Process for recycling plastic waste and high-value products produced thereby

Abstract

The present disclosure relates to a process for recycling plastic waste by pyrolysis under defined conditions in combination with catalytic hydroprocessing to obtain a variety of high-value paraffinic products having high purity and reduced aromatics content. The disclosure also relates to the high-purity paraffinic products, such as solvents, oils, and waxes, produced by the process, having an aromatics content of up to 3000 ppm.

Description

[Technical Field]

[0001] The present disclosure relates to a process for recycling plastic waste by pyrolysis and the high-value products produced thereby, such as solvents, oils and waxes. [Background technology]

[0002] The following references are considered relevant background to the subject matter disclosed herein: -WO2010 / 049824 issue -WO2010 / 106399 -WO2010 / 116211 issue -WO2010 / 136850 Identification of the above references herein is not to be inferred as relating in any way to the patentability of the subject matter disclosed herein.

[0003] Awareness of the need for waste recycling has grown significantly over the past few decades, recognizing that traditional disposal methods, such as landfilling or incineration, have enormous negative environmental and ecological impacts. Inadequate recycling processes for municipal waste are a major concern. While nearly 50% of municipal waste is currently recycled in the European Union (according to Eurostat, the EU generated 502 kg of waste per capita in 2019, of which 48% was recycled or composted), recycling rates in other First World countries are much lower. In the United States, for example, only 9% of solid municipal waste generated in 2018 was recycled. According to the U.S. Environmental Protection Agency, 292 million tons of municipal solid waste were generated in 2018, approximately 58% of which was attributable to household paper, food, and plastic waste; however, only 69 million tons were recycled or composted, the majority of which (over 66%) was wastepaper.

[0004] The main components in municipal and industrial waste are polyolefins, which are used for various household products, primarily packaging, and for agricultural needs, such as greenhouses and irrigation piping. Because only some of the polyolefin waste is recycled into new polyolefin products, it would be beneficial to provide a recycling process that allows for obtaining high-value products from additional polyolefin plastic waste. Summary of the Invention

[0005] The present disclosure provides an industrial recycling process for polyolefin waste to obtain high-value products, such as high-purity solvents, oils, and waxes. The products produced by the disclosed process have low aromatic content, typically less than 3000 ppm (e.g., less than 2000 ppm (0.2 wt%)), meeting FDA and cosmetology requirements. The disclosed process also produces high-value by-products, which can be used as fuels or additives / modifiers for bitumen and asphalt mass due to their high calorific value.

[0006] Some of the unique features of the disclosed process are the wide range of products that can be obtained, primarily due to the wide range of intermediates produced during the thermocracking step and the subsequent hydrotreating process (designed to process the thermocracking product as a whole) before separation into distinct hydrocarbon fractions. Thus, the disclosed process allows for a wide variety of products with low aromatic and impurity content to be obtained from the same polyolefin feedstock in an integrated process.

[0007] According to one aspect of the present disclosure, there is provided a process for obtaining a paraffinic product having an aromatics content of up to about 3000 ppm from a mixture of polyolefins, the process comprising: (a) thermocracking said mixture in a molten state in a thermocracking reactor under conditions comprising: (i) a pressure of up to 1 barg, (ii) a temperature in the range of about 320°C to about 450°C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the thermocracking reactor of about 2 to about 40 hours to obtain a hydrocarbon vapor stream; (b) removing volatile C1-C5 compounds from the hydrocarbon vapor stream and quenching the remainder of the hydrocarbon vapor stream to obtain a condensate stream; (c) transferring the condensate stream into a main catalytic hydrotreating unit to obtain a hydrotreated stream; (d) separating the hydrotreated stream into the following product streams: (i) a C6-C20 product stream having a boiling point of from about 60°C to about 330°C; (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C; and (iii) a C20-C70 product stream having an initial boiling point of at least about 350°C; and (e) further processing each of the product streams to obtain said paraffinic product, the paraffinic product comprising: (i) a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) C14-C32 paraffinic products having an aromatics content of up to about 3000 ppm; and (iii) C20-C70 paraffinic products with an aromatics content of up to about 3000 ppm.

[0008] According to another aspect, there is provided a process for recycling polyolefin waste, comprising: (a) thermocracking a molten waste polyolefin mixture in a thermocracking reactor under conditions comprising: (i) a pressure of up to 1 barg; (ii) a temperature in the range of about 320°C to about 450°C; (iii) the absence of oxygen; and (iv) a residence time of the mixture in the thermocracking reactor of about 2 to about 40 hours to obtain a hydrocarbon vapor stream; (b) removing volatile C1-C5 compounds from the hydrocarbon vapor stream and quenching the remainder of the hydrocarbon vapor stream to obtain a condensate stream; (c) transferring the condensate stream into a main catalytic hydrotreating unit to obtain a hydrotreated stream; (d) separating the hydrotreated stream into the following product streams: (i) a C6-C20 product stream having a boiling point of from about 60°C to about 330°C; (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C; and (iii) a C20-C70 product stream having a boiling point of at least about 350°C; and (e) further processing each of the product streams to obtain said paraffinic product, the paraffinic product comprising: (i) C6-C20 paraffinic products having an aromatics content of up to 3000 ppm; (ii) C14-C32 paraffinic products having an aromatics content of up to about 3000 ppm; and (iii) C20-C70 paraffinic products with an aromatics content of up to about 3000 ppm.

[0009] According to some embodiments, the C6-C20 paraffinic product, the C14-C32 paraffinic product, and / or the C20-C70 paraffinic product have an aromatics content of up to about 2000 ppm.

[0010] According to some other embodiments, the C6-C20 paraffinic product, the C14-C32 paraffinic product, or the C20-C70 paraffinic product each has an aromatics content of at most about 2000 ppm.

[0011] In the process of the present disclosure, a mixture of polyolefins is used as a feedstock. The term polyolefin (or poly(alkene)) is meant to refer to a linear, branched, crosslinked, or block polymer composed of or produced from olefin monomers. Polyolefins are typically obtained from plastic waste (e.g., sorted plastic waste), with or without virgin or virgin polyolefins.

[0012] According to some embodiments, the polyolefin blend comprises polyethylene and polypropylene. According to some other embodiments, the polyolefin blend comprises polyethylene in an amount ranging from 10 wt% to 90 wt%, and polypropylene in an amount ranging from 10 wt% to 90 wt%.

[0013] According to some embodiments, the polyolefin blend consists essentially of polyethylene. According to other embodiments, the polyolefin blend consists essentially of polypropylene.

[0014] According to some embodiments, the polyolefin blend comprises up to 10 wt% polystyrene. According to some embodiments, the polyolefin blend comprises up to 5 wt% polystyrene.

[0015] According to some embodiments, the polyolefin blend includes up to 5 wt % of a non-polyolefin polymer other than polystyrene (eg, polyvinyl chloride, polyethylene terephthalate, acrylonitrile butadiene styrene, nylon, polyurethane, etc.).

[0016] According to some embodiments, the process includes a pre-step, or pre-treating of the feedstock, prior to step (a). For example, if the feedstock includes plastic waste, pre-treating the feedstock can include one or more steps of separating polyolefins from the waste, washing the waste with water, dewatering the waste, shredding the waste, and removing contaminants and / or substances of concern from the waste.

[0017] The polyolefin mixture is fed in step (a) in a molten state into the thermocracking reactor. According to some embodiments, the melting of the polyolefin mixture is obtained by extrusion.

[0018] In step (a) of the process, the molten mixture is thermocracking into smaller hydrocarbon molecules. Thermocracking (or pyrolysis) refers to the breakdown of polymeric materials due to temperature. Unlike typical thermal processes used to treat plastic waste, in the thermocracking process, the cracking is carried out under inert atmospheric conditions, reducing the amount of undesirable coke and promoting a random cleavage mechanism, producing a heterogeneous mixture of paraffins, olefins, and aromatics with a wide range of chain lengths.

[0019] In step (a), the thermocracking is carried out under the following conditions: (i) a pressure of up to 1 barg, (ii) a temperature in the range of about 320°C to about 450°C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the thermolysis reactor of about 2 to about 40 hours.

[0020] The disclosed process provides a combination of conditions that result in high yields of hydrocarbon vapor products from polyolefin mixtures with minimal coke formation.

[0021] The temperature in the thermolysis reactor is maintained in the range of 320°C-450°C, which is lower than typical plastic waste treatment processes. According to some embodiments, the temperature in the thermolysis reactor is about 350°C to about 420°C. While higher temperatures are used in typical waste treatment processes to promote the formation of low molecular weight volatile products, the relatively low temperatures used in step (a) of the present process allow for a wide range of condensable hydrocarbon chain lengths, enabling a wide range of end products (described further below). The low temperatures also minimize secondary reactions in terms of aromatics formation and cracking / decomposition of waxy components.

[0022] The pressure in the thermolysis reactor is maintained at no more than about 1 barg, and according to some embodiments, no more than about 0.5 barg. The inventors have found that because the boiling points of the cracking products decrease under high pressure, pressures above 1 barg at a given operating temperature result in thermal cracking rather than vaporization of heavy hydrocarbons (the desired products in the processes described herein). Thus, under pressure cracking, more energy is required for further hydrocarbon cracking, and the average molecular weight of the gas products decreases. Thus, maintaining the pressure at a maximum of 1 barg, preferably at a maximum of about 0.5 barg, can provide both energy efficiency on the one hand and a desirable cracking product profile on the other hand.

[0023] The residence time in the thermocracking reactor is defined as the average amount of time the mixture spends in the thermocracking reactor. The inventors have found that in the process of the present disclosure, a long residence time results in the formation of light fractions, while a shorter residence time produces primarily heavy fractions; a residence time of about 2 to about 40 hours in step (a) achieves a balance of thermocracking products between light, medium, and heavy fractions, which can be further processed into various high-value products, as described below. A longer residence time also reduces the amount of olefins and allows for secondary hydrogenation of double bonds in the thermocracking reactor, ensuring lower hydrogen consumption in the hydrotreating unit and lower exothermic effects in hydrotreating (making the process safer and easier to control).

[0024] According to some embodiments, the residence time ranges from about 2 to about 30 hours. According to other embodiments, the residence time ranges from about 3 to about 20 hours. According to some other embodiments, the residence time ranges from about 3 to about 10 hours. According to still other embodiments, the residence time ranges from about 4 to about 6 hours.

[0025] According to some embodiments, the process comprises in step (a) treating the mixture in one or more thermolysis reactors arranged in parallel.

[0026] According to some embodiments, the thermolysis reactor can be a batch reactor, a semi-batch reactor, a continuous flow reactor (CFR), an auger reactor, or a combination thereof.

[0027] According to some embodiments, when a batch, semi-batch or continuous reactor is used, the thermocracking is carried out under a flow of nitrogen or other stripping agent, such as a light hydrocarbon stream, to continuously remove undesired volatiles from the reactor.

[0028] According to some embodiments, the thermocracking reactor includes a heated circulation loop defined between the reactor circulation outlet and the reactor circulation inlet for circulating a portion of the mixture therethrough during thermocracking. The circulation loop is designed to continuously circulate a portion of the mixture in and out of the thermocracking reactor. Because the viscosity of the process fluid in the reactor (i.e., the melt in its partially thermocracked form) is relatively high, it is difficult to control the temperature uniformity within the fluid. In the presently claimed process, continuous circulation of a portion of the contents of the thermocracking reactor through the heated circulation loop allows for better control of the temperature of the melt, while also allowing a small portion of the melt (i.e., the circulating portion) to be exposed to temperatures higher than those maintained within the reactor for short periods (i.e., while passing through the loop), allowing for proper heating of the mixture, while also minimizing undesirable coke formation due to the short residence time within the loop.

[0029] According to some embodiments, the temperature in the circulation loop is between about 400°C and about 450°C.

[0030] According to some embodiments, the portion of the mixture in the circulation loop during thermocracking is about 2 to about 50% of the volume of the thermolysis reactor. According to other embodiments, the portion of the mixture in the circulation loop during thermocracking is about 2 to about 30% of the volume of the thermolysis reactor.

[0031] According to some embodiments, step (a) further comprises removing a solid residue from the pyrolysis reactor. The solids removed from the pyrolysis reactor can be further processed, disposed of, or further utilized. For example, the solids (or sometimes referred to as "furnace bottoms") can be used as fuel, e.g., in waste incineration plants or cement plants, due to their high heating value (typically 36-47 MJ / kg). The solids can also be used as cement or bitumen asphalt additives, or as binders for ores.

[0032] The thermocracking step produces a broad distribution of saturated and unsaturated hydrocarbon pyrolysis products in vapor form. In step (b), volatile C1-C5 compounds are removed from the hydrocarbon vapor stream, and the remainder of the hydrocarbon stream, typically containing C6-C70 hydrocarbons, is quenched to obtain a condensate stream. The condensate stream is also referred to herein as pyrolysis oil. The non-condensable gases / vapors (C1-C5) are separated and can be utilized for energy recovery. In the disclosed process, the non-condensable gases comprise approximately 5-15% wt of the total reactor feed.

[0033] According to some embodiments, the temperature during quenching in step (b) of the process ranges from about 150°C to about 250°C.

[0034] The condensate is then treated as a whole in step (c) in a main catalytic hydrotreating unit to obtain a hydrotreated stream of condensate. Hydrotreating (or any of its linguistic variations) refers to the reduction of double bonds and aromatic bonds in the hydrocarbons of the condensate stream. In addition to the reduction of double bonds, the hydrotreating conditions applied in this process also allow for the rapid removal of heteroatoms and non-hydrocarbon compounds by converting them into volatile compounds (e.g., sulfur-organic compounds as hydrogen sulfide, nitrogen-containing compounds as ammonia, and oxygen-containing compounds as water). Thus, under the main hydrotreating conditions, in addition to olefin and aromatic saturation, simultaneous processes, namely hydrodesulfurization, denitrification, and removal of heteroatoms by removal of oxygen and / or halides, are possible.

[0035] The purpose of the primary hydrotreating is to treat all hydrocarbons in the condensate stream with hydrogen (H). This process step also reduces the bromine number of the treated stream to less than 0.5 gBr / 100 g. In the disclosed process, hydrotreating the entire condensate stream is essential to provide adequate product quality and to prevent undesired polymerization reactions from unsaturated components further downstream in the process. Furthermore, unlike known processes in which the condensate is first separated into fractions and each fraction is hydrotreated separately or sequentially in different systems, in the disclosed process, hydrotreating the entire hydrocarbon condensate (without fractionation) does not require flashing between fractions (since separate fractions are not treated) and also prevents contamination due to the treatment of different fractions in the same hydrotreater. Additionally, hydrotreating the entire condensate before separation removes resin-forming components (primarily reactive diolefins or olefins such as styrene derived from PS) and allows for the maintenance of long-term operation of the distillation column.

[0036] According to some embodiments, the main catalytic hydrotreating unit is operated in step (c) at a temperature of about 250°C to about 340°C, a pressure of at least about 45 barg, and at least about 150 Nm 3 / m 3(normal lube / cubic meter) hydrogen to condensate stream ratio.

[0037] The condensate stream is heated to a minimum operating temperature of 250°C. The temperature in the reactor is always maintained as high as possible, but not exceeding 340°C, because the inventors have found that under the conditions of the process disclosed herein, aromatic hydrogenation / saturation becomes ineffective above 340°C. The hydrogenation reaction of unsaturated components is exothermic, and the heat generated is primarily influenced by the feed composition. The higher the PP concentration in the feed, the more unsaturated compounds will be produced, which will be hydrogenated in this reactor. To control the temperature in the reactor and avoid overheating (hot spots and runaway conditions), the temperature is controlled by the H2 / HC ratio and inlet temperature. All heat input to the process is carefully controlled at maximum temperature to avoid further cracking of hydrocarbons and the formation of coke residues. Further temperature control can be obtained by introducing cold hydrogen between the catalyst beds for quenching.

[0038] According to some embodiments, the difference between the inlet temperature of the condensate stream and the temperature in the main catalytic hydrotreating unit is at most 50°C.

[0039] According to some embodiments, the main hydrotreating is carried out at a pressure in the range of 60 barg to 200 barg.

[0040] According to some embodiments, the liquid hourly space velocity (LHSV) is the ratio of the liquid feed volume to the catalyst volume flowing within 0.5 h -1 ~2.0h -1 In the main hydrotreating step of the process of this disclosure, it has been found that such LHSV values ​​allow good control over the simultaneous desulfurization in the hydrotreating reactor.

[0041] The main hydroprocessing step is a catalytic process at high temperature and pressure. According to some embodiments, the catalytic reaction occurs over a fixed catalyst bed in the presence of a high volumetric ratio of hydrogen.

[0042] According to some embodiments, the catalyst in the main hydrotreating step may be selected from alumina, silica, zeolites, noble-earth metals (such as cobalt, molybdenum, nickel, tungsten, platinum, zirconium, etc.), and alloys of metals.

[0043] According to some other embodiments, the primary catalytic hydrotreating utilizes at least one Ni-Mo catalyst.

[0044] Catalysts are typically sensitive to poisons (e.g., by arsenic, vanadium, silicon, nickel, but also by other metals and halogenates). In the main hydrotreating stage, the catalyst is typically prone to silicon poisoning, which may sometimes be present in the source material (and thus, to some extent, in the condensate stream). To protect the catalyst in the main hydrotreating reactor, the condensate stream may be fed to the main hydrotreating reactor through at least one guard bed.

[0045] Thus, according to some embodiments, the condensate stream of step (b) is passed through at least one guard bed reactor containing at least one guard bed catalyst before being introduced into step (c).

[0046] According to some embodiments, the temperature in the at least one guard bed reactor is between about 290° C. and 340° C. According to some other embodiments, the hydrogen to condensate stream ratio in the at least one guard bed reactor is between about 150 Nm 3 / m 3 is.

[0047] According to some embodiments, the condensate stream is passed through one or more traps to remove contaminants from the condensate stream before it is fed into the main hydrotreating reactor. The traps may be for metals, silicon, halides, phosphorus, etc. According to some embodiments, the one or more traps include iron oxide, iron exchange resin, clay, silica gel, alkali or alkaline earth metal oxides, activated aluminum oxide, activated carbon, molecular sieves, highly porous nickel molybdenum (NiMo), cobalt molybdenum (CoMo) catalysts, or any combination thereof. The traps can operate with or without hydrogen coverage.

[0048] After hydrotreating, the hydrotreated stream is separated into product streams in step (d) of the process. The hydrotreated stream is typically separated into three main streams based on hydrocarbon molecular weight and boiling point: (i) a C6-C20 product stream having a boiling point of about 60°C to about 330°C, (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C, and (iii) a C20-C70 product stream having an initial boiling point of at least about 350°C.

[0049] According to some embodiments, the main stream comprises: (i) a C6-C18 product stream having a boiling point of about 100°C to about 300°C, (ii) a C14-C24 product stream having a boiling point of about 300°C to about 380°C, and (iii) a C22-C70 product stream having an initial boiling point of at least about 380°C.

[0050] Each of streams (i)-(iii) is then treated separately in step (e) to obtain the final paraffinic product.

[0051] According to some embodiments, the product stream is treated in step (e) as follows: (i) catalytically hydrotreating said C6-C20 product stream followed by distillation in at least one solvent distillation column to obtain a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) catalytically hydrotreating the C14-C32 product stream followed by distillation in at least one oil distillation column to obtain a C14-C32 paraffinic product having an aromatics content of up to about 3000 ppm; and / or (iii) distilling the C20-C70 product stream in at least one wax distillation column to obtain a C20-C70 paraffinic product having an aromatics content of up to about 3000 ppm.

[0052] In some embodiments, the C20-C70 product stream can be bleached to improve the color and quality of the paraffinic product. The bleaching agent can be at least one of natural bleaching earth, acid-activated bleaching earth, activated carbon (e.g., for the removal of polyaromatic hydrocarbons and a wide range of specific contaminants), synthetic amorphous silica (e.g., for the removal of phosphatides, trace metals, and soaps), and the like.

[0053] In process step (e), the C6-C20 stream is, in some embodiments, first catalytically hydrotreated and then distilled in at least one solvent distillation column to obtain a C6-C20 paraffinic product, typically a solvent, having an aromatics content of up to about 3000 ppm, preferably up to 2000 ppm.

[0054] The catalytic hydrotreating of the C6-C20 product stream in step (e) is primarily aimed at further reducing the aromatics content of the light fraction. Low-boiling aromatics are particularly undesirable in the solvent (which is the C6-C20 product) because they can pose a health hazard. The concentration of aromatics in the C6-C20 stream can be directly affected by the presence of various contaminants (e.g., polystyrene) in the polyolefin feed mixture, and not all of them can be processed to the desired level in the main hydrotreating step.

[0055] The catalytic hydrotreating of the C6-C20 product stream in step (e) is carried out at a temperature of about 170°C to about 300°C, a pressure of at least 45 barg, and a pressure of at least 150 Nm 3 / m 3 The process is carried out under conditions involving a hydrogen to condensate stream ratio of 0.05 (normal lube / cubic meter). These conditions aim to achieve significant aromatic conversion, but also to avoid overheating, which can lead to undesirable side reactions.

[0056] In some embodiments, the C6-C20 product stream is processed by one or more distillation stages to obtain a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm, preferably up to 2000 ppm. The C6-C20 paraffinic product is typically a solvent having a boiling point between about 100° C. and about 360° C. A variety of solvents having different boiling point ranges within this wide range can be obtained by varying the distillation column parameters and / or by utilizing two or more solvent distillation columns arranged in series.

[0057] The C14-C32 product stream is catalytically hydrotreated in step (e) and subsequently distilled in at least one oil distillation column to obtain a C14-C32 paraffinic product having an aromatics content of at most about 3000 ppm, preferably at most 2000 ppm. The primary purpose of hydrotreating the C14-C32 product stream is to isomerize the normal paraffins of this hydrocarbon fraction into branched paraffins to obtain an oily product having an improved cloud point of less than -10°C and an oil pour point of less than -20°C. The cloud point and pour point are indicators of the presence of normal waxes in the oil, which are undesirable in the oily product. Another purpose of hydrotreating the C14-C32 product stream is to gently hydrocrack the long-chain hydrocarbons into shorter-chain hydrocarbons, effectively dewaxing the C14-C32 product.

[0058] According to some embodiments, catalytically hydrotreating the C14-C32 product stream in step (e) comprises hydrotreating the C14-C32 product stream at a temperature of about 310° C. to about 360° C., a pressure of at least 25 barg, and a pressure of at least 150 Nm 3 / m 3 and hydrotreating the product stream under conditions comprising a hydrogen to C14-C32 product stream ratio of

[0059] According to some other embodiments, catalytically hydrotreating the C14-C32 product stream in step (e) is carried out in two sequential hydrotreating steps: The C14-C32 product stream is treated at a temperature of about 310°C to about 360°C, a pressure of at least 30 barg, and a pressure of at least 150 Nm 3 / m 3 step (e1), comprising hydrotreating under conditions comprising a hydrogen to C14-C32 product stream ratio of The product of step (e1) is treated at a temperature of about 170°C to about 300°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm 3 / m 3Step (e2) comprising hydrotreating under conditions comprising a hydrogen to C14-C32 product stream ratio of

[0060] In step (e1), the C14-C32 product stream is isomerized, while in step (e2), the isomerized stream is further treated to convert the remaining unsaturated hydrocarbons to saturated hydrocarbons, thereby further reducing the aromatics content in the resulting oily product. Step (e2) also improves the color of the oil according to the Saybolt color scale.

[0061] According to some embodiments, the process involves dewaxing (mild hydrocracking) the C14-C32 product stream to remove easily solidifying hydrocarbons (i.e., waxes). Wax removal is typically required to produce lubricating oils that remain fluid over a wide range of temperatures. The catalytic dewaxing process involves passing the C14-C32 product stream over a catalyst whose active hydrocracking sites are accessible only to paraffinic molecules, selectively hydrocracking the waxy molecules into shorter chain products while leaving valuable lubricating oil components unchanged.

[0062] According to some embodiments, the C14-C32 product stream is processed by one or more distillation stages to obtain a C14-C32 paraffinic product having an aromatics content of up to 2000 ppm. The C14-C32 paraffinic product is typically an oil, which contains at least 50 wt% C14-C32 isoparaffinic compounds, preferably at least about 95 wt% C14-C32 isoparaffinic compounds, and has an aromatics content of 5.00 mm as measured by ISO 3104 at 40°C. 2 / s~15.00mm 2 The oil obtained after distillation typically has a boiling point of about 320°C to about 420°C.

[0063] In the disclosed process, the C20-C70 product stream is distilled in a wax distillation column in step (e) to obtain a C20-C70 paraffinic product.

[0064] According to some embodiments, the C20-C70 paraffinic product is typically a wax containing at least 95 wt% C20-C70 normal paraffinic compounds (as determined by GC / MS), with an oil content of about 10 wt% to 60 wt%, and about 3000 ppm or less of aromatic compounds. The wax obtained after distillation typically has a boiling point of at least 350°C.

[0065] According to another embodiment, the C20-C70 paraffinic product contains up to about 85 wt% isoparaffins and up to about 60 wt% n-paraffins (as determined by ASTM D5442), and up to about 3000 ppm aromatics.

[0066] The wax distillation can be carried out in one or more distillation steps, and according to some embodiments, the distillation products of each distillation step are blended in a predetermined ratio to obtain a wax product.

[0067] As previously mentioned, the paraffinic products produced by the processes of this disclosure are characterized by a low aromatic content, i.e., less than about 3000 ppm, preferably less than 2000 ppm. The paraffinic products are also characterized by low sulfur content (typically less than 10 ppm), low nitrogen content, low chlorine content, controlled paraffin ratio, etc.

[0068] According to some embodiments, the paraffinic products produced by the processes of this disclosure meet FDA requirements for the amount of polycyclic aromatic hydrocarbons (PAHs).

[0069] According to some embodiments, the oil and solvent products meet the requirements of US FDA Qualitative Testing, 21 CRF §178.3620, and are within the ultraviolet absorbance limits at specified wavelengths: 280-289 nm A<4.0, 290-299 nm A<3.3, 300-329 nm A<2.3, 330-360 nm A<0.8 (Test Method ASTM D2269-99). According to some embodiments, the wax products meet the requirements of FDA 21 CRF §172.886 for maximum ultraviolet absorbance limits for specified path lengths: 280-289 nm A<0.15, 290-299 nm A<0.12, 300-359 nm A<0.08, 360-400 nm A<0.02.

[0070] Thus, according to another aspect of the disclosure, there is provided a paraffinic solvent having a boiling point range of up to about 100°C, an initial boiling point of at least about 85°C, and a final boiling point in the range of about 150°C to about 360°C, wherein the fluid comprises normal paraffinic compounds in the range of about 15 wt% to 65 wt%, isoparaffinic compounds in the range of about 30 wt% to about 75 wt%, cycloparaffinic compounds in the range of about 0 wt% to about 35 wt%, and about 3000 ppm or less of aromatic compounds.

[0071] According to some embodiments, the paraffinic solvent contains about 2000 ppm or less of aromatic compounds.

[0072] According to some embodiments, the paraffinic solvent is obtained by the processes described herein.

[0073] According to some embodiments, the paraffinic solvent comprises C6-C20 paraffinic hydrocarbons. According to other embodiments, the paraffinic solvent consists essentially of paraffinic C6-C20 hydrocarbons.

[0074] According to some embodiments, the percentage ratio between n-paraffins and isoparaffins (ie, percent n-paraffins to percent isoparaffins) in the C6-C20 paraffinic product ranges from about 1:1.2 to about 1:2.5.

[0075] According to another embodiment, the percentage ratio between n-paraffins and isoparaffins in the C6-C20 paraffinic product ranges from about 1:1.5 to about 1:4.5.

[0076] According to some other embodiments, the percentage ratio between n-paraffins and isoparaffins in the C6-C20 paraffinic product ranges from about 1:1.2 to about 1:4.5.

[0077] According to some embodiments, the paraffinic solvent contains less than 3 ppm each of sulfur, chloride, and nitrogen.

[0078] According to some embodiments, the paraffinic solvent has an initial boiling point in the range of about 85° C. to about 110° C., a final boiling point in the range of 155° C. to 180° C., and a viscosity of 0.70 mmHg. 2 / s~0.90mm 2 / s (measured at 25°C according to ASTM D445).

[0079] According to another embodiment, the paraffinic solvent has an initial boiling point in the range of about 135°C to about 160°C, a final boiling point in the range of 185°C to 220°C, and a viscosity of 1.00 mm 2 / s~1.40mm 2 / s (measured at 25°C according to ASTM D445).

[0080] According to some other embodiments, the paraffinic solvent has an initial boiling point in the range of about 170°C to about 195°C, a final boiling point in the range of 235°C to 250°C, and a viscosity of 1.60 mmHg. 2 / s~1.90mm 2 / s (measured at 25°C according to ASTM D445).

[0081] According to some other embodiments, the paraffinic solvent has an initial boiling point in the range of about 190°C to about 210°C, a final boiling point in the range of 245°C to 270°C, and a viscosity of 1.80 mmHg. 2 / s~2.40mm 2 / s (measured at 25°C according to ASTM D445).

[0082] According to yet another embodiment, the paraffinic solvent has an initial boiling point in the range of about 205°C to about 245°C, a final boiling point in the range of 270°C to 290°C, and a viscosity of 1.95 mm 2 / s~3.10mm 2 / s (measured at 25°C according to ASTM D445).

[0083] According to a further embodiment, the paraffinic solvent has an initial boiling point in the range of about 240° C. to about 280° C., a final boiling point in the range of 335° C. to 360° C., and a viscosity of 5.50 mmHg. 2 / s~7.20mm 2 / s (measured at 25°C according to ASTM D445).

[0084] According to some other embodiments, the paraffinic solvent has an initial boiling point in the range of about 240°C to about 260°C, a final boiling point in the range of 310°C to 330°C, and a melting point of 3.30 mmHg. 2 / s~4.70mm 2 / s (measured at 25°C according to ASTM D445).

[0085] Another aspect provides the paraffinic solvents disclosed herein for use in cosmetics, paints, printing inks, plasticizers, degreasers, textiles, explosives manufacturing, detergent manufacturing, self-starting barbecue briquettes, solvent extraction (such as copper), road solvents, and wood preservatives (resins for lumber and foundry applications). Another aspect provides the paraffinic solvents disclosed herein for use as solvents in surfactant production or in pesticide compositions.

[0086] According to another aspect, there is provided an article of manufacture comprising at least one paraffinic solvent disclosed herein, said article of manufacture being selected from cosmetics, paints, plasticizers, degreasers, cleaning agents, explosives, printing inks, self-starting barbecue briquettes, extraction / infusion solutions, road solvents, wood preservatives, and pesticide compositions.

[0087] According to another embodiment, the composition comprises at least 50 wt. % C14-C32 isoparaffinic compounds, preferably at least 95 wt. % C14-C32 isoparaffinic compounds, and has a viscosity of 5.00 mm when measured at 25° C. according to ASTM D445. 2 / s~15.00mm 2 Paraffin oil having a kinematic viscosity in the range of 1000 ppm / s is provided, the fluid containing no more than about 3000 ppm aromatics.

[0088] According to some embodiments, the paraffin oil contains no more than about 2000 ppm aromatic compounds.

[0089] According to some embodiments, the paraffin oil is obtained by the processes described herein.

[0090] According to some embodiments, the paraffin oil has an initial boiling point of at least about 300°C and a final boiling point of at least about 380°C.

[0091] According to some embodiments, the paraffin oil has a boiling point of about 300°C to about 380°C.

[0092] According to some embodiments, the paraffin oil has a boiling point of about 320°C to about 420°C.

[0093] According to another aspect, there is provided the paraffinic oil disclosed herein for use in food processing, cosmetics, pharmaceutical formulations, energy storage devices, agricultural products, as a base oil, metalworking fluids, and alternative biodiesel.

[0094] According to another aspect, there is provided an article of manufacture comprising at least one paraffin oil as disclosed herein, wherein the article of manufacture is selected from food products, cosmetics, pharmaceuticals, energy storage devices, agricultural products, base oils, metalworking fluids, and alternative biodiesel.

[0095] According to yet another embodiment, a paraffinic wax is provided comprising at least 95 wt% C20-C70 normal paraffinic compounds (as determined by GC / MS), an oil content of about 10 wt% to 60 wt%, and no more than about 3000 ppm aromatic compounds.

[0096] According to a further embodiment, there is provided a paraffinic wax comprising at least 85 wt% C20-C70 paraffinic compounds and 3000 ppm or less aromatic compounds, wherein the C20-C70 paraffinic compounds comprise up to about 85 wt% C20-C70 isoparaffins and up to about 60 wt% C20-C70 n-paraffins (as determined by ASTM D5442).

[0097] According to some embodiments, the paraffinic wax contains about 2000 ppm or less of aromatic compounds.

[0098] According to some embodiments, the paraffin wax has a penetration of at least 100 (at 25°C, ASTM D1321), a freezing point of 40-60°C (ASTM D938), and a viscosity of 3-5.5 mm. 2 / s (100°C, ISO3104).

[0099] According to some other embodiments, the paraffin wax has a needle penetration (25°C, ASTM D1321) of 70-105, a freezing point (ASTM D938) of 50-65°C, and a viscosity of 4.5-7.5 mm. 2 / s (100°C, ISO3104).

[0100] According to another embodiment, the paraffin wax has a penetration of 60-95 (at 25°C, ASTM D1321), a freezing point of 60-80°C (ASTM D938), and a viscosity of 7.5-10 mm. 2 / s (100°C, ISO3104).

[0101] According to a further embodiment, the paraffin wax has a needle penetration (25°C, ASTM D1321) of 70-155, a freezing point (ASTM D938) of 50-70°C, and a viscosity of 4.5-8.0 mm. 2 / s (100°C, ISO3104).

[0102] According to yet another embodiment, the paraffin wax has a penetration of 60-120 (at 25°C, ASTM D1321), a freezing point of 55-80°C (ASTM D938), and a viscosity of 7-10 mm. 2 / s (100°C, ISO3104).

[0103] According to some embodiments, the paraffinic wax is obtained by the processes disclosed herein.

[0104] An important parameter for wax manufacturers is a low content of polycyclic aromatic hydrocarbons (PAHs), many of which are toxic, carcinogenic and mutagenic.

[0105] Another aspect provides the paraffinic waxes disclosed herein for use in shoe polish, floor polish, candles, tissue paper softeners, wax paper and paper packaging production, matches, pesticide traps, tire manufacturing, anti-ozonation formulations, lubrication aids, fertilizers, anti-caking aids, agricultural produce, fruit and / or vegetable coatings, hydrophobic coatings, concrete curing, cosmetics, hot melt adhesives (food grade), mining, road applications (road resin markings, bitumen extenders), fatty acid derivatives, PVC stabilizers, and wax emulsions.

[0106] According to another aspect, there is provided an article of manufacture comprising the paraffin-based wax disclosed herein, wherein the article of manufacture is selected from shoe polish, floor polish, candles, tissue paper softening formulations, wax paper, wax paper packaging, matches, pesticide traps, tires, anti-ozonation formulations, lubrication aids, fertilizers, anti-caking aids, produce, fruit and / or vegetable coatings, hydrophobic coatings, concrete hardeners, cosmetics, hot melt adhesives, PVC stabilizers, and wax emulsions.

[0107] As previously mentioned, the residue, solids, and hearths separated from the pyrolysis reactor during thermocracking can be used as stand-alone products. Thus, another aspect of this disclosure provides a solid product obtained by the process of this disclosure, comprising a thermocracking residue having a total solids, i.e., coke / carbon and ash content of at least 30 wt. %, and a heating value of at least 30 MJ / kg.

[0108] According to some embodiments, the solid product comprises at most 0.5 wt% sulfur, at most 0.5 wt% nitrogen, at most 0.3 wt% chlorine, and / or at most 0.01 ppm mercury.

[0109] According to some other embodiments, the solid product comprises about 5-15 wt% hydrogen.

[0110] According to another embodiment, the solid product comprises about 30-95 wt% volatile components.

[0111] According to another aspect of the present disclosure, there is provided a manufacturing facility for processing polyolefin waste into a paraffinic product having an aromatics content of up to 2000 ppm, the facility including: (A) a thermocracking reactor for receiving a mixture of polyolefins in a molten state and thermocracking said mixture to obtain a hydrocarbon vapor stream, the thermocracking reactor configured to operate under conditions including: (i) a pressure of up to 1 barg, (ii) a temperature in the range of about 320°C to about 450°C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the thermocracking reactor of about 2 to about 40 hours; (B) a quench tower in fluid communication with the thermolysis reactor and configured to receive the hydrocarbon vapor stream, remove volatile C1-C5 volatile compounds therefrom, and quench the remainder of the hydrocarbon vapor stream to obtain a condensate stream; (C) a main catalytic hydrotreating unit fluidly connected to the quench tower and configured to hydrotreat the condensate stream to obtain a hydrotreated stream; (D) a pressurized separation column fluidly connected to the main catalytic hydrotreating unit and configured to separate the hydrotreated stream into the following product streams: (i) a C6-C20 product stream having a boiling point of from about 60°C to about 330°C; (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C; and (iii) a C20-C70 product stream having a boiling point of at least about 350°C; and (E) one or more processing units in fluid communication with the pressurized separation column, the one or more processing units each configured to receive one of the product streams and process the product stream therein to obtain the paraffinic product.

[0112] According to some embodiments, the one or more processing units of the facility include at least one catalytic hydrotreating unit for hydrotreating the C6-C20 product stream, and at least one solvent distillation column for distilling the C6-C20 product stream after hydrotreating to obtain a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm, preferably up to about 2000 ppm.

[0113] According to some embodiments, the one or more processing units of the facility include at least one catalytic hydrotreating unit for hydrotreating the C14-C32 product stream, and at least one oil distillation column for distilling the C14-C32 product stream after hydrotreating to obtain a C14-C32 paraffinic product having an aromatics content of up to 3000 ppm.

[0114] According to some embodiments, the facility may operate at a temperature of about 320°C to about 360°C, a pressure of at least 25 barg, and at least 150 Nm 3 / m 3 a catalytic hydrotreating unit for treating said C14-C32 product stream under conditions comprising a hydrogen to C14-C32 product stream ratio of

[0115] According to some other embodiments, the facility includes two catalytic hydrotreating units arranged in series for treating the C14-C32 product stream at a temperature of about 310°C to about 360°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm 3 / m 3 a first catalytic hydrotreating unit for hydrotreating the C14-C32 product stream under conditions comprising a hydrogen to C14-C32 product stream ratio of at least 150 Nm; followed by a temperature of from about 170°C to about 300°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm 3 / m 3 a second catalytic hydrotreating unit for hydrotreating the product received from the first catalytic hydrotreating unit under conditions comprising a hydrogen to C14-C32 product stream ratio of

[0116] According to some embodiments, one or more processing units of the facility include at least one wax distillation column for distilling the C20-C70 product stream to obtain a C20-C70 paraffinic product having an aromatics content of up to 3000 ppm.

[0117] According to some embodiments, the facility further comprises at least one extruder for obtaining said melt of polyolefin prior to introduction into the thermolysis reactor.

[0118] According to some embodiments, the thermolysis reactor includes a heated circulation loop defined between the reactor circulation outlet and the reactor circulation inlet for circulating a portion of the mixture therethrough during thermocracking.

[0119] According to some embodiments, the facility further includes at least one guard bed reactor comprising at least one guard bed catalyst and disposed between the quench tower and the main hydrotreating unit and configured to receive the condensate stream from the quench tower and process the condensate stream therein to remove contaminants therefrom prior to hydrotreating.

[0120] According to some embodiments, the facility includes at least one contaminant trap disposed between the quench tower and the main hydrotreating unit and configured to receive the condensate stream from the quench tower and remove one or more contaminants from the condensate stream prior to hydrotreating.

[0121] As used herein, the term about is meant to encompass a ±10% deviation from the specifically stated value of a parameter, such as temperature, pressure, concentration, etc.

[0122] Whenever a numerical range is given herein, it is meant to include all recited numbers (fractional or integer) within the given range. The phrases "range" between a first indicated number and a second indicated number, and "range" from a first indicated number to a second indicated number, are used interchangeably herein and are meant to include the first and second indicated numbers and all fractional and integer numbers therebetween.

[0123] The phrase consisting essentially of is meant to indicate a composition or mixture that contains at least 98 wt% of a single component.

[0124] ppm is meant to indicate parts per million.

[0125] Throughout this specification and the claims that follow, unless the content requires otherwise, the word comprises, and variations thereof, such as comprises and compris- ing, will be understood to imply the inclusion of a stated integer or step or group of integers or steps, but not the exclusion of any integer or step or group of integers or steps.

[0126] In general, it is indicated that the term at least one as applied to any component of a product or process should be understood to encompass one, two, three, four, five, or more different instances of said component in the products or processes disclosed herein.

[0127] It will be appreciated that certain features of the present disclosure, which are described for clarity in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the disclosure, which are described for clarity in the context of a single embodiment, may also be provided separately or in any suitable subcombination, or as suitable in any other described embodiment of the disclosure. Certain features described in the context of various embodiments should not be considered essential features of those embodiments, unless the embodiment cannot function without those elements.

[0128] The processes of the present disclosure include many process steps, which may or may not be linked with other common physical-chemical processes to achieve the desired purity and morphology of each product. Unless otherwise specified, such process steps, if any, may be arranged in a different order so long as this does not affect the process's processability and its effectiveness in achieving the desired end result. As one skilled in the art will recognize, the sequence of steps may be adopted or modified depending on various economic considerations, material availability, raw materials, environmental considerations, etc.

[0129] For a better understanding of the subject matter disclosed herein, and to illustrate how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0130] [Figure 1] 1 is a schematic diagram of an exemplary process and facility according to one embodiment of the disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0131] An exemplary process and facility for carrying out the process according to one embodiment of the disclosure is shown in Figure 1. In Figure 1, the following acronyms are used: MSW-Mixed Solid Waste Preparation Unit FPU - Feed Preparation Unit CSTR - Thermocracking Reactor FL-Filter HT-Heater GB-Guard Beads MHT - Main Hydrotreater LES - Right End Stabilizer Column MFC - Main fractionation column AHT - Aromatic Hydrotreater IHT - Isomerization Hydrotreater FHT - Finishing Hydrotreater SD - Solvent Distillation OD - Oil Distillation WD - Wax Distillation WBM - Wax Blend Mixer

[0132] Returning to Figure 1, an exemplary process and facility for carrying out a process according to this disclosure is shown. The process shown in Figure 1 begins with a feedstock that includes, and sometimes consists of, a polyolefin mixture. The mixture is prepared in a mixed solid waste (MSW) preparation unit and transferred to a feed preparation unit (FPU), which typically includes at least one dryer and one extruder for drying, blending, and melting the polyolefin feedstock.

[0133] The molten mixture is fed into a thermocracking reactor (CSTR), where thermocracking of the mixture occurs, breaking down the long polyolefin chains into shorter hydrocarbon molecules. Solids are continuously removed from the CSTR, while a portion of the mixture is circulated through a forced circulation loop. In the circulation loop, a portion of the mixture is circulated back into the CSTR via a heater (HT). Such circulation facilitates better control over the overall temperature of the mixture and allows the portion of the mixture circulated through the loop to be heated to a higher temperature than in the CSTR. Because the viscosity of the melt in the reactor is relatively high, it is difficult to control the temperature uniformity within the melt; continuous circulation of a portion of the contents of the thermolysis reactor through the heated circulation loop allows for better control over the melt temperature and better control of the residence time, while also exposing a small portion of the melt (i.e., the circulated portion) to a higher temperature than that maintained in the reactor for a short period (during its passage through the loop), allowing for proper heating of the mixture, while also minimizing undesirable coke formation due to the short residence time in the loop.

[0134] Thermocracking is carried out under conditions including: (i) a pressure of up to 1 barg, preferably up to 0.5 barg; (ii) a temperature ranging from about 320°C to about 450°C, preferably from about 350°C to 420°C; (iii) the absence of oxygen; and (iv) a residence time of the mixture in the thermocracking reactor of 2 to 40 hours, preferably from about 4 to about 6 hours. Such conditions are optimal for obtaining a wide range of hydrocarbon fractions in the disclosed process, which are utilized in the process to produce a wide range of end products from a single thermocracking step. Additionally, such conditions are designed to maximize the formation of heavy products (e.g., waxy products) and minimize the formation of coke.

[0135] The pyrolysis products exit the CSTR as a hydrocarbon vapor stream and are quenched in a quench tower, where the condensable gaseous hydrocarbons (C<) are condensed into a condensate stream, while the lighter products (C-C) are released as gases and recovered for further use as an energy source or as gas products.

[0136] The condensate stream is then transferred to a main hydrotreating unit (MHT) where catalytic hydrotreating occurs to reduce the content of aromatic and olefinic hydrocarbons in the stream by hydrogenating the multiple bonds in the unsaturated hydrocarbons. In addition to reducing the multiple bonds, the hydrotreating conditions applied in this process also allow for the rapid removal of heteroatoms and non-hydrocarbon compounds by converting them into volatile compounds (e.g., sulfur-organic compounds as hydrogen sulfide, nitrogen-containing compounds as ammonia, and oxygen-containing compounds as water).

[0137] Importantly, contrary to known processes, in the disclosed process the entire condensate stream is hydrotreated without fractionation. Such hydrotreating of the entire range of thermocracking products allows a wide range of hydrocarbons to be obtained in a single hydrotreating step, together with efficient reduction of olefin and aromatic content. This allows a wide range of products to be obtained from a homogeneous, integrated manufacturing process with careful control over aromatic content.

[0138] Typically, the MHT in processes according to this disclosure involves a temperature of about 250°C to about 340°C, a pressure of at least 45 barg, and a pressure of at least 150 Nm 3 / m 3 The MHT is operated under conditions including a hydrogen to condensate stream ratio of 0.01 to 0.05 (normal lube / cubic meter). Such conditions have been found to maximize hydrotreating efficiency while also preventing undesirable polymerization of hydrocarbons in the MHT.

[0139] Because the MHT catalyst can be highly sensitive to poisoning, most particularly silicon poisoning, the condensate stream can be fed to the MHT through at least one guard bed (GB), which typically contains at least one guard bed catalyst to remove undesirable contaminants. Additionally (or alternatively), the condensate stream can be passed through one or more traps (not shown) to remove contaminants from the condensate stream, e.g., remove metals, silicon, halides, phosphorus, etc., from the stream, before feeding into the MHT.

[0140] The hydrotreated stream can be processed in a light ends stabilizer column (LES) to remove additional C1-C5 gaseous hydrotreatment products that may be contained in the hydrotreated stream, from which the C6< hydrotreated stream is typically fed to a main fractionation column (MFC) for separation into fractions based on boiling point and molecular weight. The MFC can be, for example, a tray or packed column and is typically operated at atmospheric pressure and heated to about 330°C. Three main product streams are obtained from the MFC: (i) a C6-C20 product stream having a boiling point of about 60°C to about 330°C, (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C, and (iii) a C20-C70 product stream having a boiling point of at least about 350°C.

[0141] Each of these product streams is then processed in one or more processing steps to obtain the final paraffinic product.

[0142] The C6-C20 stream is first catalytically hydrotreated in an aromatics hydrotreating unit (AHT) to further reduce the aromatic content of the light fraction. Low-boiling aromatics are particularly undesirable in the solvent because they can pose a health hazard. The stream is then distilled in at least one solvent distillation column (SD) to obtain a C6-C20 paraffinic product, i.e., solvent, having an aromatics content of at most 3000 ppm, preferably at most 2000 ppm. Catalytic hydrotreating in the AHT is carried out at temperatures of about 170°C to about 300°C, pressures of at least 45 barg, and pressures of at least 150 Nm 3 / m 3 The process can be carried out under conditions including a hydrogen to condensate stream ratio of 0.05 to 0.05 (normal lube / cubic meter). These conditions aim for significant aromatic conversion but also avoid overheating, which can lead to undesirable side reactions.

[0143] SD can involve multiple distillation stages performed in sequence, from each of which a different solvent fraction can be isolated as a separate solvent product depending on its boiling point. Thus, various solvents with different boiling ranges can be obtained by varying the distillation column parameters and / or by using two or more solvent distillation columns arranged in series.

[0144] The C14-C32 product stream is also catalytically hydrotreated. In the illustrated process, the C14-C32 product stream is first catalytically hydrotreated in an isomerization hydrotreating unit (IHT) and then in a finishing hydrotreating unit (FHT), and then distilled in one or more oil distillation columns (OD) to obtain a C14-C32 paraffinic oil product having an aromatics content of up to 3000 ppm, preferably up to 2000 ppm. According to some embodiments, the C14-C32 is an isoparaffinic oil. The purpose of the IHT is primarily to isomerize the linear paraffins of this hydrocarbon fraction into branched paraffins to obtain an oil product having an improved cloud point of less than -10 ° C and an oil pour point of less than -20 ° C, while the purpose of the FHT is to convert the remaining unsaturated hydrocarbons to saturated hydrocarbons, thereby further reducing the aromatics content in the resulting oil product.

[0145] IHT involves a temperature of about 310°C to about 360°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm 3 / m 3 The FHT can be carried out under conditions including a hydrogen to C14-C32 product stream ratio of at least 1.5%. The FHT is typically carried out at a temperature of about 170°C to about 300°C, a pressure of at least 25 barg, and at least 150 Nm 3 / m 3 The process is carried out under conditions comprising a hydrogen to C14-C32 product stream ratio of

[0146] After distillation at OD, a C14-C32 paraffinic oily product is obtained having an aromatics content of up to 2000 ppm, which contains at least 50 wt. % C14-C32 isoparaffinic compounds, preferably at least 95 wt. % C18-C27 isoparaffinic compounds and an average molecular weight of 5.00 mm as measured at 25°C according to ASTM D445. 2 / s~15.00mm 2 The oil obtained after distillation typically has a boiling point of about 300°C to about 380°C.

[0147] The C20-C70 product stream is distilled in one or more wax distillation columns (WD). In this example, two wax distillation columns, WD1 and WD2, arranged in series, are utilized. The wax products obtained from WD1 and WD2 can be standalone wax products; however, they can also be mixed in a wax blend mixer (WMB) to obtain a paraffinic wax product.

[0148] Tables 1-1 and 1-2 below show the compositions of various streams in processes according to this disclosure starting from different waste polyolefin feedstocks. [Table 1] [Table 2]

[0149] Exemplary products obtained by the process of this disclosure Tables 2-1 and 2-2 provide analytical data for various paraffinic solvents obtained by the process of this disclosure from different waste polyolefin feedstocks. Tables 2-3 through 2-5 show the chemical compositions of the various solvent fractions obtained for the different feedstocks. Table 2-4 provides additional paraffinic solvent products obtained by a process according to another embodiment of this disclosure. [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0150] Table 3 provides analytical data for the paraffinic oil product obtained by the process of this disclosure. [Table 9]

[0151] Tables 4-1 and 4-2 provide analytical data for the paraffinic wax obtained by the process of this disclosure. [Table 10] [Table 11]

[0152] Table 5 provides analytical data for the solid product, namely the dried hearth bottoms, obtained by the process of this disclosure. [Table 12]

Claims

1. 1. A process for obtaining a paraffinic product having an aromatics content of up to about 3000 ppm from a mixture of polyolefins, the process comprising: (a) thermocracking said mixture in a molten state in a thermocracking reactor under conditions comprising: (i) a pressure of up to 1 barg, (ii) a temperature in the range of about 320°C to about 450°C, (iii) the absence of oxygen, and (iv) a residence time of said mixture in said thermocracking reactor of 2 to 40 hours to obtain a hydrocarbon vapor stream; (b) removing volatile C1-C5 compounds from said hydrocarbon vapor stream and quenching the remainder of said hydrocarbon vapor stream to obtain a condensate stream; (c) transferring the condensate stream into a main catalytic hydrotreating unit to obtain a hydrotreated stream; (d) separating the hydrotreated stream into the following product streams: (i) a C6-C20 product stream having a boiling point of from about 60°C to about 330°C; (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C; and (iii) a C20-C70 product stream having a boiling point of at least about 350°C; and (e) further processing each of said product streams to obtain a paraffinic product. and the paraffinic product comprises (i) a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) a C14-C32 paraffinic product having an aromatics content of up to about 3000 ppm; and (iii) C20-C70 paraffinic products having an aromatics content of up to about 3000 ppm. The process includes:

2. 2. The process of claim 1, wherein the C6-C20 paraffinic product, the C14-C32 paraffinic product, and / or the C20-C70 paraffinic product have an aromatics content of up to about 2000 ppm.

3. 3. The process of claim 1 or 2, wherein the C6-C20 paraffinic product, the C14-C32 paraffinic product, or the C20-C70 paraffinic product each has an aromatics content of up to about 2000 ppm.

4. 4. The process of any one of claims 1 to 3, wherein the thermolysis reactor comprises a heating circulation loop defined between a circulation outlet and a circulation inlet for circulating a portion of the mixture therethrough during thermocracking.

5. 5. The process of claim 4, wherein the temperature in the circulation loop is from about 400°C to about 450°C.

6. 6. The process of claim 4, wherein the portion of the mixture in the circulation loop during thermocracking is from about 2% to about 50% of the volume of the thermolysis reactor.

7. The process of any one of claims 1 to 6, wherein step (a) further comprises removing solid residue from the thermolysis reactor.

8. The process of any one of claims 1 to 7, wherein the main catalytic hydrotreating unit operated in step (c) is carried out under conditions comprising: a temperature of about 250°C to about 340°C; a pressure of at least 45 barg, and At least 150 Nm ３ / m ３ of hydrogen to condensate stream ratio.

9. 9. The process of claim 8, wherein the difference between the inlet temperature of the second stream to the main catalytic hydrotreating unit and the temperature in the main catalytic hydrotreating unit is at most 50°C.

10. 10. The process of claim 8 or 9, wherein the main catalytic hydrotreating utilizes at least one Ni-Mo catalyst.

11. The process of any one of claims 1 to 10, wherein step (e) comprises treating each of the product streams as follows: (i) catalytically hydrotreating said C6-C20 product stream followed by distillation in at least one solvent distillation column to obtain said C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) catalytically hydrotreating said C14-C32 product stream followed by distillation in at least one oil distillation column to obtain said C14-C32 paraffinic product having an aromatics content of up to about 3000 ppm; and (iii) distilling said C20-C70 product stream in at least one wax distillation column to obtain said C20-C70 paraffinic product having an aromatics content of up to about 3000 ppm.

12. 11. The process of claim 10, wherein catalytically hydrotreating the C6-C20 product stream in step (e) is carried out under conditions comprising: a temperature of about 170°C to about 300°C; a pressure of at least 45 barg, and At least 150 Nm ３ / m ３ of hydrogen to condensate stream ratio.

13. 13. The process of claim 12, wherein the catalytic hydrotreating of the C6-C20 product stream in step (e) utilizes at least one Ni-catalyst or noble metal catalyst.

14. Catalytically hydrotreating the C14-C32 product stream in step (e) comprises hydrotreating the C14-C32 product stream at a temperature of from about 310° C. to about 360° C., a pressure of at least 25 barg, and at least 150 Nm ３ / m ３ 14. The process of any one of claims 10 to 13, carried out under conditions comprising a hydrogen to C14-C32 product stream ratio of

15. The process of any one of claims 10 to 13, wherein catalytically hydrotreating the C14-C32 product stream in step (e) is carried out in two sequential hydrotreating steps: The C16-C32 product stream is subjected to a temperature of from about 310°C to about 360°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm ３ / m ３ step (e1) comprising hydrotreating under conditions comprising a hydrogen to C14-C32 product stream ratio of The product of step (e1) is subjected to a temperature of about 170°C to about 300°C, a pressure of at least 25 barg, and a pressure of at least 150 Nm ３ / m ３ Step (e2) comprising hydrotreating under conditions comprising a hydrogen to C14-C32 product stream ratio of

16. 16. The process of any one of claims 1 to 15, wherein the condensate stream of step (b) is passed through at least one guard bed reactor containing at least one guard bed catalyst before being introduced into step (c).

17. 17. The process of claim 16, wherein the temperature in the at least one guard bed reactor is from about 290°C to about 340°C.

18. The hydrogen to condensate stream ratio in the at least one guard bed reactor is about 150 Nm ３ / m ３ 18. The process of claim 16 or 17, wherein

19. The process of any one of claims 1 to 18, wherein the mixture of polyolefins comprises polyethylene and polypropylene.

20. 20. The process of claim 19, wherein the mixture comprises polyethylene in an amount ranging from 10 wt% to 90 wt% and polypropylene polyethylene in an amount ranging from 10 wt% to 90 wt%.

21. 20. The process of claim 19, wherein the mixture consists essentially of polyethylene.

22. 20. The process of claim 19, wherein the mixture consists essentially of polypropylene.

23. The process of any one of claims 1 to 22, wherein the mixture comprises up to 10 wt% polystyrene.

24. The process of any one of claims 1 to 23, wherein the mixture comprises up to 5 wt% of a non-polyolefin polymer other than polystyrene.

25. 1. Paraffinic solvents having a boiling range of up to 100°C, an initial boiling point of at least 85°C, and a final boiling point in the range of 150°C to 360°C, including: Normal paraffinic compounds in the range of about 15 wt% to 65 wt%; isoparaffinic compounds in the range of about 30 wt % to about 75 wt %; cycloparaffinic compounds in the range of about 0 wt % to about 35 wt %; and About 3000 ppm or less aromatic compounds.

26. 26. The paraffinic solvent of claim 25 containing less than 1 wt% each of sulfur, chloride and nitrogen.

27. An initial boiling point in the range of about 85°C to about 110°C, and a final boiling point in the range of 155°C to 180°C, and a viscosity of 0.70 mm ２ / s ~ 0.90 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

28. An initial boiling point in the range of about 135°C to about 160°C, a final boiling point in the range of 185°C to 220°C, and a ２ / s ~ 1.40 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

29. An initial boiling point in the range of about 170°C to about 195°C, a final boiling point in the range of 235°C to 250°C, and a ２ / s ~ 1.90 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

30. An initial boiling point in the range of about 190°C to about 210°C, a final boiling point in the range of 245°C to 270°C, and a ２ / s ~ 2.40 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

31. An initial boiling point in the range of about 205°C to about 245°C, a final boiling point in the range of 270°C to 290°C, and a ２ / s ~ 3.10 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

32. An initial boiling point in the range of about 240°C to about 280°C, a final boiling point in the range of 335°C to 360°C, and a ２ / s ~ 7.20 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

33. An initial boiling point in the range of about 240°C to about 260°C, a final boiling point in the range of 310°C to 330°C, and a ２ / s ~ 4.70 mm ２ 27. The paraffinic solvent of claim 25 or 26, having a kinematic viscosity (measured at 25°C according to ASTM D445) in the range of 1 / s.

34. A paraffinic solvent according to any one of claims 25 to 33, obtainable by a process according to any one of claims 1 to 24.

35. 34. The paraffinic solvent according to any one of claims 25 to 33 for use in cosmetics, paints, printing inks, plasticizers, degreasers, textile industry, explosives manufacturing, detergent manufacturing, self-starting barbecue briquettes, solvent extraction (such as copper), road solvents, and wood preservatives.

36. % C14-C32 isoparaffinic compounds, preferably at least 95 wt. % C14-C32 isoparaffinic compounds, and having a viscosity of 5.00 mm when measured at 25°C according to ASTM D445. ２ / s ~ 15.00 mm ２ / s, wherein the fluid contains no more than about 3000 ppm aromatic compounds.

37. 37. The paraffin oil of claim 36, having an initial boiling point of at least about 300°C and a final boiling point of at least about 380°C.

38. Paraffin oil according to claim 36 or 37, obtainable by a process according to any one of claims 1 to 24.

39. 39. The paraffin oil according to any one of claims 36 to 38 for use in food processing, cosmetics, pharmaceutical preparations, energy storage devices, agricultural products, applications as base oils, metal working fluids, and alternative biodiesel.

40. A paraffinic wax comprising at least 95 wt% C20-C70 normal paraffinic compounds (as determined by GC / MS), an oil content of about 10 wt% to 60 wt%, and no more than about 3000 ppm aromatic compounds.

41. 1. A paraffinic wax comprising at least 85 wt. % C20-C70 paraffinic compounds, the C20-C70 paraffinic compounds comprising up to about 85 wt. % C20-C70 isoparaffins and up to about 60 wt. % C20-C70 n-paraffins (as determined by ASTM D5442), and up to about 3000 ppm aromatic compounds.

42. A paraffinic wax according to claim 40 or 41, obtainable by a process according to any one of claims 1 to 24.

43. 43. The paraffinic wax according to any one of claims 40 to 42 for use in shoe polish, floor polish, candles, tissue softening, production of wax paper and paper packaging, matches, pesticide traps, tire manufacturing, anti-ozonation formulations, lubrication aids, anti-caking aids, agricultural produce, fruit and / or vegetable coatings, hydrophobic coatings, concrete curing, fertilizers, cosmetics, hot melt adhesives (food grade), mining, road applications (road resin markings, bitumen extenders), fatty acid derivatives, PVC stabilizers, and wax emulsions.

44. 25. A solid product obtained by the process of any one of claims 1 to 24, comprising a thermocracking residue having a total solids (coke / carbon and ash) content of at least 50 wt. % and a heating value of at least 30 MJ / kg.

45. 45. The solid product of claim 44, comprising at most 0.5 wt% sulfur, at most 0.5 wt% nitrogen, at most 0.3 wt% chlorine, and / or at most 0.01 ppm mercury.

46. 46. ​​The solid product of claim 44 or 45, comprising about 5 wt% to 15 wt% hydrogen.

47. 47. The solid product of any one of claims 44 to 46, comprising about 30 wt% to 95 wt% of volatile components.

48. 1. A process for recycling polyolefin waste, said process comprising: (a) thermocracking said polyolefin waste in a molten state in a thermocracking reactor under conditions comprising: (i) a pressure of up to 1 barg, (ii) a temperature in the range of about 320°C to about 450°C, (iii) the absence of oxygen, and (iv) a residence time of said mixture in said thermocracking reactor of 2 to 40 hours to obtain a hydrocarbon vapor stream; (b) removing volatile C1-C5 compounds from said hydrocarbon vapor stream and quenching the remainder of said hydrocarbon vapor stream to obtain a condensate stream; (c) transferring the condensate stream into a main catalytic hydrotreating unit to obtain a hydrotreated stream; (d) separating the hydrotreated stream into the following product streams: (i) a C6-C20 product stream having a boiling point of from about 60°C to about 330°C; (ii) a C14-C32 product stream having a boiling point of about 300°C to about 450°C; and (iii) a C20-C70 product stream having a boiling point of at least about 350°C; and (e) further processing each of said product streams to obtain said paraffinic product. wherein the paraffinic product comprises (i) a C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) a C14-C32 paraffinic product having an aromatics content of up to about 3000 ppm; and (iii) C20-C70 paraffinic products having an aromatics content of up to about 3000 ppm. The process includes:

49. The further processing in step (e) comprises: (i) catalytically hydrotreating said C6-C20 product stream followed by distillation in at least one solvent distillation column to obtain said C6-C20 paraffinic product having an aromatics content of up to about 3000 ppm; (ii) catalytically hydrotreating said C14-C32 product stream followed by distillation in at least one oil distillation column to obtain said C14-C32 paraffinic product having an aromatics content of up to about 3000 ppm; and (iii) distilling said C20-C70 product stream in at least one wax distillation column to obtain said C20-C70 paraffinic product having an aromatics content of up to about 3000 ppm.

47. The process of claim 46, comprising:

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