Method for recovering plastic waste and high-value product produced by such method

Abstract

The present disclosure relates to a process for recovering plastic waste by a combination of thermal cracking and catalytic hydrotreating under defined conditions to obtain various high value paraffin products with high purity and reduced aromatics content. The present disclosure also relates to high purity paraffin products, such as solvents, oils and waxes having an aromatic content of at most 3000 ppm, produced by the process.

Description

Technical Field

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

[0002] The following lists references considered as background relevant to the currently disclosed subject matter:

[0003] -WO2010 / 049824

[0004] -WO2010 / 106399

[0005] -WO2010 / 116211

[0006] -WO2010 / 136850.

[0007] The confirmation of the above references herein should not be construed as meaning that these references are relevant to the patentability of the currently disclosed subject matter in any way.

[0008] Background

[0009] In the past few decades, the awareness of the necessity of waste recycling has increased significantly, recognizing that traditional disposal methods (such as landfilling or incineration) have a huge negative impact on the environment and ecology. The main concern lies in the insufficient recycling process of municipal waste. Although currently almost 50% of municipal waste in the EU is recycled (according to Eurostat, the EU produced 502 kg of waste per capita during 2019, of which 48% was recycled or composted), the recycling rate in other first-world countries is much lower. For example, in the United States, only 9% of the municipal solid waste generated during 2018 was recycled. According to the US Environmental Protection Agency, 292 million tons of municipal solid waste were generated during 2018, of which approximately 58% was attributable to household paper, food, and plastic waste; but only 69 million tons were recycled or composted, and most of it (more than 66%) was the recycling of paper waste.

[0010] The main components of municipal and industrial waste are polyolefins, which are used in a variety of household products (mainly packaging) and agricultural needs (such as greenhouses and irrigation pipes). Since only some of the polyolefin waste is recycled into new polyolefin products, it would be beneficial to provide a recycling method capable of obtaining high-value products from additional polyolefin plastic waste. Summary of the Invention

[0011] The present disclosure provides an industrial recycling method for polyolefin waste to obtain high-purity high-value products such as solvents, oils, and waxes. The products produced by the method of the present disclosure have a low aromatic compound content, generally less than 3000 ppm (e.g., less than 2000 ppm (0.2 wt%)), and meet FDA requirements and cosmetology requirements. In the method of the present disclosure, high-value by-products are also produced, which can be used as fuels or as additives / modifiers for asphalt and tar substances due to their high calorific value.

[0012] Some unique features of the method of the present disclosure are the wide range of products obtainable, which is mainly attributed to the wide range of intermediates generated during the pyrolysis step and the subsequent hydrotreating process. The hydrotreating process is configured to treat the pyrolysis products as a whole and then separate them into different hydrocarbon fractions. Thus, the method of the present disclosure is capable of obtaining multiple products with low aromatic compound content and low impurity content from the same polyolefin feedstock in an integrated process.

[0013] According to one aspect of the present disclosure, there is provided a method for obtaining a paraffinic product having an aromatic compound content of at most about 3000 ppm from a polyolefin mixture, the method comprising:

[0014] (a) In a pyrolysis reactor, pyrolyzing the molten mixture under conditions including: (i) a pressure of at most 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 pyrolysis reactor in the range of about 2 to about 40 hours to obtain a hydrocarbon vapor stream;

[0015] (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;

[0016] (c) Transferring the condensate stream to a main catalytic hydrotreating unit to obtain a hydrotreated stream;

[0017] (d) Separating the hydrotreated stream into product streams:

[0018] (i) A C6-C20 product stream having a boiling temperature in the range of about 60 °C to about 330 °C,

[0019] (ii) A C14-C32 product stream having a boiling temperature in the range of about 300 °C to about 450 °C, and

[0020] (iii) A C20-C70 product stream having an initial boiling temperature of at least about 350 °C; and

[0021] (e) Further process each of the product streams to obtain the paraffinic products, the paraffinic products comprising:

[0022] (i) A C6-C20 paraffinic product having an aromatic compound content of at most about 3000 ppm,

[0023] (ii) A C14-C32 paraffinic product having an aromatic compound content of at most about 3000 ppm, and

[0024] (iii) A C20-C70 paraffinic product having an aromatic compound content of at most about 3000 ppm.

[0025] According to another aspect, there is provided a method for recycling polyolefin waste, comprising:

[0026] (a) In a pyrolysis reactor, thermally crack a molten waste polyolefin mixture under conditions including: (i) a pressure of at most 1 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between about 2 and about 40 hours to obtain a hydrocarbon vapor stream;

[0027] (b) Remove volatile C1-C5 compounds from the hydrocarbon vapor stream and quench the remainder of the hydrocarbon vapor stream to obtain a condensed stream;

[0028] (c) Transfer the condensed stream to a main catalytic hydrotreating unit to obtain a hydrotreated stream;

[0029] (d) Separate the hydrotreated stream into product streams:

[0030] (i) A C6-C20 product stream having a boiling temperature between about 60 °C and about 330 °C,

[0031] (ii) A C14-C32 product stream having a boiling temperature between about 300 °C and about 450 °C, and

[0032] (iii) A C20-C70 product stream having a boiling temperature of at least about 350 °C; and

[0033] (e) Further process each of the product streams to obtain the paraffinic products, the paraffinic products comprising:

[0034] (i) A C6-C20 paraffinic product having an aromatic compound content of at most 3000 ppm,

[0035] (ii) A C14-C32 paraffinic product with an aromatic compound content of at most about 3000 ppm, and

[0036] (iii) A C20-C70 paraffinic product with an aromatic compound content of at most about 3000 ppm.

[0037] According to some embodiments, the aromatic compound content of the C6-C20 paraffinic product, the C14-C32 paraffinic product, and / or the C20-C70 paraffinic product is at most about 2000 ppm.

[0038] According to some other embodiments, the aromatic compound content of each of the C6-C20 paraffinic product, the C14-C32 paraffinic product, or the C20-C70 paraffinic product is at most about 2000 ppm.

[0039] In the method of the present disclosure, a polyolefin mixture is used as a raw material. The term "polyolefin" (or "poly(ene)") means a linear, branched, crosslinked, or block polymer composed of or derived from olefin monomers. Polyolefins are typically obtained from plastic waste (e.g., sorted plastic waste) with or without virgin or unprocessed polyolefins.

[0040] According to some embodiments, the polyolefin mixture contains polyethylene and polypropylene. According to some other embodiments, the polyolefin mixture contains polyethylene in an amount between 10 wt% and 90 wt% and polypropylene in an amount between 10 wt% and 90 wt%.

[0041] According to some embodiments, the polyolefin mixture consists essentially of polyethylene. According to other embodiments, the polyolefin mixture consists essentially of polypropylene.

[0042] According to some embodiments, the polyolefin mixture contains at most 10 wt% of polystyrene. According to some embodiments, the polyolefin mixture contains at most 5 wt% of polystyrene.

[0043] According to some embodiments, the polyolefin mixture contains at most 5 wt% of non-polyolefin polymers other than polystyrene (e.g., polyvinyl chloride, polyethylene terephthalate, acrylonitrile butadiene styrene, nylon, polyurethane, etc.).

[0044] According to some embodiments, the method includes a pre-step before step (a), or pre-treats the raw material. For example, when the raw material contains plastic waste, the pre-treatment of the raw material may include one or more of the following steps: separating the polyolefin from the waste, washing the waste with water, dehydrating the waste, pulverizing the waste, and removing contaminants and / or substances of interest from the waste.

[0045] In step (a), the polyolefin mixture is fed into the thermocracking reactor in a molten state. According to some embodiments, the melting of the polyolefin mixture is obtained by extrusion.

[0046] In step (a) of the method, the molten mixture is thermally cracked into smaller hydrocarbon molecules. Thermocracking (also known as thermal cracking) means the decomposition of polymeric materials by temperature. Different from typical thermal processes for treating plastic waste, in this thermocracking process, the decomposition is carried out under inert atmosphere conditions, thus reducing the amount of unwanted coke and promoting the random scission mechanism, which produces a heterogeneous mixture of paraffins, olefins and aromatic compounds with a wide range of chain lengths.

[0047] In step (a), the thermocracking is carried out under the following conditions: (i) a pressure of at most 1 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between about 2 and about 40 hours.

[0048] In the method of the present disclosure, the combination of conditions allows for a high yield of hydrocarbon vapor products to be obtained from the polyolefin mixture with the formation of a very small amount of coke.

[0049] The temperature in the pyrolysis reactor is maintained in the range of 320 °C - 450 °C, which is lower than typical plastic waste processing processes. According to some embodiments, the temperature in the pyrolysis reactor is between about 350 °C and about 420 °C. Higher temperatures are utilized in typical waste treatment processes to promote the formation of low molecular weight volatile products, while relatively lower temperatures are utilized in step (a) of the present method, allowing for a wide range of condensable hydrocarbon chain lengths to be obtained, thus enabling a wide range of final products (as will be further described below) to be obtained. The low temperature also minimizes secondary reactions regarding the formation of aromatic compounds and the degradation / cracking of wax components.

[0050] The pressure inside the pyrolysis reactor is maintained not exceeding about 1 barg, and according to some embodiments not exceeding about 0.5 barg. The inventors have found that since the boiling point of the cracking products decreases under high pressure, a pressure above 1 barg will cause heavy hydrocarbons (which are the desired products in the method described herein) to thermally crack rather than vaporize at a given operating temperature. Therefore, under pressurized cracking, more energy is required for further hydrocarbon cracking, and the average molecular weight of the gas products decreases. Therefore, maintaining the pressure at a maximum of 1 barg, preferably at most about 0.5 barg, allows for energy efficiency on the one hand and the desired cracking product profile on the other hand.

[0051] The residence time in the pyrolysis reactor is defined as the average amount of time the mixture spends in the pyrolysis reactor. The inventors have found that in the method of the present disclosure, a long residence time will result in the formation of light fractions, while a shorter residence time will mainly produce heavy fractions. A residence time between about 2 and about 40 hours in step (a) achieves a pyrolysis product balance among the light, medium, and heavy components, and these pyrolysis products can be further processed into various high-value products, as described below. A longer residence time also reduces the amount of olefins, thereby enabling secondary hydrogenation of double bonds in the pyrolysis reactor, and further ensuring lower hydrogen consumption in the hydrotreating unit and a lower exothermic effect in hydrotreating (making the process safer and easier to control).

[0052] According to some embodiments, the residence time ranges between about 2 and about 30 hours. According to other embodiments, the residence time ranges between about 3 and about 20 hours. According to some other embodiments, the residence time ranges between about 3 and about 10 hours. According to other embodiments, the residence time ranges between about 4 and about 6 hours.

[0053] According to some embodiments, the method includes treating the mixture in step (a) in one or more pyrolysis reactors arranged in parallel.

[0054] According to some embodiments, the pyrolysis reactor can be a batch reactor, a semi-batch reactor, a continuous flow reactor (CFR), a screw reactor, or a combination thereof.

[0055] According to some embodiments, in the case of using a batch reactor, a semi-batch reactor, or a continuous reactor, the pyrolysis is carried out under the flow of nitrogen or other stripping agents (such as a light hydrocarbon stream) to continuously remove unwanted volatiles from the reactor.

[0056] According to some embodiments, the pyrolysis reactor includes a heated circulation loop defined between the circulation outlet and the circulation inlet of the reactor for circulating a portion of the mixture through the heated circulation loop during pyrolysis. The circulation loop is designed to continuously circulate a portion of the mixture into and out of the pyrolysis reactor. Since the viscosity of the process fluid in the reactor (i.e., the melt in its partially pyrolyzed form) is relatively high, it is difficult to control the uniformity of the temperature within the fluid. In the presently claimed method, the continuous circulation of a portion of the contents of the pyrolysis reactor through the heated circulation loop allows for better control of the melt temperature, while also allowing a small portion of the melt (i.e., the circulated portion) to be exposed to a temperature higher than the temperature maintained in the reactor for a short period of time (during passage through the loop) to properly heat the mixture, while also minimizing the formation of unwanted coke due to the short residence time in the loop.

[0057] According to some embodiments, the temperature in the circulation loop is between about 400 °C and about 450 °C.

[0058] According to some embodiments, during pyrolysis, said portion of the mixture within the circulation loop is between about 2% and about 50% of the volume of the pyrolysis reactor. According to other embodiments, during pyrolysis, said portion of the mixture within the circulation loop is between about 2% and about 30% of the volume of the pyrolysis reactor.

[0059] According to some embodiments, step (a) further includes removing solid residues from the pyrolysis reactor. The solids removed from the pyrolysis reactor can be further processed and disposed of or further utilized. For example, the solids (or sometimes referred to as "reactor residue") can be used as fuel due to their high calorific value (usually 36 - 47 MJ / kg), such as in waste incineration plants or cement plants. The solids can also be used as cement or asphalt tar additives or as ore binders.

[0060] The pyrolysis step produces saturated and unsaturated hydrocarbon pyrolysis products in the form of a widely distributed vapor. In step (b), volatile C1 - C5 compounds are removed from the hydrocarbon vapor stream, and the remaining portion of the hydrocarbon stream (usually containing C6 - C70 hydrocarbons) is quenched to obtain a condensate stream. The condensate stream is also referred to herein as pyrolysis oil. Non - condensable gases / vapors (C1 - C5) are separated out and can be used for energy recovery. In the method of the present disclosure, the non - condensable gases account for about 5 - 15 wt% of the total reactor feed.

[0061] According to some embodiments, the temperature during quenching in step (b) of the method is in the range between about 150 °C and about 250 °C.

[0062] Then in step (c), the condensate is treated as a whole in a main catalytic hydrotreating unit to obtain a hydrotreated condensate stream. Hydrotreating (or any linguistic variant thereof) refers to reducing double bonds and aromatic bonds in the hydrocarbons of the condensate stream. In addition to reducing double bonds, the hydrotreating conditions applied in this method also rapidly remove heteroatoms and non - hydrocarbon compounds by turning them into volatile compounds (e.g., turning sulfur - organic compounds into hydrogen sulfide, nitrogen - containing compounds into ammonia, and oxygen - containing compounds into water). Thus, under the main hydrotreating conditions, in addition to the saturation of olefins and aromatic compounds, a concomitant process is achieved, namely the removal of heteroatoms by hydrodesulfurization, denitrification, deoxygenation, and / or dehalogenation.

[0063] The purpose of the main hydrotreating is to treat all hydrocarbons of the condensate stream with hydrogen (H 2 )). This process step also reduces the bromine value of the treated stream to less than 0.5 g Br 2 / 100 g. In the disclosed method, the hydrotreating of the overall condensate stream is crucial for providing proper product quality and preventing unnecessary polymerization reactions of unsaturated components downstream of the process. Additionally, in known methods, the condensate is first separated into fractions, and each fraction is hydrotreated individually or sequentially, one fraction after another, in different systems. In contrast to the known methods, in the disclosed method, the hydrotreating of the entire hydrocarbon condensate (without fractionation) does not require flushing between fractions (since individual fractions are not processed), and also prevents contamination due to the processing of different fractions in the same hydrotreating unit. Furthermore, the hydrotreating of the entire condensate prior to separation removes resin-forming components (mainly reactive dienes or olefins from PS such as styrene), enabling the long-term operation of the distillation column to be maintained.

[0064] According to some embodiments, the main catalytic hydrotreating unit operating in step (c) is carried out under conditions including: a temperature between about 250 °C and about 340 °C, a pressure of at least about 45 barg, and at least about 150 Nm 3 / m 3 (standard cubic meters per cubic meter) of hydrogen to condensate stream ratio.

[0065] The condensate stream is heated to an operating temperature of at least 250 °C. The temperature at any time in the reactor is maintained as high as possible but not higher than 340 °C because the inventors have found that under the conditions of the method disclosed herein, the hydrogenation / saturation of aromatic compounds is ineffective above 340 °C. The hydrogenation reaction of unsaturated components is an exothermic reaction, and the heat generated is mainly affected by the feed composition. A higher PP concentration in the feed produces more unsaturated compounds, which will be hydrogenated in this reactor. To control the temperature in the reactor and avoid overheating (hot spots and runaway situations), the temperature is controlled by the H 2 / HC ratio and the inlet temperature. Any heat input into the process is carefully controlled at the maximum temperature to avoid further cracking of the hydrocarbons and the formation of coke residues. Further control of the temperature can be obtained by introducing cold hydrogen between the catalyst beds for quenching.

[0066] 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.

[0067] According to some embodiments, the main hydrotreating is carried out at a pressure in the range between 60 barg and 200 barg.

[0068] According to some embodiments, the liquid hourly space velocity (LHSV) of the feed (which is the ratio of the volume of liquid feed flowing in one hour to the volume of the catalyst) is between 0.5 h -1 and 2.0 h-1 within the range. In the main hydrotreating step of the disclosed method, it has been found that this LHSV value allows for better control of the concomitant desulfurization in the hydrotreating reactor.

[0069] The main hydrotreating stage is a catalytic process at high temperature and high pressure. According to some embodiments, the catalytic reaction occurs on a fixed catalyst bed in the presence of a high volume ratio of hydrogen.

[0070] According to some embodiments, the catalyst in the main hydrotreating step can be selected from alumina, silica, zeolite, noble-earth metals (such as cobalt, molybdenum, nickel, tungsten, platinum, zirconium, etc.), and metal alloys.

[0071] According to some other embodiments, the main catalytic hydrotreating utilizes at least one Ni-Mo catalyst.

[0072] Catalysts are generally sensitive to poisons (such as arsenic, vanadium, silicon, nickel, and other metals and halides). In the main hydrotreating stage, the catalyst is generally prone to silicon poisoning, and silicon may sometimes be present in the source material (and thus may be present to some extent in the condensate stream). To protect the catalyst in the main hydrotreating reactor, the condensate stream can be fed into the main hydrotreating reactor through at least one guard bed.

[0073] Thus, according to some embodiments, the condensate stream of step (b) passes through at least one guard bed reactor including at least one guard bed catalyst before being introduced into step (c).

[0074] According to some embodiments, the temperature in 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 at least one guard bed reactor is about 150 Nm 3 / m 3 .

[0075] According to some embodiments, the condensate stream passes through one or more traps before being fed into the main hydrotreating reactor to remove contaminants from the condensate stream. The traps can be metal traps, silicon traps, halide traps, phosphorus traps, etc. According to some embodiments, one or more traps contain iron oxide, iron exchange resin, clay, silica gel, alkali metal or alkaline earth metal oxide, activated alumina, activated carbon, molecular sieve, highly porous nickel molybdenum (NiMo), cobalt molybdenum (CoMo) catalyst, or any combination thereof. The traps can operate with or without hydrogen coverage.

[0076] After hydrotreating, in step (d) of the process, the hydrotreated stream is separated into product streams. Generally, based on hydrocarbon molecular weight and boiling temperature, the hydrotreated stream is separated into three main product streams: (i) a C6-C20 product stream with a boiling temperature between about 60 °C and about 330 °C, (ii) a C14-C32 product stream with a boiling temperature between about 300 °C and about 450 °C, and (iii) a C20-C70 product stream with an initial boiling temperature of at least about 350 °C.

[0077] According to some embodiments, the main product streams include: (i) a C6-C18 product stream with a boiling temperature between about 100 °C and about 300 °C, (ii) a C14-C24 product stream with a boiling temperature between about 300 °C and about 380 °C, and (iii) a C22-C70 product stream with an initial boiling temperature of at least about 380 °C.

[0078] Then each of streams (i)-(iii) is treated separately in step (e) to obtain the final paraffinic products.

[0079] According to some embodiments, the product streams are treated in step (e) as follows:

[0080] (i) Catalytically hydrotreating the C6-C20 product stream and then distilling in at least one solvent distillation column to obtain a C6-C20 paraffinic product with an aromatic compound content of at most about 3000 ppm,

[0081] (ii) Catalytically hydrotreating the C14-C32 product stream and then distilling in at least one oil distillation column to obtain a C14-C32 paraffinic product with an aromatic compound content of at most about 3000 ppm, and / or

[0082] (iii) Distilling the C20-C70 product stream in at least one wax distillation column to obtain a C20-C70 paraffinic product with an aromatic compound content of at most about 3000 ppm.

[0083] In some embodiments, the C20-C70 product stream can be bleached to improve the color and quality of the paraffinic products. The bleaching agent can be at least one of the following: natural bleaching earth, acid-activated bleaching earth, activated carbon (e.g., for removing polycyclic aromatic hydrocarbons and a wide range of specific contaminants), synthetic amorphous silica (e.g., for selectively removing phospholipids, trace metals, and soaps), etc.

[0084] In some embodiments, in process step (e), the C6-C20 stream is 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 aromatic compound content of at most about 3000 ppm, preferably at most 2000 ppm.

[0085] The catalytic hydrotreating of the C6-C20 product stream in step (e) is mainly to further reduce the aromatic compound content of the light fractions. Low-boiling aromatic compounds in the solvent (C6-C20 product) are especially undesirable as they may pose health hazards. The concentration of aromatic compounds in the C6-C20 stream can vary directly with the presence of various contaminants (e.g., polystyrene) in the polyolefin feed mixture and may not all be processed to the desired level in the main hydrotreating step.

[0086] The catalytic hydrotreating of the C6-C20 product stream in step (e) is carried out under conditions including: a temperature between about 170 °C and about 300 °C, a pressure of at least 45 barg, and a hydrogen to condensate stream ratio of at least 150 Nm 3 / m 3 (standard cubic meters per cubic meter). These conditions are not only aimed at significantly converting aromatic compounds but also at avoiding overheating, which may lead to undesired side reactions.

[0087] According to some embodiments, the C6-C20 product stream is treated through one or more distillation stages to obtain a C6-C20 paraffinic product having an aromatic compound content of at most about 3000 ppm, preferably at most 2000 ppm. The C6-C20 paraffinic product is typically a solvent having a boiling temperature between about 100 °C and about 360 °C. By varying the parameters of the distillation column and / or by using two or more successively arranged solvent distillation columns, various solvents having different boiling temperature ranges within this broad range can be obtained.

[0088] In step (e), the C14-C32 product stream is catalytically hydrotreated and then distilled in at least one oil distillation column to obtain a C14-C32 paraffinic product with an aromatic compound content of at most about 3000 ppm, preferably at most 2000 ppm. The purpose of hydrotreating the C14-C32 product stream is mainly to isomerize the linear paraffins in this hydrocarbon fraction to branched paraffins to obtain an oil product with an improved cloud point below -10 °C and a pour point of the oil below -20 °C. The cloud point and pour point are indicators of the presence of linear waxes in the oil, which are undesirable in the oil product. Another purpose of the hydrotreating of the C14-C32 product stream is to mildly hydrocrack long-chain hydrocarbons into short-chain hydrocarbons, thereby effectively dewaxing the C14-C32 product.

[0089] According to some embodiments, catalytically hydrotreating the C14-C32 product stream in step (e) includes hydrotreating the C14-C32 product under conditions including: a temperature between about 310 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 of hydrogen to the C14-C32 product stream.

[0090] According to some other embodiments, catalytically hydrotreating the C14-C32 product stream in step (e) is carried out in two consecutive hydrotreating steps:

[0091] Step (e1), which includes hydrotreating the C14-C32 product under conditions including: a temperature between about 310 °C and about 360 °C, a pressure of at least 30 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 of hydrogen to the C14-C32 product stream; followed by:

[0092] Step (e2), which includes hydrotreating the product of step (e1) under conditions including: a temperature between about 170 °C and about 300 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 of hydrogen to the C14-C32 product stream.

[0093] In step (e1), the C14-C32 product stream is isomerized, and in step (e2), the isomerized stream is further processed to convert the remaining unsaturated hydrocarbons to saturated hydrocarbons, thereby further reducing the aromatic compound content in the resulting oil product. Step (e2) also improves the color of the oil according to the Saybolt color scale.

[0094] According to some embodiments, the method includes dewaxing (mild hydrocracking) a C14-C32 product stream to remove hydrocarbons that are prone to solidification (i.e., wax). Wax removal is generally required for the production of lubricating oils that remain fluid over a wide temperature range. The catalytic dewaxing process involves passing the C14-C32 product stream over a catalyst where the active hydrocracking sites are accessible only to paraffin molecules and selectively hydrocracking the waxy molecules into shorter-chain products while leaving the valuable lubricating oil components unchanged.

[0095] According to some embodiments, the C14-C32 product stream is processed through one or more distillation stages to obtain a C14-C32 paraffinic product having an aromatic compound content of at most 2000 ppm. The C14-C32 paraffinic product is generally an oil that contains at least 50 wt% C14-C32 isoparaffinic compounds, preferably at least about 95 wt% C14-C32 isoparaffinic compounds, and has a kinematic viscosity in the range of 5.00 mm 2 / s to 15.00 mm 2 / s as measured at 40 °C according to ISO 3104. The boiling temperature of the oil obtained after distillation is generally between about 320 °C and about 420 °C.

[0096] In the method of the present disclosure, the C20-C70 product stream is distilled in a wax distillation column in step (e) to obtain a C20-C70 paraffinic product.

[0097] According to some embodiments, the C20-C70 paraffinic product is a wax that generally contains at least 95 wt% C20-C70 n-paraffinic compounds (determined by GC / MS), an oil content between about 10 wt% and 60 wt%, and no more than about 3000 ppm of aromatic compounds. The boiling temperature of the wax obtained after distillation is generally at least 350 °C.

[0098] According to other embodiments, the C20-C70 paraffinic product contains at most about 85 wt% iso-paraffin and at most about 60 wt% n-paraffin (determined according to ASTM D5442), and no more than about 3000 ppm of aromatic compounds.

[0099] The wax distillation can be carried out through one or more distillation steps. According to some embodiments, the distillation products of each distillation step are blended at a predetermined ratio to obtain a wax product.

[0100] As described, the paraffinic products produced by the methods of the present disclosure are characterized by a low aromatic compound content, i.e., less than about 3000 ppm, preferably less than 2000 ppm. The paraffinic products are further characterized by a low sulfur content (generally less than 10 ppm), a low nitrogen content, a low chlorine content, a controllable paraffin ratio, etc.

[0101] According to some embodiments, the paraffinic products produced by the methods of the present disclosure meet the FDA requirements for the amount of polycyclic aromatic hydrocarbons (PAHs).

[0102] According to some embodiments, the oil and solvent products meet the requirements of the US FDA Qualitative Test 21 CFR §178.3620, and their ultraviolet absorbance at specific wavelengths is within the following limit ranges: 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 the FDA 21 CFR §172.886 for the maximum ultraviolet absorbance limit of a specific path length: 280 - 289 nm A < 0.15, 290 - 299 nm A < 0.12, 300 - 359 nm A < 0.08, 360 - 400 nm A < 0.02.

[0103] Thus, according to another aspect of the present disclosure, there is provided a paraffinic solvent having a boiling 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 between about 150 °C and about 360 °C, the fluid comprising normal paraffinic compounds in the range between about 15 wt% and about 65 wt%, isoparaffinic compounds in the range between about 30 wt% and about 75 wt%, naphthenic compounds in the range between about 0 wt% and about 35 wt%, and no more than about 3000 ppm aromatic compounds.

[0104] According to some embodiments, the paraffinic solvent comprises no more than about 2000 ppm of aromatic compounds.

[0105] According to some embodiments, the paraffinic solvent is obtained by the methods described herein.

[0106] According to some embodiments, the paraffinic solvent comprises C6 - C20 paraffinic hydrocarbons. According to other embodiments, the paraffinic solvent consists essentially of C6 - C20 paraffinic hydrocarbons.

[0107] According to some embodiments, the percentage ratio between normal paraffins and isoparaffins in the C6 - C20 paraffinic product (i.e., the percentage of normal paraffins and the percentage of isoparaffins) is in the range between about 1:1.2 and about 1:2.5.

[0108] According to other embodiments, the percentage ratio between the normal paraffins and the isoparaffins in the C6-C20 paraffinic product ranges from about 1:1.5 to about 1:4.5.

[0109] According to some other embodiments, the percentage ratio between the normal paraffins and the isoparaffins in the C6-C20 paraffinic product ranges from about 1:1.2 to about 1:4.5.

[0110] According to some embodiments, the paraffinic solvent contains less than 3 ppm of each of sulfur, chloride, and nitrogen.

[0111] According to some embodiments, the initial boiling point of the paraffinic solvent ranges from about 85 °C to about 110 °C, the final boiling point ranges from 155 °C to 180 °C, and the kinematic viscosity ranges from 0.70 mm 2 / s to 0.90 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0112] According to other embodiments, the initial boiling point of the paraffinic solvent ranges from about 135 °C to about 160 °C, the final boiling point ranges from 185 °C to 220 °C, and the kinematic viscosity ranges from 1.00 mm 2 / s to 1.40 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0113] According to some other embodiments, the initial boiling point of the paraffinic solvent ranges from about 170 °C to about 195 °C, the final boiling point ranges from 235 °C to 250 °C, and the kinematic viscosity ranges from 1.60 mm 2 / s to 1.90 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0114] According to some other embodiments, the initial boiling point of the paraffinic solvent ranges from about 190 °C to about 210 °C, the final boiling point ranges from 245 °C to 270 °C, and the kinematic viscosity ranges from 1.80 mm 2 / s to 2.40 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0115] According to yet other embodiments, the paraffinic solvent has an initial boiling point in the range of from about 205 °C to about 245 °C, a final boiling point in the range of from 270 °C to 290 °C, and a kinematic viscosity in the range of from 1.95 mm 2 / s to 3.10 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0116] According to additional embodiments, the paraffinic solvent has an initial boiling point in the range of from about 240 °C to about 280 °C, a final boiling point in the range of from 335 °C to 360 °C, and a kinematic viscosity in the range of from 5.50 mm 2 / s to 7.20 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0117] According to some other embodiments, the paraffinic solvent has an initial boiling point in the range of from about 240 °C to about 260 °C, a final boiling point in the range of from 310 °C to 330 °C, and a kinematic viscosity in the range of from 3.30 mm 2 / s to 4.70 mm 2 / s (as measured at 25 °C according to ASTM D445).

[0118] According to another aspect, there is provided a paraffinic solvent as disclosed herein for use in cosmetic products, coatings, printing inks, plasticizers, degreasers, textile manufacturing, explosive manufacturing, cleaning product manufacturing, self-igniting barbecue bricks, solvent extraction (copper and others), road solvents, and wood preservatives (resins for wood and foundry applications). According to another aspect, there is provided a paraffinic solvent as disclosed herein for use as a solvent in surfactant production or in pesticide compositions.

[0119] According to another aspect, there is provided an article comprising at least one paraffinic solvent as disclosed herein, the article being selected from cosmetic products, coatings, plasticizers, degreasers, cleaning products, explosive products, printing inks, self-igniting barbecue bricks, extraction / leaching solutions, road solvents, wood preservatives, and pesticide compositions.

[0120] According to another aspect, there is provided a paraffinic oil comprising at least 50 wt% C14-C32 isoparaffinic compounds, preferably at least 95 wt% C14-C32 isoparaffinic compounds, and having a kinematic viscosity in the range of from 5.00 mm 2 / s to 15.00 mm 2 / s (as measured at 25 °C according to ASTM D445), the fluid comprising no more than about 3000 ppm aromatic compounds.

[0121] According to some embodiments, the paraffinic oil contains no more than about 2000 ppm of aromatic compounds.

[0122] According to some embodiments, the paraffinic oil is obtained by the methods described herein.

[0123] According to some embodiments, the paraffinic oil has an initial boiling point of at least about 300 °C and a final boiling point of at least about 380 °C.

[0124] According to some embodiments, the boiling temperature of the paraffinic oil is between about 300 °C and about 380 °C.

[0125] According to some embodiments, the boiling temperature of the paraffinic oil is between about 320 °C and about 420 °C.

[0126] According to another aspect, there is provided a paraffinic oil as disclosed herein for use in food processing, cosmetics, pharmaceutical formulations, energy storage devices, agricultural products, as a base oil, metalworking fluids, and biodiesel alternatives.

[0127] According to another aspect, there is provided an article comprising at least one paraffinic oil as disclosed herein, the article being selected from food processing products, cosmetic products, pharmaceutical products, energy storage devices, agricultural products, base oils, metalworking fluids, and biodiesel alternatives.

[0128] According to yet another aspect, there is provided a paraffinic wax comprising at least 95 wt% of C20-C70 normal paraffinic compounds (determined by GC / MS), an oil content between about 10 wt% and 60 wt%, and no more than about 3000 ppm of aromatic compounds.

[0129] According to another aspect, there is provided a paraffinic wax comprising at least 85 wt% of C20-C70 paraffinic compounds, the C20-C70 paraffinic compounds comprising at most about 85 wt% of C20-C70 isoparaffins and at most about 60 wt% of C20-C70 normal paraffins (determined according to ASTM D5442), and no more than 3000 ppm of aromatic compounds.

[0130] According to some embodiments, the paraffinic wax contains no more than about 2000 ppm of aromatic compounds.

[0131] According to some embodiments, the paraffinic wax has a penetration (at 25 °C, ASTM D1321) of at least 100, a congealing point of 40-60 °C (ASTM D938), and a kinematic viscosity of 3-5.5 mm 2 / s (at 100 °C, ISO 3104).

[0132] According to some other embodiments, the penetration of the paraffinic wax (at 25 °C, ASTM D1321) is 70 - 105, the congealing point is 50 - 65 °C (ASTM D938), and the kinematic viscosity is 4.5 - 7.5 mm 2 / s (at 100 °C, ISO 3104).

[0133] According to other embodiments, the penetration of the paraffinic wax (at 25 °C, ASTM D1321) is 60 - 95, the congealing point is 60 - 80 °C (ASTM D938), and the kinematic viscosity is 7.5 - 10 mm 2 / s (at 100 °C, ISO 3104).

[0134] According to further embodiments, the penetration of the paraffinic wax (at 25 °C, ASTM D1321) is 70 - 155, the congealing point is 50 - 70 °C (ASTM D938), and the kinematic viscosity is 4.5 - 8.0 mm 2 / s (at 100 °C, ISO 3104).

[0135] According to yet other embodiments, the penetration of the paraffinic wax (at 25 °C, ASTM D1321) is 60 - 120, the congealing point is 55 - 80 °C (ASTM D938), and the kinematic viscosity is 7 - 10 mm 2 / s (at 100 °C, ISO 3104).

[0136] According to some embodiments, the paraffinic wax is obtained by the method disclosed herein.

[0137] For wax producers, an important parameter is the low content of polycyclic aromatic hydrocarbons (PAHs), many of which are toxic, carcinogenic, and mutagenic substances.

[0138] According to another aspect, there is provided a paraffinic wax as disclosed herein, which is used in shoe polishes, floor polishes, candles, softening of tissue paper, manufacture of wax paper and paper packaging, matches, pesticide attractants, tire manufacture, anti-ozone formulations, lubrication aids, fertilizers, anti-caking aids, agricultural products, fruit and / or vegetable coatings, hydrophobic coatings, concrete curing, cosmetics, hot melt adhesives (for food), mining, road applications (road resin markers, asphalt extensometers), fatty acid derivatives, PVC stabilizers, and wax emulsions.

[0139] According to another aspect, there is provided an article comprising a paraffinic wax as disclosed herein, the article being selected from shoe polishes, floor polishes, candles, tissue softening formulations, waxed paper, wax paper packaging, matches, pesticide lures, tires, anti-ozone formulations, lubrication aids, fertilizers, anti-caking aids, agricultural products, fruit and / or vegetable coatings, hydrophobic coatings, concrete curing agents, cosmetic products, hot melt adhesives, PVC stabilizers, and wax emulsions.

[0140] As illustrated, the residue, solids, or reactor bottoms separated from the pyrolysis reactor during pyrolysis can be used as a stand-alone product. Thus, according to another aspect of the present disclosure, there is provided a solid product obtained by the method of the present disclosure, which comprises pyrolysis residues having a total solids (i.e., coke / carbon and ash) content of at least 30 wt% and a calorific value of at least 30 MJ / kg.

[0141] According to some embodiments, the solid product comprises up to 0.5 wt% sulfur, up to 0.5 wt% nitrogen, up to 0.3 wt% chlorine, and / or up to 0.01 ppm mercury.

[0142] According to some other embodiments, the solid product comprises between about 5 and 15 wt% hydrogen.

[0143] According to other embodiments, the solid product comprises between about 30 and 95 wt% volatile components.

[0144] According to another aspect of the present disclosure, there is provided a manufacturing facility for processing polyolefin waste into a paraffinic product having an aromatic compound content of up to 2000 ppm, the facility comprising:

[0145] (A) A pyrolysis reactor configured to receive a molten polyolefin mixture and pyrolyze the mixture to obtain a hydrocarbon vapor stream, the pyrolysis reactor being configured to operate under conditions including: (i) a pressure of up to 1 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between about 2 and about 40 hours;

[0146] (B) A quench tower in fluid communication with the pyrolysis reactor and configured to receive the hydrocarbon vapor stream, remove C1-C5 volatile compounds therefrom, and quench the remainder of the hydrocarbon vapor stream to obtain a condensed stream;

[0147] (C) A main catalytic hydrotreating unit in fluid communication with the quench tower and configured to hydrotreat the condensed stream to obtain a hydrotreated stream;

[0148] (D) A pressurized separation column, which is in fluid communication with the main catalytic hydrotreating unit and is configured to separate the hydrotreated stream into product streams:

[0149] (i) A C6-C20 product stream having a boiling temperature between about 60 °C and about 330 °C,

[0150] (ii) A C14-C32 product stream having a boiling temperature between about 300 °C and about 450 °C, and

[0151] (iii) A C20-C70 product stream having a boiling temperature of at least about 350 °C; and

[0152] (E) One or more processing units, which are in fluid communication with the pressurized separation column, each of the one or more processing units being configured to receive one of the product streams and process the product stream therein to obtain the paraffinic product.

[0153] According to some embodiments, 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 aromatic compound content of at most about 3000 ppm, preferably at most about 2000 ppm.

[0154] According to some embodiments, 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 aromatic compound content of at most 3000 ppm.

[0155] According to some embodiments, the facility includes a catalytic hydrotreating unit for processing the C14-C32 product stream under conditions including: a temperature between about 320 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 of hydrogen.

[0156] According to some other embodiments, the facility includes two catalytic hydrotreating units arranged in series for processing the C14-C32 product stream: a first catalytic hydrotreating unit for processing the C14-C32 product stream under conditions including a temperature between about 310 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3processing a C14-C32 product stream under conditions of a hydrogen to C14-C32 product stream ratio; followed by a second catalytic hydrogenation unit for hydrotreating the product received from the first catalytic hydrogenation unit under conditions of a temperature between about 170 °C and about 300 °C, a pressure of at least 25 barg, and at least 150 Nm 3 / m 3 of hydrogen to C14-C32 product stream ratio.

[0157] 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 aromatic content of at most 3000 ppm.

[0158] According to some embodiments, the facility further includes at least one extruder for obtaining the polyolefin melt before introducing the polyolefin melt into the pyrolysis reactor.

[0159] According to some embodiments, the pyrolysis reactor includes a heated circulation loop defined between a circulation outlet and a circulation inlet of the reactor for circulating a portion of the mixture through the circulation loop during pyrolysis.

[0160] According to some embodiments, the facility further includes at least one guard bed reactor containing at least one guard bed catalyst, which is located between the quench tower and the main hydrotreating unit and is configured to receive the condensed stream from the quench tower and treat the condensed stream therein to remove contaminants therefrom before hydrotreating.

[0161] According to some embodiments, the facility includes at least one contaminant trap, which is located between the quench tower and the main hydrotreating unit and is configured to receive the condensed stream from the quench tower and remove one or more contaminants from the condensed stream before hydrotreating.

[0162] As used herein, the term "about" is intended to cover a deviation of ± 10% of the value of a specifically recited parameter such as temperature, pressure, concentration, etc.

[0163] Whenever a numerical range is indicated herein, it is intended to include any recited number (fraction or integer) within the indicated range. The expression of a range between a first recited number and a second recited number and the expression of a "range" from the first recited number "to" the second recited number are used interchangeably herein and are intended to include the first and second recited numbers and all fractions and integers therebetween.

[0164] The expression "consisting essentially of" means that a composition or mixture contains at least 98 wt% of a single component.

[0165] ppm means parts per million.

[0166] Throughout this specification and the following claims, unless the context requires otherwise, the word "comprise" and variations such as "comprises" or "comprising" shall 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 and steps.

[0167] In general, it should be noted that when applied to any component of a product or method, the term "at least one" shall be understood to cover one, two, three, four, five or more different occurrences of said component in the product or method disclosed herein.

[0168] It should be understood that certain features of the present disclosure that are described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for the sake of brevity, the various features of the present disclosure that are described in the context of a single embodiment may also be provided separately or in any suitable sub-combination or, where appropriate, in any other described embodiment of the present disclosure. Certain features described in the context of various embodiments should not be considered essential features of those embodiments unless the embodiment is inoperative without those elements.

[0169] The methods of the present disclosure involve a number of process steps which may or may not be associated with other common physico-chemical processes in order to achieve the desired purity and form of each product. Unless otherwise specified, the process steps, if any, may be set in a different order without affecting the operability of the method and its efficiency in achieving the desired final result. Those skilled in the art will understand that the order of the steps may be adopted and varied according to various economic aspects, material availability, raw materials, environmental considerations, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0170] For a better understanding of the subject matter disclosed herein and to illustrate how it may be carried into effect in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0171] Figure 1 is a schematic diagram of an exemplary method and facility according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0172] Figure 1 shows an exemplary method according to an embodiment of the present disclosure and a facility for carrying out said method. In Figure 1 the following acronyms are used:

[0173] MSW – Municipal Solid Waste Preparation Unit

[0174] FPU - Feed Preparation Unit

[0175] CSTR - Catalytic Pyrolysis Reactor

[0176] FL - Filter

[0177] HT - Heater

[0178] GB - Guard Bed

[0179] MHT - Main Hydrotreating Processor

[0180] LES - Light Ends Stabilizer

[0181] MFC - Main Fractionator

[0182] AHT - Aromatics Hydrotreating Processor

[0183] IHT - Isomerization Hydrotreating Processor

[0184] FHT - Finishing Hydrotreating Processor

[0185] SD - Solvent Distillation

[0186] OD - Oil Distillation

[0187] WD - Wax Distillation

[0188] WBM - Wax Blending Mixer

[0189] Go to Figure 1 , which shows an exemplary method and facility for performing the method according to the present disclosure. Figure 1 The method shown is to first feed a feedstock comprising (and sometimes consisting 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.

[0190] The molten mixture is fed into a pyrolysis reactor (CSTR), where pyrolysis of the mixture occurs, decomposing long polyolefin chains into shorter hydrocarbon molecules. Solids are continuously removed from the CSTR while a portion of the mixture is recycled through a forced circulation loop. In the circulation loop, this portion of the mixture is recycled back to the CSTR via a heater (HT). This recycling facilitates better control of the overall temperature of the mixture and enables heating a portion of the mixture recycled through the loop to a higher temperature than the CSTR. Due to the relatively high melt viscosity in the reactor, it is difficult to control the temperature uniformity within the melt; continuous circulation of a portion of the contents of the pyrolysis reactor through the heating loop allows for better control of the melt temperature and better control of the residence time, while also allowing a small portion of the melt (i.e., the recycled portion) to be exposed to a higher temperature than the temperature maintained in the reactor for a short period of time (during passage through the loop) to enable proper heating of the mixture while minimizing the formation of unwanted coke resulting from the short residence time in the loop.

[0191] Pyrolysis is carried out under the following conditions: (i) a pressure of at most 1 barg, preferably at most 0.5 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, preferably between about 350 °C and 420 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between about 2 and about 40 hours, preferably between about 4 and about 6 hours. In the method of the present disclosure, such conditions are optimal for obtaining a wide range of hydrocarbon fractions, which are used in the method to produce a wide range of final products from a single pyrolysis step. Additionally, such conditions are designed to maximize the formation of heavy products (e.g., wax products) and minimize the formation of coke.

[0192] The pyrolysis products leave the CSTR as a hydrocarbon vapor stream and are quenched in a quench tower. In the quench tower, condensable gaseous hydrocarbons (C6<) are condensed into a condensate stream, while the lighter products (C1-C5) are discharged as a gas to be collected and further used as an energy source or a gas product.

[0193] The condensate stream is then transferred to a main hydrotreating unit (MHT), where catalytic hydrotreating is carried out to reduce the aromatic hydrocarbon and olefin content in the stream by hydrogenating multiple bonds in the unsaturated hydrocarbons. In addition to reducing multiple bonds, the hydrotreating conditions applied in this method also rapidly remove heteroatoms and non-hydrocarbon compounds by converting them into volatile compounds (e.g., converting sulfur-organic compounds into hydrogen sulfide, nitrogen-containing compounds into ammonia, and oxygen-containing compounds into water).

[0194] Importantly, and contrary to known methods, in the method of the present disclosure, the entire condensate stream is hydrotreated without fractionation. Hydrotreating the entire range of pyrolysis products enables a wide range of hydrocarbons to be obtained in a single hydrotreating step while effectively reducing the olefin and aromatic compound content. This enables a wide range of products to be obtained from a unified and complete manufacturing method by carefully controlling the aromatic compound content.

[0195] Typically, the MHT in the method according to the present disclosure is carried out under conditions including: a temperature between about 250 °C and about 340 °C, a pressure of at least 45 barg, and a hydrogen to condensate stream ratio of at least 150 Nm 3 / m 3 (standard cubic meters per cubic meter). Such conditions have been found to maximize the hydrotreating efficiency while also preventing undesired hydrocarbon polymerization in the MHT.

[0196] Since the MHT catalyst can be sensitive to poisoning, especially silicon poisoning, the condensate stream can be fed into the MHT via at least one guard bed (GB), which typically contains at least one guard bed catalyst for removing undesired contaminants. Further (or alternatively), the condensate stream can be passed through one or more traps (not shown) for removing contaminants from the condensate stream before feeding the condensate stream into the MHT, such as removing metals, silicon, halides, phosphorus, etc. from the stream.

[0197] The hydrotreated stream can be processed in a light ends stabilizer (LES) to remove any additional C1 - C5 gaseous hydrotreating products that may be present in the hydrotreated stream, and from there the C6+ hydrotreated stream is fed into a main fractionation column (MFC) for separation into fractions, typically based on boiling temperature and molecular weight. The MFC can be, for example, a tray column or a packed column, typically operating at atmospheric pressure and heated to about 330 °C. Three main product streams are obtained from the MFC: (i) a C6 - C20 product stream with a boiling temperature between about 60 °C and about 330 °C, (ii) a C14 - C32 product stream with a boiling temperature between about 300 °C and about 450 °C, and (iii) a C20 - C70 product stream with a boiling temperature of at least about 350 °C.

[0198] Each of these product streams is then processed in one or more processing steps to obtain the final paraffinic products.

[0199] The C6-C20 stream is first catalytically hydrotreated in an aromatic hydrocarbon hydrotreating unit (AHT) to further reduce the aromatic hydrocarbon content of the light fractions. Low-boiling aromatic hydrocarbons are particularly undesirable in the solvent as they may 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., the solvent, with an aromatic hydrocarbon content of at most 3000 ppm, preferably at most 2000 ppm. The catalytic hydrotreating in the AHT can be carried out under conditions including: a temperature between about 170 °C and about 300 °C, a pressure of at least 45 barg, and a hydrogen to condensed stream ratio of at least 150 Nm 3 / m 3 (standard cubic meters per cubic meter). These conditions are aimed not only at significantly converting the aromatic hydrocarbons but also at avoiding overheating that could lead to undesired side reactions.

[0200] The SD can include a plurality of distillation stages in series, in each of which different solvent fractions can be separated into individual solvent products according to their boiling temperatures. Thus, by varying the parameters of the distillation column and / or by using two or more successively arranged solvent distillation columns, various solvents with different boiling temperature ranges can be obtained.

[0201] The C14-C32 product stream is also catalytically hydrotreated. In the exemplary method, the C14-C32 product stream is first catalytically hydrotreated in an isomerization hydrotreating unit (IHT), then hydrotreated 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 with an aromatic hydrocarbon content of at most 3000 ppm, preferably at most 2000 ppm. According to some embodiments, C14-C32 is an isoparaffinic oil. The purpose of the IHT is mainly to isomerize the straight-chain paraffins in this hydrocarbon fraction into branched-chain paraffins to obtain an oil product with an improved cloud point below -10 °C and an oil pour point below -20 °C, while the purpose of the FHT is to convert the remaining unsaturated hydrocarbons into saturated hydrocarbons, thereby further reducing the aromatic hydrocarbon content in the resulting oil product.

[0202] The IHT can be carried out under conditions including: a temperature between about 310 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 The FHT is generally carried out under conditions including: a temperature between about 170 °C and about 300 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3The ratio of hydrogen to the C14-C32 product stream.

[0203] After distillation in OD, a C14-C32 paraffinic oil product with an aromatic compound content of at most 2000 ppm is obtained, which contains at least 50 wt% of C14-C32 isoparaffinic compounds, preferably at least 95 wt% of C18-C27 isoparaffinic compounds, and as measured according to ASTM D445 at 25 °C, its kinematic viscosity is in the range between 5.00 mm 2 / s and 15.00 mm 2 / s. The boiling temperature of the oil obtained after distillation is typically between about 300 °C and about 380 °C.

[0204] The C20-C70 product stream is distilled in one or more wax distillation towers (WD). In this specific embodiment, two wax distillation towers, WD1 and WD2 arranged in series, are utilized. The wax products obtained from WD1 and WD2 can be independent wax products, but they can also be mixed in a wax blending mixer (WMB) to obtain a paraffinic wax product.

[0205] The following Tables 1-1 and 1-2 show the compositions of various streams starting from different waste polyolefin feeds during the process according to the present disclosure.

[0206] Table 1-1: Composition of the group during the process (wt%), raw materials are PE / PP 70:30，5％ PS

[0207]

[0208]

[0209] Table 1-2: Composition of the group during the process (wt%), raw materials are PE / PP 30:70，5％ PS

[0210]

[0211] Exemplary products obtained by the method of the present disclosure

[0212] Tables 2-1 and 2-2 provide analysis data of various paraffinic solvents obtained by the method of the present disclosure from different waste polyolefin feeds. Tables 2-3 to 2-5 show the chemical compositions of various solvent fractions obtained from different feeds. Table 2-4 provides additional paraffinic solvent products obtained by the method according to another embodiment of the present disclosure.

[0213] Table 2-1: Analysis results of paraffinic solvents, raw material PE / PP

[0214]

[0215]

[0216] *BP - Boiling Point

[0217] Table 2 - 2: Analysis results of paraffinic solvents, raw material PE / PP, 5% PP

[0218]

[0219]

[0220] *BP - Boiling Point

[0221] Table 2 - 3: Different Solvent Composition of fractions (wt%), raw material PE / PP 30 / 70 + 5% PS

[0222] 100-150℃ 150-190℃ 190-240℃ 240-280℃ 280-320℃ n-paraffin 8-20 10-21 19-27 20-31 25-36 iso-paraffin 59-65 70-74 68-75 69-77 64-72 cycloparaffin 21-27 9-17 5-6 0-4 0-4 aromatic compound 0 0 0 0 0

[0223] Table 2 - 3: Composition of different solvent fractions (wt%), raw material PE / PP 70 / 30 + 5% PS

[0224] 100-150℃ 150-190℃ 190-240℃ 240-280℃ 280-320℃ n-paraffin 15-20 16-22 25-30 26-32 37-41 iso-paraffin 45-52 58-62 64-70 68-72 58-64 cycloparaffin 26-36 19-23 4-8 0-2 0 aromatic compound 0 0 0 0 0

[0225] Table 2 - 4: Composition of different solvent fractions (wt%), raw material PE / PP 70 / 30

[0226] 100-150℃ 150-190℃ 190-240℃ 240-280℃ 280-320℃ n-paraffin 18-22 24-28 32-38 36-42 55-62 iso-paraffin 60-64 60-66 60-65 58-63 38-45 cycloparaffin 16-20 8-12 0-5 0 0 aromatic compound 0 0 0 0 0

[0227] Table 2 - 5: Analysis results of additional paraffinic solvents

[0228]

[0229] *BP - Boiling Point

[0230] Table 3 provides the analytical data of the paraffinic oil products obtained by the method of the present disclosure.

[0231] Table 3 : Analysis results of paraffinic oil, raw material PE / PP, 5% PP

[0232]

[0233]

[0234] *BP - Boiling Point

[0235] Tables 4 - 1 and 4 - 2 provide the analytical data of the paraffinic waxes obtained by the method of the present disclosure.

[0236] Table 4 - 1: Analysis results of paraffinic wax, raw material PE / PP

[0237]

[0238] Table 4 - 2: Analysis results of paraffinic wax, raw material PE / PP + 5 wt% PS

[0239]

[0240]

[0241] Table 5 provides the analysis data of the solid product (i.e., the dried reactor residue) obtained by the method of the present disclosure.

[0242] Table 5: Analysis results of solid products

[0243] Parameter Method Solid 1 Appearance Visual Black solid <![CDATA[Density (15 °C) [kg / m 3 > PN-EN ISO 3838 1273 Sulfur content [wt%] PN EN 15408:2011 0.06 Nitrogen content [wt%] PN-G-04571:1998 0.06 Chlorine content [wt%] PN-EN 15408:2011 0.17 Hydrogen content [wt%] PN-G-04571:1998 8.82 Ash content [wt%] TGA 9.85 Carbon [wt%] PN-G-04571:1998 59.10 Volatiles [wt%] PN-G-04516:1998 86.20 Calorific value [MJ / kg] Calorimeter 41.40 Mercury content [ppm] ASA 0.005 Total moisture [wt%] TGA 0.80

Claims

1. A method for obtaining a paraffinic product having an aromatic compound content of at most about 3000 ppm from a polyolefin mixture, the method comprising: (a) In a pyrolysis reactor, under conditions including: (i) a pressure of at most 1 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between 2 hours and 40 hours, pyrolyzing the mixture in a molten state to obtain a hydrocarbon vapor stream; (b) Removing volatile C1-C5 compounds from the hydrocarbon vapor stream and quenching the remaining portion of the hydrocarbon vapor stream to obtain a condensate stream; (c) Transferring the condensate stream to 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 temperature between about 60 °C and about 330 °C, (ii) A C14-C32 product stream having a boiling temperature between about 300 °C and about 450 °C, and (iii) A C20-C70 product stream having a boiling temperature of at least about 350 °C; and (e) Further treating each of the product streams to obtain a paraffinic product, the paraffinic product comprising: (i) A C6-C20 paraffinic product having an aromatic compound content of at most about 3000 ppm, (ii) A C14-C32 paraffinic product having an aromatic compound content of at most about 3000 ppm, and (iii) A C20-C70 paraffinic product having an aromatic compound content of at most about 3000 ppm.

2. The method according to claim 1, wherein the aromatic compound content of the C6-C20 paraffinic product, the C14-C32 paraffinic product, and / or the C20-C70 paraffinic product is at most about 2000 ppm.

3. The method according to claim 1 or 2, wherein the aromatic compound content of each of the C6-C20 paraffinic product, the C14-C32 paraffinic product, or the C20-C70 paraffinic product is at most about 2000 ppm.

4. The method according to any one of claims 1 to 3, wherein the pyrolysis reactor includes a heating circulation loop defined between a circulation outlet and a circulation inlet for circulating a portion of the mixture through the heating circulation loop during pyrolysis.

5. The method according to claim 4, wherein the temperature in the circulation loop is between about 400 °C and about 450 °C.

6. The method according to any one of claims 4 or 5, wherein during pyrolysis, the portion of the mixture within the circulation loop is between about 2% and about 50% of the volume of the pyrolysis reactor.

7. The method according to any one of claims 1 to 6, wherein step (a) further includes removing solid residues from the pyrolysis reactor.

8. The method according to 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 between about 250 °C and about 340 °C, a pressure of at least 45 barg, and At least 150 Nm 3 / m 3 hydrogen to condensate stream ratio.

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

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

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

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

13. The method according to 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. The method according to any one of claims 10 to 13, wherein the catalytic hydrotreating of the C14-C32 product stream in step (e) is carried out under conditions including: a temperature between about 310 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 .

15. The method according to any one of claims 10 to 13, wherein the catalytic hydrotreating of the C14-C32 product stream in step (e) is carried out in two consecutive hydrotreating steps: Step (e1), which comprises hydrotreating the C16-C32 product stream under conditions including: a temperature between about 310 °C and about 360 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 ; and then performing Step (e2), which comprises hydrotreating the product of step (e1) under conditions including: a temperature between about 170 °C and about 300 °C, a pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 / m 3 of hydrogen to C14-C32 product stream ratio.

16. The method according to any one of claims 1 to 15, wherein the condensed stream of step (b) passes through at least one guard bed reactor comprising at least one guard bed catalyst before being introduced into step (c).

17. The method according to claim 16, wherein the temperature in the at least one guard bed reactor is between about 290 °C and about 340 °C.

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

19. The method according to any one of claims 1 to 18, wherein the polyolefin mixture comprises polyethylene and polypropylene.

20. The method according to claim 19, wherein the mixture comprises an amount of polyethylene between 10 wt% and 90 wt% and an amount of polypropylene between 10 wt% and 90 wt%.

21. The method according to claim 19, wherein the mixture consists essentially of polyethylene.

22. The method according to claim 19, wherein the mixture consists essentially of polypropylene.

23. The method according to any one of claims 1 to 22, wherein the mixture comprises at most 10% by weight of polystyrene.

24. The method according to any one of claims 1 to 23, wherein the mixture comprises at most 5% by weight of non-polyolefin polymers other than polystyrene.

25. A paraffinic solvent having a boiling range of at most 100 °C, an initial boiling point of at least 85 °C, and a final boiling point between 150 °C and 360 °C, the solvent comprising: n-paraffinic compounds in the range between about 15% and 65% by weight; iso-paraffinic compounds in the range between about 30% and about 75% by weight; cycloparaffinic compounds in the range between about 0% and about 35% by weight; and not more than about 3000 ppm of aromatic compounds.

26. The paraffinic solvent according to claim 25, which comprises less than 1% by weight of each of sulfur, chlorides, and nitrogen.

27. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range of 0.70 mm 2 / s to 0.90 mm 2 / s (measured at 25 °C according to ASTM D445).

28. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range of 1.00 mm 2 / s to 1.40 mm 2 / s (measured at 25 °C according to ASTM D445).

29. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range between 1.60 mm 2 / s and 1.90 mm 2 / s (measured at 25 °C according to ASTM D445).

30. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range of 1.80 mm 2 / s to 2.40 mm 2 / s (measured at 25 °C according to ASTM D445).

31. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range between 1.95 mm 2 / s and 3.10 mm 2 / s (measured at 25 °C according to ASTM D445).

32. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range of 5.50 mm 2 / s to 7.20 mm 2 / s (measured at 25 °C according to ASTM D445).

33. The paraffinic solvent according to claim 25 or 26, having 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 kinematic viscosity in the range between 3.30 mm 2 / s and 4.70 mm 2 / s (measured at 25 °C according to ASTM D445).

34. The paraffinic solvent according to any one of claims 25 to 33, which is obtained by the method according to any one of claims 1 to 24.

35. The paraffinic solvent according to any one of claims 25 to 33, which is used in cosmetic products, coatings, printing inks, plasticizers, degreasing agents, textile manufacturing, explosive manufacturing, cleaning product manufacturing, self-igniting barbecue bricks, solvent extraction (copper and others), road solvents, and wood preservatives.

36. A paraffinic oil comprising at least 50 wt% of C14-C32 isoparaffinic compounds, preferably at least 95 wt% of C14-C32 isoparaffinic compounds, and having a kinematic viscosity in the range between 5.00 mm 2 / s and 15.00 mm 2 / s as measured at 25 °C according to ASTM D445, the fluid comprising no more than about 3000 ppm of aromatic compounds.

37. The paraffinic oil according to claim 36, which has an initial boiling point of at least about 300 °C and a final boiling point of at least about 380 °C.

38. The paraffinic oil according to claim 36 or 37, which is obtained by the method according to any one of claims 1 to 24.

39. The paraffinic oil according to any one of claims 36 to 38, which is used in food processing, cosmetics, pharmaceutical formulations, energy storage devices, agricultural products, applications as base oils, metalworking fluids, and biodiesel substitutes.

40. A paraffinic wax comprising at least 95% by weight of C20-C70 n-paraffinic compounds (determined by GC / MS), an oil content between about 10% and 60% by weight, and not more than about 3000 ppm of aromatic compounds.

41. A paraffinic wax comprising at least 85% by weight of C20-C70 paraffinic compounds and not more than about 3000 ppm of aromatic compounds, the C20-C70 paraffinic compounds comprising at most about 85% by weight of C20-C70 iso-paraffins and at most about 60% by weight of C20-C70 n-paraffins (determined according to ASTM D5442).

42. The paraffinic wax according to claim 40 or 41, which is obtained by the method according to any one of claims 1 to 24.

43. The paraffinic wax according to any one of claims 40 to 42, which is used in the manufacture of shoe polishes, floor polishes, candles, tissue softening, waxed paper and paper packaging, matches, pesticide lures, tire manufacture, anti-ozone formulations, lubricant aids, anti-caking aids, agricultural products, fruit and / or vegetable coatings, hydrophobic coatings, concrete curing, fertilizers, cosmetics, hot melt adhesives (for food), mining, road applications (road resin markings, asphalt extensometers), fatty acid derivatives, PVC stabilizers and wax emulsions.

44. A solid product obtained by the method according to any one of claims 1 to 24 and comprising pyrolysis residues with a total solids (coke / carbon and ash) content of at least 50% by weight and a calorific value of at least 30 MJ / kg.

45. The solid product according to claim 44, which comprises at most 0.5% by weight of sulfur, at most 0.5% by weight of nitrogen, at most 0.3% by weight of chlorine and / or at most 0.01 ppm of mercury.

46. The solid product according to claim 44 or 45, which comprises between about 5% and 15% by weight of hydrogen.

47. The solid product according to any one of claims 44 to 46, which comprises between about 30% and 95% by weight of volatile components.

48. A method for recycling polyolefin waste, which comprises: (a) In a pyrolysis reactor, pyrolyzing the molten polyolefin waste under conditions including: (i) a pressure of at most 1 barg, (ii) a temperature in the range between about 320 °C and about 450 °C, (iii) the absence of oxygen, and (iv) a residence time of the mixture in the pyrolysis reactor between 2 hours and 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 condensed stream; (c) Transferring the condensed stream to 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 with a boiling temperature between about 60 °C and about 330 °C, (ii) A C14-C32 product stream with a boiling temperature between about 300 °C and about 450 °C, and (iii) A C20-C70 product stream with a boiling temperature of at least about 350 °C; and (e) Further processing each of the product streams to obtain the paraffinic products, the paraffinic products comprising: (i) A C6-C20 paraffinic product with an aromatic compound content of at most about 3000 ppm, (ii) A C14-C32 paraffinic product with an aromatic compound content of at most about 3000 ppm, and (iii) A C20-C70 paraffinic product with an aromatic compound content of at most about 3000 ppm.

49. The method according to claim 46, wherein the further processing in step (e) comprises: (i) Catalytically hydrotreat the C6-C20 product stream and then distill it in at least one solvent distillation column to obtain the C6-C20 paraffinic product with an aromatic compound content of at most about 3000 ppm, (ii) Catalytically hydrotreat the C14-C32 product stream and then distill it in at least one oil distillation column to obtain the C14-C32 paraffinic product with an aromatic compound content of at most about 3000 ppm, and (iii) Distill the C20-C70 product stream in at least one wax distillation column to obtain the C20-C70 paraffinic product with an aromatic compound content of at most about 3000 ppm.

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