Co-processing of waste plastic pyrolysis oil and bio-renewable raw materials

Abstract

A process for producing a liquefied hydrocarbon material suitable for use as a fuel or as a blending component in a fuel is provided, which includes co-processing a pyrolysis oil from a waste plastic feedstock and a bio-renewable feedstock comprising triglycerides in a catalytic cracking process under catalytic cracking conditions in the presence of a solid catalyst to provide a cracked product, which can be fractionated to provide at least one of a gasoline fraction and a middle distillate fraction.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 236,758, filed August 25, 2021, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to a process for producing liquefied hydrocarbon materials suitable for use as fuels or as blending components in fuels, in which waste plastic pyrolysis oil is co-processed with bio-renewable feedstocks in a catalytic cracking process. [Background technology]

[0003] The catalytic cracking process is commonly used in oil refineries as a method for converting non-renewable petroleum feedstocks to produce lower boiling fractions suitable for use as fuels, without the need for additional hydrogen.

[0004] Due to increasing demand for liquid transportation fuels, dwindling reserves of "easy oil" (crude oil that is easily accessible and recoverable), and increasing constraints on the carbon dioxide emissions of such fuels, it is becoming increasingly important to develop means to efficiently produce liquid transportation fuels from alternative sources.

[0005] Due to their large-scale availability, biomass-based feedstocks such as lipid feedstocks (e.g., fats and / or oils derived from plants, animals, and / or microorganisms) and waste plastics are important sources of feedstocks with great potential to address the growing demand for alternative liquid fuels. Biomass provides a source of renewable carbon. Waste plastics have great potential to address the growing demand for "circular economy" processes.

[0006] Although research and development of processes for producing liquid fuels is currently ongoing, there remains a need to provide improved processes for producing hydrocarbons with low carbon dioxide emissions that are useful as liquid fuels or fuel blend components. Summary of the Invention

[0007] In a first aspect, there is provided a process comprising co-processing a pyrolysis oil derived from a waste plastic feedstock and a bio-renewable feedstock comprising triglycerides in a catalytic cracking process under catalytic cracking conditions in the presence of a solid catalyst to provide cracked products.

[0008] In a second aspect, there is provided a fuel component obtainable by the process described above.

[0009] In a third aspect, there is provided a method for producing a fuel comprising producing a cracked product as defined above, optionally fractionating the cracked product to provide a cracked product fraction, and blending the cracked product or the cracked product fraction with another fuel component to provide a fuel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] definition The term "post-consumer" refers to a source of a material that occurs after an end consumer has used the material in a consumer good or product.

[0011] The term "post-industrial" refers to sources of materials that arise during the manufacture of a good or product.

[0012] The term "polyethylene" refers to a polymer that contains a majority (>50 mole %) of units derived from ethylene monomers.

[0013] The term "polypropylene" refers to a polymer that contains a majority (>50 mole %) of units derived from propylene monomers.

[0014] The term "Cn hydrocarbons" or "Cn" is used herein with its well-known meaning (i.e., "n" is an integer value) to refer to hydrocarbons having that number of carbon atoms. The term "Cn+ hydrocarbons" or "Cn+" refers to hydrocarbons having that number of carbon atoms or more. The term "Cn- hydrocarbons" or "Cn-" refers to hydrocarbons having that number of carbon atoms or less.

[0015] The term "LPG" means liquefied petroleum gas in the form of a mixture containing mainly propane and butane (i.e. at least 95% by volume of propane and butane), with not more than 2% by volume of C2- compounds and not more than 3% by volume of C5+ compounds, where the C2- compounds are alkanes or alkenes having 2 or fewer carbon atoms and the C5+ compounds are alkanes or alkenes having 5 or more carbon atoms.

[0016] The term "gasoline" is used to describe the hydrocarbon streams recovered within the cut point range of about 95° F. (35° C.) to about 427° F. (220° C.). Hydrocarbons in the gasoline boiling range contain primarily C5 to C12 hydrocarbons.

[0017] The term "middle distillate" is used to describe the hydrocarbon streams recovered within the cut point range of about 427° F. (220° C.) to about 650° F. (343° C.). Hydrocarbons in the middle distillate boiling range contain primarily C11 to C20 hydrocarbons.

[0018] The term "octane number" refers to the percentage of isooctane in a mixture of isooctane and n-heptane that has the same knock resistance as the fuel currently being tested according to ASTM D2699 and D2700. Octane numbers typically range from 0 to 100, with higher values ​​indicating better fuel performance. Octane number is unitless.

[0019] The term "Research Octane Number (RON)" refers to the octane number obtained by testing according to ASTM D2699 at lower engine speeds and temperatures, typically about 600 rpm.

[0020] The term "Motor Octane Number (MON)" refers to the octane number obtained by testing at higher engine speeds and temperatures, typically around 900 rpm, according to ASTM D2700. RON is typically higher than MON because engine inefficiencies inherently increase with increasing temperature.

[0021] The term "Antiknock Index" is defined as the arithmetic average of the two octane numbers as follows: (RON+MON) / 2.

[0022] The terms "wt %" or "vol %" refer to the weight percentage or volume percentage, respectively, of a component based on the total weight or volume of the material in which the component is included. In a non-limiting example, 10 grams of a component in a total of 100 grams of material containing 10 grams of the component is 10 wt % of the component.

[0023] pyrolysis oil Pyrolysis oil is produced by pyrolyzing (i.e., thermally decomposing organic matter in the absence of oxygen) waste plastic feedstock, either catalytically or non-catalytically, and via a continuous or batch process. Pyrolysis of waste plastics is well known in the art.

[0024] After pyrolysis of waste plastic raw materials, the pyrolysis products may include gas, solids (char), one or more oily phase(s), and an aqueous phase. The oily phase(s), optionally including water, may be used as pyrolysis oil in the present disclosure. The pyrolysis oil may be separated from the pyrolysis products by any known method, including filtration, centrifugation, cyclone separation, extraction, membrane separation, and / or phase separation.

[0025] The waste plastic feedstock that is pyrolyzed can include post-consumer polymers, post-industrial polymers, or a combination thereof. An example of a post-industrial waste polymer can be waste polymer generated during the manufacture or shipping of a good or product that is collected by the manufacturer as unusable material (i.e., trimmings, off-spec material, start-up waste).

[0026] The waste plastic raw material to be pyrolyzed may be a single type of waste plastic or a combination of two or more types of waste plastic.

[0027] Plastic materials are classified and labeled by their manufacturers to help improve sorting of plastic materials. Currently, plastic materials are differentiated into seven categories defined by the Society of the Plastics Industry (SPI), with each category having its own resin identification code. Each number represents a specific type of plastic, and generally, they can only be recycled together with other plastics that have the same number. Plastic materials include polyethylene terephthalate (PET or PETE), which is a polymer having a resin identification code of 1; high density polyethylene (HDPE), which is a polymer having a resin identification code of 2; polyvinyl chloride (PVC), which is a polymer having a resin identification code of 3; low density polyethylene (LDPE), which is a polymer having a resin identification code of 4; polypropylene (PP), which is a polymer having a resin identification code of 5; polystyrene (PS), which is a polymer having a resin identification code of 6; and other plastics having a resin identification code of 7 (i.e., those not listed under codes 1-6), such as multi-layer plastics, blended plastics, and other resins such as polycarbonate (PC) and acrylonitrile-butadiene-styrene (ABS).

[0028] The waste plastic feedstock to be pyrolyzed may be selected from HDPE, LDPE, polypropylene, and combinations thereof.

[0029] HDPE is generally 0.940g / cm 3 Ultra (e.g. 0.945-0.97g / cm 3 ) The polymer densities provided herein are determined according to ASTM D792.

[0030] LDPE is ethylene homopolymer, or 0.915 g / cm 3 ~0.940g / cm 3 LDPE is composed of ethylene / α-olefin copolymers comprising at least one C3-C10 α-olefin (e.g., C3-C4 α-olefin) having a density of 0.1 to 0.25 mm and containing long chain branches with a broad MWD. ​​LDPE includes linear low density polyethylene (LLDPE). LLDPE is a linear ethylene / α-olefin copolymer containing a heterogeneous short chain branching distribution comprising units derived from ethylene and at least one C3-C10 α-olefin comonomer, or at least one C4-C8 α-olefin comonomer, or at least one C6-C8 α-olefin comonomer. LLDPE is characterized by little, if any, long chain branching, in contrast to conventional LDPE.

[0031] The polypropylene may be a polypropylene homopolymer or a copolymer predominantly of polypropylene.

[0032] Other plastics (Resin Identification Codes 1, 3, 6, and / or 7), such as polyethylene terephthalate, polyvinyl chloride, polystyrene, and polycarbonate, are less desirable in the pyrolyzed waste plastic feedstock. If present, they are preferably present in an amount of less than 5% by weight (e.g., less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight) of the total weight of the dry waste plastic. Preferably, the individual content of any less desirable plastic is less than 1% by weight (e.g., less than 0.5% by weight, or less than 0.1% by weight) based on the total weight of the dry waste plastic feedstock.

[0033] The pyrolysis oil may comprise primarily C4 to C30 hydrocarbons. The pyrolysis oil may have a C4 to C30 hydrocarbon content of at least 55% (e.g., at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) by weight, based on the weight of the pyrolysis oil.

[0034] The pyrolysis oil may comprise primarily C5-C25, C5-C22, or C5-C20 hydrocarbons, or may comprise at least about 55% (e.g., at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) by weight of C5-C25, C5-C22, or C5-C20 hydrocarbons, based on the weight of the pyrolysis oil.

[0035] The pyrolysis oil may contain paraffins (n-paraffins, isoparaffins, or both), naphthenes, olefins, aromatics, and other compounds.

[0036] The pyrolysis oil may have a paraffin content of at least 20 wt% (e.g., 25 wt%, or at least 30 wt%, or at least 35 wt%, or at least 40 wt%, or at least 45 wt%, or at least 50 wt%). Additionally or alternatively, the pyrolysis oil may have a paraffin content of 90 wt% or less (e.g., 85 wt% or less, or 80 wt% or less, or 75 wt% or less, or 70 wt% or less, or 65 wt% or less, or 60 wt% or less, or 55 wt% or less). In some embodiments, the pyrolysis oil may have a paraffin content in the range of 20-90 wt% (e.g., 25-90 wt%, or 25-55 wt%, or 30-90 wt%, or 40-80 wt%, or 40-70 wt%, or 40-65 wt%).

[0037] The pyrolysis oil may have an n-paraffin to isoparaffin weight ratio of at least 0.001:1 (e.g., at least 0.1:1, or at least 0.2:1, or at least 0.5:1, or at least 1:1, or at least 2:1, or at least 3:1, or at least 4:1, or at least 5:1, or at least 6:1, or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1). Additionally or alternatively, the pyrolysis oil may have an n-paraffin to isoparaffin weight ratio of 100:1 or less (e.g., 75:1 or less, or 50:1 or less, or 40:1 or less, or 30:1 or less). In some embodiments, the pyrolysis oil can have a weight ratio of n-paraffins to isoparaffins ranging from 0.1:1 to 100:1 (e.g., from 1:1 to 100:1, or from 4:1 to 100:1, or from 15:1 to 100:1).

[0038] The pyrolysis oil may have a naphthene content of at least 1 wt% (e.g., at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%, or at least 6 wt%, or at least 7 wt%, or at least 8 wt%, or at least 9 wt%, or at least 10 wt%, or at least 11 wt%, or at least 12 wt%, or at least 13 wt%, or at least 14 wt%, or at least 15 wt%). Additionally or alternatively, the pyrolysis oil may have a naphthene content of 50 wt% or less (e.g., 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less). In some embodiments, the pyrolysis oil may have a naphthene content in the range of 2 to 50 wt%.

[0039] The pyrolysis oil may contain at least 1 wt% (e.g., at least 2 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%) of olefins. Additionally or alternatively, the pyrolysis oil may contain 60 wt% or less (e.g., 55 wt% or less, or 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less, or 15 wt% or less, or 10 wt% or less, or 5 wt% or less, or 2 wt% or less, or 1 wt% or less). In some embodiments, the pyrolysis oil may have an olefin content in the range of 2 to 60 wt% (e.g., 10 to 40 wt%). The pyrolysis oil may be hydrogenated at the production facility to reduce the olefin content.

[0040] The pyrolysis oil may contain at least 1 wt% aromatics (e.g., at least 2 wt%, or at least 3 wt%, or at least 4 wt%, or at least 5 wt%). Additionally or alternatively, the pyrolysis oil may contain 50 wt% or less aromatics (e.g., 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less). In some embodiments, the pyrolysis oil may have an aromatics content in the range of 2-50 wt% (e.g., 5-30 wt%).

[0041] In some embodiments, about 10% by weight, alternatively 25% by weight, or alternatively 50% by weight or more of the as-produced pyrolysis oil is characterized by a boiling point of less than 370° C. In other embodiments, about 90% by weight, alternatively 95% by weight, or alternatively 99% by weight or more of the pyrolysis oil is characterized by a boiling point of less than 650° C.

[0042] The paraffin, naphthene, olefin, and aromatics contents can vary widely depending on the severity of the thermal cracking unit. At more severe conditions (e.g., higher temperatures and longer residence times), the aromatics and olefins contents increase relative to the paraffin and naphthene contents.

[0043] It should be noted that all of the weight percentages of hydrocarbons cited above may be measured using gas chromatography-mass spectrometry (GC-MS).

[0044] The pyrolysis oil may exhibit an API gravity of at least 28 (e.g., at least 29, or at least 30, or at least 31, or at least 32, or at least 33) at 15° C. Additionally or alternatively, the pyrolysis oil may exhibit an API gravity of 50 or less (e.g., 49 or less, or 48 or less, or 47 or less, or 46 or less, or 45 or less, or 44 or less) at 15° C. In some embodiments, the pyrolysis oil exhibits an API gravity in the range of 28-50 (e.g., 29-48, or 30-45) at 15° C.

[0045] Pyrolysis oil has a density of at least 0.6 g / cm at 15°C. 3 (e.g., at least 0.65 g / cm 3 , or at least 0.7 g / cm 3 Additionally or alternatively, the pyrolysis oil may have a density of 1 g / cm at 15° C. 3 Less than (e.g., 0.95 g / cm 3 or less than 0.9g / cm 3 or less than 0.85g / cm 3In some embodiments, the pyrolysis oil may have a density of 0.6 to 1 g / cm at 15° C. 3 (For example, 0.65 to 0.95 g / cm 3 or 0.7~0.9g / cm 3 ) range of density.

[0046] The pyrolysis oil may be subjected to one or more processing steps before being introduced into downstream units such as a cracking zone. Examples of suitable processing steps may include, but are not limited to, separation of less desirable components (e.g., nitrogen-containing compounds, oxygenates, and / or olefins and aromatics), distillation to provide a specific pyrolysis oil composition, and preheating. In some embodiments, the pyrolysis oil may be sent directly from the pyrolysis oil source without any pretreatment before any downstream use.

[0047] Bio-renewable raw materials Bio-renewable feedstocks, including triglycerides, are derived from biological source(s) rather than from fossil fuel-based sources such as crude (mineral) oil or shale oil or coal.

[0048] Renewable feedstocks can include any feedstock that contains triglycerides. Renewable feedstocks can be vegetable oils, animal oils, algae oils, or any combination thereof. Representative examples of renewable feedstocks include camelina oil, canola oil, corn oil, soybean oil, rapeseed oil, soybean oil, rapeseed oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, yellow and brown grease, tallow, lard, fish oil, algae oil, sewage sludge, and the like.

[0049] In addition to triglycerides, renewable feedstocks typically contain other lipid components such as diglycerides, monoglycerides, and free fatty acids (FFAs). Renewable feedstocks preferably contain at least 75% by weight (e.g., at least 80%, at least 85%, at least 90%, 80-99.9%, or 90-99.5%) of triglycerides. Typical vegetable or animal oil glycerides and FFAs contain aliphatic hydrocarbon chains in their structure having from about 8 to about 30 carbon atoms. The aliphatic carbon chains in the glycerides or FFAs may be fully saturated or mono-, di-, or poly-unsaturated.

[0050] Renewable feedstocks may contain varying amounts of impurities, such as metals, water, phosphorus, silicon, alkali metals, alkaline earth metals, and the like.

[0051] Renewable feedstocks may be pretreated to remove impurities and filtered to remove solids.

[0052] Catalytic cracking Catalytic cracking involves contacting at least one hydrocarbonaceous feedstream with a cracking catalyst under catalytic cracking conditions to produce cracked products. In this disclosure, cracked products are anything that can be removed from the reactor (liquids, solids, volatile materials) except for the catalyst. Examples of cracked products from the catalytic cracking processes described herein include one or more of hydrogen, light olefins (fewer than 5 carbon atoms), light paraffins, olefins and paraffins having more than 5 carbon atoms, and coke.

[0053] The catalytic cracking reaction may be carried out in a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor, preferably using a fluidized bed reactor. The fluidized bed reactor may be configured to include a selection from the list consisting of a riser, a downer, multiple risers, and multiple downers, and combinations thereof.

[0054] The process of the present disclosure is preferably carried out as a continuous process. The use of a continuous process offers the advantage that there is no need to change the reaction conditions. As a result, easy handling and very good results can be achieved.

[0055] In some embodiments, the catalytic cracking process is a fluid catalytic cracking (FCC) process. The use of an FCC process allows for easy handling and high throughput, which results in advantageously particularly high yields.

[0056] When catalytic cracking is carried out in one or more of a fixed bed reactor, a moving bed reactor, and a fluidized bed reactor, the cracking conditions may include a temperature of 400°C to 600°C and a pressure of 40 kPa to 725 kPa. The temperature may be 420°C or higher, for example 440°C or higher, for example 450°C or higher, for example 460°C or higher, for example 470°C or higher, with an upper limit of 570°C or lower, for example 550°C or lower, for example 540°C or lower, for example 530°C or lower, for example 525°C or lower, for example 520°C or lower. The pressure may be from a low pressure of 40 kPa, for example 55 kPa, for example 65 kPa, for example 70 kPa, to a high pressure of 650 kPa, for example 675 kPa, for example 700 kPa, for example 725 kPa.

[0057] When catalytic cracking is carried out in a fluidized bed reactor, the reaction conditions are: -1 ~50h -1 Within the range (for example, 1h -1 ~40h -1 , or 2 hours -1 ~20h -1 The residence time in the fluidized bed reactor can be in the range of 100 milliseconds to 10 seconds (e.g., 1 second to 5 seconds, or 2 seconds to 4 seconds).

[0058] The weight ratio of the catalyst to the total amount of mixed feedstock (e.g., pyrolysis oil and bio-renewable feedstock) introduced into and contacted with the catalyst in the catalytic cracking zone (sometimes referred to as the "catalyst to oil ratio" or "catalyst:oil ratio") can be within the range of 2:1 to 10:1 (e.g., 3:1 to 9:1, or 4:1 to 8:1, or 5:1 to 7:1).

[0059] Suitable catalysts for use herein may be cracking catalysts comprising either large pore molecular sieves or a mixture of at least one large pore molecular sieve catalyst and at least one medium pore molecular sieve catalyst. Suitable large pore molecular sieves include zeolite beta, ZSM-10, and faujasites, particularly zeolite Y, ultrastable Y (USY), rare earth exchanged Y (REY), and rare earth exchanged ultrastable Y (REUSY). Examples of suitable medium pore molecular sieves include ZSM-5, ZSM-11, ZSM-22, ZSM-48, and MCM-22. The cracking catalyst may be mixed with a binder and then formed into a desired shape (e.g., extruded pellets). Suitable binders include silica, silica-alumina, alumina, clay, or other known inorganic binders. A mixed catalyst may include two or more molecular sieves mixed in a common catalyst pellet, or may include a mixture of catalyst pellets of various types of catalyst materials.

[0060] In the process of the present disclosure, the ratio of pyrolysis oil to bio-renewable feedstock (pyrolysis oil:bio-renewable feedstock) can be in the range of 5:1 to 1:19 by weight. The ratio of pyrolysis oil to bio-renewable feedstock is defined as parts of pyrolysis oil to parts of bio-renewable feedstock. In other words, a ratio of pyrolysis oil to bio-renewable feedstock of 1:19 by weight (pyrolysis oil:renewable feedstock) means a mixture containing 1 part pyrolysis oil and 19 parts bio-renewable feedstock (5% pyrolysis oil and 95% bio-renewable feedstock by weight, provided that (i.e., in the case of a mixture of pyrolysis oil and bio-renewable feedstock) the sum of pyrolysis oil and bio-renewable feedstock is 100% by weight). The ratio of pyrolysis oil:bio-renewable feedstock can be 4:1 or less by weight, or 2:1 or less by weight, or 1:1 by weight. Additionally, the ratio can be 1:7 or more by weight, or 1:10 or more by weight, or 1:7 or more by weight, or 1:5 or more by weight, or 1:4 or more by weight, or 1:3 or more by weight.

[0061] The pyrolysis oil and the bio-renewable feedstock can be introduced into the reactor where the catalytic cracking process is carried out using different feedstock feed lines. If the pyrolysis oil and the bio-renewable feedstock are added using different feed lines, good temperature control may be easier to achieve. In a continuous process, the energy required for cracking is usually provided by a heated catalyst. Therefore, the temperature is highest near the catalyst inlet. If the feedstock cracks easily due to excessively high temperatures, this feedstock can be injected from a later position (further from the catalyst inlet) to reduce coking.

[0062] The pyrolysis oil and the bio-renewable feedstock can be introduced into the reactor where the catalytic cracking process is carried out using the same feedstock supply line. Such a procedure facilitates the feedstock supply. It is also possible to combine these approaches, i.e., to supply a mixture of pyrolysis oil and bio-renewable feedstock using a single feedstock supply line, in addition to supplying one or both of the pyrolysis oil and the bio-renewable feedstock using additional (separate) feedstock supply line(s).

[0063] A fossil-based fraction may also be introduced into the cracking reactor in which the catalytic cracking process is carried out, in which case the fossil-based fraction is co-processed with the pyrolysis oil and the bio-renewable feedstock.

[0064] The fossil fraction and the pyrolysis oil can be introduced into the reactor in which the catalytic cracking process is carried out using different feedstock feed lines and / or using the same feedstock feed line. Similarly, the fossil fraction and the bio-renewable feedstock can be introduced into the cracking reactor using different feedstock feed lines and / or using the same feedstock feed line. The appropriate method of feeding each fraction varies depending on the actual process conditions and the required temperature control. Furthermore, the fossil fraction may be premixed with the bio-renewable feedstock and the pyrolysis oil, or with the bio-renewable feedstock and the pyrolysis oil.

[0065] The fossil feedstock may be any conventional fossil feedstock typically used in fuel refining (e.g. catalytic cracking). Preferably, the fossil feedstock is a hydrocarbon feedstock. The fossil distillate feedstock may be a gas oil (GO) feedstock, a vacuum gas oil (VGO) feedstock, a Fischer-Tropsch wax, or any combination thereof.

[0066] The process of the present disclosure may further include fractionating the catalytic cracking product to provide at least a gasoline fraction and a middle distillate fraction. These fractions are the most valuable for transportation fuels, and therefore it is preferable to separate these fractions from less valuable fractions. In addition to the gasoline and middle distillate streams, fractions derived from fractionation may include a gas stream and a distillation bottoms. The fractionation may include any suitable distillation means, including distillation under atmospheric pressure, or distillation or evaporation under reduced pressure.

[0067] The present disclosure further relates to a fuel component obtainable by the process of the present disclosure. The fuel component may be a transportation fuel component. The fuel component may be used as a fuel as such or may be blended with other fuel components (renewable and / or petroleum fuel components) to provide a fuel.

[0068] The process of the present disclosure results in a unique composition of cracked products due to the unique combination of waste plastic pyrolysis oil and bio-renewable feedstocks. That is, in addition to conventional cracked products, the present disclosure provides fuel components with specific chemical compositions. Specifically, the fuel components of the present disclosure differ from conventional fuel components in boiling range, isoparaffin / n-paraffin content, aromatics content, olefin content, octane number, density, and / or sulfur content.

[0069] The present disclosure further relates to a method for producing a fuel, comprising producing a cracked product as defined above, optionally fractionating the cracked product to obtain a cracked product fraction, and blending the cracked product or the cracked product fraction with another fuel component to provide a fuel. The method for producing a fuel may further comprise optional refining of the cracked product or a fraction thereof. EXAMPLES

[0070] The following illustrative examples are intended to be non-limiting.

[0071] Catalytic tests were performed on the following feedstocks: vacuum gas oil (VGO), waste plastic pyrolysis oil (PPO), soybean oil (SBO), 50%VGO / 50%PPO, 50%VGO / 50%PPO, 50%VGO / 50%SBO, and 50%SBO / 50%PPO.

[0072] Catalytic cracking experiments were carried out in an Advanced Cracking Evaluation (ACE) Model C unit (Kayser Technology Inc). The reactor used in the ACE unit was a fixed fluidized reactor with an internal diameter of 1.6 cm. Nitrogen was used as the fluidizing gas and was introduced from both the bottom and the top. The top fluidizing gas was used to carry the feedstock injected from a calibrated syringe feed pump through a three-way valve.

[0073] Catalytic cracking of each feedstock was carried out at atmospheric pressure and a temperature of 975° F. In each experiment, a constant amount of feedstock was injected at a rate of 1.2 g / min for 75 seconds. The catalyst / oil ratio was 6. After the 75 seconds of feedstock injection, the catalyst was stripped with nitrogen for 525 seconds.

[0074] During the catalytic cracking and stripping process, liquid products were collected in sample vials attached to a glass receiver placed at the end of the reactor outlet and maintained at -15°C. Gaseous products were collected in a closed stainless steel vessel (12.6 L) pre-filled with N2 at 1 atm. As soon as the injection of the feed was completed, the gaseous products were mixed with a motorized stirrer rotating at 60 rpm. After the stripping process, the gas products were mixed for an additional 10 min to ensure homogenization. The final gas products were analyzed using a refinery gas analyzer (RGA).

[0075] After completion of the stripping process, in-situ catalyst regeneration was performed in the presence of air at 1300°F. The regenerated flue gas was passed through a catalytic converter filled with CuO pellets (LECO Inc.) to oxidize CO to CO2. The flue gas was then analyzed by an online infrared (IR) analyzer located downstream of the catalytic converter. The coke deposited during the cracking process was calculated from the CO2 concentration measured by the IR analyzer.

[0076] The results are summarized in Table 1. [Table 1]

[0077] It is believed that there is a synergistic effect in the co-processing of plastic pyrolysis oil (PPO) and soybean oil (SBO). The hydrogen yields of the 100% PPO and 100% SBO feedstocks were 0.04% and 0.05%, respectively, while the hydrogen yield of the co-processed 50% PPO / 50% SBO feedstock was 0.03%, lower than either of the pure feedstocks. The propylene yield of the PPO / SBO co-feedstock (5.81%) was also lower than the 100% PPO and 100% SBO feedstocks (6.75% and 5.97%, respectively). The total C4 olefins yield of the PPO / SBO co-feedstock (5.80%) was lower than the numerical average of the two 100% pure feedstocks (the average of 6.75% and 5.97% is 6.36%). Without wishing to be bound by theory, it is believed that hydrogen transfer exists between PPO and SBO. Hydrogen transfer between these two feedstocks is highly desirable as it improves product yields, selectivities, and product properties.

[0078] Several advantages of co-processing PPO and SBO were observed. Cracking of 100% PPO resulted in high conversion but low coke yield, which may adversely affect the heat balance of FCC units. High gasoline yield was achieved, but with low octane due to high n-paraffin content. Cracking of 100% SBO resulted in good conversion and higher coke yield than PPO. Gasoline yield was low due to the presence of oxygen in the feed, but with high octane due to high aromatics content. Compared with the cracking of 100% PPO, cracking of PPO / SBO co-feed obviously reduced n-paraffins and increased aromatics, thus improving the octane of gasoline. The coke yield was also good, which can meet the heat balance requirements of most FCC units.

[0079] To quantify the benefits of co-processing PPO and SBO feedstocks, the results for a 100% PPO feedstock, the cracking results for a 100% SBO feedstock, and the numerical averages of these were compared to a 50 / 50 PPO / SBO co-feed. The results are summarized in Table 2. [Table 2-1] [Table 2-2]

[0080] The results in Table 2 show that co-processing increased the gasoline yield by 5%, but decreased the yields of LPG, light cycle oil, and heavy cycle oil. The olefin content of gasoline decreased by 7%, and the octane number increased by 3-5%, indicating that the properties of gasoline were improved by co-processing. Furthermore, co-processing reduced the loss of hydrocarbons to undesirable by-products (e.g., carbon monoxide, carbon dioxide, and water by 14%, 4%, and 8%, respectively). Due to the high concentration of oxygen in triglyceride oil, the loss of hydrocarbons due to the formation of carbon monoxide, carbon dioxide, and water has been problematic. These reductions suggest that it is possible to increase the yield of renewable gasoline from bio-renewable feedstocks by co-feeding waste plastic pyrolysis oil.

Claims

1. A catalytic cracking process comprising co-processing waste plastic pyrolysis oil derived from the pyrolysis of a waste plastic feedstock and a bio-renewable feedstock comprising triglycerides under catalytic cracking conditions in the presence of a solid catalyst to provide a cracked product; The above process, wherein the solid catalyst comprises at least one large pore faujasite zeolite or a mixture of at least one large pore faujasite zeolite and at least one medium pore zeolite selected from ZSM-5, ZSM-11, ZSM-22, ZSM-48, and MCM-22.

2. The waste plastic raw material is (a) comprises post-consumer polymers, post-industrial polymers, or a combination thereof; or (b) selected from high density polyethylene, low density polyethylene, polypropylene, or any combination thereof; or (c) containing less than 1% by weight of a polymer selected from polyethylene terephthalate, polyvinyl chloride, polystyrene, polymers of Resin Identification Code Number 7, and any combination thereof; 2. The process of claim 1.

3. The pyrolysis oil has the following characteristics: (a) a C4 to C30 hydrocarbon content of at least 55 wt.%; (b) a paraffin content in the range of 20 to 90 wt. %; (c) an API gravity of at least 28 at 15° C.; and (d) at least 0.6 g / cm at 15°C ３ Density of The process of claim 1 , wherein the process comprises one or more of the following: (a) the biorenewable feedstock comprises at least 75% by weight triglycerides; or (b) the bio-renewable feedstock comprises a vegetable oil, an animal oil, an algae oil, or a combination thereof; or (c) the bio-renewable feedstock comprises camelina oil, canola oil, corn oil, soybean oil, rapeseed oil, soybean oil, rapeseed oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, coconut oil, castor oil, peanut oil, palm oil, mustard oil, yellow and brown grease, tallow, lard, fish oil, algae oil, sewage sludge, or any combination thereof; 2. The process of claim 1.

5. 2. The process of claim 1, wherein the ratio of the pyrolysis oil to the bio-renewable feedstock (pyrolysis oil:bio-renewable feedstock) is selected to be within at least one of the following ranges: 5:1 to 1:19 by weight, 4:1 or less by weight, 2:1 or less by weight, 1:1 or less by weight, 1:7 or more by weight, 1:5 or more by weight, 1:4 or more by weight, and 1:3 or more by weight.

6. 2. The process of claim 1, comprising introducing the pyrolysis oil and the bio-renewable feedstock into a reactor in which the catalytic cracking process is carried out via different feedstock supply lines.

7. 2. The process of claim 1, comprising introducing the pyrolysis oil and the bio-renewable feedstock into a reactor in which the catalytic cracking process is carried out via the same feedstock supply line.

8. (a) pre-mixing the pyrolysis oil and the bio-renewable feedstock in a mixing vessel to form a mixture; introducing the mixture into the reactor; or (b) separately introducing a portion of the pyrolysis oil and / or the bio-renewable feedstock into the reactor using separate feed supply lines; 8. The process of claim 7.

9. 2. The process of claim 1, comprising introducing a fossil-based fraction into a reactor in which the catalytic cracking process is carried out and co-processing with the pyrolysis oil and the bio-renewable feedstock. (a) introducing the fossil fraction and the pyrolysis oil into the reactor using at least one of different feedstock supply lines and the same feedstock supply line; and introducing the fossil-based fraction and the bio-renewable feedstock into the reactor using at least one of different feedstock supply lines and the same feedstock supply line; or (b) the fossil fraction is at least one of gas oil, vacuum gas oil, Fischer-Tropsch wax, and any combination thereof; 10. The process of claim 9.

11. 10. The process of any one of claims 6, 7, and 9, wherein the reactor is a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor.

12. 2. The process of claim 1, wherein the catalytic cracking conditions include a temperature of from 400° C. to 600° C. and a pressure of from 40 kPa to 725 kPa.

13. 10. The process of claim 1, wherein the catalytic cracking process is carried out at a catalyst to oil ratio of from 2:1 to 10:

1.

14. 10. The process of claim 1, comprising fractionating the cracked product to provide at least one of a gasoline fraction and a middle distillate fraction.

15. A method comprising producing a cracked product according to the process of any one of claims 1 to 14, optionally fractionating the cracked product to provide a cracked product fraction, and blending the cracked product or the cracked product fraction with another fuel component to provide a fuel.