Process of blending and preparing waste plastics and bio-based raw materials

Abstract

Provided is a composition comprising a blend of waste plastic and bio-based raw material. Also provided is a process for preparing a stable blend of plastic and bio-based raw material that can be stored or transported as required. The amount of plastic in the blend constitutes 20 wt% or less of the blend. This blend can be passed through a conversion unit for the conversion of waste plastic and bio-based raw material. The conversion process produces clean monomers and chemical intermediates for polymerization.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Provisional Application No. 63 / 359,546, filed on July 8, 2022, the entire disclosure of which is incorporated herein by reference in its entirety.

Background Art

[0002] As part of efforts to combat global warming, there has been a rapidly growing movement in the industry to produce chemicals and fuels from renewable resources such as bio - based feedstocks and bio - oils. With the increasing demand for liquid transportation fuels, the depletion of "easy oil" (crude oil that is easily accessible and recoverable), and the strengthening of restrictions on the carbon footprint of such fuels, it has become increasingly important to develop routes for efficiently producing liquid transportation fuels from alternative resources. Biomass - based feedstocks, such as feedstocks containing triglycerides (e.g., fats and oils derived from plants, animals, and microorganisms), are important feedstocks for non - fossil - fuel - derived energy sources because they can be utilized on a large scale. Biomass provides a renewable carbon source. Despite ongoing research and development in the manufacturing processes of liquid fuels, there is still a need to provide improved processes for producing low - carbon - footprint hydrocarbons useful as liquid fuels or fuel blend components.

[0003] On the other hand, the world has witnessed a very rapid growth in plastic production. According to the Plastics Europe Market Research Group, the world's plastic production volume was 335 million tons in 2016, 348 million tons in 2017, 359 million tons in 2018, and 367 million tons in 2020. According to McKinsey & Company, the world's plastic waste volume is estimated to reach 460 million tons per year by 2030 if the current trajectory continues.

[0004] Disposable plastic waste has become an increasingly important environmental issue. At present, there seem to be few options for recycling waste plastics such as polyethylene and polypropylene into value-added chemical products or fuel products. Currently, only a small amount of polyethylene and polypropylene are recycled via chemical recycling, and these recycled and purified polymer pellets are pyrolyzed in a pyrolysis unit to produce fuel (naphtha, diesel), feedstock for a steam cracker, or slack wax. Most (over 80%) are incinerated, landfilled, or discarded.

[0005] The current methods of chemical recycling via pyrolysis cannot have a major impact on the plastics industry. Current pyrolysis operations produce poor-quality fuel components (products in the naphtha and diesel ranges), but the amount is small enough that these products can be blended into the fuel supply. However, to address environmental issues, such simple blending cannot continue in order to recycle very large amounts of waste polyethylene and polypropylene. The as-produced products from the pyrolysis unit are of too poor quality to be blended in large quantities into transportation fuels.

[0006] Processes for converting waste plastics into hydrocarbon lubricants are known. For example, U.S. Patent No. 3,845,157 discloses decomposing waste or unused polyolefins to form gaseous products such as ethylene / olefin copolymers, which are further processed to produce synthetic hydrocarbon lubricants. U.S. Patent No. 4,642,401 discloses heating pulverized polyolefin waste at a temperature of 150 to 500 °C and a pressure of 20 to 300 bar to produce liquid hydrocarbons. U.S. Patent No. 5,849,964 discloses a process for depolymerizing waste plastic materials into a volatile phase and a liquid phase. The volatile phase is separated into a gas phase and a condensate. The liquid phase, condensate, and gas phase are purified into liquid fuel components using standard purification techniques. U.S. Patent No. 6,143,940 discloses a procedure for converting waste plastics into heavy wax compositions. U.S. Patent No. 6,150,577 discloses a process for converting waste plastics into lubricating oils. European Patent Application Publication No. 0620264 discloses a process for producing lubricating oils from waste or unused polyolefins, comprising thermally decomposing the waste in a fluidized bed to form a waxy product, optionally using hydrotreating, and then catalytically isomerizing and fractionating to recover the lubricating oil.

[0007] Other documents related to processes for converting waste plastics into lubricating oils include U.S. Patent Nos. 6,288,296, 6,774,272, 6,822,126, 7,834,226, 8,088,961, 8,404,912, and 8,696,994, and U.S. Patent Application Publication Nos. 2021 / 0130699, 2019 / 0161683, 2016 / 0362609, and 2016 / 0264885. The foregoing patent documents are hereby incorporated by reference in their entirety.

[0008] Worldwide, the recycling and upcycling of plastic waste have attracted significant attention for resource and environmental conservation. The mechanical recycling of plastic waste is considerably limited because the types, properties, additives, and contaminants of the collected plastics vary. Usually, the quality of recycled plastics deteriorates. Chemical recycling into starting materials or value-added chemicals has emerged as a more desirable method.

[0009] However, to industrially and massively chemically recycle disposable plastics to reduce their environmental impact, a more robust process is needed. In this improved process, a "circular economy" for waste polyethylene and waste polypropylene plastics should be established, and used waste plastics need to be effectively recycled as starting materials for polymers or value-added chemicals or fuels. By establishing such a circular economy and also utilizing renewable resources such as bio-based raw materials, the environmental benefits of such recycling processes can be further enhanced.

Summary of the Invention

[0010] In one embodiment, provided is a composition of a blend of waste plastic and a bio-based raw material, which is for converting the waste plastic in a conversion unit (e.g., a purification process unit).

[0011] In one embodiment, provided is an integrated process for recycling plastic waste, in which the waste plastic and the bio-based (bio) raw material are simultaneously converted in a conversion unit. This conversion process produces clean monomers for polymerization and aromatic chemical intermediates.

[0012] In one embodiment, provided is a process for preparing a blend of waste plastic and biofeedstock (or a combination of biofeedstocks), the blend being for directly converting waste plastic in a catalytic process unit that simultaneously converts the biofeedstock and the waste plastic.

[0013] In another embodiment, provided is a process for preparing a stable blend of waste plastic and biofeedstock for storage, transportation, or supply to a conversion unit. The process includes first selecting waste plastics including polyethylene, polypropylene, and polystyrene. These waste plastics then pass through a blend preparation unit where a stable blend of waste plastic and biofeedstock is produced. This stable blend can ultimately be supplied to a conversion unit for directly converting the waste plastic and biofeedstock into valuable chemicals and fuels.

[0014] The term "bio" refers to biochemical and / or natural chemicals that exist in nature. Thus, a bio feedstock or bio-oil will include such natural chemicals. Preferred starting biofeedstocks for blend preparation include triglycerides and fatty acids, plant-derived oils (such as palm oil, canola oil, corn oil, and soybean oil), and animal-derived fats and oils (such as tallow, lard, schmalz (e.g., chicken fat), and fish oil), as well as mixtures thereof.

[0015] Among other factors, it has been found that the blend of waste plastics and bio-based raw materials can be adjusted, and this blend can be stabilized to the extent that it can be stored or transported as required. Furthermore, this blend can be converted into valuable chemicals or fuels in a conversion unit. The combined use of waste plastics and bio-based raw materials significantly improves the environmental aspects of the conversion process. Additionally, by incorporating the conversion unit as part of a refinery operation, waste plastics can be recycled efficiently and effectively, while also complementing the refining operations in the preparation of high-value products such as gasoline, jet fuel, base oil, and diesel. However, it has also been found that by adding a refining operation, clean LPG (propane, propylene, butane, and butene) and naphtha can be efficiently and effectively produced from the blend of bio-based raw materials and waste plastics, and ultimately polyethylene and / or polypropylene polymers can be produced. Throughout the process from recycled plastics to polymer products with product quality equivalent to that of virgin polymers, the plus economy is realized, and by utilizing the blend of bio-based raw materials and waste plastics, the environmental aspects of the recycling process are also enhanced. The use of the blend of the present invention can also save energy and is more environmentally friendly than conventional recycling processes.

Brief Description of the Drawings

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Figure 1

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Figure 2

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Figure 3

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Figure 5

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Figure 6

Mode for Carrying Out the Invention

[0022] A novel blend of plastic and bio-based raw material, and a process for preparing the blend are disclosed. This blend can be used when directly converting plastics in a conversion unit such as a purification process unit.

[0023] In one embodiment, a process is provided for preparing a homogeneous liquid blend of plastic, preferably waste plastic, and bio-based raw material at a high temperature and supplying it to a purification unit. This process includes first selecting a plastic, preferably waste plastic, including polyethylene, polypropylene, and / or polystyrene. These waste plastics then pass through a high-temperature blend preparation unit to produce a homogeneous liquid blend of waste plastic and petroleum. This high-temperature homogeneous liquid blend is supplied to a purification conversion unit for directly converting the waste plastic into valuable chemicals and fuels.

[0024] A homogeneous blend at high temperature is produced by melting the plastic with a high-temperature bio-based material to produce a high-temperature homogeneous liquid blend of the plastic melt and the bio-based material. The preferred range of plastic in the blend is about 1-20 wt%. In one embodiment, conditions for preparing the high-temperature liquid blend include heating the blend to a temperature above the melting point of the plastic while vigorously mixing it with the bio-based material. Preferred process conditions include heating to 250-550°F, having a residence time at the final heating temperature of 5-240 minutes, and having an atmospheric pressure of 0-10 psig. This can be carried out in open air and preferably also under an inert atmosphere without oxygen.

[0025] In one embodiment, a process is provided for preparing a stable blend of plastic, preferably waste plastic, and a bio-based material for storage, transportation, or supply to a purification unit. This process includes first selecting a plastic, preferably waste plastic, including polyethylene, polypropylene, and / or polystyrene. These waste plastics then pass through a stable blend preparation unit where a stable blend of the waste plastic and the bio-based material is produced. This stable blend can be supplied to a purification and conversion unit for directly converting the waste plastic into valuable chemicals and fuels.

[0026] The stable blend of the present invention is produced by a two-step process. In the first step, a homogeneous liquid blend of a plastic melt and a bio-based raw material is produced at a high temperature. The preferred range of the plastic composition in the blend is about 1 to 20 wt%. In one embodiment, the conditions for preparing the high-temperature liquid blend include heating the plastic to a temperature above its melting point while vigorously mixing it with the bio-based raw material. Preferred process conditions include heating to 250 - 550°F, having a residence time at the final heating temperature of 5 - 240 minutes, and having an atmospheric pressure of 0 - 10 psig. This can be carried out even in open air, and preferably can also be carried out under an inert atmosphere without oxygen.

[0027] In the second step, the high-temperature blend is cooled to a temperature below the melting point of the plastic while continuously and vigorously mixing it with the bio-based raw material, and further cooled to a low temperature, preferably ambient temperature, to produce a stable blend.

[0028] The resulting composition contains a stable blend of waste plastic and bio-based raw material and is for directly converting waste plastic in a conversion unit such as a purification process unit. The resulting composition is novel and brings many advantages.

[0029] The stable blend is made from a bio-based raw material and 1 - 20 wt% of plastic waste, and the plastic is mainly polyethylene, polypropylene and / or polystyrene, and the plastic is in the form of finely dispersed micron-sized particles.

[0030] The stable blend can be fed to a catalytic conversion process for simultaneously converting the bio-based raw material and waste plastic into chemical raw materials.

[0031] By implementing these concepts, several advantages are realized.

[0032] For example, FIG. 1 is a simplified process diagram of a basic case of a waste plastic pyrolysis process commonly carried out in today's industry. Generally, waste plastics are sorted together (1). The washed waste plastics 2 are converted into off-gas 4 and pyrolysis oil (liquid product) in the pyrolysis unit 3. The off-gas 4 from the pyrolysis unit is used as fuel for operating the pyrolysis unit. The on-site distillation unit separates the pyrolysis oil to produce naphtha and diesel 5 products, which are sold in the fuel market. The heavy pyrolysis oil fraction 6 is recycled to the pyrolysis unit 3 to maximize the fuel yield. The char 7 is removed from the pyrolysis unit 3. The heavy fraction 6 is rich in long-chain linear hydrocarbons and is very waxy (i.e., it produces paraffinic wax when cooled to ambient temperature). The wax can be separated from the heavy fraction 6 and sold in the wax market.

[0033] In this process, waste plastics are not pyrolyzed. Instead, a blend of biofeedstock and waste plastics is prepared. Thus, the pyrolysis step can be avoided, which results in significant energy savings.

[0034] The blend is prepared in a high-temperature blend preparation unit with an operating temperature exceeding the melting point of the plastic (about 150 - 300 °C), and a homogeneous liquid blend of plastic and biofeedstock at high temperature can be produced. The homogeneous liquid blend of plastic and biofeedstock at high temperature can then be directly supplied to a conversion unit such as a purification unit.

[0035] Alternatively, the blend is prepared in a stable blend preparation unit, and the homogeneous liquid blend at high temperature is cooled to ambient temperature in a controlled manner so that it can be easily stored and transported. By using this method, a stable blend can be prepared at a facility away from the refinery and transported to the refining unit. The stable blend is then heated to a temperature above the melting point of the plastic and fed to the purification conversion unit. The stable blend is a physical mixture of micron-sized plastic particles finely suspended in the biofeedstock. This mixture is stable, and the plastic particles do not precipitate or aggregate even after long-term storage.

[0036] The significance of heating the blend to a temperature above the melting point of the plastic becomes clear when using a single plastic. However, when the waste plastic is composed of multiple waste plastics, it will exceed the melting point of the plastic with the highest melting point. Therefore, it must exceed the melting points of all plastics. Similarly, when cooling the blend to a temperature below the melting point of the plastic, that temperature must be cooled to a temperature below the melting points of all the plastics constituting the blend.

[0037] The stable blend of plastic and biofeedstock can be stored for a long time at ambient temperature and normal pressure. During storage, no polymer aggregation or chemical / physical degradation of the blend is observed. This facilitates the handling of waste plastic materials during storage or transportation.

[0038] The stable blend can be easily handled by using standard pumps typically used in refineries or warehouses, or pumps equipped with transport tanks. Depending on the blend, it may be necessary to heat the blend to a temperature above its pour point in order to transfer the blend using a pump or supply it to a conversion unit (e.g., within a refinery). During heating, no polymer aggregation is observed.

[0039] For supply to the conversion unit, the stable blend is further heated to a temperature exceeding the melting point of the plastic, producing a homogeneous liquid blend of the biofeedstock and the plastic. This homogeneous liquid blend at this high temperature is directly supplied to a petroleum refining process unit to convert the waste plastic and the biofeedstock into high-value and sustainable products with high yields.

[0040] Also, compared to the pyrolysis unit, these blend preparation units operate at much lower temperatures (about 500°C - 600°C vs. 120°C - 300°C). Therefore, this process is much more energy-efficient in preparing purified raw materials derived from waste plastics than pyrolysis processes such as thermal decomposition.

[0041] The use of the waste plastic / biofeedstock blend of the present invention further increases the overall yield of hydrocarbons obtained from the waste plastic. This increase in yield is significant. The hydrocarbon yield using this blend can reach up to 98%. In contrast, pyrolysis produces a significant amount of light products of about 10 - 30 wt% and about 5 - 10 wt% char from plastic waste. These light hydrocarbons are used as fuel for operating the pyrolysis plant as described above. Therefore, the liquid hydrocarbon yield from the pyrolysis plant is at most 70 - 80%.

[0042] When this blend is passed through a purification unit such as an FCC unit, only a small amount of off-gas is generated. In the purification unit, a (catalytic) catalytic cracking process different from the pyrolysis process used in pyrolysis is used. Using the catalytic process can minimize the generation of undesirable light by-products such as methane and ethane. In the purification unit, efficient product fractionation is carried out, and all hydrocarbon product streams can be efficiently utilized to produce high-value materials. In the co-feed of the refinery, only about 2% of off-gas (H2, methane, ethane, ethylene) is generated. The C3 stream and the C4 stream are captured to produce useful products such as cyclic polymers and / or high-quality fuel products. Therefore, the use of the biofeedstock / plastic blend of the present invention not only leads to an increase in hydrocarbons from waste plastics, but also realizes a more energy-efficient recycling process compared to heat treatment processes such as pyrolysis.

[0043] Figure 2 shows a method for preparing a high-temperature homogeneous blend of plastic and biofeedstock according to this process. This blend can be used for direct injection into the conversion unit. The preferred range of the plastic composition in the blend is about 1-20 wt%. When waste plastics of high molecular weight polypropylene (average molecular weight of 250,000 or more) or high-density polyethylene (density exceeding 0.93 g / cc) are mainly used as at least 50 wt% of waste plastics, for example, the amount of waste plastics used in the blend is more preferably about 10 wt%. The reason is that the pour point and viscosity of the blend increase.

[0044] Preferred conditions for the preparation of the blend include heating the plastic to a temperature above the melting point of the plastic while vigorously mixing it with the biofeedstock. Preferred process conditions include heating to a temperature of 250-550°F, a residence time at the final heating temperature of 5-240 minutes, and an atmospheric pressure of 0-10 psig. This can also be carried out in open air, and preferably can also be carried out under an inert atmosphere without oxygen.

[0045] Referring to FIG. 2 of the drawings, a step-by-step preparation process for preparing a high-temperature homogeneous blend of plastic and bio-based raw materials is shown. The mixed waste plastics are sorted to produce consumer post-use waste plastics 21 containing polyethylene and / or polypropylene. The waste plastics are cleaned (22) and then mixed with bio-based raw material oil 24 in a high-temperature blend preparation unit 23. After mixing in 23, a homogeneous blend of plastic and bio-oil is recovered (25). Optionally, a filtration device (not shown) can be added to remove undissolved plastic particles or solid impurities present in the liquid blend. The blend of plastic and bio-oil can then be passed through a catalytic conversion unit 27. Optionally, the conversion unit can co-process vacuum gas oil 20 or other conventional raw materials from a refinery.

[0046] In one embodiment, the conversion unit can be a catalytic purification unit such as an FCC unit.

[0047] FIG. 3 shows a method for preparing a stable blend of plastic and oil. The stable blend is produced by a two-step process in a stable blend preparation unit. In the first step, a high-temperature homogeneous liquid blend of plastic melt and bio-based raw materials is produced. This step is the same as the high-temperature blend preparation process described in FIG. 2. The preferred range of the plastic composition in the blend is about 1 to 20 wt%. When waste plastics of high molecular weight polypropylene (average molecular weight of 250,000 or more) or high-density polyethylene (density exceeding 0.93 g / cc) are mainly used as at least 50 wt% of the waste plastics, for example, the amount of waste plastics used in the blend is more preferably about 10 wt%. The reason is that the pour point and viscosity of the blend increase.

[0048] Preferred conditions for the preparation of the high-temperature homogeneous liquid blend in the first step include heating the plastic to a temperature above its melting point while vigorously mixing it with the bio-based material. Preferred process conditions include heating to a temperature of 250 - 550°F, a residence time at the final heating temperature of 5 - 240 minutes, and an atmospheric pressure of 0 - 10 psig. This can be carried out in open air and preferably also under an inert atmosphere without oxygen. During mixing, any diluent 26 can be added.

[0049] In the second step, the high-temperature blend is cooled to a temperature below the melting point of the plastic while continuously and vigorously mixing. It is further cooled to a low temperature, preferably ambient temperature, to produce a stable blend of plastic and oil.

[0050] The stable blend has been found to be a close physical mixture of the plastic and the bio-based material. The plastic is in a "de-aggregated" state in the bio-based material. The plastic maintains a finely dispersed state of micron-sized solid particles in the bio-based material at a temperature below the melting point of the plastic, especially at ambient temperature. The blend is stable and easy to store and transport. At the refinery, the stable blend can be heated above the melting point of the plastic in a preheater to produce a high-temperature homogeneous liquid blend of the plastic and the bio-based material. This high-temperature liquid blend can then be fed to a conversion unit.

[0051] Figure 3 shows further details of the preparation of a stable blend. The stable blend is created in a two-step process in a stable blend preparation unit 100. As shown, clean waste 22 is passed through a high-temperature blend preparation unit 23. The selected plastic waste 22 is mixed with a biofeedstock oil 24 and heated in unit 23 to a temperature above the melting point of the plastic. The mixing is often carried out very vigorously. During mixing, any diluent 26 can be added. The mixing and heating conditions can generally be heating at a temperature in the range of about 250 - 550°F and heating with a residence time of 5 - 240 minutes at the final heating temperature. The heating and mixing can be carried out in open air or under an inert atmosphere without oxygen. As a result, a homogeneous liquid blend 101 of plastic and oil at high temperature is obtained. Optionally, a filtration device (not shown) can be added to remove undissolved plastic particles or solid impurities present in the high-temperature homogeneous blend.

[0052] Next, the high-temperature blend 101 is cooled in unit 102 to a temperature below the melting point of the plastic while continuing to mix the blend of plastic and bio-oil. During mixing and cooling, any diluent 103 can be added. The cooling is usually continued to ambient temperature, producing a stable blend of plastic and oil 29. At the refinery, the stable blend can be fed to a preheater 30, which heats the blend to a temperature above the melting point of the plastic to produce a homogeneous mixture at high temperature of the plastic / bio-oil blend 105, and then this mixture is fed to a purification conversion unit 27. Optionally, the conversion unit can co-process vacuum gas oil or other conventional refining feedstocks.

[0053] Preferred plastic starting materials for this process are selected waste plastics mainly containing polyethylene and polypropylene (plastic recycling classification types 2, 4, and 5). The pre-selected waste plastics are washed, shredded or pelletized, and supplied to the blend preparation unit. Figure 4 shows the type classification of plastics regarding the recycling of waste plastics. Classification types 2, 4, and 5 are high-density polyethylene, low-density polyethylene, and polypropylene, respectively. Waste plastics of polyethylene and polypropylene can be used in any combination. In this process, it is preferred to use at least some waste plastics of polyethylene. Polystyrene (classification 6) may also be present.

[0054] To minimize contaminants such as N, Cl, S, etc., it is very important to properly select waste plastics. Plastic wastes including polyethylene terephthalate (plastic recycling classification type 1), polyvinyl chloride (plastic recycling classification type 3), and other polymers (plastic recycling classification type 7) need to be selected to less than 5%, preferably less than 1%, most preferably less than 0.1%. This process can tolerate a moderate amount of polystyrene (plastic recycling classification type 6). Waste polystyrene needs to be selected to less than 20%, preferably less than 10%, most preferably less than 5%.

[0055] By washing the waste plastics, metal contaminants such as sodium, calcium, magnesium, aluminum, etc., and non-metal contaminants from other waste sources can be removed. Non-metal contaminants include contaminants from Group IV of the periodic table such as silica, contaminants from Group V such as phosphorus compounds and nitrogen compounds, contaminants from Group VI such as sulfur compounds and oxygen compounds, and halide contaminants from Group VII such as fluorides, chlorides, iodides, etc. Residual metals, non-metal contaminants, and halides need to be removed to less than 50 ppm, preferably less than 30 ppm, most preferably less than 5 ppm.

[0056] The term "bio" refers to biochemical and / or natural chemical substances existing in nature. Thus, bio feedstock or bio-oil will contain such natural chemical substances. Preferred starting bio feedstocks for blend preparation include triglycerides, fatty acids, plant-derived oils (such as palm oil, canola oil, corn oil, and soybean oil), and animal-derived fats and oils (such as tallow, lard, schmalz (e.g., chicken fat), and fish oil), and mixtures thereof. In one embodiment, the bio feedstock can include biomass pyrolysis oil prepared by pyrolyzing bio feedstock materials.

[0057] The most preferred bio feedstocks are palm oil and tallow, which have a high degree of saturation and an iodine number of 70 or less (i.e., a low degree of unsaturation). The iodine number (iodine number or iodine value) is a measure of the unsaturation of fats, oils, and waxes. It is determined by measuring the mass (in grams) of iodine consumed by 100 g of the substance. The higher the value, the higher the degree of unsaturation of the substance. This is similar to using the bromine number to measure the unsaturation of petroleum samples.

[0058] It has been found that bio feedstocks containing polyunsaturated fatty acids with a high iodine number, such as soybean oil (iodine number 130), do not form a stable blend with plastics. However, a bio feedstock mixture consisting of a bio feedstock with a low iodine number (≤70) and a bio feedstock with a high iodine number (>70) can form a stable blend with plastics. It has been found that bio feedstock mixtures with an iodine number of about 95 or less form a stable blend with plastics. In one embodiment, the mixture of bio feedstocks has an iodine number of 91 or less.

[0059] Furthermore, the blend of plastic and bio-based raw materials can be blended with other diluent hydrocarbons such as heptane as needed to change the properties of the blend, such as viscosity or pour point, to facilitate handling or processing. Preferred blended hydrocarbon raw materials include standard petroleum-based raw materials such as vacuum gas oil (VGO), aromatic solvents, or light cycle oil (LCO). In one embodiment, the blended hydrocarbon raw material includes atmospheric gas oil, VGO, or heavy fractions recovered from other refining operations. In another embodiment, the blended hydrocarbon raw material includes LCO, heavy cycle oil (HCO), FCC naphtha, gasoline, diesel, toluene, or aromatic solvents derived from petroleum. To lower the viscosity, a portion of the liquid FCC products (such as naphtha and LCO) can also be recycled to the blend. In one embodiment, no petroleum raw material is used, and only bio-based raw materials are used to prepare the blend and mix with the blend.

[0060] Without wishing to be bound by theory, the prepared stable blend is a close physical mixture of plastic and bio-based raw materials for the catalytic conversion unit. This process produces a stable blend of bio-based raw materials and plastic, with the plastic in a "de-aggregated" state. This blend is stable and easy to store and transport. At the refinery, the stable blend is preheated to a temperature above the melting point of the plastic to produce a homogeneous liquid blend of plastic and bio-based raw materials at high temperature, and then this high-temperature liquid blend is fed to the conversion unit. Thereafter, both the bio-based raw materials and the plastic are simultaneously converted in the conversion unit using a typical refining catalyst containing zeolite and other active components such as silica alumina, alumina, and clay.

[0061] Catalytic conversion units such as fluid catalytic cracking (FCC) units, hydrocracking units, and hydrotreating units can convert a homogeneous liquid blend of plastic and biofeedstock at high temperature in the presence of a catalyst using simultaneous conversion of plastic and biofeedstock. The presence of a catalyst in the conversion unit enables the conversion of waste plastics into high-value products at an operating temperature lower than typical pyrolysis temperatures. In hydrogenation processing units (hydrocracking units and hydrotreating units), hydrogen is added to the unit to improve the conversion of plastics.

[0062] The fluid catalytic cracking process is a preferred mode of catalytic conversion of a stable blend. The selection of the catalyst can be optimized to maximize monomer production for the manufacture of virgin plastics.

[0063] The yield of undesirable by-products (off-gas, tar, coke) is lower than that of typical pyrolysis processes. This blend can also produce additional synergistic effects resulting from the interaction of plastic and biofeedstock during the conversion process.

[0064] A stable blend of plastic and biofeedstock enables more efficient recycling of waste plastics and enables truly circular and sustainable production of plastics and chemicals. This is much more energy-efficient than current pyrolysis processes and enables recycling with a lower carbon footprint. The improved process enables the establishment of a much larger circular economy by efficiently converting waste plastics into virgin-quality polymers or valuable chemicals and fuels.

[0065] A dedicated conversion unit for converting a blend of plastic and biofeedstock produces sustainable low-carbon chemical intermediates and fuels without using petroleum feedstocks. Alternatively, a blend of plastic and biofeedstock can be supplied to a petroleum refining conversion unit for co-processing with petroleum-based oils.

[0066] Figure 5 shows one embodiment of the integrated process of the present invention, in which the blend is sent to a fluid catalytic cracking (FCC) unit. The same numbers in Figure 5 corresponding to Figures 2 and 3 refer to the same item / unit. As shown in the figure, a blend of plastic and oil is prepared (25). The blend is generally heated to a temperature above the melting point of the plastic, if necessary, and then sent to the FCC unit 27 of the refinery. In another embodiment, the heated blend (and optionally co-blended VGO co-feed) is passed through the FCC unit or each is passed directly, but separately through the FCC unit. From the FCC unit, various hydrocarbon streams can be recovered. These streams can be used as feedstock for a steam cracker or for the production of chemicals, or for the preparation of clean gasoline, jet fuel or diesel fuel.

[0067] The following examples are provided as illustrations of the blends and processes of the present invention and are not intended to be limiting.

Example

[0068] [Example 1] Characteristics of Plastic Samples and Biofeedstocks Used for Blend Preparation

[0069] Five plastic samples (low density polyethylene (LDPE, Plastic A), high density polyethylene (HDPE, Plastic B), two polypropylene samples with an average molecular weight of about 12,000 (PP, Plastic C) and about 250,000 (PP, Plastic D), and polystyrene (PS, Plastic E)) were purchased and their characteristics are summarized in Table 1.

Table 1

[0070] The biofeedstocks used to prepare blends with the plastic melt included palm oil, tallow and soybean oil, and their characteristics are shown in Table 2.

Table 2

[0071] Thermogravimetric analysis (TGA) was performed on Plastic A (LDPE) and Plastic C (polypropylene) to confirm that the plastic materials were thermally stable at temperatures well above the melt preparation temperature. The TGA results shown in Figure 6 indicate that the LDPE sample was stable up to 800°F and the polypropylene sample was stable up to 700°F.

[0072] [Example 2] Preparation of a Stable Blend of Palm Oil and Plastic

[0073] Several blends of palm oil and plastic were prepared by adding plastic pellets (Plastics A - D) to palm oil (Bio - raw material #1).

[0074] The following procedure was used. At ambient temperature, palm oil (a waxy solid) was placed in a beaker. The palm oil was heated with a heating mantle while stirring with a magnetic stirrer. The temperature of the palm oil was gradually increased to 270°F - 400°F, and then the pre - weighed plastic pellets (solids) were slowly added to the hot palm oil while stirring and heating. After the plastic pellets were dissolved, the stirred solution was held at the final temperature for an additional 30 minutes for blends using LDPE and polypropylene (Plastic C), and 60 minutes for blends using HDPE and polypropylene (Plastic D). Then, the blend was cooled to ambient temperature while stirring. Visual observation showed that the mixture was completely homogeneous. When cooled to ambient temperature, the blend of plastic and palm oil showed the appearance of the waxy solid of palm oil, but the hardening temperature (or solidification temperature) was different from that of the palm oil at the start of the procedure.

[0075] To evaluate the need for material handling, the pour point (by ASTM D5950-14) and viscosity (by ASTM D445) of the blend were measured. Further, the content of high-temperature heptane-insoluble substances was measured according to the procedure of ASTM D3279. In the high-temperature heptane-insoluble method, the weight percentage of substances in the oil that are insoluble in high-temperature heptane at 80 °C is measured. In this method, a 0.8-micron membrane filter is used to separate the insoluble substances. The heptane-insoluble content provides information about the undissolved plastics in the blend.

[0076] The stability of the material was observed by visual inspection. The blend of plastic and palm oil was stable, and no changes were observed during the three-month observation period.

[0077] Table 3 below summarizes the list of prepared samples and their properties.

Table 3

[0078] The pour point and viscosity values are used as guidelines for equipment selection and operating procedures. The blends prepared by adding plastics have a moderately increased pour point and viscosity compared to the pure bio-based case. These changes can be accommodated with minor or no changes in typical refining operation equipment. The blend tank is heated to a temperature above the pour point to change the physical state of the blend into a liquid that can be easily transferred. Subsequently, the liquid blend can be transferred to a transport container or a refining unit via pump transport by a pump, gravity discharge, or transfer by a pressure difference.

[0079] The stable blend remains a physical mixture at temperatures up to 80°C. The plastic was separated from the blend using a hot heptane insolubility test. At 80°C, all the waxes in the palm oil dissolved in the heptane solvent (Example 2-1), and the heptane-insoluble solids were only 0.02 wt%. The weight percentage of the heptane-insoluble substances is derived from the undissolved plastic filtered through a 0.8-micron membrane filter. The amounts recovered as solid substances in Examples 2-2 and 2-4 indicate that the heptane-insoluble solids are 7.6 wt% and 7.8 wt%, respectively, which is almost the same as the amount of plastic added for blend preparation. Since the recovered amount is 2.2 wt% - 2.4 wt% less, it is suggested that the blend may contain very fine submicron-sized particles. The heptane-insoluble results in Table 3 clearly show that the plastic is a physical mixture of solid particles dispersed in the palm oil in the 80°C blend, and most of the plastic particles can be separated by a 0.8-micron filter.

[0080] [Example 3] Preparation of a Stable Blend of Tallow and Plastic

[0081] Several blends of tallow and plastic samples were prepared by adding plastic pellets to the tallow raw material (Bio-feedstock #2).

[0082] The procedure described in Example 2 was used for these blend preparations.

Table 4

[0083] The blends prepared by adding plastic to tallow had moderately increased pour points and viscosities compared to the pure bio-based case, similar to the results of the palm oil shown in Example 2.

[0084] The weight percentage of heptane-insoluble substances recovered as solids is in good agreement with the amount of plastic added to the blend preparation. In the base case of tallow (Example 3-1), only 0.04 wt% of heptane-insoluble matter is contained, while in the stable blends (Examples 3-2 and 3-4), 7.7 wt% and 8.6 wt% of heptane-insoluble solids are contained, which is almost the same as the amount of plastic added for blend preparation. Since the recovered amount is 1.4 wt% to 2.3 wt% less than the amount of plastic input, it is suggested that the blend may contain very fine particles of submicron size. The heptane-insoluble results in Table 4 clearly show that the plastic is a physical mixture of solid particles dispersed in palm oil in the blend at 80 °C, and most of the plastic particles can be separated by a 0.8-micron filter.

[0085] [Example 4] Preparation of a Blend of Soybean Oil and Plastic (Comparative Example)

[0086] An attempt was made to prepare a blend of soybean oil (bio-based raw material #3) and plastic using the procedure described in Example 2 and plastic pellets (Plastics A - D). Surprisingly, soybean oil and plastic did not form a homogeneous liquid melt at high temperature even when heated together as in the case of palm oil or tallow. When the mixture was heated above the melting point of the plastic, the pellets softened and lost their shape. However, instead of forming a homogeneous liquid as in other cases, the plastic melt formed a separate liquid phase from soybean oil (SBO). Upon cooling, the plastic phase aggregated to form large plastic solid pieces. The reason for this is thought to be that the unsaturation of SBO is much higher. This is also evident from the lower H / C ratio compared to tallow and palm oil, and also from the measured iodine value. This also explains why most petroleum raw materials and highly saturated oils and fats determined by the iodine value can easily dissolve plastics.

Table 5

[0087] [Example 5] Preparation of a Blend of Soybean Oil, Palm Oil, and Plastic

[0088] A mixture of soybean oil and palm oil in a weight ratio of 1:1 (mixed bio - raw material) was prepared. Using the mixed bio - raw material, plastic pellets (Plastic A and C) were added to a 1:1 mixture of palm oil and soybean oil (Bio - raw material #1 and Bio - raw material #3), and a blend of palm oil, soybean oil, and plastic was successfully prepared. Therefore, soybean oil can be used as a component of the mixed bio - raw material. The stable blend showed a good shelf - life and did not change for several months. These results indicate that by using soybean oil together with another bio - raw material to lower the degree of unsaturation, soybean oil can also be used as a bio - raw material for preparing a stable blend with plastic.

[0089] This test also shows an acceptable iodine value for successfully preparing a stable blend of plastic and bio - raw material. The iodine value of a 1:1 mixture of soybean oil and palm oil is estimated to be 91. These results indicate that as long as the overall unsaturation of the mixed bio - raw material is 95 or less in iodine value, preferably 91 or less, soybean oil or other highly unsaturated oils can also be used as bio - raw materials for preparing a stable blend with plastic.

Table 6

[0090] [Example 6] Preparation of a Blend of Soybean Oil, Tallow, and Plastic

[0091] A 1:1 mixture of soybean oil and tallow was prepared (mixed biofeedstock). Using the mixed biofeedstock, a blend of tallow, soybean oil, and plastic was successfully prepared by adding plastic pellets (Plastics A and C) to a 1:1 mixture of tallow and soybean oil (Biofeedstock #1 and Biofeedstock #3). The stable blend showed a good shelf life and no changes were observed for several months. These results again show that soybean oil can also be used as a biofeedstock for preparing a stable blend with plastic by lowering the degree of unsaturation when used with another biofeedstock.

[0092] This test also shows the iodine value acceptable for successfully making a stable blend of plastic and biofeedstock. The iodine value of the 1:1 mixture of soybean oil and tallow is estimated to be 88.

Table 7

[0093] To investigate the effect of processing waste plastic and biofeedstock in an FCC unit, laboratory tests were carried out using a fluid catalytic cracking (FCC) process with a stable blend of plastic and biofeedstock. In this test, two FCC catalysts were used. One was a ZSM-5-containing FCC catalyst made of ZSM-5 zeolite (a medium-pore zeolite with a 10-membered ring), and the other was a USY-containing FCC catalyst made of USY (a medium-pore zeolite with a 12-membered ring). Three biofeedstocks, palm oil, soybean oil, and tallow, were used.

[0094] (Catalyst) The catalytic cracking experiment was conducted in an ACE (Advanced Cracking Evaluation) Model C unit manufactured by Kayser Technology Inc. (Texas, USA). The reactor used in the ACE unit was a fixed fluidized bed reactor with an inner diameter of 1.6 cm. Nitrogen was used as the fluidizing gas and introduced from both the bottom and the top. The upper fluidizing gas was used to carry the feed injected from a calibrated syringe pump through a three-way valve. The experiment was conducted at atmospheric pressure and a temperature of 975°F. In each experiment, a fixed amount of 1.5 grams of feed was injected at a rate of 1.2 grams / minute for 75 seconds. The catalyst / oil ratio was maintained at 6. After 75 seconds of feed injection, the catalyst was stripped with nitrogen for 525 seconds. During the catalytic cracking and stripping processes, the liquid products were collected in sample vials attached to a glass receiver at the end of the reactor outlet and maintained at -15°C. The gaseous products were collected in a sealed stainless steel container (12.6 L) pre-filled with N2 at 1 atm. The gaseous products were mixed by an electric stirrer rotating at 60 rpm immediately after the feed injection was completed. After stripping, the gas products were mixed for an additional 10 minutes to ensure homogeneity. The final gas products were analyzed using a refined gas analyzer (RGA). After the completion of the stripping process, in-situ catalyst regeneration was carried out in the presence of air at 1300°F. The regeneration exhaust gas passed through a catalytic converter filled with CuO pellets (LECO Inc.) to oxidize CO to CO2. Then, the exhaust gas was analyzed with an on-line IR analyzer installed downstream of the catalytic converter. The coke deposited during the cracking process was calculated from the CO2 concentration measured by the IR analyzer.

[0095] The gaseous products, mainly C1 to C7 hydrocarbons, were analyzed by RGA. The RGA is a customized Agilent 7890B GC equipped with three detectors, namely, a flame ionization detector (FID) for hydrocarbons and two thermal conductivity detectors for nitrogen and hydrogen. A methanizer was also installed in the RGA to quantify trace amounts of CO and CO2 in the gas products when bio-based raw materials such as soybean oil, palm oil, or tallow were decomposed. The gas products were classified into dry gas (C2-hydrocarbons and hydrogen) and LPG (C3 and C4 hydrocarbons). CO and CO2 were excluded from the dry gas. Their yields were reported separately. The liquid products were weighed and analyzed by simulated distillation GC (Agilent 6890) using the ASTM D2887 method. The liquid products were divided into gasoline (C5 to 430°F), LCO (430°F to 650°F, light cycle oil), and HCO (650°F+, heavy cycle oil). The gasoline (C5+ hydrocarbons) in the gaseous products was combined with the gasoline in the liquid products to obtain the total gasoline. The light fraction (C 5- ) in the liquid products was also subtracted from the liquid products and re-added to the C3 and C4 species using an empirical distribution. The material balance was between 98% and 101% in most of the experiments.

[0096] For the gasoline portion of the liquid products, detailed hydrocarbon analysis (DHA) was also performed using an Agilent 6890A and Hydrocarbon Expert software from Separation Systems Inc. (Florida) to analyze PONA and octane (RON and MON). DHA analysis was not performed on the gasoline portion of the gaseous products. However, the DHA results still provided valuable information for evaluating the characteristics of the (catalytic) cracking products.

[0097] [Example 7] Direct conversion of plastics and palm oil via FCC (using ZSM-5 catalyst)

[0098] Laboratory tests of the fluid catalytic cracking (FCC) process were carried out using stable blends of plastics and bio-based raw materials (Examples 2-2 and 5-1), and an FCC catalyst made of ZSM-5 zeolite was used. The results are summarized in Table 8.

Table 8

[0099] The results in Table 8 show that blends of waste plastics and bio-based raw materials (palm oil and soybean oil) are well-converted with the ZSM-5-containing FCC catalyst. Surprisingly, the medium-pore 10-membered ring ZSM-5 catalyst can convert more than 95 wt% of the plastic / bio-based raw material blend under typical FCC process conditions (Examples 7-1 to 7-3). Due to the high conversion rate, the yields of LCO and HCO are very low. In all these cases, very high yields of LPG and aromatics are obtained, indicating that this process can be used for the production of raw materials for polymer and chemical manufacturing without using petroleum resources.

[0100] Even when 10 wt% of plastics was added to palm oil, there were only slight changes in the performance of the FCC unit in terms of conversion rate and the yields of dry gas and coke. This suggests that the co-processing of waste plastics and bio-based raw materials is easily feasible (Examples 7-1 and 7-2). When 10 wt% of low-density polyethylene (Plastic A) was blended with palm oil, the yields of coke and dry gas increased only slightly, but significant increases in the LPG yield (35 wt% vs. 37 wt%) and the total aromatics yield (76 wt% vs. 81 wt% in the gasoline fraction) were observed. The significant increase in the LPG yield and aromatics yield from the plastic-containing blend was completely unexpected. This clearly shows that the synergistic effect of the bio-based raw material and plastic blend increases the yields of LPG and aromatics.

[0101] When 10 wt% of plastics was blended with palm oil and soybean oil (Example 7-3), it also showed consistent results of high LPG and aromatic compound production.

[0102] These results indicate that the ZSM-5 catalyst prepared with mesoporous zeolite is a favorable catalyst for the production of LPG olefins and aromatic compounds when converting bio-based raw materials / plastic blends.

[0103] The high yield of LPG by this process is important. LPG and LPG olefins are favorable raw materials for the production of polyethylene and polypropylene.

[0104] The high yield of aromatics by this process is also very important because these aromatics can be used in the production of polystyrene or polyethylene terephthalate. Another surprising discovery was the selectivity of para-xylene to total xylene. When using the ZSM-5 catalyst, the xylene produced in this process is substantially para-xylene, and the para-xylene selectivity is about 61 - 70% (ratio to the total xylene production). Para-xylene is the most desirable xylene isomer for the production of polyethylene terephthalate polymers.

[0105] This process is more suitable for the production of chemical substances, but a part of the products can be used in the production of premium gasoline fuel. The gasoline produced by this process has an excellent octane number exceeding 100 because of the high aromatic content in the gasoline fraction. Due to the high conversion rate, the yields of LCO and HCO are low.

[0106] [Example 8] Direct conversion of plastic and palm oil via FCC (using USY catalyst)

[0107] Laboratory tests of the fluid catalytic cracking (FCC) process were carried out using a stable blend of plastic and palm oil (Examples 2-2 and 5-1) and an FCC catalyst made of USY zeolite, and the results are summarized in Table 9.

Table 9

[0108] The results in Table 9 show that the blend of waste plastics and bio-based raw materials (palm oil and soybean oil) is well-converted over the USY-containing FCC catalyst. The overall conversion rate of the blend is 86 - 87% under typical FCC process conditions (Examples 8-1 to 8-3). In all these cases, a low dry gas yield (undesirable product) and high yields of LPG, gasoline, and LCO (desirable products) are obtained, indicating that this process can be used for the co-production of raw materials for chemical manufacturing and premium renewable fuels without using petroleum resources.

[0109] Even when 10 wt% of plastics was added to palm oil, only slight changes occurred in terms of the conversion rate and the yields of dry gas and coke in the performance of the FCC unit. This indicates that the co-processing of waste plastics and bio-based raw materials is easily feasible (Examples 8-1 and 8-2). Even when low-density polyethylene (Plastic A) was blended with palm oil at 10 wt%, only slight effects on the product yields were observed: LPG yield (19.5 wt% vs 21.3 wt%), gasoline yield (45.4 wt% vs 44.9 wt%), LCO (10.9 wt% vs 10.0 wt%), and HCO yield (3.2 wt% vs 3.3 wt%). However, due to the paraffinic nature of the plastic, a 3-point decrease in the gasoline octane number was observed (from 91 to 88).

[0110] When 10 wt% of plastics was blended with palm oil and soybean oil (Example 8-3), consistent results of high LPG and gasoline production were also shown.

[0111] When using the USY catalyst, no synergistic effect between the biofeedstock and plastic was observed, nor was the para-xylene selectivity observed with the ZSM-5 catalyst shown in Example 7-2. Compared to the ZSM-5 catalyst (Example 8-2 vs. Example 7-2), the USY catalyst had a much higher yield of LCO (10.0 wt% vs. 1.4 wt%) and also a much higher yield of HCO (3.3 wt% vs. 0.7 wt%). Furthermore, USY showed a much higher coke selectivity (6.7 wt% vs. 1.7 wt%) and a lower off-gas yield (2.2 wt% vs. 6.5 wt%). These results indicate that the USY catalyst made of large-pore zeolite is a preferred FCC catalyst for the simultaneous production of chemical feedstocks and premium fuels.

[0112] Part of the product can be used in the production of premium fuels. The gasoline produced in this process has an octane number of 91 - 88. Due to the paraffinic nature of the plastic, adding polyethylene plastic slightly reduces the octane number. Due to the flexibility of the refinery blend, this reduction in octane number can be compensated for by fine-tuning the blend.

[0113] The high yield of LPG by this process is important. LPG and LPG olefins are preferred feedstocks for the production of polyethylene and polypropylene.

[0114] The high yield of aromatics by this process is also important because these aromatics can be used in the production of polystyrene or polyethylene terephthalate.

[0115] [Example 9] Direct conversion of plastic and tallow via FCC (using ZSM-5 catalyst)

[0116] Laboratory tests of the fluid catalytic cracking (FCC) process were carried out using a stable blend of plastic and biofeedstock (Examples 3-2, 3-4, and 6-1) and an FCC catalyst made of ZSM-5 zeolite, and the results are summarized in Table 10.

Table 10

[0117] The results in Table 10 show that blends of waste plastics and bio-based raw materials (tallow and soybean oil) are well-converted over the ZSM-5-containing FCC catalyst. Similar to the co-processing with palm oil, the ZSM-5 catalyst showed a very high conversion rate of over 95 wt% of the plastic / bio-based raw material blend under typical FCC process conditions (Examples 9-1 to 9-4). Due to the high conversion rate, the yields of LCO and HCO are very low. In all these cases, very high LPG and aromatic yields are obtained, indicating that this process can be used to produce raw materials for polymer and chemical manufacturing without using petroleum resources.

[0118] Even when 10 wt% of polyethylene or polypropylene plastic was added to tallow, only slight changes occurred in terms of the conversion rate and the yields of dry gas and coke in the performance of the FCC unit. This suggests that the co-processing of waste plastics and bio-based raw materials can be easily carried out (Examples 9-1 vs. 9-2 and 9-3). Different from the case of palm oil shown in Example 7-2, blending 10 wt% of low-density polyethylene (Plastic A) and polypropylene (Plastic C) into tallow did not show a synergistic effect on the LPG yield and the aromatic yield. The LPG yield (36.5 wt% vs. 35.5 - 36.4 wt%) and the total aromatic yield (80.6 wt% in the gasoline fraction vs. 80.3 - 80.6 wt%) were the same as in the case of plastic co-feed.

[0119] When 10 wt% of plastic was blended into tallow and soybean oil (Example 9-4), it also showed consistent results of high LPG and aromatic compound production, as well as high para-xylene selectivity.

[0120] The high yields of LPG and aromatics shown in Table 10 again indicate that the ZSM-5 catalyst made of medium pore zeolite is a favorable catalyst for the production of LPG olefins and aromatic compounds from the blend of plastic and bio-feedstock (such as animal fat). When the ZSM-5 catalyst is used, the xylene produced in this process is substantially paraxylene, and the paraxylene selectivity is about 65 - 67% (ratio to the total xylene production).

[0121] [Example 10] Direct conversion of plastic and animal fat via FCC (using USY catalyst)

[0122] Laboratory tests of the fluid catalytic cracking (FCC) process were carried out using a stable blend of plastic and animal fat bio-feedstock (Examples 3-2, 3-4, and 6-1), and an FCC catalyst made of USY zeolite. The results are summarized in Table 11.

Table 11

[0123] The results in Table 11 show that the blend of waste plastic and bio-feedstock (animal fat and soybean oil) is well-converted by the USY-containing FCC catalyst. The overall conversion rate of the blend is 85 - 87% under typical FCC process conditions (Examples 10-1 to 10-4). In all these cases, a low dry gas yield (undesirable product) and high yields of LPG, gasoline, and LCO (desirable products) are obtained, indicating that this process can be used for the simultaneous production of raw materials for chemical manufacturing and premium fuels without using petroleum resources.

[0124] Even when 10 wt% of plastic was added to tallow, only slight changes occurred in the performance of the FCC unit in terms of conversion rate and yields of dry gas and coke. This indicates that co-processing of waste plastics and bio-based raw materials can be easily carried out (Examples 10-1, 10-2, and 10-3). When low-density polyethylene (Plastic A) or polypropylene (Plastic C) was blended with tallow at 10 wt%, the LPG yield increased slightly (20.1 wt% vs. 21.6 - 22.6 wt%), but had only a slight impact on the yields of other products: gasoline yield (44.6 wt% vs. 43.6 - 44.3 wt%), LCO (10.5 wt% vs. 10.2 - 11.0 wt%), and HCO yield (3.5 wt% vs. 3.2 - 3.3 wt%). No decrease in gasoline octane number was observed with the co-feed of polyethylene, and it was confirmed that the gasoline octane number increased by 2 points with the co-feed of polypropylene (88.0 vs. 87.9 vs. 92.3).

[0125] These results indicate that the USY catalyst made of large-pore zeolite is a preferred catalyst for simultaneously producing chemical raw materials and premium renewable fuels.

[0126] As used in this disclosure, the words "comprises" or "comprising" are intended as open-ended transitional terms meaning including the recited elements but not necessarily excluding other unrecited elements. The phrase "consists essentially of" or "consisting essentially of" is intended to mean excluding other elements that are essential to the composition. The phrase "consisting of" or "consists of" is intended as a transitional phrase meaning excluding everything except the recited elements, except for trace impurities.

[0127] All patents and publications referenced herein are incorporated herein by reference to the extent not inconsistent herewith. It will be understood that the specific structures, functions, and operations of the above-described embodiments are not necessary for practicing the present invention and are included in the description merely to completely exemplify the exemplary embodiments or multiple embodiments. Further, it will be understood that the specific structures, functions, and operations described in the above-referenced patents and publications can be implemented in combination with the present invention, but they are not essential for its implementation. Accordingly, it is understood that the present invention can be practiced as specifically described without actually departing from the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A blend of a bio-based raw material and 1 to 20 wt% plastic based on the weight of the blend, wherein the plastic comprises polyethylene and / or polypropylene.

2. The blend according to claim 1, wherein the amount of plastic in the blend constitutes 1 to 10 wt% of the blend.

3. The blend according to claim 1, wherein the plastic comprises low density polyethylene.

4. The blend according to claim 1, wherein the plastic comprises high density polyethylene.

5. The blend according to claim 3, wherein the blend comprises 1 to 10 wt% low density polyethylene.

6. The blend according to claim 4, wherein the blend comprises 1 to 10 wt% high density polyethylene.

7. The blend according to claim 1, wherein the plastic comprises polypropylene having an average molecular weight M in the range of 5,000 to 150,000 ｗ ​

8. The plastic contains polypropylene having an average molecular weight M in the range of 150,000 to 400,000. ｗ The blend according to claim 1, comprising polypropylene having an average molecular weight M in the range of 150,000 to 400,000.

9. The blend according to claim 7, wherein the blend comprises 1 to 10 wt% polypropylene.

10. The blend according to claim 8, wherein the blend comprises 1 to 10 wt% polypropylene.

11. The blend according to claim 1, wherein the plastic comprises a mixture of polyethylene and polypropylene.

12. The blend according to claim 1, wherein the bio-based raw material comprises triglycerides, fatty acids, plant-derived oils, animal-derived fats and oils, or a mixture thereof.

13. The blend according to claim 12, wherein the plant-derived oil comprises palm oil, canola oil, corn oil, soybean oil, or a mixture thereof.

14. The blend according to claim 12, wherein the bio-based raw material comprises tallow, lard, schmalz, or fish oil.

15. The blend according to claim 1, wherein the bio-based raw material comprises palm oil, tallow, soybean oil, or a mixture thereof.

16. The blend according to claim 1, wherein the bio-based raw material comprises a mixture of palm oil and soybean oil.

17. The blend according to claim 1, wherein the bio-based raw material comprises a mixture of tallow and soybean oil.

18. The blend according to claim 1, wherein the bio-based raw material comprises pyrolysis oil of biomass.

19. The blend according to claim 1, wherein the bio-based raw material comprises a bio-based raw material or a mixed bio-based raw material having an iodine value of 95 or less.

20. The blend according to claim 1, having an iodine value of 91 or less.

21. The blend according to claim 1, wherein a petroleum raw material stream containing LCO or gasoline is added to reduce the blend viscosity.

22. The blend according to claim 1, wherein the petroleum raw material constitutes 0 to 50 vol% of the blend.

23. The blend according to claim 1, wherein the blend is at a temperature below the melting point of the plastic and the plastic in the blend is composed of micron-sized particles that are finely dispersed.

24. The blend according to claim 1, wherein the temperature of the blend exceeds the melting point of the plastic.

25. The blend according to claim 1, wherein the blend contains waste plastic.

26. A process for preparing a stable blend of plastic and bio raw material, comprising: (a) mixing a bio raw material with a plastic containing polyethylene and / or polypropylene, and heating the mixture during mixing to a temperature that exceeds the melting point of the plastic but is less than 550°F; (b) cooling the plastic melt and the bio raw material liquid blend to a temperature below the melting point of the plastic. The above process.

27. The process according to claim 26, wherein the cooling in (b) is carried out with continuous stirring.

28. The process according to claim 26, wherein the heating is carried out at a temperature of 250 - 550°F and the residence time at the final heating temperature is 5 - 240 minutes.

29. The process according to claim 26, wherein the cooling is continued until the ambient temperature is reached.

30. A process for converting waste plastic into chemical substances and recycled fuel, comprising: (a) selecting waste plastic containing polyethylene and / or polypropylene; (b) preparing a blend of a bio raw material and the selected plastic, wherein the blend contains the selected plastic at about 20 wt% or less; (c) passing the blend through a catalytic conversion unit. The above process.

31. A blend prepared by mixing a bio raw material and a plastic containing polyethylene and / or polypropylene together and heating the mixture while mixing to a temperature that exceeds the melting point of the plastic.

32. The blend according to claim 31, wherein the plastic is waste plastic.

33. A blend prepared by the process according to claim 26.

34. The blend according to claim 33, wherein the plastic is waste plastic.

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