Circular Economy of Waste Plastics to Polypropylene via Refined FCC Unit

Abstract

Provided is a continuous process for converting waste plastics to recycle for polypropylene polymerization. The process includes the steps of selecting a waste plastic comprising polyethylene and / or polypropylene, and preparing a stable blend of petroleum and the selected plastic. The amount of plastic in the blend comprises less than 20 wt% of the blend. The blend is passed to a refinery FCC unit. Liquefied petroleum gas C 3 The olefin / paraffin mixture is recovered from the FCC unit. 3 Paraffin and C 3 The olefins are separated into different fractions, 3 The olefin fraction is passed to a propylene polymerization reactor and 3 The paraffinic fraction is optionally passed to a dehydrogenation unit to produce additional propylene.

Description

[Technical field]

[0001] (background) The world has witnessed a very rapid growth in plastic production. According to PlasticsEurope Market Research Group, global plastic production was 335 million tonnes in 2016, 348 million tonnes in 2017, 359 million tonnes in 2018, and 367 million tonnes in 2020. According to McKinsey & Company, global plastic waste is estimated to be 460 million tonnes per year by 2030 if the current trajectory continues. [Background technology]

[0002] Single-use plastic waste is becoming an increasingly significant environmental issue. At present, there appear to be few options for recycling polyethylene and polypropylene waste plastics into value-added chemical and fuel products. Currently, only small amounts of polyethylene and polypropylene are recycled via chemical recycling, and this recycled and cleaned polymer pellets are pyrolyzed in pyrolysis units to produce fuels (naphtha, diesel), steam cracker feedstock, or slack wax. The vast majority (>80%) is incinerated, landfilled, or disposed of.

[0003] Current methods of chemical recycling via pyrolysis are not capable of making a significant impact on the plastics industry. Current pyrolysis operations produce poor quality fuel components (naphtha and diesel range products) but in small enough quantities that these products can be blended into the fuel supply. However, to recycle the very large quantities of waste polyethylene and waste polypropylene required to address environmental concerns, such simple blending cannot continue. The raw products from pyrolysis units are too poor quality to be blended in large quantities (e.g., 5-20 vol.% blends) into transportation fuels.

[0004] Processes for converting waste plastics into hydrocarbon lubricants are known. For example, US Patent No. 3,845,157 discloses the cracking of waste or virgin polyolefins to form gaseous products such as ethylene / olefin copolymers, which are further processed to produce synthetic hydrocarbon lubricants. US Patent No. 4,642,401 discloses the heating of pulverized polyolefin waste at temperatures between 150 and 500°C and pressures between 20 and 300 bar to produce liquid hydrocarbons. US Patent No. 5,849,964 discloses a process for depolymerizing waste plastic materials into volatile and liquid phases. The volatile phase is separated into a gas phase and a condensate. The liquid, condensate and gas phases are refined into liquid fuel components using standard refining techniques. US Patent No. 6,143,940 discloses a procedure for converting waste plastics into heavy wax compositions. US Patent No. 6,150,577 discloses a process for converting waste plastics into lubricating oils. EP 0 620 264 A1 discloses a process for producing lubricants from waste or virgin polyolefins by thermally cracking the waste in a fluidized bed to form a waxy product, optionally using hydrotreating, followed by catalytic isomerization and fractionation to recover the lubricants.

[0005] US Patent Application Publication No. 2021 / 0130699 discloses a process and system for producing recycle-containing hydrocarbons from recycled waste. The recycled waste is pyrolyzed to form a pyrolysis oil composition, at least a portion of which can be cracked to form a recycled olefin composition.

[0006] Other documents relating to processes for converting waste plastics into lubricants 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. 2019 / 0161683, 2016 / 0362609 and 2016 / 0264885. The aforementioned patent documents are incorporated herein by reference in their entirety.

[0007] Globally, recycling and upcycling of plastic waste has attracted great interest to save resources and the environment. Mechanical recycling of plastic waste is quite limited due to the different types, properties, additives, and contaminants of the collected plastics. Usually, recycled plastics are of reduced quality. Chemical recycling into starting materials or value-added chemicals has emerged as a more desirable method.

[0008] However, more robust processes are needed for industrial large-scale chemical recycling of single-use plastics to reduce their environmental impact. These improved processes should establish a "circular economy" for waste polyethylene and polypropylene plastics, effectively recycling post-consumer waste plastics as starting material for polymers or value-added chemical products or fuels. Summary of the Invention

[0009] Provided is a continuous process for converting waste plastics into recycled polypropylene polymerization. The process includes selecting waste plastics that include polyethylene and / or polypropylene. These waste plastics are blended with a petroleum feedstock. The resulting blend is generally a stable blend and homogenous mixture, especially at temperatures below the melting point of the waste plastics. The blend contains up to about 20% by weight of the selected waste plastic. The blend is then passed through an FCC unit of a refinery along with conventional refined hydrocarbon feedstocks such as VGO.

[0010] Integrating this process into oil refinery is an important aspect of the process and can achieve a circular economy with single-use waste plastics such as polypropylene. Thus, the blend is passed through a refinery FCC unit. The blend is passed at a temperature above the pour point so that the blend can be pumped into the refinery FCC unit. The blend is heated to a temperature above the melting point of the plastic before being injected into the reactor. From the FCC unit, a liquefied petroleum gas C3 olefin / paraffin mixture is recovered. The C3 olefin / paraffin mixture is separated into a C3 paraffin fraction and a C3 olefin fraction. The C3 olefins are passed through a propylene polymerization reactor to produce polypropylene. Optionally, the C3 paraffins are sent to a dehydrogenation unit to produce additional propylene. This propylene can be used to produce polypropylene.

[0011] Refineries generally have their own supply of hydrocarbons that flows through the refinery units. A key aspect of this process is that it does not adversely affect the refinery's operations; the refinery must still produce valuable chemicals and fuels. Otherwise, integrating this process into an oil refinery would not be a viable solution. Therefore, the flow rates must be carefully monitored.

[0012] The volume of waste plastic / petroleum blend flow to the refinery unit can comprise any practical or accommodable volume percent (vol%) of the total flow (total flow) to the refinery unit. In general, the blend flow can be up to about 100 vol% of the total flow (i.e., at this maximum, the blend flow is the total flow not including the refinery flow). In one embodiment, the blend flow is up to about 50 vol% of the total flow (i.e., the refinery flow plus the blend flow).

[0013] Among other factors, it has been found that the addition of refinery operations can efficiently and effectively recycle waste plastics while complementing the refinery operations in the preparation of high value products such as gasoline, jet fuel, base oils and diesel. However, it has also been found that the addition of refinery operations can efficiently and effectively produce clean propane and propylene from waste plastics for the production of ultimate polypropylene polymer. Positive economics are realized throughout the process from recycled plastics to polypropylene products with product qualities equivalent to virgin polymers. [Brief description of the drawings]

[0014] [Figure 1] Figure 1 shows the current practice of pyrolyzing waste plastics to produce fuel or wax (base case).

[0015] [Diagram 2] Figure 2 illustrates the present process for preparing a hot, homogenous liquid blend of plastic and petroleum feedstocks and how the blend is fed to a refining and conversion unit.

[0016] [Diagram 3] FIG. 3 shows the details of the stable blend preparation process and how the stable blend is fed to the purification and conversion unit.

[0017] [Figure 4] Figure 4 shows the classification of plastic types for recycling waste plastics.

[0018] [Diagram 5] FIG. 5 shows the process where the prepared blend is passed through a refining FCC unit.

[0019] [Figure 6] FIG. 6 shows the present process for establishing a circular economy of waste plastics, in which the blend is passed through a refined FCC feed pre-treatment unit prior to the refined FCC unit.

[0020] [Figure 7] FIG. 7 graphically illustrates the thermogravimetric analysis (TGA) of the thermal stability of polyethylene and polypropylene.

[0021] [Figure 8] FIG. 8 graphically illustrates the thermogravimetric analysis (TGA) of the thermal stability of four waste plastic samples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] This process provides a method to recycle waste polyethylene and / or waste polypropylene into virgin polypropylene, establishing a circular economy by combining separate industrial processes. The majority of polyethylene and polypropylene polymers are used for single-use plastics and are discarded after use. This single-use plastic waste is becoming an increasingly important environmental issue. At present, there seem to be few options to recycle polyethylene and polypropylene waste plastics into value-added chemical and fuel products. Currently, only a small amount of polyethylene / polypropylene is recycled via chemical recycling, and this recycled and cleaned polymer pellets are pyrolyzed in a pyrolysis unit to produce fuels (naphtha, diesel), steam cracker feedstock, or slack wax.

[0023] Polypropylene is widely used in a variety of consumer and industrial products. It has mechanical durability and high chemical resistance, making it the second most widely produced commodity plastic after polyethylene. Polypropylene is widely used in packaging, films, carpet and clothing fibers, molded articles, and extruded pipes. Today, only a small fraction of post-consumer polypropylene products are collected for recycling. This is due to the inefficiency and ineffectiveness of recycling efforts mentioned above.

[0024] FIG. 1 shows a diagram of waste plastic fuel or wax pyrolysis as commonly practiced in industry today. Typically, waste plastics are sorted together (1). The cleaned waste plastics 2 are converted to off-gas 4 and pyrolysis oil (liquid products) in a pyrolysis unit 3. The off-gas 4 from the pyrolysis unit is used as fuel to operate the pyrolysis unit. An on-site distillation unit separates the pyrolysis oil to produce naphtha and diesel 5 products, which are sold to the fuel market. The heavy pyrolysis oil fraction 6 is recycled to the pyrolysis unit 3 to maximize fuel yield. 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., forms paraffinic wax when cooled to ambient temperature). Wax can be separated from the heavy fraction 6 and sold to the wax market.

[0025] However, in this process, waste plastics are not pyrolyzed. Rather, a stable mixture of petroleum feedstock and waste plastics is prepared. Thus, the pyrolysis step can be avoided, which is a significant energy saving.

[0026] The blend is prepared in a high temperature blend preparation unit with an operating temperature above the melting point of the plastic (approximately 150-250°C) to create a hot, homogeneous liquid blend of plastic and oil that can be fed directly to the refining unit.

[0027] Alternatively, the blend is prepared in a stable blend preparation unit and the hot homogenous liquid blend is cooled in a controlled manner to ambient temperature for easy storage and transport. Using this method, the stable blend can be prepared at a facility remote from the refinery and transported to the refining unit. The stable blend is then heated to a temperature above the melting point of the plastics and fed to the refining conversion unit. The stable blend is a physical mixture of microcrystalline plastic particles finely suspended in a petroleum-based oil. This mixture is stable and the plastic particles do not settle or agglomerate even when stored for long periods of time.

[0028] The significance of heating the blend above the melting point of the plastic is clear when a single plastic is used. However, when the waste plastic is composed of multiple waste plastics, the melting point of the plastic with the highest melting point will be exceeded. Thus, the melting points of all the plastics must be exceeded. Similarly, when the blend is cooled to a temperature below the melting point of the plastic, the temperature must be below the melting points of all the plastics that make up the blend.

[0029] Compared to pyrolysis units, these blend preparation units operate at much lower temperatures (approximately 500-600°C versus 120-250°C). Therefore, the process is a much more energy-efficient process for preparing refined feedstock from waste plastics than thermal decomposition processes such as pyrolysis.

[0030] The use of the waste plastic / petroleum blend of the present invention further increases the overall yield of hydrocarbons obtained from waste plastics. This increase in yield is significant. The hydrocarbon yield using the present blend can reach up to 98%. In contrast, pyrolysis produces a significant amount of light products from plastic waste, about 10-30 wt% and about 5-10 wt% char. These light hydrocarbons are used as fuel to run the pyrolysis plant, as mentioned above. Thus, the liquid hydrocarbon yield from the pyrolysis plant is up to 70-80%.

[0031] When the blend is passed through a refinery unit, such as an FCC unit, only a small amount of off-gas is produced. The refinery unit uses a (catalytic) catalytic cracking process, which is different from the thermal cracking process used in pyrolysis. The catalytic process minimizes the production of undesirable light by-products such as methane and ethane. The refinery unit provides efficient product fractionation, allowing efficient utilization of all hydrocarbon product streams to produce high value materials. The refinery co-feed produces only about 2% off-gas (H2, methane, ethane, ethylene). The C3 and C4 streams are captured to produce useful products such as cyclic polymers and high quality fuel products. Thus, the use of the oil / plastic blend of the present invention not only leads to increased hydrocarbons from waste plastics, but also provides a more energy-efficient recycling process compared to thermal treatment processes such as pyrolysis.

[0032] The process converts single-use waste plastics in bulk by blending them with petroleum product streams and integrating them into oil refinery operations. The resulting process produces feedstocks for polymers (liquefied petroleum gas (LPG), C3 olefin streams for propylene polymerization units), high-quality gasoline, diesel fuel, jet fuel, and / or high-quality base oils.

[0033] In general, the process provides a circular economy for polypropylene plants. Polypropylene is produced via polymerization of pure propylene. Clean propylene can be produced from a propane dehydrogenation unit. Propylene can also be obtained from an oil refinery fluid catalytic cracking (FCC) unit, which produces a mixture of propylene and propane liquefied petroleum gas (LPG). Pure propylene is separated from the mixture using a propane / propylene splitter, a high efficiency distillation column (PP splitter).

[0034] By adding a refinery operation to upgrade the waste plastics to higher value products (gasoline, jet fuel and diesel, base oils) and to produce clean propane and propylene for the production of ultimate polypropylene polymer, positive economics are realized throughout the process from recycled plastics to a polypropylene product with qualities equivalent to virgin polymer. Also, by integrating the recycling process with an oil refinery operation, a more energy efficient and effective process is achieved while avoiding the problems of the refinery operation.

[0035] The integration of refinery operations is also very important in another aspect. Waste plastics contain contaminants such as calcium, magnesium, chlorides, nitrogen, sulfur, dienes, and heavy components, which prevent their products from being used in large quantities for blending transportation fuels. It has been found that by passing these products through a refinery unit, the contaminants can be captured in a pretreatment unit and their negative impacts can be reduced. The fuel components can be further upgraded in a suitable refinery unit using chemical conversion processes, and the final transportation fuel produced by the integrated process can be of higher quality and meet the fuel quality requirements. The integrated process produces a much cleaner and purer propane stream for the propane dehydrogenation unit and ultimately for polypropylene production. The mass production of these specifications makes the "circular economy" of recycled plastics possible.

[0036] The carbon going in and out of the refinery is “transparent,” meaning that not all molecules from the waste plastics are cycled back to the polyolefin plant and become the exact olefin product, but it is nevertheless considered a “credit” since the net “green” carbon going in and out of the refinery is positive. These integrated processes result in a significant reduction in the amount of virgin feedstock required for a polypropylene plant.

[0037] In some cases, the energy required to convert waste plastics into clean fuels is less than the energy required to produce fuels from virgin petroleum feedstocks. As collection and processing of waste plastics improves, energy efficiency will improve further. Such fuels produced from blends of waste plastics and oils contain recycled content and have a lower carbon footprint than corresponding fuels produced from pure petroleum feedstocks. The process allows the production of clean gasoline, jet fuel and diesel from waste plastics that contain recycled content and have a low CO2 footprint (low carbon footprint).

[0038] FIG. 2 shows a method for preparing a hot homogenous blend of plastic and oil feedstock for use in the process, which is injected directly into the refinery unit, in which a hot homogenous liquid blend of plastic and oil is prepared in a hot blend preparation unit. The preferred range of plastic composition in the blend is about 1-20 wt%. When high molecular weight polypropylene (average molecular weight 250,000 or more) waste plastic or high density polyethylene (density greater than 0.93 g / cc) is mainly used as waste plastic, for example at least 50 wt%, the amount of waste plastic used in the blend is more preferably about 10 wt%. This is because the pour point and viscosity of the blend will be higher.

[0039] Preferred conditions for the preparation of hot homogenous liquid blends include vigorously mixing the plastic with the petroleum feedstock while heating it to a temperature above the melting point of the plastic. Preferred process conditions include heating to a temperature of 250-500°F, a residence time at the final heating temperature of 5-240 minutes, and atmospheric pressure of 0-10 psig. This can be done in open air or preferably under an oxygen-free inert atmosphere.

[0040] Referring to FIG. 2 of the drawings, a step-by-step preparation process for preparing a hot homogenous liquid blend is shown. The mixed waste plastics are sorted to produce post-consumer waste plastics 21 containing polyethylene and / or polypropylene. The waste plastics are cleaned (22) and then mixed with oil 24 in a hot blend preparation unit 23. After mixing in 23, a homogenous blend of plastics and oil is recovered (25). Optionally, a filtration device can be added (not shown) to remove undissolved plastic particles or solid impurities present in the hot liquid blend. The hot blend of plastics and oil is then combined with a refinery feedstock such as VGO 20 to produce a mixture of plastic / oil blend and VGO 26, which can then be passed to a refinery unit. In this process, in one embodiment, the refinery unit is an FCC unit.

[0041] FIG. 3 shows a method for preparing a stable blend of plastics and oil for use in the present process. The stable blend is made by a two-step process in a stable blend preparation unit. In the first step, a hot homogeneous liquid blend of plastic melt and oil feedstock is produced. This step is the same as the hot blend preparation described in FIG. 2. The preferred range of plastic composition in the blend is about 1-20 wt%. If high molecular weight polypropylene (average molecular weight ≧250,000) waste plastics or high density polyethylene (density above 0.93 g / cc) are mainly used as waste plastics, for example at least 50 wt%, the amount of waste plastic used in the blend is more preferably about 10 wt%. The reason is that the pour point and viscosity of the blend will be higher.

[0042] Preferred conditions for the preparation of hot homogenous liquid blends include vigorously mixing the plastic with the petroleum feedstock while heating it to a temperature above the melting point of the plastic. Preferred process conditions include heating to a temperature of 250-500°F, a residence time at the final heating temperature of 5-240 minutes, and atmospheric pressure of 0-10 psig. This can be done in open air or preferably under an oxygen-free inert atmosphere.

[0043] In the second step, the hot blend is cooled to a temperature below the melting point of the plastic while being continuously and vigorously mixed with the oil feedstock, and then further cooled to a lower temperature, preferably ambient temperature, to produce a stable blend of plastic and oil.

[0044] The stable blend is found to be an intimate physical mixture of plastic and oil feedstock. The plastic is in a "deagglomerated" state. The plastic maintains a fine dispersion of solid particles in the oil feedstock below the melting point of the plastic, especially at ambient temperatures. The blend is stable and easy to store and transport. At the refinery, the stable blend is heated in a preheater above the melting point of the plastic to produce a hot homogenous liquid blend of plastic and oil. This hot liquid blend can then be fed to the refinery unit as a co-feed along with conventional refinery feedstocks.

[0045] Further details of the preparation of the stable blend are shown in FIG. 3. The stable blend is made by a two step process in the stable blend preparation unit 100. As shown, clean waste 22 is passed through the stable blend preparation unit 100. Selected plastic waste 22 is heated and mixed with refinery feedstock oil 24. The plastic waste is heated to a temperature above the melting point of the plastic to melt the plastic. The petroleum feedstock is mixed with the heated plastic at 23. The mixing is often very vigorous. The mixing and heating conditions can generally be heating at a temperature in the range of about 250-500°F with a residence time of 5-240 minutes at the final heating temperature. The heating and mixing can be done in open air or under an oxygen-free inert atmosphere. The result is a hot homogenous liquid blend of plastic and oil 25. Optionally, a filtration device can be added (not shown) to remove any undissolved plastic particles or solid impurities present in the hot homogenous blend.

[0046] The hot blend 25 is then cooled to a temperature below the melting point of the plastic while continuing to mix with the oil feedstock 101. Cooling is typically continued to ambient temperature to produce a stable blend of plastic and oil 102. At the refinery, the stable blend can be fed to a preheater 29, which heats the blend above the melting point of the plastic to produce a mixture of plastic / oil blend and VGO 26, which is then fed to a refinery conversion unit.

[0047] The preferred plastic starting material for the process is sorted waste plastics containing mainly polyethylene and polypropylene (plastic recycling classification types 2, 4, and 5). The pre-sorted waste plastics are washed, shredded or pelletized, and fed to the blend preparation unit. Figure 4 shows the plastic type classification for waste plastics recycling. Classification types 2, 4, and 5 are high density polyethylene, low density polyethylene, and polypropylene, respectively. Polyethylene and polypropylene waste plastics can be used in any combination. It is preferred to use at least some polypropylene waste plastic in the process. Polystyrene (class 6) can also be present in limited amounts.

[0048] Proper sorting of waste plastics is very important to minimize contaminants such as N, Cl, and S. Plastic waste including polyethylene terephthalate (Plastic Recycle Classification Type 1), polyvinyl chloride (Plastic Recycle Classification Type 3) and other polymers (Plastic Recycle Classification Type 7) should be sorted to less than 5%, preferably less than 1%, and most preferably less than 0.1%. The process can tolerate moderate amounts of polystyrene (Plastic Recycle Classification Type 6). Waste polystyrene should be sorted to less than 20%, preferably less than 10%, and most preferably less than 5%.

[0049] Washing of waste plastics can remove metal contaminants such as sodium, calcium, magnesium, aluminum, and non-metallic contaminants from other waste sources. Non-metallic contaminants include contaminants from Group IV of the periodic table such as silica, contaminants from Group V such as phosphorus and nitrogen compounds, contaminants from Group VI such as sulfur compounds, and halide contaminants from Group VII such as fluorides, chlorides, iodides, etc. Residual metal, non-metallic contaminants, and halides should be removed to less than 50 ppm, preferentially less than 30 ppm, and most preferentially less than 5 ppm.

[0050] If washing does not adequately remove the metal, non-metallic contaminants, and halide impurities, a separate guard bed can be used to remove the metal and non-metallic contaminants.

[0051] The petroleum with which the waste plastics are blended is generally the petroleum feedstock for the refinery. The petroleum blend oil is preferably the same as the petroleum feedstock for the refinery. The petroleum may also include petroleum-derived oil or petroleum-based materials. In one embodiment, the petroleum feedstock may include atmospheric gas oil, vacuum gas oil (VGO), atmospheric resid, or heavies recovered from other refining operations. In one embodiment, the petroleum feedstock with which the waste plastics are blended includes VGO. In one embodiment, the petroleum feedstock with which the waste plastics are blended includes light cycle oil (LCO), heavy cycle oil (HCO), FCC naphtha, gasoline, diesel, toluene, and / or petroleum-derived aromatic solvents.

[0052] Figure 5 illustrates one embodiment of the integrated process of the present invention where the blend is sent to a fluid catalytic cracking (FCC) unit. Like numbers in Figure 5 that correspond to Figures 2 and 3 refer to like items / units. As shown, a blend is prepared at 25 and then mixed with a co-feed of vacuum gas oil (VGO) 20. The blend is typically heated to a temperature above the melting point of the plastic prior to mixing with the co-feed VGO. This co-feed mixture of the blend and conventional VGO refinery stock 26 is then sent to the refinery's FCC unit 28. In another embodiment, the heated blend and the VGO co-feed are each passed directly, but separately, through the FCC unit.

[0053] The fluid catalytic cracking (FCC) process is widely used in the refining industry to convert atmospheric gas oil, vacuum gas oil, atmospheric residual oil and heavies recovered from other refining operations into high octane gasoline, light fuel oil, heavy fuel oil, olefin-rich light gas (LPG) and coke. FCC uses highly active zeolite catalysts to crack heavy hydrocarbon molecules at reactor temperatures of 950-990°F in the riser with short contact times of a few minutes or less. LPG streams containing olefins (propylene, butylene) are typically upgraded to produce alkylate gasoline or for use in the production of chemical products. Conventional FCC units can be used.

[0054] Refineries generally have their own hydrocarbon feed that flows through the refinery unit. In this case, the hydrocarbon feed is VGO20, as shown in FIG. 5. The volume of the blend stream flowing to the refinery unit (here the FCC unit) can constitute any practical or accommodable volume percent (vol%) of the overall stream (total flow) to the refinery unit. In general, the blend flow rate can be up to about 50 vol% of the total flow rate (i.e., refinery flow rate and blend flow rate) for practical reasons. In one embodiment, the blend flow rate is up to about 100 vol% of the total flow rate. In another embodiment, the blend volumetric flow rate is up to about 25 vol% of the total flow rate. About 50 vol% has been found to be a very practical amount in terms of impacts on the refinery, while at the same time providing good results and being accommodable. It is important to avoid adverse effects on the refinery and its products. If the amount of plastic in the final blend exceeds 20 wt% of the final blend, problems may arise in the operation of the FCC unit. Final blend means the plastic / oil blend and any co-feed petroleum. The plastic / oil blend may comprise up to 100% by volume of the feed to the refinery unit, in which case it is the final blend.

[0055] In Figure 5, the FCC unit 28 cracks the plastic / oil hot blend combined with a co-feed oil feedstock (co-feed oil feed) to produce liquefied petroleum gas (LPG) in C3 and C4 olefin / paraffin streams 31 and 32, as well as gasoline 33 and heavy ends 30. The C3 olefin / paraffin mixture stream, which is a mixture of propane and propylene, is sent to a propane / propylene splitter (PP splitter) 40 and separated to produce pure streams of propane 41 and propylene 42. Propylene 42 is fed to a propylene polymerization unit 43 to produce polypropylene.

[0056] Pure propane 41 can be fed to a propane dehydrogenation unit 44 to produce additional propylene 35, and then finally to a propylene polymerization unit 43 to produce polypropylene.

[0057] Dehydrogenation of propane is widely used in industry to produce propylene. The reaction is endothermic and conversion is maintained by multi-stage reactors and interstage heaters. The units are typically operated at high temperature (>900°F) and low pressure (<50 psig) in the presence of a precious metal (Pt) catalyst. The multi-stage process produces a propylene / propane mixture of approximately 85% purity. This stream is sent to a propane / propylene (PP) splitter, a highly efficient distillation column. The splitter produces a pure propylene stream of 99.5-99.8% purity.

[0058] The PP splitter unit and / or the propane dehydrogenation unit can be located away from the refinery, near the refinery, or within the refinery. The propane / propylene mixture is sent to the PP splitter by truck, barge, rail car, or pipeline. The PP splitter unit and the propane dehydrogenation unit are preferably located in close proximity to the refining FCC unit.

[0059] The C4 stream 32 and other hydrocarbon product streams (such as the heavy fraction 30) from the FCC unit 28 are sent to an appropriate refining unit 34 for upgrading to clean gasoline, diesel, or jet fuel. The gasoline 33 from the FCC unit may be passed directly to a gasoline pool 35 or may be further upgraded (not shown) before being sent to the gasoline pool.

[0060] The polypropylene polymer 45 produced in the propylene polymerization unit 43 can be made into a consumer product 46 .

[0061] Figure 6 shows an integrated process of the present invention as shown in Figure 5, where the blend and the co-feed of hydrocarbon refinery stream 26 are first sent to a fluid catalytic cracking (FCC) feed pretreatment unit 27. Numbers in Figure 6 that are the same as those in Figure 5 refer to the same streams or refinery units.

[0062] FCC feed pretreaters typically use bimetallic (NiMo or CoMo) alumina catalyst in a fixed bed reactor at reactor temperatures of 660-780°F and pressures of 1,000-2,000 psi with H2 gas flow to hydrogenate the feed. Purified FCC feed pretreaters are effective in removing sulfur, nitrogen, phosphorus, silica, dienes and metals that impair the catalytic performance of the FCC unit. The units also hydrogenate aromatics and improve the liquid yield of the FCC unit.

[0063] The pretreated hydrocarbons from the feed pretreater 27 may be distilled to produce LPG, naphtha, and a heavy fraction. The heavy fraction is sent to an FCC unit 28 to further produce C3, C4, FCC gasoline, and a heavy fraction (represented as 31, 32, 33, and 30, respectively). The C4 stream and naphtha from the feed pretreater may be passed to other upgrading processes within the refinery for the production of gasoline, diesel, and jet fuel.

[0064] Polypropylene is produced from the monomer propylene via chain growth polymerization. Ziegler-Natta or metallocene catalysts are used to catalyze the polymerization of propylene into polypropylene polymers to achieve the desired properties. These catalysts are activated with specialized cocatalysts, including organoaluminum compounds. Industrial polymerization processes use either gas phase polymerization in fluidized bed reactors or bulk polymerization in loop reactors. Gas phase polymerization is typically carried out at temperatures between 50 and 90 °C and pressures between 8 and 35 atm in the presence of H2. Bulk polymerization proceeds at 60-80 °C and at pressures of 30-40 atm to keep the propylene in a liquid state.

[0065] The propylene polymerization unit 43 is preferably located near the refinery so that the feedstock (propylene) can be transported via pipeline. For petrochemical plants located remotely from the refinery, the feedstock can be delivered via truck, barge, rail car, or pipeline.

[0066] The benefits of a circular economy and effective and efficient recycling campaigns are realised through this integrated process.

[0067] The following examples are provided to further illustrate the present process and its advantages. These examples are intended to be illustrative and not limiting. EXAMPLES

[0068] [Example 1] Characteristics of virgin plastic samples and raw materials used for blend preparation

[0069] Four plastic samples were purchased (low density polyethylene (LDPE, Plastic A), high density polyethylene (HDPE, Plastic B), and two polypropylene samples with average molecular weights of approximately 12,000 (PP, Plastic C) and approximately 250,000 (PP, Plastic D)) and their properties are summarized in Table 1. [Table 1]

[0070] The petroleum feedstocks used to prepare stable blends with plastics include hydrotreated vacuum gas oil (VGO), Aromatic 100 solvent, light cycle oil (LCO), and diesel, the properties of which are shown below in Table 2. Aromatic 100 is a commercially available aromatic solvent produced from petroleum-based materials and contains primarily C9-C10 di- and tri-alkylbenzenes. [Table 2]

[0071] Thermogravimetric analysis (TGA) was performed on Plastic A (LDPE) and Plastic C (polypropylene) to confirm that the plastic materials are thermally stable at temperatures well above the melt preparation temperature. The TGA results, shown in Figure 7, indicate that the LDPE sample is stable up to 800°F and the polypropylene sample is stable up to 700°F.

[0072] [Example 2] Direct conversion of plastics and VGO via FCC using USY catalyst

[0073] Laboratory tests were conducted using a fluid catalytic cracking (FCC) process with stable blends of plastics and VGO using FCC catalysts containing USY zeolite to study the effect of treating waste plastics and vacuum gas oil in a refinery FCC unit. The plastics used were low density polyethylene (LDPE, Plastic A) with a density of 0.925 g / mL at 25°C and polypropylene (PP, Plastic C) with an average molecular weight of 12,000. A base case (Example 2-1) using only VGO feed was compared with three blend runs including a 5 / 95% blend of LDPE / VGO (Example 2-2), a 10 / 90 wt% blend of LDPE / VGO (Example 2-3), and a 5 / 95 wt% blend of PP / VGO (Example 2-4). The catalyst was an equilibrium catalyst taken from a commercial FCC plant.

[0074] FCC experiments were performed in a Model C ACE (advanced cracking evaluation) unit manufactured by Kayser Technology Inc., using regenerated equilibrium catalyst (Ecat) from a refinery. The reactor was a fixed flow reactor using N2 as the fluidizing gas. Catalytic cracking experiments were performed at atmospheric pressure and a reactor temperature of 975°F. The catalyst / oil ratio was varied between 5 and 8 by varying the amount of catalyst. Gas products were collected and analyzed using a refinery gas analysis unit (RGA) equipped with a GC with FID detector. In-situ regeneration of spent catalyst was performed in the presence of air at 1300°F, and the regenerated flue gas was passed through an IR cell to determine the flue gas composition, which was used to calculate the coke yield. Liquid products were weighed and analyzed by GC for simulated distillation (D2887) and C5 - Compositional analysis was performed. Mass balance showed that the crude oil was composed of coke, dry gas components, LPG components, gasoline (C5, ~430°F), light cycle oil (LCO, 430-650°F), and heavy cycle oil (HCO, 650°F). + The yield of 1,2-dichloro-1,2-diphenyl-2,3-diphenyl-1,4-tetrahydrofuran (1,2-diphenyl-2,4-diphenyl-1,5-dimethyl-2,6-dimethyl-2,7-dimethyl-2,8-diphenyl-1,5-dimethyl-2,7-diphenyl-1,6-dimethyl-2,8-diphenyl-1,6-dimethyl-2,7 ... [Table 3]

[0075] The results in Table 3 show that co-feeding 5-10 wt% plastics results in negligible changes in FCC unit performance, indicating that co-processing of plastics is readily feasible up to 10 wt%. Up to 20 wt% can be done without performance issues, but equipment with proper controls is required to address the increased viscosity and pour point. To lower the viscosity and pour point, light cycle oil (LCO), heavy cycle oil (HCO), FCC naphtha, gasoline, diesel, toluene, and / or petroleum-derived aromatic solvents can be added to the blend formulation.

[0076] Because plastics are more easily cracked than VGO, blends increased conversion slightly. The addition of plastics to the FCC feed slightly increased coke yields, but did not significantly change dry gas yields. Yields of LPG, C3, and C4 olefins increased moderately. LCO and HCO yields decreased slightly. Gasoline yields were similar. Because the cracked products made from plastics are paraffinic, blends with plastics reduced octane numbers by about 1-2. Due to the flexibility of refinery operations, such octane reductions can be easily compensated for by using blends or by adjusting FCC process operations and catalyst / additive mixes. The hydrocarbon compositions of all co-feed products are within the range of typical FCC gasoline. [Example 3] Characteristics of waste plastic samples

[0077] Four waste plastic samples were purchased for blend preparation and their properties are summarized in Table 4. FT-IR was used to identify the general nature of the plastics. In addition to identifying the main polymer species, the FT-IR data also revealed that all of these recycled plastic samples contained various amounts of calcium carbonate and talc. To estimate the amount of potentially recoverable hydrocarbons, each sample was calcined at 1000°F for 3 hours under N2. The recoverable hydrocarbons were assumed to be equal to the loss-on-ignition (LOI) (%). The inorganic residue after calcination was analyzed by ICP analysis. The LOI values ​​and ICP analysis were used to estimate the impurities (wt%) in the as-received plastics and are reported in Table 4 below. The most common impurities present in waste plastics are Ca, Mg, Si, and Ti, which can originate from the manufacturing of plastic consumer products such as calcium carbonate, silica, and talc, which are commonly used as fillers. Al, Fe, P, and Zn are also present in significant amounts. [Table 4]

[0078] Thermogravimetric analysis (TGA) was performed on the waste plastic samples to confirm that the plastic material is thermally stable at temperatures well above the melt preparation temperature. The TGA results shown in Figure 8 indicate that the plastic samples are stable up to 700°F.

[0079] [Example 4] Direct conversion of waste plastics and VGO via FCC using USY catalyst

[0080] Laboratory tests were conducted using a fluid catalytic cracking (FCC) process with a stable blend of waste plastics and VGO using an FCC catalyst containing USY zeolite to study the effect of processing waste plastics and vacuum gas oil in a refinery FCC unit. The plastics used were Waste Plastic #1 (Plastic E) and Waste Plastic #2 (Plastic F). A base case using only VGO feed (Example 4-1) was compared with two blend runs including a 5 / 95% blend of Plastic E / VGO (Example 4-2) and a 5 / 95 wt% blend of Plastic F / VGO (Example 4-3). The catalyst was an equilibrium catalyst taken from a commercial FCC plant. [Table 5]

[0081] The results in Table 5 show that co-feeding 5 wt% waste plastics only results in minor changes in the performance of the FCC unit, indicating that co-processing plastics at 5 wt% is readily feasible.

[0082] Because waste plastics are more easily cracked than VGO, blends increased conversion slightly. The addition of waste plastics to the FCC feed increased coke yields slightly, but dry gas yields were largely unchanged. LPG, C3, and C4 olefin yields increased moderately, and LCO and HCO yields decreased slightly. Gasoline yields were comparable. Because the cracked products made from plastics are paraffinic, blends with plastics reduced octane numbers by about 1-1.5. Due to the flexibility of refinery operations, such octane reductions can be easily compensated for by using blends or by adjusting FCC process operations and catalyst / additive mixes. The hydrocarbon compositions of all co-feed products are within the range of typical FCC gasoline.

[0083] [Example 5] Fluid catalytic cracking of plastic and petroleum blends to produce fuels with recycled content and a low CO2 footprint

[0084] The gasoline, LCO, HFO from Examples 2 and 4 can be sent to the corresponding blending pools and blended into finished gasoline, jet fuel, diesel or marine oil with recycled content and low CO2 footprint. A portion of the LCO and HFO can be further processed in other refining units to produce clean gasoline, jet fuel and diesel with recycled content and low CO2 footprint.

[0085] [Example 6] Feeding recycled C3 to a PP splitter for the production of propylene and subsequent production of polypropylene resin and polypropylene consumer products

[0086] The propane streams produced via co-feeding the plastic / oil blend to the FCC unit according to Examples 2 and 4 are suitable feedstocks for the production of propylene with recycled content. At least some, if not all, of these streams are fed to a PP splitter. The propylene is processed in a polymerization unit to produce polyethylene resins containing recycled polyethylene / polypropylene derived materials, but the quality of the newly produced polypropylene is indistinguishable from virgin polypropylene made entirely from virgin petroleum resources. This polypropylene resin containing recycled materials can be further processed to produce a variety of polypropylene products for consumer product needs. These polypropylene consumer products contain chemically recycled circular polymers, but the quality of those products is indistinguishable from those made from entirely virgin polypropylene polymers. These chemically recycled polymer products are different from mechanically recycled polymer products, which are of inferior quality to polymer products made from virgin polymers.

[0087] As used in this disclosure, the words "comprises" or "comprising" are intended as open-ended transitional phrases, meaning the inclusion of the indicated elements, but not necessarily the exclusion of other unspecified 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 the exclusion of all other than the recited elements, except for only trace impurities.

[0088] All patents and publications referenced herein are incorporated herein by reference to the extent that they are not inconsistent therewith. It will be understood that the specific above-described structures, functions, and operations of the above-described embodiments are not necessary to practice the present invention, but are included in the description merely to complete the exemplary embodiment or embodiments. It will be further understood that the specific structures, functions, and operations described in the above-referenced patents and publications can be practiced in combination with the present invention, but are not essential to its practice. Thus, it will be 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 continuous process for converting waste plastics into recycling for polypropylene polymerization, comprising: (a) selecting waste plastics comprising polyethylene and / or polypropylene; (b) preparing a blend of petroleum and the selected waste plastic, the blend comprising no more than 20 wt.% of the selected waste plastic; (c) passing the blend through a refining FCC unit at a temperature above the melting point of the plastic; (d) extracting liquefied petroleum gas C from the FCC unit; ３ recovering the olefin / paraffin mixture; (e) The above C ３ Paraffin and C ３ separating the olefins into different fractions; (f) The above C ３ passing the olefins through a propylene polymerization reactor; The above process comprising:

2. 10. The process of claim 1, wherein the gasoline and heavy fractions are recovered from a refinery FCC unit.

3. 2. The process of claim 1, wherein the blend of (b) is a high temperature homogenous blend of waste plastic and petroleum.

4. 2. The process of claim 1, wherein the blend of (b) is a stable blend of waste plastic and petroleum.

5. 2. The process of claim 1, wherein the waste plastics selected in (a) are plastics from classification groups 2, 4, and / or 5.

6. C ４ 10. The process of claim 1, wherein the stream and the heavy fraction are recovered from the FCC unit distillation column and further processed in a refinery to obtain clean gasoline, diesel, or jet fuel.

7. 10. The process of claim 1, wherein the volumetric flow rate of the blend in (c) flowing to the refining FCC unit comprises up to about 100 volume percent of the total hydrocarbon flow rate flowing to the FCC unit.

8. 10. The process of claim 1, wherein the volumetric flow rate of the blend in (c) flowing to the refining FCC unit comprises up to about 50 volume percent of the total hydrocarbon flow rate flowing to the FCC unit.

9. 9. The process of claim 8, wherein the blended flow rate comprises up to about 25 volume percent of the total flow rate to the FCC unit.

10. 2. The process of claim 1, wherein in (b) the blend of petroleum and selected waste plastic is prepared by heating the waste plastic to a temperature above the melting point of the plastic, mixing with petroleum, and then cooling the blend to a temperature below the melting point of the waste plastic.

11. 2. The process of claim 1, wherein the petroleum oils in the blend include atmospheric gas oils, vacuum gas oil (VGO) atmospheric resid, petroleum derived oils, petroleum based materials, and / or heavies recovered from refining operations.

12. 2. The process of claim 1, wherein the petroleum in the blend comprises light cycle oil (LCO), heavy cycle oil (HCO), FCC naphtha, gasoline, diesel, toluene, and / or petroleum derived aromatic solvents.

13. A continuous process for converting waste plastics into recycling for polypropylene polymerization, comprising: (a) selecting waste plastics comprising polyethylene and / or polypropylene; (b) preparing a blend of petroleum and the selected waste plastic, the blend comprising no more than 20 wt.% of the selected plastic; (c) passing the blend through a refining FCC unit; (d) extracting liquefied petroleum gas C from the FCC unit; ３ recovering the olefin / paraffin mixture; (e) The above C ３ Paraffin and C ３ separating the olefins into different fractions; (f) The above C ３ passing the olefins through a propylene polymerization reactor; (g) The above C ３ passing the paraffins through a dehydrogenation unit to produce propylene; The above process comprising:

14. 14. The process of claim 13, wherein the gasoline and heavy fractions are recovered from a refinery FCC unit.

15. 14. The process of claim 13, wherein the blend of (b) is a high temperature homogenous blend of waste plastic and petroleum.

16. 14. The process of claim 13, wherein the blend of (b) is a stable blend of waste plastic and petroleum.

17. 14. The process of claim 13, wherein the waste plastics selected in (a) are plastics from classification groups 2, 4, and / or 5.

18. C ４ 14. The process of claim 13, wherein the stream and the heavy fraction are recovered from the FCC unit distillation column and further processed in a refinery to obtain clean gasoline, diesel, or jet fuel.

19. 14. The process of claim 13, wherein the volumetric flow rate of the blend in (c) flowing to the refining FCC unit comprises up to about 100 volume percent of the total hydrocarbon flow rate flowing to the FCC unit.

20. 14. The process of claim 13, wherein the volumetric flow rate of the blend in (c) flowing to the refining FCC unit comprises up to about 50 volume percent of the total hydrocarbon flow rate flowing to the FCC unit.

21. 14. The process of claim 13, wherein the blended flow rate comprises up to about 25 volume percent of the total flow rate to the FCC unit.

22. 14. The process of claim 13, wherein the blend of petroleum and the selected waste plastic in (b) is prepared by heating the waste plastic to a temperature above the melting point of the plastic, mixing with petroleum, and then cooling the blend to a temperature below the melting point of the waste plastic.

23. 14. The process of claim 13, wherein the petroleum oils in the blend include atmospheric gas oils, vacuum gas oils (VGO), atmospheric residua, petroleum-derived oils, petroleum-based materials, and / or heavies recovered from refining operations.

24. 14. The process of claim 13, wherein the petroleum in the blend comprises light cycle oil (LCO), heavy cycle oil (HCO), FCC naphtha, gasoline, diesel, toluene, and / or petroleum derived aromatic solvents.

25. 1. A process for converting waste plastics into chemicals useful for the preparation of polypropylene, comprising: (a) selecting waste plastics comprising polyethylene and / or polypropylene; (b) preparing a blend of petroleum and the selected waste plastic, the blend comprising no more than 20 wt.% of the selected plastic; (c) passing the blend through a refining FCC unit; Including the above process.

26. A continuous process for converting waste plastics into recycling for polypropylene polymerization, comprising: (a) selecting waste plastics comprising polyethylene and / or polypropylene; (b) preparing a blend of petroleum and the selected waste plastic, the blend comprising no more than 20 wt.% of the selected waste plastic; (c) passing the blend through a feed pre-treatment unit for a refinery FCC unit at a temperature above the melting point of the plastic; (d) recovering a heavy fraction from said feed pre-treatment unit and passing said heavy fraction to said refinery FCC unit; (e) extracting liquefied petroleum gas C from the FCC unit; ３ recovering the olefin / paraffin mixture; (e) The above C ３ Paraffin and C ３ separating the olefins into different fractions; (f) The above C ３ passing the olefins through a propylene polymerization reactor; The above process comprising:

27. A process for converting waste plastics into recycling for the preparation of low carbon footprint fuels, comprising: (a) selecting waste plastics comprising polyethylene and / or polypropylene; (b) preparing a blend of petroleum and the selected waste plastic, the blend comprising no more than 20 wt.% of the selected plastic; (c) passing the blend through a refining FCC unit; Including the above process.

28. 28. The process of claim 27, wherein the low carbon footprint fuel comprises gasoline, jet fuel, diesel, and / or marine oil.

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