Density Test. 3 .

16. The method according to claim 14, wherein the plastic material containing a halogenated component in particulate form is characterized by an apparent density greater than 200 kg / m3measured according to ASTM D1895-17 Method B. 3 .

17. The process according to claim 7, wherein the composition of plastic contained in the plastic material containing halogenated components comprises at least one selected from the group consisting of: • polyethylene: 10-100% • polypropylene: 0-50% • polystyrene: 0-50% • polyester: 0-20% • sum of cellulose, polyurethane and polyamide polymers: 0-20% • inorganic filler: 0-30% • chlorinated polymer in an amount such that the weight of chlorine is 0.05-15% with respect to the total weight of the plastic material containing halogenated components.

18. The process according to claim 7, wherein the ratio between the sum of moles of alkali metals belonging to Group IA and the sum of moles of halogens contained in the plastic material containing halogenated components is from 10:1 to 1 :

1.

19. The process according to claim 18, wherein the ratio between the sum of moles of alkali metals belonging to Group IA and the sum of moles of halogens contained in the plastic material containing halogenated components is from 3:1 to 3:

2.

20. The process according to claim 7, wherein the amount of inert agent added is such that simultaneously: • the ratio between the sum of moles of alkali metals belonging to Group IA and the sum of moles of halogens contained in the plastic material containing halogenated components is at most 20:1, and • the ratio between the mass of alkali metals belonging to Group IA and the mass of the plastic material containing halogenated components is at least 1 :1000.

21. The process according to claim 7, wherein the inert agent is an alkali metal belonging to Group IA of the Periodic Table, selected from lithium, sodium, potassium, rubidium, cesium and combinations thereof.

22. The process according to claim 21, wherein the metal is a mixture of lithium and metallic sodium.

23. The process according to claim 7, wherein the inert agent is a sodium compound selected from carbonates, bicarbonates, carboxylates, biphenyl, cyclopentadiene, butyl, butyryl, oxides, hydroxides, alkyl sulfonates and alkyl benzenesulfonates.

24. The process according to claim 23, wherein the sodium carboxylate compound is selected from stearate, palmitate, neopentanoate and octanoate.

25. The process according to claim 7, wherein the inert agent is a lithium compound selected from methyl, butyl, aspartate, acetate, carbonate, bicarbonate, stearate, oxide, hydroxide.

26. The process according to claim 7, wherein the inert agent further comprises up to 10% by weight of a ketal with respect to the total weight of the inert agent.

27. The process according to claim 7, wherein the hydrocarbon stream is a vacuum residue.

28. The process according to claim 7, carried out by extrusion.

29. The process according to claim 7, carried out in a two-stage manner, comprising: • a first stage in which the plastic material containing halogenated components and the inert agent are mixed to produce a first composition; then • a second stage in which the first composition is mixed with the hydrocarbon stream, producing the final composition of the plastic material.

30. The process according to claim 29, wherein the plastic material containing halogenated components is pre-heated to a temperature of at least 150°C.

31. The process according to claim 29, wherein the apparatus is an extruder.

32. The process according to claim 7, carried out in one or more apparatuses selected from extruders, static mixers, dynamic mixers, stirred reactors.

33. The method of claim 7, wherein the minimum mixing area measured on the final composition of plastic material is less than or equal to 0.03 mm 2 .

34. The process according to claim 7, further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by means of a thermal or catalytic conversion process, optionally in the presence of an inert agent.

35. The process according to claim 7, further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by means of a visbreaking process, optionally in the presence of an inert agent.

36. The process according to claim 7, further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by means of a cracking process, optionally in the presence of an inert agent.

37. The process according to claim 36, wherein the cracking process is a hydrocracking process.

38. The process according to claim 7, further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by means of a catalytic or non-catalytic hydroconversion process, optionally in the presence of an inert agent.

39. The process according to claim 7, further comprising the step of converting the final composition of the plastic material into a hydrocarbon product by means of a catalytic hydroconversion process with Eni Slurry Technology (EST), optionally in the presence of an inert agent.

40. The process according to claim 34, wherein the hydrocarbon product is selected from light distillates, heavy distillates, gases.

41. The process according to claim 40, wherein the hydrocarbon product is selected from naphtha, atmospheric gas oil (AGO), light vacuum gas oil (LGVO) and heavy vacuum gas oil (HVGO).

Images