Method for producing naphtha and gas oil from pyrolysis of plastics

Abstract

The present invention relates to producing hydrocarbon products from a polymer feed. In particular, the present invention relates to producing naphtha and gas oil from a polymer feed by pyrolysis and hydrogenation of the fluid product stream from the pyrolysis.

Description

Technical Field

[0001] The present invention relates to producing hydrocarbon products from a polymer feed. In particular, the present invention relates to producing naphtha and diesel from a polymer feed by pyrolysis and hydrogenation of the fluid product stream from pyrolysis.

Background Art

[0002] Plastics are one of the most commonly used materials due to their low cost and versatility. They are often produced for single-use purposes and account for approximately 10% of the commercial and household waste generated.

[0003] Plastic waste poses unique problems because it is not biodegradable and can remain in the environment for centuries if not disposed of using appropriate methods. Currently widely used methods for handling plastic waste include landfilling, incineration, and recycling. Since the current capacity of recycling and incineration facilities is small compared to landfilling capacity, most plastic waste ends up being landfilled. This is not consistent with the current efforts towards increased recycling and the use of environmental processes.

[0004] In incineration, some of the energy stored in the plastic returns in the form of thermal energy that can be used to generate steam, which can then be used to generate electricity. One of the biggest drawbacks of the incineration method is the production of carcinogenic furans and dioxin emissions. Another drawback of the incineration method is the form of the product. Incineration generates heat, but loses that energy when transported over long distances, so it can only be utilized in the immediate vicinity.

[0005] Plastic waste can be reused to produce new plastic products and recover plastic materials that can be used to produce new plastic products. However, the reuse of plastics requires time and labor-intensive collection and sorting, which makes the method less technically and economically feasible. Sorting plastics is difficult, cross-contamination is almost always inevitable, and recycled products that can only be used for low-grade applications are produced. Thorough cleaning before the reuse process is also necessary, generating additional waste.

[0006] The pyrolysis of plastics is one of the most promising plastic disposal methods for recovering energy from waste plastics in gaseous, liquid, and solid forms while minimizing the impurities emitted. Pyrolysis is the thermal decomposition of materials at high temperatures in the absence of oxygen. Therefore, neither combustion nor oxidation occurs. In the pyrolysis of plastics, plastic waste is heated to a high temperature and the waste is decomposed into combustible gaseous, liquid, and solid products.

[0007] Pyrolysis is considered the third reuse method as an excellent way to recover energy from plastic waste or produce useful products such as energy sources and chemical feedstocks. Compared with incineration, pyrolysis produces fewer toxic gases and has a higher energy recovery efficiency. Pyrolysis products are much more flexible and easier to transport compared to the thermal energy produced during incineration.

[0008] Pyrolysis is also less affected by cross-contamination of plastics than the reuse of plastics. Therefore, it does not require thorough sorting and is more feasible than the reuse of plastics. Pyrolysis is considered a promising green technology because even its gaseous by-products have a significant calorific value and can be reused in the pyrolysis stage to reduce the energy required for the pyrolysis plant.

[0009] The pyrolysis of plastics has typically focused on the conditions applied during pyrolysis in order to maximize the yield of a particular desired product, such as wax. Except for simply fractionating the product distribution obtained by optimizing the pyrolysis process, downstream separation has rarely been considered. However, although there are numerous factors (including, for example, operating temperature, heat consumption rate, residence time) that affect product yield and product composition, adjusting these typically shifts the distribution towards lighter products, increasing losses to non-condensable gases or towards long carbon chain waxes produced at the expense of lighter fractions. This compromises the adjustment of pyrolysis conditions to shift the product distribution towards a particular desired product where separation and collection are difficult or too inefficient and the amount of hydrocarbon fractions outside the target product is small. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] Therefore, it is desirable to develop a new method designed to more efficiently obtain useful product streams from the pyrolysis of plastics. MEANS FOR SOLVING THE PROBLEMS

[0011] Surprisingly, it has been found that by performing controlled pyrolysis in a rotary kiln reactor and hydrogenating the pyrolysis products obtained from the reactor prior to further processing, the distribution of hydrocarbon products by the pyrolysis process can be improved. In particular, the method has surprisingly been found to effect hydrocracking of a fraction containing a combination of naphtha and gas oil separated from heavier hydrocarbon products by pyrolysis, resulting in naphtha and gas oil in advantageous yields that can be efficiently separated from each other.

[0012] Accordingly, an aspect of the present invention is a method for producing naphtha and gas oil from a polymer feed, comprising: (i) preparing a polymer feed comprising at least 80 wt% polyolefin polymer, (ii) melting the polymer feed to prepare a molten polymer feed; (iii) feeding the molten polymer feed to a rotary kiln reactor comprising a plurality of sequential heating zones, each zone of the rotary kiln being operated at a temperature of 300 °C to 800 °C to pyrolyze the molten polymer feed to produce a fluid product stream and a solid char product; (iv) separating the solid char product from the fluid product stream; (v) C 5+ feeding the liquid fraction of the fluid product stream containing hydrocarbons to a hydrogenation reactor to hydrogenate the liquid fraction to produce a hydrogenated hydrocarbon product stream; (vi) fractionating the hydrogenated hydrocarbon product stream to produce a light hydrogenated fraction containing C 5-20 hydrocarbons; (vii) hydrocracking the light hydrogenated fraction to produce a light hydrocarbon product stream enriched in C 5-10 hydrocarbons; and (viii) fractionating the light hydrocarbon product stream from (vii) to produce a naphtha fraction and a light oil fraction. provided is a method comprising:

[0013] By pyrolyzing the plastic polymer in a temperature-controlled rotary kiln and hydrogenating the effluent from the kiln, the method has been found to provide an advantageous distribution of hydrocarbon products. In particular, by using this method, the yield of the light fraction containing C 5-20 hydrocarbons may be improved, which can be hydrocracked to provide a product enriched in C 5-10 hydrocarbons. In this method, this enriched C 5-20 stream can be separated particularly cleanly into a naphtha fraction (C 5-10 ) and a light oil fraction (C 10-20 ).

[0014] Of course, C 5-20Certain further product streams containing hydrocarbons within the range of also be efficiently separated from the enhanced C streams formed in accordance with the present invention. For example, a kerosene fraction containing hydrocarbons can be isolated from the enhanced C hydrocarbon stream. 5-20 stream. 8-16 For example, a kerosene fraction containing hydrocarbons can be isolated from the enhanced C 5-20 hydrocarbon stream.

[0015] A further aspect of the present invention is an apparatus for producing naphtha and gas oil from a polymer feed, comprising: (i) means for melting a polymer feed comprising at least 80 wt% polyolefin polymer to provide a molten polymer feed; (ii) a rotary kiln reactor configured to receive the molten polymer feed from part (i), the rotary kiln being configured to provide a plurality of sequential heating zones, each zone of the rotary kiln being operated at a temperature of 300 °C to 800 °C to pyrolyze the molten polymer feed and produce a fluid product stream and a solid char product; (iii) means for separating the solid char product from the fluid product stream; and (iv) a hydrogenation reactor configured to receive the liquid fraction of the fluid product stream containing C 5+ hydrocarbons and hydrogenate the liquid fraction to produce a hydrogenated hydrocarbon product stream; (v) means for fractionating the hydrogenated hydrocarbon product stream to produce a light hydrogenated fraction containing C 5-20 hydrocarbons; (vi) a hydrocracking reactor configured to catalytically crack the light hydrogenated fraction in the presence of hydrogen to produce a light hydrocarbon product stream enriched in C 5-10 hydrocarbons; and (vii) means for fractionating the light hydrocarbon product stream from (vi) to produce a naphtha fraction and a gas oil fraction. is provided.

[0016] In some embodiments, the apparatus may, for example, obtain a kerosene fraction from, for example, the enhanced C produced in part (vi).5-20 Additional means for obtaining other product streams may be included, such as from hydrocarbon streams. However, it will also be recognized that such isolated fractions can be obtained by the fractionation means of step (vii).

Brief Description of the Drawings

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Modes for Carrying Out the Invention

[0018] Polymer feed The polymer feed preferably comprises at least 80 wt% of a polyolefin polymer, such as at least 85 wt% of a polyolefin polymer. Preferably, the polymer feed comprises at least 90 wt% of a polyolefin polymer, preferably at least 95 wt% of a polyolefin polymer, such as at least 99 wt% of a polyolefin polymer. In some examples, the polymer feed consists essentially of a polyolefin polymer, such as a polyolefin polymer having only trace amounts of impurities and not significantly affecting the process or the product being formed.

[0019] Preferably, the polymer feed comprises or consists essentially of waste plastics. Sources of such waste materials include bags, bottles, films, sheets, fibers, fabrics, pipes, and other molded or extruded forms.

[0020] Thus, other plastic polymers may be present at 20 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less, such as 1 wt% or less of the polymer feed. Examples of other plastic materials include aromatic plastic polymers such as polystyrene; halogenated plastic polymers such as polyvinyl chloride and polytetrafluoroethylene; and polyester plastic polymers such as polyethylene terephthalate. In some examples, these polymers may cause gum formation, disrupt operation, and require cleaning, and thus are preferably limited in the polymer feed. Halogen-containing polymers may also form hydrohalic acids during pyrolysis, which may cause corrosion problems or require additional processing steps and / or equipment to neutralize or trap the acids.

[0021] As will be appreciated, the polymer feed may, in some instances, contain residual impurities that may be present in the waste plastic, such as dirt, paper, adhesives and pigments from labels, for example, or metals. Preferably, such impurities are present in the polymer feed in an amount of less than 5 wt%, preferably less than 1 wt%.

[0022] In some embodiments, the method may include removing non-polyolefin polymers and / or non-plastic impurities using, for example, a magnet for removing metals or an optical sorting process, prior to providing the feed to the method.

[0023] Preferably, the polyolefin polymer in the feed comprises, or consists essentially of, polyethylene and polypropylene. For example, the polyolefin polymer may comprise at least 90 wt% polyethylene and polypropylene, preferably at least 95 wt% polyethylene and polypropylene, such as at least 99 wt% polyethylene and polypropylene. The polyethylene may be any form of polyethylene, but preferably comprises, or consists essentially of, high-density polyethylene (HDPE) and low-density polyethylene (LDPE). Thus, the polymer feed may comprise, or consist essentially of, high-density polyethylene (HDPE), low-density polyethylene (LDPE) and polypropylene. In some preferred embodiments, the polyolefin polymer in the feed comprises, or consists essentially of, polyethylene (such as LDPE and HDPE), for example at least 90 wt% polyethylene, preferably at least 95 wt% polyethylene, such as at least 99 wt% polyethylene. In some preferred embodiments, the polyolefin polymer in the feed comprises at least 40 wt% polyethylene, preferably at least 50 wt% polyethylene.

[0024] Both LDPE and HDPE are polymers of ethylene and have the formula (CH2CH2). n The properties of polyethylene, and thus its classification as LDPE or HDPE and its uses, depend on factors such as molecular weight, branching, and density. LDPE preferably has a molecular weight of 30,000 - 50,000 g / mol and a density of 0.910 - 0.925 g / cm 3 . HDPE preferably has a molecular weight of 200,000 - 500,000 g / mol and a density of 0.941 - 0.980 g / cm 3 . LDPE preferably has branches at 1 - 4% carbon atoms, more preferably 1 - 3% carbon atoms, and even more preferably 1.5 - 2.5% carbon atoms. HDPE preferably has fewer branches than LDPE, for example, less than 2% carbon atoms, preferably less than 1% carbon atoms, more preferably less than 0.5% carbon atoms, and even more preferably less than 0.1% carbon atoms. Since LDPE generally has more branches than HDPE, it has weaker intermolecular forces between chains, lower tensile strength, and higher elasticity than HDPE. In contrast, HDPE is known for its high strength-to-density ratio. HDPE is generally used in the production of many items, including plastic bags, plastic bottles, pipes, and containers. LDPE is generally used in parts that require flexibility, such as snap-on lids, trays, and containers, and plastic wrap.

[0025] Polypropylene is a polymer of propylene and has the formula (CH(CH3)CH2). n Preferably, the density of polypropylene is 0.895 - 0.92 g / cm 3 . Polypropylene can have a melting point of 130°C - 170°C depending on its stereoregularity. Generally, the properties of polypropylene may be considered similar to those of polyethylene, but the methyl group improves the mechanical properties and heat resistance. Generally, polypropylene is tough and flexible and has good fatigue resistance. Therefore, polypropylene can be used for hinges. Polypropylene can also be used in applications that require high temperatures, such as medical applications that require the use of an autoclave or kettle.

[0026] In addition, polyethylene and polypropylene may be copolymerized with other monomers. The monomers to be selected depend on the required properties. For example, PE may be copolymerized with vinyl acetate or acrylate. These copolymers can be used respectively in the foams of the soles of sports shoes and in packaging and sports goods. In particular, polyethylene and polypropylene may be copolymerized. For example, a random copolymer of polypropylene and polyethylene can be used in plastic pipework.

[0027] Polyvinyl chloride (PVC) is a polymer containing chlorine. The main product of PVC pyrolysis is hydrochloric acid (HCl), and the yield of pyrolysis oil is low. The toxic and corrosive properties of HCl not only damage the processing equipment but also have an adverse impact on the environment and human health. For these reasons, it is particularly preferred not to use PVC for pyrolysis or to use only a small amount. Such a small amount is ideally less than 0.1% by weight of the polymer feed, preferably less than 0.07% by weight, more preferably less than 0.05% by weight. In order to remove the hydrochloric acid that may be present / formed during the treatment, calcium oxide may be added to the plastic feed material. It will be recognized that the amount of calcium oxide used may vary depending on the amount of chlorine-containing polymer, such as PVC, in the polymer feed. Calcium oxide may be added in an amount of 1% to 5% by weight, preferably 2% to 4% by weight, more preferably 2.5% to 3.5% by weight, based on the plastic feed. Calcium oxide is preferably added to the polymer feed before pyrolysis, for example, before being fed into the kiln. For example, calcium oxide may be added to the polymer feed in the melt extruder before entering the kiln, such as by adding calcium oxide to the hopper that supplies the feed plastic to the melt extruder.

[0028] The polymer feed is preferably melted to provide a molten plastic feed for pyrolysis. The polymer feed may be processed prior to melting, for example, by extrusion, cutting and / or shearing, to change the shape and / or size of the plastic. The plastic feed may be in the form of pellets, flakes, threads or fibers, films, and may be cut. Preferably, the plastic feed is processed to increase the surface area, whereby melting can be assisted.

[0029] For example, the polymer feed is preferably melted prior to pyrolysis by following extrusion of the plastic feed and then melting, or by conveying the molten plastic for pyrolysis in a rotary kiln. For example, melting is preferably carried out in a melt extruder. Alternatively, the polymer feed may be melted at the inlet to a heated rotary kiln or within the melting zone of the kiln before the heating zone where pyrolysis occurs. The step of melting the polymer feed may include heating the polymer feed to a temperature of 200 to 400 °C, preferably 250 to 350 °C, more preferably 265 to 325 °C. The melt extruder may preferably include a heated screw extruder that can be heated in any suitable manner, for example, using an electric heater. In other embodiments, the polymer feed may be melted by microwave heating.

[0030] Pyrolysis The pyrolysis of the polymer feed is carried out by providing the molten polymer feed to a plurality of sequential heating zones of a rotary kiln reactor. Rotary kilns are known to those skilled in the art and typically can include a substantially cylindrical (e.g., tube-shaped) reactor configured to rotate about its long axis (i.e., the axis extending along its length through the center of the circular cross-section of the reactor tube). The rotary kiln can have a variety of exact configurations but typically has an inlet at one end of the reactor and an outlet at the opposite end. The molten polymer feed can be supplied to the kiln from a melt extruder through any suitable means, such as a suitable transfer pipe. The rotary kiln is inclined to provide a height difference between its two ends such that the polymer feed and intermediate pyrolysis products (i.e., pyrolysis products formed from the feed that still exist in the kiln and may or may not undergo further cracking before exiting the kiln) can move under gravity from the inlet to the outlet while the kiln is rotating. The rotation of the kiln is not particularly limited and can rotate, for example, at a speed of 0.1 to 5 rpm, such as 0.1 to 2 rpm.

[0031] The pyrolysis can generally be carried out using any suitable conditions known to those skilled in the art and is carried out by heating the polymer feed in the absence of oxygen. The pyrolysis is preferably carried out under an inert atmosphere, such as nitrogen or argon, preferably nitrogen. Thus, in a preferred embodiment, the rotary kiln is maintained under an inert gas atmosphere, preferably nitrogen.

[0032] As described, the rotary kiln includes a plurality of heating zones, preferably four or more sequential heating zones, and preferably each heating zone is operated at a higher temperature than the previous zone. Each heating zone of the rotary kiln is preferably operated at a temperature of 300 °C to 800 °C, and preferably each zone of the rotary kiln is operated at a temperature of 310 °C to 720 °C, such as 400 °C to 670 °C. In a preferred embodiment, the polymer feed undergoes a temperature increase as it passes through the kiln from zone to zone. For example, in a preferred embodiment, the four or more sequential heating zones include sequential zones that operate from 310 °C to 600 °C in the first zone to 480 °C to 710 °C in the final zone. Preferably, the final zone among the plurality of zones is heated to a higher temperature than the other heating zones. By heating to a higher temperature in the final zone, it is not necessary to maintain a high temperature that can cause overcracking of the polymer feed throughout the kiln, and it has been found that the loss of hydrocarbon products containing char is reduced and the processability of the char is increased. In some embodiments, the heating zone may include at least six sequential heating zones. The heating zones suitably include separate, discrete heating zones, such that each zone is heated to a predetermined temperature and each subsequent zone is heated to a higher temperature. The flow of material through the kiln (i.e., the polymer feed and intermediate pyrolysis products) may be substantially constant along its length. Thus, by varying the length of each heating zone within the kiln, the residence time in each heating zone can be appropriately varied. In some preferred embodiments, each heating zone is of equal length, providing an equal residence time within each zone, but this is not essential.

[0033] The temperature of the zone referred to herein is understood to refer to the temperature of the wall of the rotary kiln in each zone, and it will be recognized that the exact temperature of the polymer or pyrolysis material within the reactor can vary.

[0034] By providing a pyrolysis process using the rotary kiln described, light hydrocarbons (e.g., C5-C20 ) ratio can be increased, and moreover, the formation of non-condensable gas due to overcracking is minimized, and it has been found that other beneficial hydrocarbon fractions and products such as wax and char are also produced. In particular, surprisingly, approximately 60% by weight of the condensable hydrocarbon product obtained from the kiln (i.e., the condensable liquid separated from the char) is within the range of gas oil or lighter, i.e., has a boiling point of about 350 °C or lower. The heavier hydrocarbons in the product preferably form waxes having a melting point of less than 100 °C, preferably 85 °C or lower. Thus, the liquid hydrocarbon product stream from the kiln is C 5-20 a light hydrogenated fraction containing hydrocarbons, and C 20+ a hydrogenated wax fraction containing hydrocarbons and having a melting point of less than 100 °C, preferably 85 °C or lower. In some preferred embodiments, the wax fraction may advantageously be further separated to provide three separate wax fractions (30 / 40 grade, 50 / 60 grade, and 70 / 80 grade waxes) having freezing points in the ranges of 30 - 40 °C, 50 - 60 °C, and 70 - 80 °C, respectively. The use of a rotary kiln advantageously results in continuous production of hydrocarbon products, with the polymer feed being continuously supplied to the inlet of the kiln and the product being continuously withdrawn from the outlet.

[0035] The pyrolysis vessel may be operated at atmospheric pressure (1 atm), for example, approximately 101 kPa. Preferably, the rotary kiln is operated at a slight negative pressure, for example, less than 50 kPa below atmospheric pressure, preferably less than 10 kPa below atmospheric pressure, more preferably less than 0.1 kPa below atmospheric pressure, and most preferably less than 0.01 kPa below atmospheric pressure, for example, maintained at 90 kPa to 101 kPa, or preferably 95 kPa to 101 kPa. Thus, the rotary kiln is preferably operated at approximately atmospheric pressure or a slight negative pressure of 0.9 bar or more in absolute pressure, for example, 0.95 bar or more in absolute pressure. As will be appreciated, the pressure within the rotary kiln can be controlled by controlling and balancing the flow, particularly the flow of gas entering and exiting the reactor. In particular, the slight negative pressure within the kiln may simply be the result of withdrawing the product from the outlet of the kiln through the condensation system.

[0036] The residence time in the reactor can be varied by controlling the flow rate of the polymer feed entering the kiln and the flow of the product exiting the kiln, as well as by the configuration of the kiln itself. For example, to provide the desired flow of feed and intermediate pyrolysis products through the kiln, the physical orientation of the kiln (i.e., the degree to which the kiln is inclined from horizontal) and / or the speed of rotation of the kiln may be varied. By using a rotary kiln having a plurality of heating zones in the present method, the residence time of the polymer feed and intermediate pyrolysis products in the kiln and within each heating zone can be advantageously controlled. Thereby, to vary the product composition, for example, to vary the method in response to changes in the polymer feed, to maintain a constant product composition, or to vary the method to vary the distribution of various products (e.g., the amounts of various hydrocarbon fractions) to meet requirements, the method can be easily adapted. As will be appreciated, the residence time may be varied according to the operating conditions inside the kiln. Preferably, the residence time in the kiln is from 30 minutes to 120 minutes, more preferably from 40 minutes to 70 minutes. As previously discussed, the kiln may include a final zone that is heated to a higher temperature than the preceding zones. Thus, the residence time of the feed inside the kiln may be 30 to 60 minutes, for example 40 to 50 minutes, at a temperature of 310°C to 600°C, and in the final zone 5 to 30 minutes, for example 10 to 20 minutes, at a temperature of 480°C to 710°C. The residence time refers to the time it takes for the molten feed present in the kiln to pass from the inlet to the outlet, but it should be recognized that the pyrolysis vapors formed during processing may exit the kiln more rapidly in the gas phase. A flow of an inert gas, preferably nitrogen, is provided at the inlet of the kiln to provide an inert atmosphere and to provide a gas flow for carrying the pyrolysis vapors to the outlet of the kiln.

[0037] The heating of the rotary kiln may be by any suitable means, preferably the rotary kiln is an indirectly heated rotary kiln containing one or more heaters, and the walls of the kiln are heated from the outside to effect heating of the material within the kiln. For example, the kiln may include a rotary kiln surrounded by a furnace or having any suitable heater configured to heat the walls of the kiln. As will be appreciated, the one or more heaters may be separate and arranged to heat each heating zone of the kiln separately, or the one or more heaters may be combined. For example, the heater may include a furnace having a plurality of burners at different points along the length of the kiln, each burner being controllable (e.g., by controlling the fuel flow to the burner) to provide a different heating output, and in some examples, the furnace may include a common volume surrounding the kiln and a common exhaust outlet for the combustion gases from all the burners. Nevertheless, it will be recognized that any suitable heater may be provided to heat the heating zones of the kiln.

[0038] The method preferably may also include, following the heating zone, a step of cooling and condensing the pyrolysis products. For example, the kiln may include one or more condensers at or connected to the vapor outlet of the kiln. For example, the kiln may include a vapor outlet for providing a gas containing pyrolysis vapors to one or more condensers and a char outlet for receiving solid char from the kiln. The means for cooling and condensing the pyrolysis products may include any suitable condenser or condenser system. Preferably, the one or more condensers may be provided with a gaseous fluid product stream of pyrolysis products from the vapor outlet of the kiln. The fluid product stream may be a vapor stream that may contain a liquid or solid (e.g., fine char particles) as an aerosol, and the condenser is configured to provide a liquid fraction containing hydrocarbons along with the non-condensable gas. It will be recognized that the one or more condensers may, for example, 5+ be configured to provide a liquid fraction containing hydrocarbons. The one or more condensers may, for example, 5+It may include a quench tower configured to condense a liquid fraction containing hydrocarbons, and optionally C remaining in the gaseous emissions from the quench tower 5+ It may include one or more additional condensation stages configured to condense hydrocarbons and optionally to condense and separate an LPG fraction from the gas. Thus, the condensation system for condensing the vapors from the kiln may include a quench tower and preferably a first condensation stage operable at about 50 - 70 °C and may include, for example, one or more tube and shell condensers and a second condensation stage operable at about 10 - 30 °C. The non-condensable gas may, in some embodiments, be used to provide fuel for heating the kiln.

[0039] Pyrolysis products Pyrolysis in the kiln produces a fluid product stream and a solid char product, and preferably the pyrolysis products from the kiln consist essentially of the fluid product stream and the char. The fluid product stream typically contains hydrocarbons of a range of diverse chain lengths including a liquid fraction containing hydrocarbons and a non-condensable gas fraction 5+ The fluid product stream preferably consists essentially of a non-condensable gas fraction and a liquid fraction containing hydrocarbons, and the non-condensable gas fraction is separated from the liquid fraction prior to the hydrogenation step (v). For example, the non-condensable gas may be appropriately withdrawn from the fluid product stream during condensation, where the fluid product stream is condensed to provide a liquid fraction and the non-condensable gas can be removed. As will be appreciated, the composition of the liquid fraction can depend on the processing conditions and the manner in which the non-condensable gas is separated. For example, in some instances, the liquid fraction may contain a small proportion of lighter hydrocarbons, such as C4 hydrocarbons, but preferably less than 1 wt%, for example less than 0.5 wt% or less than 0.1 wt%. Preferably, the non-condensable gas comprises less than 30 wt%, more preferably less than 25 wt%, for example less than 20 wt% of the fluid product stream. Preferably, C 5+ hydrocarbons and a liquid fraction containing hydrocarbons, and the non-condensable gas fraction is separated from the liquid fraction prior to the hydrogenation step (v). For example, the non-condensable gas may be appropriately withdrawn from the fluid product stream during condensation, where the fluid product stream is condensed to provide a liquid fraction and the non-condensable gas can be removed. As will be appreciated, the composition of the liquid fraction can depend on the processing conditions and the manner in which the non-condensable gas is separated. For example, in some instances, the liquid fraction may contain a small proportion of lighter hydrocarbons, such as C4 hydrocarbons, but preferably less than 1 wt%, for example less than 0.5 wt% or less than 0.1 wt%. Preferably, the non-condensable gas comprises less than 30 wt%, more preferably less than 25 wt%, for example less than 20 wt% of the fluid product stream. Preferably, C 5+The liquid fraction containing hydrocarbons accounts for at least 60% by weight, preferably at least 65% by weight, more preferably at least 70% by weight, for example at least 75% by weight, for example about 80% by weight of the total emissions from the kiln (the total emissions include the liquid fraction, non-condensable gas and char).

[0040] The non-condensable gas may typically contain C1-C4 hydrocarbon gases and in some preferred embodiments is recycled to heat the kiln and / or to heat and melt the polymer feed. In some embodiments, the C3 and C4 hydrocarbon gases from the non-condensable gas, and the C4 gas recovered from the liquid fraction, may be separated and provided as an LPG product stream. Any C present in the non-condensable gas from the condensation, if present 5+ The hydrocarbons may be recovered and combined with the liquid fraction or its downstream products (e.g., up to the naphtha fraction).

[0041] The solid char product preferably accounts for 15% by weight or less, preferably 10% by weight or less of the emissions from the kiln. The solid char product may in some embodiments contain 10-60% by weight of carbon, for example 20-40% by weight of carbon, which refers to the carbon content of the char itself, and the remainder contains various non-pyrolyzable materials present in the polymer feed, such as inorganic materials and metals, as will be recognized.

[0042] The method preferably includes the step of separating solid char product from the fluid product stream. Such separation can be carried out in any suitable manner known for separating solids from a fluid stream. Most of the char is obtained from the rotary kiln as a solid product stream and is thus separated from the pyrolysis vapors by providing the char from a char outlet from the kiln, separate from the vapor outlet. Nevertheless, some char may still be present as an aerosol in the vapors exiting the kiln that are condensed. Such residual char in the liquid product may be removed in any suitable manner. Preferably, the condensed fluid product stream is separated from the residual solid char using decanter centrifugation or tricanter centrifugation. For example, the liquid from a condenser, such as a quench tower, may be combined with water and separated in a tricanter centrifuge that separates solid char from the pyrolysis oil liquid fraction and water. The liquid fraction may, in some embodiments, be filtered before being sent to a hydrogenation step to remove any residual solids.

[0043] Since the rotary kiln can continuously remove char from the reactor (e.g., as compared to a stirred tank reactor), the method does not need to stop the process to remove solid residues, such as char or other non-volatile residues, from the reactor and can operate continuously. This allows the process to also continuously produce the desired range of hydrocarbon products without the need (as in a tank reactor) to remove the char product to avoid downtime and cleaning.

[0044] C 5+The liquid fraction from the kiln containing hydrocarbons may have a freezing point in the range of, for example, 40°C to 60°C, such as 45°C to 55°C (e.g., 60°C or less, or 55°C or less), and / or a density of 0.6 g / ml to 0.9 g / ml, such as 0.7 g / ml to 0.8 g / ml. Depending on the polymer feed to the kiln, the liquid hydrocarbon fraction may contain sulfur at a concentration of less than 30 mg / kg (measured according to ASTM D5453-19a), but in some examples, the sulfur concentration can be at least 5 mg / kg or at least 10 mg / kg. Depending on the feed composition and any steps taken to remove chlorine (e.g., in PVC) from the feed, the liquid hydrocarbon fraction may contain chlorine at a concentration of less than 100 mg / kg (measured according to UOP 779-08), preferably less than 80 mg / kg, but in some examples, the chlorine concentration can be at least 10 mg / kg, or at least 40 mg / kg, such as at least 60 mg / kg. It will be appreciated that in some examples, such impurities may be reduced by treating or controlling the composition of the polymer feed prior to pyrolysis. The liquid hydrocarbon fraction from the kiln may have a bromine index of, for example, 10 to 50 gBr / 100 g, preferably 10 to 30 gBr / 100 g, such as 15 to 25 gBr / 100 g.

[0045] Hydrogenation C from the kiln 5+ The liquid fraction of the fluid product stream containing hydrocarbons is hydrogenated to provide a hydrogenated product stream. Preferably, C 5+ The entire liquid fraction of the fluid product stream containing hydrocarbons (i.e., all of the pyrolysis products excluding char and non-condensable gas) is sent to a hydrogenation reactor and hydrogenated to produce a hydrogenated hydrocarbon product stream.

[0046] Hydrocarbon streams containing those derived from the pyrolysis of plastics may typically contain various heteroatoms, such as N, S, O, as impurities, which may adversely affect the properties of the hydrocarbon products. The pyrolysis of polyolefin plastics also typically produces a mixture of olefins and saturated hydrocarbons. Olefins and heteroatom-containing hydrocarbons are more chemically reactive than paraffins. By performing hydrogenation of the entire liquid fraction of the fluid product stream from the kiln prior to further fractionation or processing steps, side reactions of olefins or heteroatom-containing hydrocarbons, such as polymerization, can be advantageously avoided. In addition, since the boiling points of olefin and heteroatom-containing hydrocarbon molecules change compared to saturated hydrocarbons, the presence of heteroatom-containing molecules and olefins may then be more cleanly separable depending on the carbon number.

[0047] Hydrogenation can be carried out in any suitable manner, preferably including contacting the liquid fraction of the fluid product stream with a hydrogenation catalyst and hydrogen gas at a temperature of 250 °C to 400 °C, preferably 250 °C to 350 °C. Due to the exothermic hydrogenation reaction, it will be recognized that the temperature can appropriately rise from the inlet to the outlet of the hydrogenation reactor. Therefore, the temperature of the catalyst bed in the hydrogenation reactor can vary from 250 °C to 400 °C, preferably 250 °C to 350 °C. The pressure in the hydrogenation reactor can preferably be 3 MPa to 10 MPa, preferably 4 MPa to 6 MPa (in some examples, the pressure can be higher, such as up to 20 MPa). The liquid hourly space velocity (LHSV) of the fluid product stream through the reactor can be 0.5 kg / kg / hr to 10 kg / kg / hr, preferably 0.5 kg / kg / hr to 4 kg / kg / hr, more preferably 0.7 kg / kg / hr to 2.5 kg / kg / hr, most preferably 0.8 kg / kg / hr to 1.5 kg / kg / hr, for example 0.9 kg / kg / hr to 1.3 kg / kg / hr. The ratio of hydrogen gas to the feed liquid in the hydrogenation can appropriately be 300 NV / NV to 1000 NV / NV, preferably 400 NV / NV to 600 NV / NV, for example 450 NV / NV to 550 NV / NV. The hydrogen consumption during the hydrogenation step varies based on the feed to the hydrogenation reactor and other conditions, but can be, for example, in the range of 6 to 12 gH2 / kg, for example 8 to 10 gH2 / kg.

[0048] Hydrogenation can be carried out in any suitable reactor for contacting the liquid fraction with hydrogen gas. Preferably, the hydrogenation reactor includes a fixed bed reactor. The aspect ratio of the fixed bed reactor can be any suitable ratio, such as 5:1 to 20:1, preferably 8:1 to 16:1, for example 10:1 to 14:1, for example about 12:1. The hydrogenation reactor is preferably a trickle bed reactor. In some embodiments, the hydrogenation reactor can alternatively be a fluidized bed reactor or a microchannel reactor.

[0049] The hydrogenation catalyst may be any suitable catalyst, preferably a metal catalyst. The metal hydrogenation catalyst preferably contains a metal selected from Group VIII of the periodic table. Preferably, the catalyst contains Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and / or Pt. For example, the catalyst contains Ni, Co, Mo, W, Cu, Pd, Ru, Pt. In a preferred embodiment, the catalyst is selected from CoMo, NiMo, or Ni, preferably NiMo. The hydrogenation catalyst is preferably supported on a carrier such as bauxite, alumina, silica, silica-alumina, or zeolite. Preferably, the catalyst is supported on alumina. For example, the hydrogenation catalyst may include NiMo supported on alumina (NiMo / Al2O3).

[0050] The hydrogenation reactor may include a gas recirculation loop for recycling hydrogen passing through the reactor. Hydrogenation preferably includes hydrodesulfurization, and the gas-phase H2S concentration in the reactor can be 0.05% - 0.5%, for example, about 0.1%. In some embodiments, H2S can be introduced into the recycle gas by passing the CS2 liquid at ambient temperature and reaction pressure.

[0051] In some preferred embodiments, hydrogenation includes providing the hydrogenation effluent to a second hydrogenation stage that can be carried out under substantially the same conditions as the first hydrogenation step. The second hydrogenation step can be carried out at a higher initial temperature than the first hydrogenation step in some examples, but due to the low exotherm, the temperature can still remain in the range of 250°C - 350°C, preferably 300°C - 350°C. The second hydrogenation step can be carried out with a longer contact time, for example, a lower liquid hourly space velocity than the first hydrogenation step. The second hydrogenation step has a minimal effect on heteroatom removal, but advantageously, olefins in the hydrogenation product stream, especially C 5-20It has been found that the presence of olefins within the range can be reduced. In some embodiments, the first and second hydrogenation steps may include a combined hydrogenation step corresponding to performing the first hydrogenation step and the second hydrogenation step continuously. For example, by increasing the length of the catalyst bed or decreasing the flow rate of the feed through the reactor, a single hydrogenation step with an increased contact time through the catalyst bed, or preferably a single hydrogenation step, may use a hydrogenation reactor including two catalyst beds with different catalysts having different activities. In such a hydrogenation step, the hydrogen consumption during the hydrogenation step can be, for example, at least 9 gH2 / kg.

[0052] After the hydrogenation step, the hydrogenated hydrocarbon product stream can have a freezing point, for example, within the range of 40°C to 60°C, such as 50°C to 60°C, or for example, 60°C or lower. The freezing point referred to herein can be measured by ASTM D938-12 (2017). The hydrogenated hydrocarbon product stream can have a density of 0.7 g / ml to 0.9 g / ml, such as 0.75 g / ml to 0.85 g / ml. Depending on the hydrogenation conditions and the sulfur content of the feed to the hydrogenation, the hydrogenated hydrocarbon product stream can contain sulfur at a concentration of less than 15 mg / kg (measured by ASTM D5453-19a), preferably less than 10 mg / kg, more preferably less than 5 mg / kg, such as less than 2 mg / kg. Depending on the hydrogenation conditions and the chlorine content of the feed to the hydrogenation, the hydrogenated hydrocarbon product stream can contain chlorine at a concentration of less than 15 mg / kg (measured by UOP 779-08), preferably less than 10 mg / kg, such as less than 5 mg / kg, or less than 2 mg / kg. The hydrogenated hydrocarbon product stream preferably has a bromine index of less than 2 gBr / 100 g, preferably less than 1 gBr / 100 g, such as less than 0.7 gBr / 100 g, or for example, 0.5 gBr / 100 g or less. As will be appreciated, the hydrogenation conditions can be selected to provide the bromine index described above, and / or the levels of sulfur and / or chlorine. Thus, if necessary, the hydrogenation conditions can be adjusted to increase the contact time, increase the ratio of hydrogen gas to the feed liquid, or use a more active catalyst.

[0053] Fractionation of the hydrogenated hydrocarbon product stream The method includes fractionating a hydrogenated hydrocarbon product stream to produce a light hydrogenated fraction containing C 5-20 hydrocarbons. It will also be recognized that the light hydrogenated fraction may contain small amounts of heavier hydrocarbons up to about C 25 and small amounts of C4 hydrocarbons. However, the light hydrogenated fraction preferably contains less than 2 wt%, such as less than 1 wt%, of C 21+ hydrocarbons and / or less than 1 wt%, preferably less than 0.5 wt%, of C4 hydrocarbons. For example, the light hydrogenated fraction preferably consists essentially of C5-C 20 hydrocarbons. Preferably, the light hydrogenated fraction containing C 5-20 hydrocarbons (e.g., components boiling up to 350° C.) comprises more than 50 wt% of the hydrogenated hydrocarbon product stream, preferably more than 55 wt% of the hydrogenated hydrocarbon product stream.

[0054] C 5-10 naptha fraction and C 10-20 light oil fraction are desired, and C 8-16 kerosene fraction may also be produced. Surprisingly, however, first fractionating the hydrogenated hydrocarbon product stream to provide a light hydrogenated C 5-20 fraction and a C 20+ wax fraction has been found to achieve increased efficiency. Without wishing to be bound by any particular theory, the method results in generally only small proportions (less than 2 wt%) of C 5-8 hydrocarbons in the liquid fraction of the fluid product stream from the kiln, and thus separation of the hydrogenated hydrocarbon product stream in the manner described minimizes the processing loss of naptha fraction hydrocarbons during this separation step (e.g., as compared to the initial separation of naptha as a light fraction from other products that can typically be done). The subsequent hydrocracking step then results in an advantageous distribution of hydrocarbons, enabling the production of naptha and light oil fractions in higher yields and efficiencies. Thus, the fractionation step preferably separates the hydrogenated hydrocarbon product stream into C 5-20a light hydrogenated fraction containing hydrocarbons and a C 20+ wax fraction. Additionally, as discussed previously, performing a fractionation step after hydrogenation can help avoid loss of some of the desired C 5-20 hydrocarbons as non-condensable gas or contamination of the light hydrogenated fraction by longer hydrocarbons due to the difference in boiling points of olefins and heteroatom-containing species compared to paraffins.

[0055] The fractionation can be carried out using any suitable fractionation means, such as a fractionation column, or by fractional condensation. Preferably, the step of fractionating the hydrogenated hydrocarbon product stream comprises fractionating in a fractionation column.

[0056] The fractionation may preferably include providing the hydrogenated hydrocarbon product stream to a vacuum distillation system. The fractionation may include, for example, using a reboiler configured to improve liquid evaporation efficiency and heat exchange in the reboiler, equipped with a jet spray evaporation device and a forced flow mechanism, configured to improve evaporation of the liquid.

[0057] The evaporation temperature of the liquid in the fractionation (e.g., the liquid exiting the reboiler) can be 260°C to 320°C, preferably 270°C to 300°C, for example 280°C to 290°C. It has been found that minimization of the decomposition of the hydrocarbon product stream can be achieved under such conditions. The evaporation output can be, for example, 0.5 kW to 2 kW, for example 0.9 kW to 1.3 kW. The evaporation pressure can be 3 to 8 kPa absolute (e.g., the pressure above the liquid in the reboiler), preferably 4 to 6 kPa absolute. The condensation of the evaporation product can be carried out by cooling to approximately less than 25°C, for example about 20°C. The hydrocarbon product stream can be fed to the fractionation at a temperature of, for example, 60°C to 300°C, for example 70°C to 200°C, for example 80°C to 120°C, for example approximately 100°C. The reflux rate in the fractionation can be, for example, 0.5 l / hr to 2 l / hr, for example 0.8 l / hr to 1.2 l / hr. The vacuum system may suitably include a cooling trap, for example a cooling trap at approximately -78°C or below, to prevent loss of light components.

[0058] In some embodiments, the method may further include fractionating a light hydrogenated fraction containing hydrocarbons formed in step (vi) before the hydrocracking step. 5-20 The further fractionation step may separate one or more of a crude naphtha fraction (crude C 5-10 hydrocarbon fraction), a crude light oil fraction (crude C 10-20 hydrocarbon fraction) and a crude kerosene fraction (crude C 8-16 hydrocarbon fraction) at least partially from the remaining light hydrogenated fraction. One or more of the crude fractions at least partially separated from the light hydrogenated fraction can be blended with other materials (e.g., fossil fuel materials). In particular, one or more of the crude fractions at least partially separated can be blended with naphtha, gas oil or kerosene derived from petroleum produced by conventional refining methods.

[0059] For example, the crude kerosene fraction can be blended with gas oil produced from conventional petroleum refining methods to improve its performance characteristics at low temperatures. As a further example, the crude kerosene fraction can be blended with naphtha derived from crude oil to produce naphtha-kerosene jet fuel (Jet B). The crude naphtha, gas oil, and / or kerosene fraction at least partially separated from the light hydrogenated fraction (C 5-20 ) can be blended with a fossil fuel-derived material in an amount of at least 5 wt%, preferably at least 10 wt%, more preferably at least 15 wt%, for example at least 20 wt% of the blended fuel composition.

[0060] By replacing at least a portion of the conventional fossil fuel with a fuel derived from waste plastics, the amount of waste present in a landfill or targeted for disposal in a landfill can be reduced. Further, unlike some methods of forming biofuels that require the use of food crops, such as corn, sugar cane, and vegetable oils, as sources of biomass, waste plastics are readily available and do not require dedicated land to produce sufficient starting material.

[0061] The further fractionation step of forming the crude naphtha, gas oil, and / or kerosene fraction can be carried out using any suitable apparatus known in the art, such as a fractionation column, or by fractional concentration. Preferably, the step of fractionating the light hydrogenated fraction includes fractionating in a fractionation column.

[0062] Preferably, the further fractionation step comprises providing the light hydrogenated fraction stream to a vacuum distillation system comprising a distillation column. The column may include a reboiler, such as an electrically heated reboiler, and a condenser that can be cooled to approximately -20 °C to -10 °C, such as approximately -15 °C. The distillation column may have a bottom temperature of about 200 °C to 250 °C, preferably 215 °C to 235 °C, such as 220 °C to 230 °C, and a top temperature of about 150 °C to 200 °C, preferably 160 °C to 180 °C, such as 165 °C to 175 °C. The pressure at the top of the distillation column can be 30 to 70 kPa absolute, such as 40 to 60 kPa absolute, such as about 50 kPa absolute. The reflux ratio in the column can be 2:1 to 4:1, preferably 2.5:1 to 3.5:1, such as about 3:1.

[0063] Once separated, up to 80 wt%, preferably up to 70 wt%, more preferably up to 50 wt% of the crude naphtha fraction (C 5-10 ), crude light oil fraction (C 10-20 ) and / or crude kerosene fraction (C 8-16 ) separated from the light hydrogenated fraction can be blended with fossil fuels.

[0064] The remaining C 5-20 hydrocarbons may be combined to reform the light hydrogenated fraction, and the reformed light hydrogenated fraction is further processed as defined in steps (vii) and (viii).

[0065] Hydrocracking The process includes a step of hydrocracking the light hydrogenated fraction to produce a light hydrocarbon product stream enriched in C 5-10 hydrocarbons.

[0066] Most of the pyrolysis liquid is composed of the light hydrogenated fraction (i.e., mostly C 5-20 hydrocarbons), yet this light hydrogenated fraction has been found to typically have too low a concentration of naphtha-range hydrocarbons to efficiently separate the naphtha fraction. For example, the C 5-20 fraction contains less than 15 wt%, such as less than 10 wt% of C5-8 It may contain hydrocarbons. However, the level of naphtha-range hydrocarbons is sufficient such that the light hydrogenated C 5-20 fraction cannot be provided as a light oil fraction without removing the lighter hydrocarbons. C 5-20 It has been found that by hydrocracking the fraction, a hydrocarbon mixture that can be easily separated in the naphtha and gas oil ranges can be obtained, and the above problems can be addressed.

[0067] The hydrocracking step can be carried out in any suitable manner using any suitable hydrocracking reactor known in the art. Preferably, the hydrocracking step is carried out in a fixed-bed reactor, preferably a trickle-bed reactor. The reactor is preferably an isothermal reactor. Preferably, the reactor does not have a gas recycle loop.

[0068] The hydrocracking catalyst can be any suitable catalyst, preferably a metal catalyst, particularly a sulfur-based hydrocracking catalyst. The metal hydrocracking catalyst preferably contains a metal selected from Group VIII of the periodic table. Preferably, the catalyst contains Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and / or Pt. For example, the catalyst contains Ni, Co, Mo, W, Cu, Pd, Ru, Pt. In a preferred embodiment, the metal is selected from NiMo or Pt, preferably NiMo. The hydrocracking catalyst is preferably supported on a carrier, such as bauxite, alumina, silica, silica-alumina or zeolite. Preferably, the hydrocracking catalyst is supported on a zeolite, such as USY or mordenite zeolite. For example, the hydrocracking catalyst may contain NiMo or Pt supported on a zeolite and can be used in combination with a sulfurizing agent, such as CS2.

[0069] In a preferred embodiment, the hydrocracking step includes contacting the light hydrogenated fraction with the hydrocracking catalyst at a temperature of 250°C to 400°C, preferably 300 to 350°C. Preferably, the hydrocracking step is carried out at a pressure of 3 to 10 MPa, preferably 4 to 8 MPa, for example 5 to 7 MPa.

[0070] The liquid hourly space velocity (LHSV) of the light hydrogenated fraction through the hydrocracking reactor is 0.5 h -1 ~5 h -1 , preferably 0.5 h -1 ~3 h -1 , more preferably 0.7 h -1 ~2 h -1 , most preferably 0.8 h -1 ~1.5 h -1 , for example 0.9 h -1 ~1.3 h -1 and can be, for example. The ratio of hydrogen gas to the feed liquid in hydrogenation can suitably be 100 NV / NV to 500 NV / NV, preferably 150 NV / NV to 250 NV / NV, for example 180 NV / NV to 220 NV / NV. The H2S level in the reactor can be approximately 500 to 1500 ppm, for example 800 ppm to 1200 ppm, for example about 1000 ppm. The sulfur level can suitably be maintained using CS2 mixed with the feed to the hydrocracking reactor.

[0071] In some embodiments, the method may include a step of washing the light hydrogenated fraction prior to hydrocracking to remove metals and other impurities, such as washing with water. Optionally, the light hydrogenated fraction may be treated with an H2S absorbent, for example at an elevated temperature, to remove H2S from the light hydrogenated fraction.

[0072] It will be appreciated that the hydrocracking step can produce some non-condensable gas products in addition to the light hydrocarbon product stream enriched in C 5-10 hydrocarbons. However, preferably, the liquid recovery from hydrocracking is at least 90 wt%, preferably 95 wt% or more.

[0073] The method further includes a step of fractionating the light hydrocarbon product stream from the hydrocracking step to produce a naphtha fraction, a light gas oil fraction, and optionally a kerosene fraction. The naphtha fraction suitably contains C 5-10 hydrocarbons and preferably contains at least 90 wt% of C5-10 Hydrocarbons, preferably at least 95 wt% C 5-10 Hydrocarbons, such as at least 98 wt% C 5-10 contain hydrocarbons. The light naphtha fraction is suitably C 10-20 contains hydrocarbons and preferably at least 90 wt% C 10-20 Hydrocarbons, preferably at least 95 wt% C 10-20 Hydrocarbons, such as at least 98 wt% C 10-20 contains hydrocarbons. A suitable kerosene fraction is C 8-16 contains hydrocarbons and preferably at least 90 wt% C 8-16 Hydrocarbons, preferably at least 95 wt% C 8-16 Hydrocarbons, such as at least 98 wt% C 8-16 contains hydrocarbons.

[0074] Alternatively or in addition, fractionate the naphtha fraction formed in step (viii) further to form a kerosene fraction, i.e., C 8-10 hydrocarbons may be at least partially separated. In some embodiments, fractionate the light naphtha fraction formed in step (viii) further to form a kerosene fraction, i.e., C 10-16 at least a portion of the hydrocarbons may be separated. Thus, in addition to the naphtha and light naphtha fractions formed in accordance with the above method, C separated from the naphtha fraction formed in step (viii) 8-10 hydrocarbons, and / or C separated from the light naphtha fraction 10-16 from hydrocarbons, a kerosene fraction may also be isolated.

[0075] The light hydrocarbon product stream and / or the fractions of the naphtha and / or light oil fractions formed as a result can be carried out using any suitable apparatus, such as a distillation column known in the art. Preferably, fractionation comprises providing the light hydrocarbon product stream to a vacuum distillation system comprising a distillation column. The column may include a reboiler, such as an electrically heated reboiler, and a condenser that can be cooled to approximately -20°C to -10°C, such as about -15°C. The distillation column can have a bottom temperature of about 200°C to 250°C, preferably 215°C to 235°C, such as 220°C to 230°C, and a top temperature of about 150°C to 200°C, preferably 160°C to 180°C, such as 165°C to 175°C. The pressure at the top of the distillation column can be 30 to 70 kPa absolute, such as 40 to 60 kPa absolute, such as about 50 kPa absolute. The reflux ratio in the column can be 2:1 to 4:1, preferably 2.5:1 to 3.5:1, such as about 3:1.

[0076] Thus, the method produces a naphtha fraction and a light oil fraction that can be provided for downstream use or further processing into other products. In some embodiments, the method also isolates a kerosene fraction, specifically for downstream use or further processing into other products. In some embodiments, if it is desired to increase the proportion of naphtha or kerosene produced, the method may include a process for producing a naphtha or kerosene fraction that recycles the light oil fraction from the fractionation of the light hydrocarbon product stream and provides it to the hydrocracking step together with the light hydrogenated fraction. In this way, the separated light oil fraction can be recycled until it is completely hydrocracked into naphtha or kerosene fraction species. As previously described, since wax is also produced by the method, the method may include a process for producing a naphtha fraction and wax in which minimization of the loss of intermediate light oil fraction hydrocarbons is achieved. In fact, by operating the method in this way, surprisingly, by operating a pyrolysis process that produces a liquid effluent containing a large proportion (e.g., more than 50% by weight) of light oil hydrocarbons, it is possible to provide the advantageous production of both wax and naphtha fraction.

[0077] Generally, unless otherwise specified or not apparent from the context, herein C x-y When referring to a hydrocarbon fraction, it will be appreciated that the fraction contains at least 70 wt%, preferably at least 80 wt%, more preferably at least 90 wt%, for example at least 95 wt%, for example at least 98 wt% of the hydrocarbons included in the stated range. In some preferred embodiments, C x-y the hydrocarbon fraction can consist essentially of hydrocarbon molecules having from x to y carbon atoms.

[0078] For reference, unless otherwise specified or it is not clear that the opposite meaning is intended, all percentages referred to in this application in terms of concentration are weight percentages (wt%).

[0079] The method of the present invention can be carried out using the features of various apparatuses described herein, and it will be appreciated that the apparatuses can be configured to perform the processing steps described herein.

[0080] The present invention will be further described by the following examples, which are provided for illustrative purposes and are in no way intended to limit the scope of the claimed invention, and with reference to the following figures. [Examples]

Examples

[0081] Pyrolysis Waste plastic feeds containing HDPE, LDPE and polypropylene were melted in a melt extruder and the molten feed stream was provided to the inlet of a rotary kiln. The feed stream contained calcium oxide to avoid corrosion due to the formation of HCl from any unremoved PVC in the feed. The melt extruder was a screw extruder and was heated by an electric heater.

[0082] The rotary kiln included a rotating stainless steel drum having a length of about 80 feet (24.3 m) and an inner diameter of about 6 feet (1.8 m). The drum was rotated at a speed of 0.1 - 2 rpm and operated at a pressure slightly below atmospheric pressure under a nitrogen atmosphere. The rotary kiln was heated in four sequential heating zones of equal length, with the first three zones operating at temperatures of 315 °C - 595 °C and the last heating zone operating at 480 °C - 705 °C. The heating of the kiln was carried out by inducing combustion gas into an external jacket surrounding the rotating drum, which was divided into compartments to control the heating of each heating zone by burning natural gas. The residence time in the kiln was 60 minutes, i.e., 45 minutes in the first three zones and 15 minutes in the last zone.

[0083] The emissions from the rotary kiln were char, as well as C 5+ a hydrocarbon liquid fraction and non - condensable gases (C 1-4 hydrocarbon gas and nitrogen - containing) containing a fluid product stream. The fluid product stream was withdrawn from the kiln in the vapor phase through an evaporate outlet and sent to a condensation system, while the char was collected from a divided char outlet configured to receive solids from the kiln.

[0084] The C of the fluid product stream 5+The hydrocarbon liquid fraction was separated from the non-condensable gas in the condensation system, and a portion of the non-condensable gas was sent for fuel heating of the rotary kiln. The condensation system included a quench tower and tube and two tube and shell condensers arranged in series to receive the gas from the quench tower. The fluid product stream was provided to the quench tower above the liquid sump and then drawn up through four spray headers. The liquid was pumped out of the liquid sump of the quench tower, passed through a cooling heat exchanger (cooled to 60 °C), and then sent to the spray headers. The spray headers of the quench tower were configured to spray in countercurrent to cool the evaporate rising through the tower into condensate, and then the liquid fell into the liquid sump. The spray also functions to wash off the entrained char and prevent it from moving as an aerosol to the operation of downstream units. The flow of the cooled liquid from the quench tower was mixed with water, separated by tricanter centrifugation to remove the entrained char and other solid impurities, and then the oil phase was returned to the quench tower or sent downstream for hydrogenation. Any gas not condensed in the quench tower could be passed through the tube and shell condenser. The first condenser was operated at about 20 °C and was configured to provide a condensate spray for removing the entrained char from the first condenser and the pipeline between the quench tower and the condenser. The condensate from the first condenser was provided for hydrogenation together with the liquid from the quench tower. The condensate from the second tube and shell condenser (operated at about 10 °C) could be sent for hydrogenation together with other liquids or combined with the naphtha fraction downstream. C 5+ The hydrocarbon liquid fraction can be stored in an intermediate storage tank configured to receive the liquid from the condensation system and send the liquid to a hydrogenation reactor.

[0085] C condensed from the pyrolysis evaporate of the kiln 5+ The hydrocarbon liquid fraction was found to have the following properties. Freezing point: 52 °C Density (60 °C): 0.779 g / ml Bromine index: 20 gBr / 100 g Sulfur (ASTM D5453-19a): 22 mg / kg Chlorine (UOP 779-08): 79 mg / kg Silicon (ASTM D5185-18): 6 mg / kg Metal (ASTM D5185-18): less than 1 mg / kg Note: a. The metals tested include Cr, Cu, Pb, Ni, Zn, Mn, Cd, As, Co, and Sb. b. The detection limit of ICP of the analytical institution was 1 mg / kg.

[0086] C 5+ Perform simulated distillation of the hydrocarbon liquid fraction, and the results are shown in Figure 1. C 5+ The carbon number distribution determined by gas chromatography (GC) in the hydrocarbon liquid fraction is shown in Figure 2. As can be seen, the pyrolysis products contain a significant proportion (approximately 60 wt%) of gas oil range or lower (boiling point up to about 350 °C) hydrocarbons. The analysis also shows that the pyrolysis products contain hydrocarbons within the naphtha range in a very small proportion (less than 2 wt%). The GC analysis of the products showed the presence of various isomers and n-paraffins in addition to olefins and small amounts of other hydrocarbon species. 5-8 It was shown that the pyrolysis products contain hydrocarbons within the naphtha range in a very small proportion (less than 2 wt%). The GC analysis of the products showed the presence of various isomers and n-paraffins in addition to olefins and small amounts of other hydrocarbon species.

Example

[0087] Hydrogenation All of the hydrocarbon liquid fractions from Example 1 were sent to a fixed-bed hydrogenation reactor having a catalyst bed aspect ratio of 12:1 and containing a NiMo / Al2O3 hydrogenation catalyst. The temperature setting at the inlet of the reactor was 260 - 270 °C, and the pressure was 5.0 MPa. The feed was at 1.1 h 5+ -1 ​The LHSV and a hydrogen gas to feed ratio of 500 NV / NV were obtained. The gas-phase H2S concentration was approximately 0.1%. A portion of the recycle gas was introduced by passing CS2 liquid at ambient temperature and reaction pressure and skimming. The temperature at the reactor outlet was approximately 350 °C, providing a temperature rise of approximately 90 °C through the reactor. Hydrogen consumption was about 8.2 g H2 / kg. During hydrogenation, C 3-4 (LPG) gas or C 1-2 gas, no significant feed cracking was observed.

[0088] The hydrogenated product was found to have a bromine index of 2 g Br / 100 g. Therefore, the initial temperature at the reactor inlet was 305 °C, the outlet temperature was 330 °C, and the LHSV was 0.7 h -1 The hydrogenated product was sent to a second equivalent hydrogenation. The product recovery over the two hydrogenation steps was greater than 95%.

[0089] The product hydrogenated twice was analyzed and had the following properties. Freezing point: 54 °C Density (60 °C): 0.806 g / ml Bromine index: 0.5 g Br / 100 g Sulfur (ASTM D5453-19a): 14 mg / kg Chlorine (UOP 779-08): 12 mg / kg Silicon (ASTM D5185-18): 6 mg / kg Metal (ASTM D5185-18): less than 1 mg / kg Note: The metals tested included Cr, Cu, Pb, Ni, Zn, Mn, Cd, As, Co, Sb, Mo, Al.

[0090] By GC, the hydrogenated product was also found to substantially contain no olefins observed prior to hydrogenation.

Example

[0091] Fractionation Next, the hydrogenated product was fractionated in a single cut to obtain light hydrogenated C5-20 Hydrocarbon fraction and C 20+ A wax fraction was obtained. The fractionation was carried out in a distillation column using vacuum distillation. The distillation system included a reboiler equipped with a jet spray evaporation device and a forced flow mechanism to improve the evaporation efficiency and heat exchange of the liquid in the reboiler. The distillation was operated under the following conditions. Evaporation temperature (liquid exiting the reboiler): ~275 °C Evaporation pressure (above the liquid in the reboiler): 4 - 6 kPa (absolute pressure) Evaporation output: ~1.1 kW Cooling water temperature: ~20 °C Pressure at the condenser outlet: ~1 kPaA Sample liquid (approx. 100 °C) supply rate: 2 - 2.5 kg / hr Reflux rate: ~1 liter / hr (Cooling trap temperature of the vacuum pump): -78 °C

[0092] By distillation, light hydrogenated C 5-20 Hydrocarbon fraction and C 20+ A wax fraction was produced. C 20+ The wax fraction was found to contain a part of the hydrocarbons of the length of gas oil (mostly C 18 and C 19 ), and therefore, preferably, to compensate for this, the temperature of the reboiler may be raised, for example, to approximately 285 °C or higher.

[0093] Light hydrogenated C 5-20 The hydrocarbon fraction had a density of 0.803 g / ml at 20 °C and a bromine index of 0.5. The level of sulfur remaining in the fraction was 13 mg / kg. Light hydrogenated C 5-20 The hydrocarbon fraction was washed with industrial soft water to remove water-soluble impurities and passed through an H2S adsorbent to remove the remaining H2S in the fraction.

[0094] Light hydrogenated C 5-20 Simulated distillation of the hydrocarbon fraction was performed, and the results are shown in Figure 3. Light hydrogenated C 5+The carbon number distribution determined by gas chromatography (GC) in the hydrocarbon fraction is shown in Figure 4. As can be seen, the light hydrogenated C 5-20 hydrocarbon fraction contains almost all of the carbon chains within this range, and the C 21-25 hydrocarbons present are only in a very small proportion.

[0095] The light hydrogenated C 5-20 hydrocarbon fraction also contains only a small proportion of C 5-10 hydrocarbons (components boiling below about 180 °C and less than 10 wt%), and the C 10-20 separation of this naphtha fraction from the light oil fraction is an inefficient process. This results in inefficiencies and waste due to separating either a sub-optimal light oil fraction containing too many light hydrocarbons or a very small amount of naphtha fraction hydrocarbons from the light oil.

Examples

[0096] Hydrocracking A sample of the light hydrogenated C 5-20 hydrocarbon fraction from Example 3 was subjected to hydrocracking in a constant temperature trickle bed reactor system having a catalyst loading capacity of 1 L and no gas recycle loop. A commercial grade sulfur-based hydrocracking catalyst (NiMo / zeolite) was used as the catalyst. CS2 was used as the sulfur agent mixed with the feed to maintain the H2S level in the reactor during the hydrocracking process.

[0097] The conditions in the hydrocracking reactor were as follows. Catalyst loading: 1 L Reaction pressure: 6 MPa (gauge) Reactor temperature: ~335 °C Liquid hourly space velocity: 1.0 V / V / hr H2 to oil ratio: 200 NV / NV H2S level: ~1000 ppmv

[0098] The liquid recovery of the hydrocracking product was 95%, and the gas loss as LPG or similar volatile substances was only slight. Tail gas analysis showed C1-2 showed that the generation was less than 0.5 wt% of the feedstock heading towards hydrocracking. The analysis of the carbon number distribution of the hydrocracking products showed 63% light oil conversion (C 10+ ).

[0099] The simulated distillation of the hydrocracking products was carried out and the results are shown in Figure 5, where the simulated distillation of the hydrocracking products marked with "O" is compared with the C 5-20 hydrocarbon fraction from Example 3. The carbon number distribution determined by gas chromatography (GC) in the hydrocracking products is shown in Figure 6, where the carbon number distribution of the hydrocracking products marked with "O" is compared with the C 5-20 hydrocarbon fraction from Example 3. As can be seen, the carbon number distribution was redistributed by hydrocracking to obtain a significant enhancement of hydrocarbons in the naphtha range smaller than C 10 .

Examples

[0100] Fractionation of the hydrocracking products The hydrocracking products from Example 4 were separated in a vacuum distillation system using a 40 mm ID packed distillation column with up to 40 theoretical plates, an electrically heated reboiler, and a condenser cooled with cold ethanol (-15°C).

[0101] The distillation was operated under the following conditions. Top column pressure: ~50 kPa (absolute pressure) Top column temperature: ~168°C Feedstock loading: ~2.6 kg / batch Reflux ratio: 3:1 Bottom column temperature: 225°C

[0102] The separation was carried out as batch distillation, but it should be recognized that it could also be carried out continuously, preferably continuously.

[0103] 4.8 kg of naphtha fraction was collected and compared with 4.4 kg of light oil fraction. Compared with the C from Example 3 before hydrocracking 5-20Compared with the hydrocarbon distribution in the hydrocarbon fraction, it was demonstrated that after hydrocracking, there was a much more equal split between the naphtha fraction and the light oil fraction. The total material loss in the fraction was approximately 13 wt%, mainly due to the loss of volatile substances to the vacuum pump caused by insufficient cooling, which can be avoided by providing additional or more efficient cooling.

[0104] The simulated distillation of two fractions separated from the hydrocracking products was carried out, and the results are shown in Figure 7, where the simulated distillation of the naphtha fraction labeled "Y" is compared with the light oil fraction labeled "Z". The carbon number distribution determined by gas chromatography (GC) of the two fractions separated from the hydrocracking products is shown in Figure 8, where the carbon number distribution of the naphtha fraction labeled "Y" is compared with the light oil fraction labeled "Z". As can be seen, the naphtha fraction and the light oil fraction are cleanly separated, and the C 11+ in the naphtha fraction is only in very small amounts, and the C 10 or smaller ones in the light oil fraction were only in very small amounts.

[0105] The naphtha fraction was analyzed, and the results are shown in Table 1, indicating that the naphtha fraction mainly contains n- and iso-paraffins, along with some naphthenes and aromatics. The naphtha fraction also contains less than 1% olefins. The analysis of the light oil fraction pretreated with an H2S absorbent at high temperature to remove residual H2S is shown in Table 2. The light oil fraction has a cetane number of about 64, only 5.5 mg / kg of sulfur, and minimal other impurities. Therefore, this method can advantageously produce a naphtha fraction and a light oil fraction that can be easily separated from the thermal decomposition of waste plastic feed.

Table 1

Table 2

[0106] In addition, as shown in FIG. 6, the hydrocracking product contains C 8-16 hydrocarbons, and thus, enhanced C 5-20 The kerosene fraction can be isolated from the hydrocarbon stream. Similarly, FIG. 8 illustrates that the naphtha fraction (Y) and the light oil fraction (Z) also contain hydrocarbons that can be isolated to form kerosene.

[0107] FIG. 9 schematically shows the process flow of a system for carrying out this method. The polymer feed is pyrolyzed in the rotary kiln reactor 2, and the fluid effluent from the kiln containing all of the agglomerated liquid from the pyrolysis is provided to the hydrogenation reactor 4. The hydrogenated hydrocarbon stream from the reactor 4 is sent to the fractionation stage 6 to obtain a C 20+ wax fraction 10 and a C 5-20 hydrocarbon fraction 8 (gas oil / naphtha fraction). The C 5-20 hydrocarbon fraction 8 is sent to the hydrocracking stage 12, where the C 5-20 hydrocarbon fraction 8 undergoes hydrocracking, and the C 5-10 hydrocarbons in the stream are enhanced. Then, the hydrocracked stream from 12 is separated in the fractionation stage 14 to obtain a naphtha fraction 16, a light oil fraction 18, and a kerosene fraction 20 may also be obtained.

Claims

1. A method for producing naphtha and diesel fuel from polymer feed, (i) A step of preparing a polymer feed containing at least 80% by weight of a polyolefin polymer, (ii) A step of melting the polymer feed to prepare a molten polymer feed, (iii) The molten polymer feed is heated in a rotary kiln including a plurality of sequential heating zones. The step of sending to a transformer, wherein each zone of the rotary kiln is operated at a temperature of 300°C to 800°C to thermally decompose the molten polymer feed and produce a fluid product flow and a solid char product, (iv) A step of separating the solid char product from the fluid product flow, (v) C ５＋ A step of sending the liquid fraction of the fluid product stream containing hydrocarbons to a hydrogenation reactor, hydrogenating the liquid fraction to produce a hydrogenated hydrocarbon product stream, (vi) The hydrogenated hydrocarbon product stream is fractionated, C ５－２０ A step of producing a light hydrogenated fraction containing hydrocarbons, (vii) Hydrocracking the light hydrogenated fraction, C ５－１０ Hydrocarbon-fortified light coal The steps of producing a hydrogen ion product flow, and (viii) The light hydrocarbon product stream from (vii) is fractionated to obtain a naphtha fraction and a diesel fraction. Steps to produce The method, including the method described above.

2. C ５－１０ The method according to claim 1, further comprising the step of obtaining a kerosene fraction from a hydrocarbon-enhanced light hydrocarbon product stream.

3. The kerosene fraction is obtained by the step of fractionating the light hydrocarbon stream from (vii). The method according to claim 2.

4. The method according to claim 1, wherein the step of fractionating the hydrogenated hydrocarbon product stream includes fractionation using a fractional distillation column.

5. The method according to claim 1, wherein the rotary kiln includes four or five or more sequential heating zones.

6. The method according to claim 1, wherein the rotary kiln is maintained under a nitrogen atmosphere.

7. The method according to claim 1, wherein the rotary kiln is operated at approximately atmospheric pressure or at a slight negative pressure of 0.9 bar or more in absolute pressure, for example, 0.95 bar or more in absolute pressure.

8. The method according to claim 1, wherein each zone of the rotary kiln is operated at a temperature of 310°C to 720°C, preferably 400°C to 650°C.

9. The method according to claim 1, wherein the final zone of a plurality of zones is heated to a higher temperature than the other heating zones, preferably the plurality of heating zones include sequential zones in which one or more zones are operated at 310°C to 600°C and subsequent final zones are operated at 480°C to 700°C.

10. The method according to claim 1, wherein the polymer feed comprises at least 85% by weight of a polyolefin polymer, preferably at least 90% by weight of a polyolefin polymer, more preferably at least 95% by weight of a polyolefin polymer, for example, at least 99% by weight of a polyolefin polymer.

11. The method according to claim 1, wherein the polyolefin polymer comprises or is essentially composed of polyethylene and polypropylene, for example, the polyolefin polymer comprises at least 90% by weight of polyethylene and polypropylene, preferably at least 95% by weight of polyethylene and polypropylene, for example at least 99% by weight of polyethylene and polypropylene.

12. The method according to claim 1, wherein the polymer feed is melted in a melt extruder.

13. The method according to claim 12, wherein the melt extruder is heated to a temperature of 250°C to 350°C, preferably 265°C to 325°C.

14. The method according to claim 1, wherein calcium oxide is added to the polymer feed, preferably in an amount of up to 3% by weight.

15. The method according to claim 1, wherein at least a portion of the non-condensable gas fraction is reused to heat a rotary kiln and / or to melt a polymer feed.

16. The method according to claim 1, wherein the solid char product accounts for 15% by weight or less, preferably 10% by weight or less, of the discharge from the kiln.

17. The method according to claim 1, wherein the hydrogenation reactor in step (v) includes a fixed-bed reactor, preferably an irrigation-bed reactor.

18. The method according to claim 1, wherein the solid char product is separated from the fluid product stream at least partially by decanter centrifugation or tricanter centrifugation.

19. The fluid product flow consists of a non-condensable gas fraction and C ５＋ The method according to claim 1, comprising a liquid fraction containing hydrocarbons, wherein the non-condensable gaseous fraction is separated from the liquid fraction before step (v).

20. The method according to claim 1, wherein the hydrogenation of a liquid fraction comprises contact with a hydrogenation catalyst, the hydrogenation catalyst being a metal catalyst, preferably the metal hydrogenation catalyst comprising a metal selected from Group VIII of the periodic table, preferably the catalyst comprising a catalyst containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and / or Pt, for example, Ni, Co, Mo, W, Cu, Pd, Ru, Pt, preferably the catalyst being selected from CoMo, NiMo or Ni, more preferably the catalyst being NiMo; and / or the catalyst being supported on a carrier preferably selected from bauxite, alumina, silica, silica-alumina or zeolite, preferably on alumina.

21. C ５－２０ The light hydrogenated fraction containing hydrocarbons undergoes a further fractionation step to obtain crude C ５－１０ hydrocarbon fraction, crude C １０－２０ hydrocarbon fraction, and / or crude C ８－１６ hydrocarbon fraction is at least partially separated, and the remaining light hydrogenated C ５－２０ hydrocarbon proceeds to the hydrocracking step. The method according to claim 1

22. The method according to claim 21, wherein at least one or more partially separated crude hydrocarbon fractions are blended with a fossil fuel material.

23. The method according to claim 22, wherein the fossil fuel material is selected from naphtha, kerosene, or diesel fuel.

24. C ５－１０ , C ８－１６ and / or C １０－２０ 80% by weight or less, preferably 70% by weight or less, and more preferably 50% by weight or less of the crude hydrocarbon fraction is C ５－２０ The method according to any one of claims 21 to 23, wherein separation is obtained from a light hydrogenated fraction containing hydrocarbons.

25. The method according to claim 1, wherein the step of hydrocracking includes contacting a light hydrogenation fraction with a hydrocracking catalyst at a temperature of 250°C to 400°C, preferably 300°C to 350°C, and / or at a pressure of 3 to 10 MPa, preferably 4 to 8 MPa.

26. Apparatus for producing naphtha and diesel fuel from polymer feed, (i) Means for preparing a molten polymer feed by melting a polymer feed containing at least 80% by weight of a polyolefin polymer, (ii) A rotary kiln reactor configured to receive the molten polymer feed from part (i), and configured to provide a plurality of sequential heating zones, each zone of the rotary kiln configured to be operated at a temperature of 300°C to 800°C to thermally decompose the molten polymer feed and produce a fluid product flow and a solid char product, (iii) means for separating the solid char product from the fluid product flow, (iv) C from part (iii) ５＋ The liquid fraction of the fluid product stream containing hydrocarbons is received. A hydrogenation reactor configured to hydrogenate the liquid fraction and produce a stream of hydrogenated hydrocarbon products, (v) The hydrogenated hydrocarbon product stream is fractionated, C ５－２０ Means for producing a light hydrogenated fraction containing hydrocarbons, (vi) In the presence of hydrogen, the light hydrogenated fraction is catalytically cracked to obtain C ５－１０ Hydrocracking reactor configured to produce a hydrocarbon-enhanced light hydrocarbon product stream, and (vii) The light hydrocarbon product stream from (vi) is fractionated to obtain a naphtha fraction and a diesel fraction. means for production The apparatus, including the above.

27. C ５－１０ The apparatus according to claim 26, comprising means for obtaining a kerosene fraction from a hydrocarbon-enhanced light hydrocarbon product stream.

28. A means for fractionating the light hydrocarbon product stream in part (vii) is the kerosene fraction The apparatus according to claim 27, arranged to produce.

29. The apparatus according to claim 26, wherein means for fractionating a hydrogenated hydrocarbon product stream include a fractionation column configured to receive a hydrogenated hydrocarbon product stream from a hydrogenation reactor.

30. Crude C ５－１０ Hydrocarbon fraction, crude C １０－２０ hydrocarbon fraction and / or crude C ８－１６ C for at least partial separation of hydrocarbon fractions ５－２０ The apparatus according to claim 26, further comprising means for fractionating a light hydrogenated fraction containing hydrocarbons.

31. C ５－２０ The apparatus according to claim 30, wherein the means for fractionating a light hydrogenated fraction containing hydrocarbons includes a fractional distillation column configured to receive the light hydrogenated fraction produced in part (v).

32. The apparatus according to claim 26, wherein the rotary kiln is configured to provide four or more sequential heating zones, and preferably the rotary kiln is configured to operate as described in any one of claims 6 to 9.

33. The apparatus according to claim 26, wherein the means for melting the polymer feed includes a melt extruder and is configured to heat the polymer feed at a temperature of preferably 250°C to 350°C, preferably 265°C to 325°C.

34. The apparatus according to claim 26, configured to reuse the gaseous fraction of the hydrogenation product stream for heating a rotary kiln and / or for melting a polymer feed.

35. The apparatus according to claim 26, wherein the hydrogenation reactor in part (iv) includes an irrigation bed reactor, and preferably the catalyst is as described in claim 20.

36. The apparatus according to claim 26, wherein means for separating solid char products from a fluid product stream include decanter centrifugation or tricanter centrifugation for receiving the fluid product stream from a rotary kiln, and / or includes a char outlet from the rotary kiln, and separately from the char outlet, an evaporate outlet from the rotary kiln.

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