Catalytic process for producing olefins, alkanes and / or aromatics from mixtures of natural oils and / or fats

Abstract

The present invention provides processes for converting one or more bio-oils (C1-C5 alcohols and / or water with or without co-feed) to one or more C2-C5 olefins and / or one or more aromatic compounds. In one exemplary aspect, the process may be a single stage process performed in a reactor for the direct conversion of one or more bio-oils to a mixture of olefinic (e.g., C2-C5) and aromatic (e.g., BTEX) using one or more catalysts, the catalyst comprises a zeolite doped with one or more dopants and a doped or undoped alumina catalyst. Systems for performing these methods are also provided.

Description

Cross-reference to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 518,032, filed August 7, 2023, the entire contents of which are expressly incorporated herein by reference. Technical Field

[0002] The present invention provides systems and methods for the catalytic conversion of bio-based oils, fatty acids and / or esters, and more specifically, provides catalytic methods leading to the direct conversion of bio-based oils, fatty acids and / or esters into olefinic mixtures (e.g., C2-C5) and aromatic compounds. Background Technology

[0003] There is a growing demand for the use of biomass to partially replace petroleum resources for the synthesis of fuels and chemical feedstocks. The limited supply and rising costs of crude oil, coupled with the need to reduce carbon dioxide emissions from fossil fuels, have spurred the search for alternative methods for producing hydrocarbon products such as bionaphtha, biodiesel, and bio-based chemical feedstocks. Biomass, composed of organic matter derived from living organisms, is a major renewable energy source worldwide. Therefore, there is significant interest in using bioethanol and / or fermentation-based byproducts (e.g., oils, fatty acids / esters) to synthesize basic feedstocks for fuels and / or chemicals. The root reaction for converting ethanol into basic feedstocks for fuels or chemicals is the dehydration or dehydrogenation of ethanol, followed by ethylene oligomerization or aldol condensation for the production of chemicals.

[0004] Vegetable oils (i.e., bio-oils) are common raw materials for biofuels and chemicals, and can be converted into liquid fuels due to their high energy density, liquid nature, and availability as renewable feedstocks. In addition to edible vegetable oils with diverse fatty acid compositions, non-edible vegetable oils and waste cooking oils have also received considerable attention because they do not compete with food sources.

[0005] The conversion of such bio-oils (typically comprising fatty acids / esters) into fuels, hydrocarbons, or chemical feedstocks typically consists of a two-step process: i) hydrodeoxygenation to remove oxygen functional groups, followed by ii) catalytic cracking and / or isomerization to fuels and fuel precursors. However, the use of low-quality and / or waste cooking oils often requires additional processing due to their high free fatty acid content and susceptibility to rancidity, resulting in poor quality bio-based fuels. Furthermore, this conventional method requires two steps, yielding bio-based fuel products but not producing light olefins. Finally, the first step of hydrodeoxygenation requires hydrogen, increasing production costs, followed by a second step of high-temperature cracking for fuel production. Therefore, improved systems and methods are still needed for converting bio-oils, fatty acids / esters, or mixtures thereof into fuels, hydrocarbons, or chemical feedstocks. Summary of the Invention

[0006] In certain aspects of the subject matter of this invention, challenges related to bio-oil conversion can be addressed by incorporating one or more features described herein or in a comparable / equivalent manner that will be understood by those skilled in the art. Aspects of the subject matter of this invention relate to methods and systems for producing one or more olefins.

[0007] This invention discloses an exemplary method for converting one or more bio-oils into one or more olefins and / or aromatic compounds. In one exemplary aspect, the method for producing one or more olefins includes contacting an input stream with one or more catalysts in at least one reactor to form an output stream containing said one or more olefins, said input stream containing one or more bio-oils, and a first catalyst of said one or more catalysts comprising a first zeolite and one or more first dopants. The at least one reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of about 1 to about 10 bar, and a time of about 0.5 h. -1 approximately 10 hours -1 Heavy space velocity (WHSV).

[0008] In some aspects, the at least one reactor comprises two or more catalyst beds. In some aspects, the at least one reactor comprises one or more catalyst beds, wherein the method further comprises impregnating at least one of the one or more catalyst beds with a first catalyst and a second catalyst. In some aspects, the at least one reactor may be a single-bed reactor. In a particular aspect, the single-bed reactor may be a fixed-bed reactor. In other aspects, the single-bed reactor may be a fluidized-bed reactor. In still other aspects, the single-bed reactor may be a moving-bed reactor.

[0009] In some aspects, the one or more olefins include C2-C5 olefins. In some aspects, the one or more olefins include a primary first olefin, wherein the primary first olefin is propylene. In certain aspects, the one or more olefins further include ethylene. In some aspects, the amount of the one or more C2-C5 olefins present in the output stream may be from about 65% by weight to about 85% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. In a particular embodiment, the amount of the one or more C2-C5 olefins present in the output stream is from about 75% by weight to about 80% by weight based on the hydrocarbon products in the output stream.

[0010] In some aspects, the output stream further includes one or more aromatic compounds. In a particular aspect, the amount of the one or more aromatic compounds in the output stream is from about 65% by weight to about 80% by weight based on the output stream.

[0011] In some aspects, the first dopant of the first catalyst in one or more of the catalysts comprises boron, phosphorus, or a combination thereof. In a particular aspect, the boron is present in the first catalyst in an amount from about 0.5 wt% to about 3 wt%. In another aspect, the boron is present in the first catalyst in an amount of at least about 2 wt%. In a particular aspect, the phosphorus is present in the first catalyst in an amount from about 1 wt% to about 5 wt%. In another aspect, the phosphorus is present in the first catalyst in an amount of at least about 3 wt%.

[0012] In some respects, the first zeolite may comprise ZSM-5 zeolite.

[0013] In some aspects, the output stream may contain saturates, wherein the total amount of saturates present in the output stream does not exceed about 20% by weight based on the output stream. In a particular aspect, the total amount of saturates present in the output stream may be from about 5% by weight to about 15% by weight. In other aspects, the total amount of saturates present in the output stream may be from about 5% by weight to about 10% by weight.

[0014] In some aspects, before contacting the input stream with the at least one catalyst, the method includes combining the input stream with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols. In one aspect, the one or more C1-C5 alcohols comprise ethanol. In another aspect, the one or more C1-C5 alcohols comprise methanol. In yet another aspect, the one or more C1-C5 alcohols comprise isobutanol. In still another aspect, the one or more C1-C5 alcohols comprise a mixture of at least C4 alcohols, a mixture of at least C5 alcohols, or a mixture of at least C4 alcohols and C5 alcohols.

[0015] In some respects, the one or more bio-oils are produced through a fermentation process.

[0016] In some aspects, the method may include removing at least a portion of the C2 olefins from the output stream.

[0017] In some aspects, the method may include removing at least a portion of the C4 olefins from the output stream.

[0018] In some aspects, the method may include removing at least a portion of the C5 olefins from the output stream.

[0019] In some aspects, the method may include removing at least a portion of the aromatic compounds from the output stream.

[0020] In some aspects, the temperature can be from about 350°C to about 500°C. In other aspects, the temperature can be from about 450°C to about 500°C.

[0021] In some respects, the heavy time-space velocity can be approximately 2.0 h. -1 To approximately 5.0h -1 In other respects, the gravity hourly space velocity can be approximately 3.0 h. -1 To approximately 5.0h -1 .

[0022] In some aspects, the second catalyst in the one or more catalysts may be a second zeolite and one or more second dopants. In particular aspects, the first zeolite and the second zeolite may be the same or different, and the one or more first dopants and the one or more second dopants may be the same or different.

[0023] In some aspects, the second catalyst in one or more of the catalysts may be a doped or undoped alumina catalyst. In a particular aspect, the doped alumina catalyst includes zirconium, titanium, tungsten, silicon, fluorine, or any combination thereof in neutral or ionic form. In a particular aspect, the second catalyst in one or more of the catalysts may be silicated γ-alumina, zirconated γ-alumina, titanated γ-alumina, niobium γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, aluminosilicate catalyst, or any combination thereof.

[0024] In another exemplary method for producing olefins, the method includes contacting an input stream with at least a first catalyst and a second catalyst in a single reactor to form an output stream comprising one or more olefins, the input stream comprising one or more bio-oils, and the single reactor being operated at a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and for about 0.5 h. -1 approximately 10 hours -1 The weight space velocity (WHSV). The first catalyst may be a first zeolite and one or more first dopants.

[0025] In some aspects, the second catalyst may be a second zeolite and one or more second dopants. In particular aspects, the first zeolite and the second zeolite may be the same or different, and the one or more first dopants and the one or more second dopants may be the same or different.

[0026] In some aspects, the second catalyst may be a doped or undoped alumina catalyst. In a particular aspect, the doped alumina catalyst may be zirconium, titanium, tungsten, silicon, fluorine, or any combination thereof in neutral or ionic form. In a particular aspect, the second catalyst may be silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, aluminosilicate catalyst, or any combination thereof.

[0027] In some aspects, the single reactor includes one or more catalyst beds, and the method further includes impregnating at least one of the one or more catalyst beds with a first catalyst and a second catalyst. In a particular aspect, the one or more catalyst beds are stacked relative to each other within the single reactor.

[0028] In some aspects, the method includes adding one or more first dopants to the first catalyst before contacting the input stream. In some aspects, the method includes adding one or more second dopants to the second catalyst before contacting the input stream.

[0029] In some aspects, the one or more olefins comprise C2-C5 olefins. In some aspects, the one or more olefins comprise a primary first olefin, wherein the primary first olefin is propylene. In certain aspects, the one or more olefins further comprise ethylene. In some aspects, the amount of the one or more C2-C5 olefins present in the output stream may be from about 65% by weight to about 85% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. In a particular embodiment, the amount of the one or more C2-C5 olefins present in the output stream is from about 75% by weight to about 80% by weight based on the hydrocarbon products in the output stream.

[0030] In some aspects, the output stream further includes one or more aromatic compounds. In a particular aspect, the amount of the one or more aromatic compounds in the output stream is from about 65% by weight to about 80% by weight based on the output stream.

[0031] In some aspects, one or more first dopants of the first catalyst comprise boron, phosphorus, or combinations thereof. In a particular aspect, the boron is present in the first catalyst in an amount from about 0.5 wt% to about 3 wt%. In another aspect, the boron is present in the first catalyst in an amount of at least about 2 wt%. In a particular aspect, the phosphorus is present in the first catalyst in an amount from about 1 wt% to about 5 wt%. In another aspect, the phosphorus is present in the first catalyst in an amount of at least about 3 wt%.

[0032] In some respects, the first zeolite may comprise ZSM-5 zeolite.

[0033] In some aspects, the output stream may contain saturated hydrocarbons, wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 20% by weight based on the output stream. In a particular aspect, the total amount of saturated hydrocarbons present in the output stream may be from about 5% by weight to about 15% by weight. In other aspects, the total amount of saturated hydrocarbons present in the output stream may be from about 5% by weight to about 10% by weight.

[0034] In some aspects, before contacting the input stream with the first catalyst, the method includes combining the input stream with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols. In one aspect, the one or more C1-C5 alcohols include ethanol. In another aspect, the one or more C1-C5 alcohols include methanol. In another aspect, the one or more C1-C5 alcohols include isobutanol. In yet another aspect, the one or more C1-C5 alcohols include a mixture of at least C4 alcohols, a mixture of at least C5 alcohols, or a mixture of at least C4 alcohols and C5 alcohols.

[0035] In some respects, the one or more bio-oils are produced through a fermentation process.

[0036] In some aspects, the method may include removing at least a portion of the C2 olefins from the output stream.

[0037] In some aspects, the method may include removing at least a portion of the C4 olefins from the output stream.

[0038] In some aspects, the method may include removing at least a portion of the C5 olefins from the output stream.

[0039] In some aspects, the method may include removing at least a portion of the aromatic compounds from the output stream.

[0040] In some aspects, the temperature can be from about 350°C to about 500°C. In other aspects, the temperature can be from about 450°C to about 500°C.

[0041] In some respects, the weight time space velocity (WHSV) can be approximately 2.0 h. -1 To approximately 5.0h -1 In other respects, the weight time space velocity (WHSV) can be approximately 3.0 h. -1 To approximately 5.0h -1 .

[0042] In another exemplary method for producing olefins, the method includes contacting an input stream in at least one reactor with at least a first catalyst and a second catalyst to form an output stream comprising one or more olefins, the input stream comprising one or more bio-oils, the first catalyst comprising zeolite and two dopants, and the second catalyst comprising a doped or undoped alumina catalyst. The at least one reactor is operated at a temperature of about 450°C to about 500°C, a gauge pressure of about 1 to about 2 bar, and for about 2.0 h. -1 To approximately 5.0h -1 Heavy space velocity (WHSV).

[0043] In some aspects, the first dopant of the two dopants may be boron, and the second dopant may be phosphorus. In a particular aspect, the boron is present in the first catalyst at an amount of at least about 2% by weight, and the phosphorus is present in the catalyst at an amount of at least about 3% by weight.

[0044] In some respects, the zeolite may comprise ZSM-5 zeolite.

[0045] In some aspects, the doped alumina catalyst may be silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, silica-alumina catalyst, or any combination thereof.

[0046] In some aspects, the method includes combining the input stream with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols before contacting the input stream with the first and second catalysts.

[0047] In one aspect, the one or more C1-C5 alcohols comprise ethanol. In another aspect, the one or more C1-C5 alcohols comprise methanol. In yet another aspect, the one or more C1-C5 alcohols comprise isobutanol. In still another aspect, the one or more C1-C5 alcohols comprise a mixture of at least C4 alcohols, a mixture of at least C5 alcohols, or a mixture of at least C4 alcohols and C5 alcohols.

[0048] In some respects, the one or more bio-oils are produced through a fermentation process.

[0049] In some aspects, the method may include removing at least a portion of the C2 olefins from the output stream.

[0050] In some aspects, the method may include removing at least a portion of the C4 olefins from the output stream.

[0051] In some aspects, the method may include removing at least a portion of the C5 olefins from the output stream.

[0052] In some aspects, the method may include removing at least a portion of the aromatic compounds from the output stream.

[0053] It should be understood that all combinations of the foregoing concepts and the additional concepts discussed in more detail below (provided that these concepts do not contradict each other) are considered part of the inventive subject matter disclosed herein. Specifically, all combinations of the subject matter protected by the claims of this disclosure are considered part of the inventive subject matter disclosed herein. It should also be understood that terms expressly used herein and that may also appear in any disclosure incorporated by reference should be given the meaning most consistent with the specific concepts disclosed herein. Attached Figure Description

[0054] The accompanying drawings, which are incorporated in and form part of this specification, illustrate specific aspects of the subject matter disclosed herein and, together with the specification, help to explain some principles relating to the disclosed aspects. In the drawings: Figure 1 This is a graphical representation of the typical composition of gaseous products associated with the co-cracking of bio-oil and ethanol using previous methods.

[0055] Figure 2 This is a schematic diagram of an exemplary system for converting one or more bio-oils into olefins and aromatic compounds, wherein the first input feed comprises one or more bio-oils, and optionally water and / or one or more C1-C5 alcohols as a co-feed. Detailed Implementation

[0056] In the following description, specific details are set forth in order to provide a thorough understanding of the various aspects. However, those skilled in the art will understand that this disclosure can be practiced without these details. In other instances, well-known structures have not been shown or described in detail to avoid unnecessarily obscuring the description of the aspects. Unless the context requires otherwise, throughout the specification and the following claims, the word “comprising” and its variations (e.g., “including”) should be interpreted as having an open, inclusive meaning, i.e., “including but not limited to”. Furthermore, the headings provided herein are for convenience only and do not constitute an explanation of the scope or meaning of the claimed disclosure.

[0057] Throughout this specification, references to "an aspect" or "one aspect" mean that a particular feature, structure, or characteristic described in connection with that aspect is included in at least one aspect. Therefore, the phrases "in an aspect" or "in one aspect" appearing in different places throughout this specification do not necessarily refer to the same aspect. Furthermore, a particular feature, structure, or characteristic may be combined in one or more aspects in any suitable manner. Additionally, as used in this specification and the appended claims, unless the context clearly indicates otherwise, the singular forms "a," "an," and "the" include plural referents. It should also be noted that unless the context clearly indicates otherwise, the term "or" is generally used in its meaning including "and / or."

[0058] The word “about” immediately preceding a numerical value indicates a range of ±10% of that value. For example, “about 50” means 45 to 55, “about 25,000” means 22,500 to 27,500, and so on. Furthermore, the phrase “less than about” or “greater than about” should be understood according to the specific meaning of the term “about” as used herein.

[0059] "Weight time space velocity (WHSV)" refers to the weight time space velocity and is defined as the weight of feed flowing per hour per unit weight of catalyst.

[0060] As used herein, "unsaturated hydrocarbons" are organic compounds consisting entirely of carbon and hydrogen atoms and containing double or triple bonds between two adjacent carbon atoms. Examples of unsaturated hydrocarbons include alkenes, dienes, and alkynes.

[0061] As used herein, “aromatic compound” or “aromatic compound” refers to any substance in a large class of unsaturated organic compounds characterized by containing one or more planar rings of carbon atoms linked by two different types of covalent bonds (e.g., benzene, naphthalene, etc.).

[0062] As used herein, “trace” or “trace level” refers to an amount less than 2%. In some respects, “trace” or “trace level” can refer to an amount less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.1%, about 0.1% to about 1.8%, or about 1% to about 1.5%.

[0063] "Single-stage conversion" refers to a process that occurs within a single reactor system.

[0064] As used herein, “saturated hydrocarbon” refers to one or more C2-C5 alkane hydrocarbons. In some respects, saturated hydrocarbons may include ethane, propane, butane, pentane, or any combination thereof.

[0065] Unless otherwise stated, all yields and conversions described herein are by weight.

[0066] The use of biomass pyrolysis oil (e.g., bio-oil) to partially replace fossil fuels is crucial for alleviating the shortage of conventional transportation fuels. Crude bio-oil has high oxygen and water content, leading to several undesirable properties such as low calorific value, high corrosivity, and high viscosity. Therefore, upgrading the crude bio-oil is a necessary step for its high-grade utilization. Oxygen can be removed from the bio-oil in the form of CO, CO2, and H2O through catalytic cracking on acidic zeolites. Thus, the oxygenated bio-oil can be converted into an aromatic-rich liquid fuel. Aromatics can be used to produce commercial gasoline and important chemicals such as benzene, toluene, and xylene (BTX). Different zeolites have been tested in bio-oil cracking studies, and HZSM-5 was found to have the best performance, corresponding to the highest hydrocarbon yield, followed by HY and silicalite, while only small amounts of hydrocarbons were produced on silicate and H-mordenite. It has been observed that HZSM-5 is superior to HY in aromatics production during bio-oil cracking. Furthermore, nickel-modified HZSM-5 catalysts have been developed and used in bio-oil cracking. However, it has been observed that the catalysts used in these bio-oil cracking processes deactivate rapidly and severely, resulting in low yields of liquid hydrocarbons. Without theoretical constraints, two reasons can lead to this phenomenon: (1) bio-oils contain some large-molecule sugar and phenol oligomers, which are non-volatile and prone to coking, indicating the need for separation pretreatment; and (2) due to the high oxygen content and unsaturation of the components in bio-oils, the corresponding effective hydrogen-to-carbon ratio is low. Therefore, the cracking process favors the formation of products with low hydrogen-to-carbon ratios, such as coke. As used herein, “coke” refers to high-molecular-weight and high-boiling-point carbon deposits that form during the process and may be present on the catalyst. Such coke material leads to yield losses and may deactivate the catalyst during the process.

[0067] Therefore, to suppress coke formation during bio-oil cracking, it is necessary to increase the overall hydrogen-to-carbon ratio of the feedstock, for example, by introducing co-cracking reactants with a high hydrogen-to-carbon ratio into the reaction. Two types of compounds are suitable for co-cracking: (1) gas oil from fluidized bed catalytic cracking (FCC) feedstocks, and (2) aliphatic alcohols. Previous studies on the co-cracking of bio-oil model compound mixtures with gas oil have shown that the introduction of gas oil is beneficial for converting the model compounds into liquid and gaseous hydrocarbons. Other studies have reported co-cracking processes using hydrodeoxygenated bio-oil with gas oil, achieving high gasoline yields of over 40% by weight. Aliphatic alcohols (e.g., methanol and ethanol) exhibit excellent reactivity in processes similar to catalytic cracking and therefore have potential for use in co-cracking processes. In further studies, it was found that the introduction of methanol can extend the catalyst lifetime in the cracking of bio-oil model compounds.

[0068] Other studies have found that co-cracking of distillate fractions from bio-oil molecular distillation with ethanol enriches ketones and acids in the bio-oil while lacking large-molecule sugars and phenolic oligomers, resulting in higher reactivity compared to crude bio-oil. Oil phase yields were found to be as high as 25.9% by weight, with hydrocarbon (primarily aromatic compounds) content reaching 98.3%. However, selectivity for C3-C4 hydrocarbons was also high, indicating significant potential for increasing aromatic yields by promoting aromatization during the cracking process.

[0069] Compared to the classic two-step process (i.e., hydrodeoxygenation and cracking) used to upgrade bio-oil to the main aromatic compounds, the ability to crack bio-oil as a single feedstock, or via co-cracking of bio-oil feedstock and bio-based aliphatic alcohols, produces significant fractions of i) C2-C4 olefins and ii) aromatic compounds in a single step without the presence of external hydrogen. Figure 1 The typical composition of the gaseous products associated with the co-cracking of bio-oil and ethanol using the previously described method is shown. The C2-C4 hydrocarbon fraction has an extremely high alkane content compared to the C2-C4 olefin content.

[0070] The aspects of the subject matter disclosed herein provide methods in which a catalyst system is used to convert bio-oils, fatty acids / esters, or mixtures thereof into a mixture of alkenes (including a primary first olefin) in high yields at a competitive cost. According to this disclosure, the method for the single-step conversion of one or more bio-oils, fatty acids / esters, or mixtures thereof into a mixture of alkenes (e.g., C2-C5) and a low content of saturated hydrocarbons can be carried out in a single reactor (e.g., using a single catalyst bed or stacked catalyst beds impregnated with at least one catalyst). The C2-C5 olefins can be readily oligomerized as a base feedstock for the high-yield production of fuels.

[0071] As used herein, “bio-oil” includes triglycerides, lipids / fats, or derivatives thereof. In some aspects, said bio-oil or mixtures thereof include edible and non-edible (e.g., waste) vegetable oils, such as corn oil, soybean oil, olive oil, peanut oil, rapeseed oil (including canola oil), coconut oil, palm oil, or animal-based products, such as tallow or lard. In some aspects, said bio-oil, fatty acid / ester, or mixtures thereof may undergo partial or complete hydrogenation and / or olefin isomerization before being used as feedstock. In some aspects, said bio-oil includes fatty acids / esters derived from triglycerides, for example, through hydrolysis of triglycerides to fatty acids or transesterification with alcohols to fatty acid esters. In some aspects, said bio-oil or mixtures thereof may be produced by a fermentation process. Table 1 provides compositional variations of common triglyceride bio-oils.

[0072] In some aspects, the methods described herein can be carried out in a single-bed reactor (e.g., a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor). In other aspects, the methods described herein can be carried out in a single stacked-bed reactor. For example, in a particular aspect, bio-oils, fatty acids / esters, or mixtures thereof (e.g., corn oil) can be converted into an olefin mixture (e.g., C2-C5) in a single reactor having a first catalyst in the top portion of the reactor and a second catalyst in the portion of the reactor below the first catalyst. In a single-stage process (e.g., using a single-bed reactor, such as a single-bed reactor with mixed catalyst beds) or in a two-stage process (e.g., using a stacked-bed reactor, where each catalyst bed is impregnated with at least one catalyst), the resulting C2-C5 olefin mixture is suitable for oligomerization at relatively low temperatures and pressures to extract cuts for gasoline, jet, or diesel fuels, depending on the oligomerization catalyst selected. Furthermore, in some aspects, the single-bed reactor or stacked-bed reactor can be defined as a fixed-bed reactor, while in other aspects, a fluidized-bed reactor can be used.

[0073] This invention provides systems and methods for the catalytic conversion of bio-oils, fatty acids / esters, or mixtures thereof (e.g., corn oil and aliphatic alcohols). Typically, the catalytic methods according to this disclosure include dehydration, dehydrogenation, skeletal carbon construction, “cracking,” and aromatization, thereby producing low molecular weight olefins (e.g., C2-C5) and aromatic compounds (e.g., benzene, toluene, ethylbenzene, and xylene, commonly referred to as “BTEX”) with high carbon yields. Furthermore, such catalytic methods can produce low amounts of saturated hydrocarbons (e.g., no more than about 20 by weight, based on the output stream, for the conversion of a given one or more bio-oils to their respective olefins and the conversion of such respective olefins to other hydrocarbons). In this single-stage process, the catalyst mixture can produce a C2-C5 olefin mixture, thereby providing low molecular weight olefins in yields with good carbon accountability, the carbon accountability being defined as the ratio of the number of carbon moles fed into the system as one or more bio-oils to the number of carbon moles leaving the system from the added C2-C5 olefin and aromatic mixture. Furthermore, the use of recycled streams of specific olefins (e.g., C2-C5) advantageously maximizes the ability to form desired olefins (e.g., propylene, butene, or mixtures thereof) and BTEX. In some respects, said mixtures of olefins are suitable for oligomerization at relatively low temperatures and pressures to extract fractions for gasoline, jet fuel, or diesel fuel, depending on the oligomerization catalyst selected.

[0074] To address the aforementioned challenges and to define the methods for converting one or more bio-oils into viable feedstocks for high fuel yields, a method has been developed capable of converting one or more bio-oils in high yields into a mixture of C2-C5 olefins (containing the primary olefins) and optionally aromatic fractions consisting primarily of bio-based BTEX components via a single unit operation (e.g., in a single reactor or a single reactor segment, without intermediate separation). This mixture is readily separable for use as a chemical feedstock or readily oligomerized in high yields as a base feedstock for fuel. As described herein, the ability to complete multiple unit operations and chemical conversions in a single reaction process offers implementers favorable economics due to reduced fixed and variable costs, less capital investment, lower energy consumption, increased productivity, and maximized site profitability. Therefore, unlike current systems and methods, the method described herein is a one-step process that produces both fuel precursors and value-added chemical building blocks without requiring hydrogen.

[0075] Therefore, according to this disclosure, the conversion of a co-feed of one or more bio-oils, and optionally water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof) is carried out in a similar manner to convert to a mixture of C2-C5 olefins in high yield and carbon balance. Without being theoretically limited, exemplary single reaction steps include i) dehydrating the alcohol to ethers and / or olefins, ii) oligomerizing light olefins (particularly ethylene) to C2-C5 olefins. 4+ iii) skeletal rearrangement, iv) cracking of larger olefins and alkylated aromatics into lighter olefins (e.g., ethylene, propylene, butene) and C 5+ The process involves: v) hydrogen transfer to produce small amounts of aromatic compounds and saturated hydrocarbons; vi) alkylation of the aromatic compounds by olefins, alcohols, and / or ethers; and vii) decarboxylation and / or decarbonylation of ester and acid functional groups. Thus, at approximately 300°C to approximately 600°C, a vaporized stream of a co-feed of one or more bio-oils and optionally water and / or C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof) is passed through a single fixed catalyst bed containing a physical mixture (which optionally contains a first portion of doped zeolite (e.g., zeolite doped with boron, phosphorus, and optionally one or more additional dopants) combined with a second catalyst) to produce a C2-C5 olefin mixture and optionally aromatic compounds, which can be separated for sale or, after removal of condensate, oligomerized "as is" as a primary jet fuel and / or diesel fuel. In some respects, the second catalyst may be the same or different doped zeolites. In some respects, the second catalyst may be silicate-treated, zirconate-treated, titanate-treated, niobium-treated, or fluorinated γ-alumina.

[0076] Furthermore, the systems and methods of the present invention may optionally include the recycling of one or more specific olefin fractions (e.g., C2+C4+C5 or C2+C5, etc.) and / or water in a closed-loop process configuration, while co-feeding one or more bio-oils.

[0077] This can maximize the yield of selected olefins and / or aromatic compounds. For example, by using the systems and methods provided by the present invention, the recycling of the C2+C4+C5 olefin fraction in combination with one or more bio-oils as feedstocks produces an improved carbon yield of propylene. Selective recycling of the C2+C5 olefin fraction can produce improved combined yields of propylene and butene. Furthermore, recycling of the C4+C5 olefin fraction can produce improved combined yields of ethylene and propylene. Recycling the selected olefin fraction enables the production of olefins for use in the production of chemicals and / or fuels. Exemplary single-step reactions may include i) in-situ dehydration of alcohols to ethers and / or olefins, ii) oligomerization of light olefins (particularly ethylene) to C2+C4+C5 olefins. 4+ iii) skeletal rearrangement, iv) cracking of larger olefins and alkylated aromatics into lighter olefins (e.g., ethylene, propylene, butene) and C 5+ The process involves: v) hydrogen transfer to produce small amounts of aromatic compounds and saturated hydrocarbons; vi) alkylation of the aromatic compounds by olefins, alcohols, and / or ethers; and vii) decarboxylation and / or decarbonylation of ester and acid functional groups. Therefore, recycling the selected olefin fraction and / or any water produced or optionally co-feed enables targeted production of alkenes and / or aromatics for use in the production of chemicals and / or fuels.

[0078] Unlike the conversion of ethylene, the conversion of propylene and other higher molecular weight olefins (C... 4+ This invention enables the easy oligomerization of one or more bio-oils on a variety of catalysts, both zeolite and non-zeolite. The present disclosure enables the conversion of one or more bio-oils into an olefin mixture primarily comprising C2-C5 olefins and low contents of saturated hydrocarbons in a single-stage or two-stage reactor configuration, providing a pathway to an economical method for converting one or more bio-oils into a base feedstock for chemicals and / or fuels. The method according to the invention includes a scheme comprising a “single”-stage conversion of an aqueous mixture of one or more bio-oils into a primary olefin mixture (including a primary first olefin), which can be separated to isolate key low-molecular-weight olefins used as building blocks throughout the industry, or can be readily oligomerized in high yields to C2-C5 olefins. 10+ Hydrocarbon or diesel fractions. The specific catalytic system described in this article enables the minimization of saturated hydrocarbon production, thereby maximizing the production of middle distillates and optionally present aromatic compounds, which is both an asset and an advantage from a sustainability perspective for ethanol refineries.

[0079] In a single reactor configuration, converting one or more bio-oils into desired fuel products or fuel product precursors (e.g., C2-C5 olefins), such as in the case of C1-C5 alcohols or mixtures thereof, can reduce processing costs. In one aspect, a method for converting one or more bio-oils into one or more C2-C5 olefins is provided. In some aspects, the method comprises a single catalyst system (e.g., doped zeolite), while in other aspects, the method comprises two or more catalyst systems (e.g., a dehydration catalyst and doped zeolite).

[0080] In one aspect, a method for producing one or more olefins may include: contacting an input stream with one or more catalysts in at least one reactor to form an output stream comprising said one or more olefins, wherein said input stream comprises one or more bio-oils, and said reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of about 1 to about 10 bar, and a time of about 0.5 h. -1 approximately 10 hours -1 The input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). The catalyst comprises zeolite and one or more dopants, wherein the one or more dopants may comprise one or more first metal dopants, one or more second metal dopants, or both. In a particular aspect, the method may further comprise adding the one or more dopants to the catalyst prior to contacting the input stream.

[0081] In certain aspects, the one or more olefins in the output stream will comprise one or more first olefins. Non-limiting examples of first olefins include ethylene, propylene, butene, etc. In some aspects, the one or more first olefins may comprise the same olefin, while in other aspects, the one or more first olefins may comprise a mixture of different olefins. For example, in some aspects, the one or more first olefins may comprise a dominant first olefin, such as propylene. As used herein, "dominant first olefin" may be present in a higher weight percentage than any other single olefin in the one or more first olefins, for example, in an amount of at least about 20 wt%, at least about 25 wt%, or at least about 30 wt% based on the one or more first olefins. In some aspects, the dominant first olefin may be present in an amount of about 35 wt% to about 40 wt% based on the one or more first olefins, in an amount of about 40 wt% to about 45 wt% based on the one or more first olefins, or in an amount of about 40 wt% to about 50 wt% based on the one or more first olefins. Further consideration is that the dominant first olefin may be present in an amount between any of these ranges.

[0082] The production of type A, X, and Y zeolites typically involves mixing and heating a solution of sodium aluminate and sodium silicate, subsequently forming a sodium aluminosilicate gel. This silica- and alumina-containing compound enters the liquid phase, from which the zeolite forms through crystallization. Thus, the coarse crystalline zeolite containing the original alkali metal can then be converted to an intermediate ammonium form, followed by calcination at 500–550 °C to remove the ammonium counterion, thereby yielding its final hydrogen form. Commercially produced hydrogen-form zeolites (e.g., Clariant, Zeolyst, etc.) are typically used in cracking, isomerization, and alcohol-to-olefins chemistry, with a residual sodium content of less than or equal to 0.05% by weight (e.g., 500 ppm). Higher residual sodium contents (e.g., >2500 ppm) severely deactivate calcium zeolite catalysts, making them unacceptable for chemistry requiring highly acidic catalytic activity.

[0083] Non-limiting examples of suitable zeolites include crystalline silicates of the ZSM-5 (MFI framework), BEA, CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, or dealuminated crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, and / or boron-modified crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, or molecular sieves of the silica-aluminophosphate type of the AEL group. In some aspects, when the zeolite is ZSM-5 zeolite, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 23 to about 400. In certain aspects, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 40 to about 300.

[0084] In some aspects, the zeolite may be doped with one or more dopants (also referred to as doped zeolite). In some aspects, the zeolite may be doped with one or more non-metallic dopants (also referred to as non-metallic doped zeolite). Non-limiting examples of non-metallic dopants include boron, phosphorus, germanium, etc. In one aspect, the one or more non-metallic dopants contain only boron and phosphorus.

[0085] In some respects, the zeolite may be doped with only one dopant. In one respect, the zeolite is doped with only boron. In another respect, the zeolite is doped with only phosphorus. In yet another respect, the zeolite is doped with both boron and phosphorus.

[0086] In some aspects, the zeolite may be doped with one or more metal dopants (also referred to herein as metal-doped zeolite). Non-limiting examples of one or more metal dopants include sodium, potassium, lithium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof. In some aspects, the one or more metal dopants include one or more first metal dopants, one or more second metal dopants, or any combination thereof. In a particular aspect, the one or more first metal dopants may include Group 1A metals, such as sodium, lithium, potassium, or any combination thereof, and the one or more second metal dopants may include Group 2A metals, such as magnesium, calcium, strontium, or barium, or any combination thereof. In a particular aspect, the one or more metal dopants may not be derived from Group 1A or Group 2A, but may include, for example, non-limiting examples of iron, tellurium, selenium, cobalt, nickel, lanthanum and / or other lanthanides, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0087] In some respects, the zeolite may be doped with only one metal dopant. In one respect, the zeolite is doped with only sodium. In another respect, the zeolite is doped with only lithium. In yet another respect, the zeolite is doped with only potassium.

[0088] In certain aspects, the catalyst may comprise a zeolite doped with one or more first nonmetallic dopants and one or more metallic dopants. In some aspects, the catalyst may comprise a zeolite doped with boron, phosphorus, or both, and sodium, lithium, potassium, or any combination thereof. In one aspect, the catalyst may comprise a zeolite doped with sodium, boron, and phosphorus. In other aspects, the catalyst may comprise a zeolite doped with lithium, boron, and phosphorus. In still other aspects, the catalyst may comprise a zeolite doped with potassium, boron, and phosphorus. In any of the foregoing aspects, the zeolite may be ZSM-5 zeolite.

[0089] Boron and phosphorus can be present in the catalyst in a variety of different amounts. In some aspects, the amount of boron present in the catalyst can be from about 0.5% by weight to about 3% by weight, including all sub-ranges in between. In a particular aspect, the amount of boron present in the catalyst can be from about 1% by weight to about 3% by weight, including all sub-ranges in between. In one aspect, the amount of boron present in the catalyst can be at least about 2% by weight.

[0090] In some aspects, the amount of phosphorus present in the catalyst can be from about 1% by weight to about 5% by weight, including all sub-ranges in between. In a particular aspect, the amount of phosphorus present in the catalyst can be from about 2% by weight to about 4% by weight, including all sub-ranges in between. In one aspect, the amount of phosphorus present in the catalyst can be at least about 3% by weight.

[0091] In some aspects, the amount of boron present in the catalyst may be from about 0.5% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 1% by weight to 5% by weight. In a particular aspect, the amount of boron present in the catalyst may be from about 1% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 2% by weight to 4% by weight. In one aspect, the amount of boron present in the catalyst may be at least about 2% by weight, and the amount of phosphorus present in the catalyst may be at least about 3% by weight.

[0092] In some aspects, the doped zeolite may be further doped with additional dopants (also referred to as other dopants), which may or may not contain metallic or non-metallic dopants. In one aspect, the zeolite is doped with one or more non-metallic dopants, one or more metallic dopants, and one or more additional dopants. In another aspect, the zeolite is doped with one or more non-metallic dopants and one or more other dopants. In yet another aspect, the zeolite is doped with one or more metallic dopants and one or more other dopants. Non-limiting examples of additional dopants include iron, tellurium, selenium, cobalt, nickel, lanthanum and / or other lanthanides, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0093] One or more catalysts, either particulate or extruded, can be used in the reactions described herein. For example, in some aspects, the one or more catalysts, either particulate or extruded, may have a particle size greater than at least about 0.05 mm, about 0.1 mm, or greater, or from about 0.05 mm to about 4.0 mm, including all subranges in between. In one aspect, the one or more catalysts, either particulate or extruded, may have a particle size from about 0.4 to about 2.5 mm.

[0094] In another aspect, two or more catalysts can be implemented for converting one or more bio-oils into desired fuel products or fuel product precursors (e.g., C2-C5 olefins and / or aromatic compounds) in a single reactor configuration, as in the case of one or more bio-oils or mixtures thereof. In some aspects, the method includes: contacting an input stream with at least a first catalyst and a second catalyst in a single reactor to form an output stream comprising the one or more first olefins (including a predominant first olefin) and optionally one or more aromatic compounds, wherein the input stream comprises one or more bio-oils, and the single reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and about 0.5 h. -1 approximately 10 hours -1The input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). The first catalyst comprises zeolite and one or more dopants, wherein the one or more dopants comprise one or more first dopants, one or more second dopants, or both. Furthermore, the two catalysts may be in a stacked bed configuration or mixed together. While two or more catalyst systems are described herein with respect to a single reactor configuration, such systems are also contemplated herein to be implemented in a dual-reactor configuration, wherein at least the first catalyst is in a first reactor and at least the second catalyst is in a second reactor.

[0095] Exemplary catalyst combinations that can be used in two or more catalyst systems and methods of the invention described herein (e.g., physical mixing in a single-bed reactor) for the formation of olefins and / or aromatics may comprise a doped zeolite as a first part (e.g., a first catalyst) and may comprise the same or different doped zeolites as a second part (e.g., a second catalyst). In some aspects, the second catalyst comprises silicate-, zirconate-, titanate-, niobium-, or fluorinated γ-alumina, undoped γ-alumina, zeolite (undoped or doped), a silica-alumina catalyst, a solid acid, or any combination thereof. In some aspects, the first catalyst may comprise a zeolite doped with boron, phosphorus, or a combination thereof, and the second catalyst may comprise undoped γ-alumina, zirconate-doped γ-alumina, or both. In one aspect, the first catalyst may comprise a zeolite doped with sodium, potassium, or lithium, or any combination thereof, and the second catalyst may comprise a zeolite doped with sodium, potassium, or lithium, or any combination thereof. In some aspects, the first catalyst may comprise a zeolite doped with magnesium, calcium, strontium, barium, or any combination thereof, and the second catalyst may comprise undoped γ-alumina, zirconated γ-alumina, or both. In one aspect, the second catalyst may comprise a doped or undoped alumina catalyst. In one aspect, each of the two catalysts may be a doped zeolite, but with a different SiO2 / AlO3 ratio or a different group, or each may comprise different dopants, or each may comprise different dopant loadings.

[0096] Non-limiting examples of suitable zeolites include crystalline silicates of the ZSM-5 (MFI framework), BEA, CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, or dealuminated crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, and / or boron-modified crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON groups having a SiO2 / AlO3 ratio greater than 10, or silica-alumina phosphate type molecular sieves of the AEL group. In some aspects, when the zeolite is ZSM-5 zeolite, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 23 to about 400. In certain aspects, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 40 to about 300.

[0097] In some aspects, the zeolite may be doped with one or more dopants (also referred to as doped zeolite). In some aspects, the zeolite may be doped with one or more non-metallic dopants (also referred to as non-metallic doped zeolite). Non-limiting examples of non-metallic dopants include boron, phosphorus, germanium, etc. In one aspect, the one or more non-metallic dopants include only boron and phosphorus.

[0098] In some respects, the zeolite may be doped with only one dopant. In one respect, the zeolite is doped with only boron. In another respect, the zeolite is doped with only phosphorus. In yet another respect, the zeolite is doped with only both boron and phosphorus.

[0099] In some aspects, the zeolite may be doped with one or more metal dopants (also referred to herein as metal-doped zeolite). Non-limiting examples of one or more metal dopants include sodium, potassium, lithium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof. In some aspects, the one or more metal dopants include one or more first metal dopants, one or more second metal dopants, or any combination thereof. In a particular aspect, the one or more first metal dopants may comprise Group 1A metals, such as sodium, lithium, potassium, or any combination thereof, and the one or more second metal dopants may comprise Group 2A metals, such as magnesium, calcium, strontium, or barium, or any combination thereof. In a particular aspect, the one or more metal dopants may not be derived from Group 1A or Group 2A, but may include, for example, non-limiting examples of iron, tellurium, selenium, cobalt, nickel, lanthanum and / or other lanthanides, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0100] In some respects, the zeolite may be doped with only one metal dopant. In one respect, the zeolite is doped with only sodium. In another respect, the zeolite is doped with only lithium. In yet another respect, the zeolite is doped with only potassium.

[0101] In certain aspects, the catalyst may comprise a zeolite doped with one or more first nonmetallic dopants and one or more metallic dopants. In some aspects, the catalyst may comprise a zeolite doped with boron, phosphorus, or both, and sodium, lithium, potassium, or any combination thereof. In one aspect, the catalyst may comprise a zeolite doped with sodium, boron, and phosphorus. In other aspects, the catalyst may comprise a zeolite doped with lithium, boron, and phosphorus. In still other aspects, the catalyst may comprise a zeolite doped with potassium, boron, and phosphorus. In any of the foregoing aspects, the zeolite may be ZSM-5 zeolite.

[0102] Boron and phosphorus can be present in the catalyst in a variety of different amounts. In some aspects, the amount of boron present in the catalyst can be from about 0.5% by weight to about 3% by weight, including all sub-ranges in between. In a particular aspect, the amount of boron present in the catalyst can be from about 1% by weight to about 3% by weight, including all sub-ranges in between. In one aspect, the amount of boron present in the catalyst can be at least about 2% by weight.

[0103] In some aspects, the amount of phosphorus present in the catalyst can be from about 1% by weight to about 5% by weight, including all sub-ranges in between. In a particular aspect, the amount of phosphorus present in the catalyst can be from about 2% by weight to about 4% by weight, including all sub-ranges in between. In one aspect, the amount of phosphorus present in the catalyst can be at least about 3% by weight.

[0104] In some aspects, the amount of boron present in the catalyst may be from about 0.5% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 1% by weight to 5% by weight. In a particular aspect, the amount of boron present in the catalyst may be from about 1% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 2% by weight to 4% by weight. In one aspect, the amount of boron present in the catalyst may be at least about 2% by weight, and the amount of phosphorus present in the catalyst may be at least about 3% by weight.

[0105] In some aspects, the doped zeolite may be further doped with additional dopants (also referred to as other dopants), which may or may not contain metallic or non-metallic dopants. In one aspect, the zeolite is doped with one or more non-metallic dopants, one or more metallic dopants, and one or more additional dopants. In another aspect, the zeolite is doped with one or more non-metallic dopants and one or more other dopants. In yet another aspect, the zeolite is doped with one or more metallic dopants and one or more other dopants. Non-limiting examples of additional dopants include iron, tellurium, selenium, cobalt, nickel, lanthanum and / or other lanthanides, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0106] One or more catalysts, either particulate or extruded, can be used in the reactions described herein. For example, in some aspects, the one or more catalysts, either particulate or extruded, may have a particle size greater than at least about 0.05 mm, about 0.1 mm, or greater, or from about 0.05 mm to about 4.0 mm, including all subranges in between. In one aspect, the one or more catalysts, either particulate or extruded, may have a particle size from about 0.4 to about 2.5 mm.

[0107] In a particular aspect, the method includes: contacting an input stream with at least a first catalyst and a second catalyst in a single reactor to form an output stream comprising one or more first olefins (including a predominant first olefin) and optionally one or more aromatic compounds, wherein the input stream comprises one or more bio-oils, and the single-bed reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and a time of about 0.5 h. -1 approximately 10 hours -1The weight hourly space velocity (WHSV) is measured, wherein the first catalyst comprises zeolite and one or more dopants; and the second catalyst comprises doped or undoped alumina catalyst, the alumina catalyst comprising one or more of zirconium (Zr), titanium (Ti), tungsten (W), fluorine (F), or silicon (Si) in neutral or ionic form. Furthermore, the two catalysts may be mixed together in a single-bed reactor. The input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof).

[0108] In other aspects, a method for producing one or more olefins may include: contacting an input stream containing said one or more bio-oils with a first catalyst in a stacked bed reactor to form a first mixture containing one or more first olefins (including a predominant first olefin) and optionally one or more aromatic compounds. The stacked bed reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and for about 0.5 h. -1 approximately 10 hours -1 The method involves a weight hourly space velocity (WHSV) of [amount missing], and the first catalyst comprises doped or undoped zeolite. The input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). The method further includes contacting the first mixture with at least a second catalyst, wherein the second catalyst comprises an alumina catalyst comprising one or more of zirconium (Zr), titanium (Ti), tungsten (W), fluorine (F), or silicon (Si) in neutral or ionic form to produce an output stream comprising one or more olefins (e.g., C2-C5 olefins) and / or aromatic compounds. In this case, the first catalyst may be impregnated into a first catalyst bed of the stacked bed reactor, and the second catalyst may be impregnated into a second catalyst bed of the stacked bed reactor.

[0109] Regarding the output stream, the first olefin (e.g., a C2-C5 olefin) may be present in an amount of at least 60 wt% based on the total amount of unsaturated hydrocarbons present in the gas phase of the output stream (excluding CO, CO2, and hydrogen). The first olefin may be present in an amount of at least 70 wt% based on the total amount of unsaturated hydrocarbons present in the output stream. The first olefin may be present in an amount of at least 80 wt% based on the total amount of unsaturated hydrocarbons present in the output stream. The first olefin may be present in an amount of at least 90 wt% based on the total amount of unsaturated hydrocarbons present in the output stream. The first olefin may be present in an amount of about 65 wt% to about 95 wt%, about 65 wt% to about 85 wt%, or about 70 wt% to about 80 wt% based on the total amount of unsaturated hydrocarbons present in the output stream, including all sub-ranges therebetween. The amount of the one or more aromatic compounds may be present in an amount of about 65 wt% to about 80 wt% or about 75 wt% to about 80 wt% based on the total amount of unsaturated hydrocarbons present in the output stream, including all sub-ranges therebetween. Further regarding the output stream, the method disclosed herein may further include removing at least a portion of the C2 olefin from the output stream. The method may include removing at least a portion of the C4 olefins from the output stream. The method may include removing at least a portion of the C5 olefins from the output stream. The method may include removing at least a portion of one or more aromatic compounds from the output stream.

[0110] In certain aspects, the one or more olefins in the output stream may comprise one or more first olefins. Non-limiting examples of first olefins include ethylene, propylene, butene, etc. In some aspects, the one or more first olefins may comprise the same olefin, while in other aspects, the one or more first olefins may comprise a mixture of different olefins. For example, in some aspects, the one or more first olefins may comprise a dominant first olefin, such as propylene. As used herein, "dominant first olefin" may be present in a higher weight percentage than any other single olefin in the one or more first olefins, for example, in an amount of at least about 20 wt%, at least about 25 wt%, or at least about 30 wt% based on the one or more first olefins. In some aspects, the dominant first olefin may be present in an amount of about 35 wt% to about 40 wt% based on the one or more first olefins, in an amount of about 40 wt% to about 45 wt% based on the one or more first olefins, or in an amount of about 40 wt% to about 50 wt% based on the one or more first olefins. Further consideration is that the dominant first olefin may be present in an amount between any of these ranges.

[0111] In some aspects, the one or more unsaturated hydrocarbons present in the output stream may comprise one or more low-carbon-strength unsaturated hydrocarbons. In one aspect, all of the said unsaturated hydrocarbons may be low-carbon-strength unsaturated hydrocarbons. As used herein, "low-carbon-strength" when used to modify unsaturated hydrocarbons (e.g., one or more unsaturated hydrocarbons) means that the carbon strength is at least about 50% lower than the typical carbon strength of its petroleum equivalent.

[0112] In some aspects, the one or more unsaturated hydrocarbons present in the output stream may comprise one or more zero-carbon-strength hydrocarbons. In one aspect, all of the unsaturated hydrocarbons may be zero-carbon-strength hydrocarbons. As used herein, "zero-carbon-strength" when used to modify unsaturated hydrocarbons (e.g., one or more unsaturated hydrocarbons) means that the carbon strength is at least about 90% to 100% lower than the typical carbon strength of its petroleum equivalent.

[0113] In some aspects, the one or more unsaturated hydrocarbons present in the output stream may comprise one or more hydrocarbons with negative carbon strength. In one aspect, all of the one or more hydrocarbons may be hydrocarbons with negative carbon strength. As used herein, "negative carbon strength" when used to modify unsaturated hydrocarbons means a carbon strength that is more than 100% lower than the typical carbon strength of its petroleum equivalent.

[0114] In some aspects, the output stream contains saturated hydrocarbons. In a particular aspect, the total amount of saturated hydrocarbons present in the output stream does not exceed about 20% by weight. In another aspect, the total amount of saturated hydrocarbons present in the output stream does not exceed about 15% by weight. In other aspects, the total amount of saturated hydrocarbons present in the output stream can be from about 5% by weight to about 15% by weight or from about 5% by weight to about 10% by weight, including all subranges in between.

[0115] Regarding the reactor, the reactor can operate at temperatures from about 300°C to about 600°C, including all sub-ranges within this range. The reactor can operate at temperatures from about 350°C to about 500°C, including all sub-ranges within this range. The reactor can operate at temperatures from about 450°C to about 500°C, including all sub-ranges within this range. The reactor can operate at gauge pressures from about 1 to about 10 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures from 1 to about 5 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures from 1 to about 2 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures of about 5 or lower. The reactor can operate for about 0.5 hours. -1 approximately 10 hours -1 The reactor operates at a gravity time space velocity, including all sub-ranges in between. The reactor can operate at approximately 1.0 h... -1 To approximately 5.0h -1 Approximately 2.0 hours -1To approximately 5.0h -1 Approximately 3.0 hours -1 To approximately 5.0h -1 or about 5.0h -1 approximately 10 hours -1 The reactor operates at a heavy time space velocity, including all sub-ranges in between. The reactor can be a fixed-bed reactor. The reactor can be a fluidized-bed reactor. The reactor can be a moving-bed reactor.

[0116] This disclosure also describes a method for converting one or more bio-oils into one or more first olefins (including a major first olefin) and / or one or more aromatic compounds using a single catalyst system. The use of a single catalyst system may be desirable in various situations, such as when the output stream is acceptable for some portion of unconverted one or more bio-oils and associated oxygenates, or when the catalyst is continuously regenerated during operation; this can be implemented, for example, in a fluidized bed reactor or a moving bed reactor. For the purposes of this disclosure, “oxygenate” refers to a hydrocarbon with a chemical structure containing oxygen as a component. In some aspects, the one or more bio-oils in the input stream of the single catalyst system may be one or more edible or non-edible (e.g., waste) vegetable oils, such as corn oil, soybean oil, olive oil, peanut oil, rapeseed oil (including canola oil), coconut oil, palm oil, or animal-based products, such as tallow or lard. In some aspects, the bio-oils, fatty acids / esters, or mixtures thereof may undergo partial or complete hydrogenation and / or may be olefin isomerized before being used as feedstock. In some aspects, the bio-oil comprises fatty acids / esters derived from triglycerides, for example, through hydrolysis of the bio-oil to fatty acids or transesterification with alcohols to fatty acid esters. In some aspects, the bio-oil, fatty acids / esters, or mixtures thereof can be produced by a fermentation process. In some aspects, the input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof).

[0117] Converting one or more bio-oils into desired fuel products or fuel product precursors (e.g., C2-C5 olefins and / or aromatic compounds) using a single catalyst system, such as in the case of one or more bio-oils or mixtures thereof, can, for example, reduce processing costs and simplify and optimize the conversion method, which cannot be achieved with a dual catalyst system otherwise. In these methods, the single catalyst system comprises only one catalyst, such as a zeolite. In some aspects, the sole catalyst is not a doped or undoped alumina catalyst. In certain aspects, the zeolite may be a zeolite doped with one or more non-metallic dopants (e.g., boron, phosphorus, both) and optionally further doped with additional dopants.

[0118] In one aspect, the catalyst may comprise a zeolite and one or more dopants, wherein the one or more dopants comprise one or more first dopants (e.g., boron, phosphorus, or both). In another aspect, the catalyst may comprise a zeolite and one or more first dopants, wherein the one or more first metal dopants comprise boron, phosphorus, or both, and optionally include one or more dopants.

[0119] Alternatively or additionally, the one or more dopants may comprise one or more second dopants (e.g., beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof). In one aspect, a catalyst may comprise zeolite and one or more first nonmetallic dopants and one or more second metallic dopants, wherein the one or more second metallic dopants comprise calcium, magnesium, strontium, or any combination thereof. In another aspect, the catalyst may comprise zeolite and one or more second metallic dopants and one or more nonmetallic dopants, wherein the one or more second metallic dopants comprise magnesium, calcium, strontium, or barium, or any combination thereof, and wherein the one or more nonmetallic dopants comprise boron, phosphorus, or a combination thereof.

[0120] Non-limiting examples of zeolites used for olefin formation may include doped zeolites, such as crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON group having a SiO2 / AlO3 ratio greater than 10, and / or boron-modified crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON group having a SiO2 / AlO3 ratio greater than 10, or dealuminated crystalline silicates of the ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON group having a SiO2 / AlO3 ratio greater than 10. In some aspects, when the zeolite is ZSM-5 zeolite, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 23 to about 400. In certain aspects, the ZSM-5 zeolite may have a SiO2 / AlO3 ratio of about 40 to about 300.

[0121] In some aspects, the zeolite may be doped with one or more metal dopants (also referred to herein as metal-doped zeolite). Non-limiting examples of one or more metal dopants include sodium, potassium, lithium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof. In some aspects, the one or more metal dopants comprise one or more first metal dopants, one or more second metal dopants, or any combination thereof. In a particular aspect, the one or more first metal dopants may comprise Group 1A metals, such as sodium, lithium, potassium, or any combination thereof, and the one or more second metal dopants may comprise Group 2A metals, such as magnesium, calcium, strontium, or barium, or any combination thereof. In a particular aspect, the one or more metal dopants may not be derived from Group 1A or Group 2A, but may include, for example, non-limiting examples of iron, tellurium, selenium, cobalt, nickel, lanthanum and / or other lanthanides, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0122] In some aspects, the zeolite may be doped with one or more non-metallic dopants. Zeolites doped with one or more non-metallic dopants are also referred to herein as non-metallic doped zeolites. Non-limiting examples of non-metallic dopants include boron, phosphorus, germanium, etc. In one aspect, the one or more non-metallic dopants contain only boron and phosphorus.

[0123] In some respects, the zeolite may be doped with only one dopant. In one respect, the zeolite is doped with only boron. In another respect, the zeolite is doped with only phosphorus. In yet another respect, the zeolite is doped with both boron and phosphorus.

[0124] In some respects, the zeolite may be doped with only one metal dopant. In one respect, the zeolite is doped with only sodium. In another respect, the zeolite is doped with only lithium. In yet another respect, the zeolite is doped with only potassium.

[0125] In certain aspects, the catalyst may comprise a zeolite doped with one or more first nonmetallic dopants and one or more metallic dopants. In some aspects, the catalyst may comprise a zeolite doped with boron, phosphorus, or both, and sodium, lithium, potassium, or any combination thereof. In one aspect, the catalyst may comprise a zeolite doped with sodium, boron, and phosphorus. In other aspects, the catalyst may comprise a zeolite doped with lithium, boron, and phosphorus. In still other aspects, the catalyst may comprise a zeolite doped with potassium, boron, and phosphorus. In any of the foregoing aspects, the zeolite may be ZSM-5 zeolite.

[0126] Boron and phosphorus can be present in the catalyst in a variety of different amounts. In some aspects, the amount of boron present in the catalyst can be from about 0.5% by weight to about 3% by weight, including all sub-ranges in between. In a particular aspect, the amount of boron present in the catalyst can be from about 1% by weight to about 3% by weight, including all sub-ranges in between. In one aspect, the amount of boron present in the catalyst can be at least about 2% by weight.

[0127] In some aspects, the amount of phosphorus present in the catalyst can be from about 1% by weight to about 5% by weight, including all sub-ranges in between. In a particular aspect, the amount of phosphorus present in the catalyst can be from about 2% by weight to about 4% by weight, including all sub-ranges in between. In one aspect, the amount of phosphorus present in the catalyst can be at least about 3% by weight.

[0128] In some aspects, the amount of boron present in the catalyst may be from about 0.5% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 1% by weight to 5% by weight. In some aspects, the amount of boron present in the catalyst may be from about 1% by weight to about 3% by weight, and the amount of phosphorus present in the catalyst may be from about 2% by weight to 4% by weight. In one aspect, the amount of boron present in the catalyst may be at least about 2% by weight, and the amount of phosphorus present in the catalyst may be at least about 3% by weight.

[0129] In one exemplary aspect, a method for producing one or more olefins using a single catalyst system may include contacting an input stream containing the one or more bio-oils with a catalyst in a reactor to form an output stream containing the one or more first olefins (including the primary olefin) and optionally one or more aromatic compounds, wherein the catalyst is substantially composed of a zeolite doped with boron and phosphorus and optionally one or more additional dopants. The input stream may further contain a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). The reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and for about 0.5 h. -1 approximately 10 hours -1 Heavy space velocity (WHSV).

[0130] In some aspects, the method may include regenerating the catalyst after contacting the input stream with the catalyst in a reactor. In some aspects, the regeneration of the catalyst may be performed by purging any gaseous or liquid hydrocarbons or oxygen-containing substances from the reactor, followed by introducing air and / or oxygen, optionally oxygen diluted with an inert gas or vapor, to burn off any solid carbon deposits on the catalyst. In some aspects, the method may include a system in which the catalyst is circulated between a reactor and a regeneration reactor, in which the catalyst is contacted with the input stream, and in the regeneration reactor, the catalyst is contacted with air and / or oxygen (optionally oxygen diluted with an inert gas or vapor) to burn off any solid carbon deposits on the catalyst.

[0131] In some aspects, the method may further include contacting another input stream with a regenerated catalyst (e.g., a regenerated catalyst) in a reactor to form another output stream comprising one or more C2-C5 olefins and / or aromatic compounds, said other input stream comprising one or more bio-oils and optionally water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). Those skilled in the art will understand that the regenerated catalyst will have a lower concentration of boron, phosphorus, or both compared to the catalyst before regeneration.

[0132] Regarding the reactor, the reactor can operate at temperatures from about 300°C to about 600°C, including all sub-ranges within this range. The reactor can operate at temperatures from about 350°C to about 500°C, including all sub-ranges within this range. The reactor can operate at temperatures from about 450°C to about 500°C, including all sub-ranges within this range. The reactor can operate at gauge pressures from about 1 to about 10 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures from 1 to about 5 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures from 1 to about 2 bar, including all sub-ranges within this range. The reactor can operate at gauge pressures of about 5 or lower. The reactor can operate for about 0.5 hours. -1 approximately 10 hours -1 The reactor operates at a gravity time space velocity, including all sub-ranges in between. The reactor can operate at approximately 1.0 h... -1 To approximately 5.0h -1 Approximately 2.0 hours -1 To approximately 5.0h -1 Approximately 3.0 hours -1 To approximately 5.0h -1 or about 5.0h -1 approximately 10 hours -1The reactor operates at a heavy time space velocity, including all sub-ranges in between. The reactor can be a fixed-bed reactor. The reactor can be a fluidized-bed reactor. The reactor can be a moving-bed reactor.

[0133] Further regarding the output stream, the methods disclosed herein may further include removing at least a portion of the major olefin. The method may include removing at least a portion of the C2 olefin from the output stream. The method may include removing at least a portion of the C3 olefin from the output stream. The method may include removing at least a portion of the C4 olefin from the output stream. The method may include removing at least a portion of the C5 olefin from the output stream. The method may include removing at least a portion of one or more aromatic compounds from the output stream.

[0134] In one exemplary aspect, a method for producing one or more olefins using a dual-catalyst system may include contacting an input stream in at least one reactor with at least a first catalyst and a second catalyst to form an output stream comprising the one or more olefins, the input stream comprising one or more bio-oils, the first catalyst comprising a zeolite and two dopants, and the second catalyst comprising a doped alumina catalyst. The input stream may further comprise a co-feed of water and / or one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 and / or C5 alcohols, or any combination thereof). The output stream comprises one or more first olefins (including the primary olefin), and optionally one or more aromatic compounds. The first catalyst consists of a zeolite (e.g., ZSM-5 zeolite) doped with boron and / or phosphorus, and optionally one or more additional dopants. The second catalyst consists of a doped alumina catalyst, such as silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, a silica-alumina catalyst, or any combination thereof. The reactor is maintained at a temperature of approximately 450°C to approximately 500°C, a gauge pressure of approximately 1 to approximately 2 bar, and for approximately 2.0 hours. -1 To approximately 5.0h -1 The weight hourly space velocity (WHSV) is [value missing]. The boron is present in the first catalyst at an amount of about 2% by weight, and the phosphorus is present in the catalyst at an amount of about 3% by weight. The zeolite may be ZSM-5 zeolite.

[0135] Figure 2An exemplary reactor system 1000 is illustrated. As shown, input 100, such as one or more bio-oils, optionally having inert water and / or a co-feed of one or more C1-C5 alcohols (e.g., methanol, ethanol, isobutanol, a mixture of at least C4 alcohols, a mixture of at least C5 alcohols, or a mixture of at least C4 and C5 alcohols), can be fed into reactor 300 to produce output 200, such as an olefin mixture containing a primary olefin and optionally one or more aromatic compounds. Furthermore, recirculation streams R1, R2, and R3 can recycle C2, C4, and C5 olefins back to input 100, respectively, to be fed back into reactor 300. Water 400 as a byproduct can be any water that is co-fed into reactor 300, and can also be generated in situ through reactor 300 via ethanol dehydration to ethylene, thus being condensed and removed and / or partially recycled back to input material 100, fed back to reactor 300 as an inert co-feed (not shown), as part of output 200.

[0136] Reactor 300 can have various configurations. In some aspects, the reactor is a single-bed reactor (e.g., a single fixed-bed reactor, a single fluidized-bed reactor, a single moving-bed reactor). In these aspects, the individual catalyst beds (not shown) of reactor 300 can be impregnated with two or more catalysts to form a mixed catalyst bed.

[0137] In other aspects, reactor 300 may include two or more catalyst beds (e.g., a stacked configuration). In these aspects, a first catalyst bed may include one or more catalysts impregnated therein, and a second catalyst bed may include one or more catalysts impregnated therein. For example, the first catalyst bed may include a first catalyst comprising zeolite doped with at least one or more dopants (e.g., boron, phosphorus, or both); and the second catalyst bed may include a second catalyst comprising silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, zeolite (undoped or doped), a silica-alumina catalyst, a solid acid, or any combination thereof. The doped zeolite of the first catalyst may be further doped with one or more metallic or non-metallic dopants. Alternatively or additionally, the doped zeolite may be doped with at least one or more other dopants. In other aspects, the first catalyst bed may include a mixture of the first catalyst and the second catalyst impregnated therein.

[0138] In some respects, the first catalyst bed does not contain the second catalyst. Alternatively or additionally, the second catalyst bed does not contain the first catalyst.

[0139] In other aspects, the reactor system may include two or more reactors in series. In these aspects, for example, when a first reactor and a second reactor are present, the first reactor, the second reactor, or both may have any reactor configuration disclosed herein (e.g., structural design, such as single-bed, mixed-bed, stacked-bed, etc.). In some aspects, the first reactor and the second reactor have the same configuration (e.g., structural design). In other aspects, the first reactor and the second reactor have different configurations (e.g., structural design). Alternatively or additionally, the first reactor and the second reactor may operate under the same process conditions (e.g., temperature, pressure, gravity hourly space velocity, etc.). In other aspects, the first reactor and the second reactor may operate under different process conditions. Alternatively or additionally, the first reactor and the second reactor may each have a catalyst bed, and both beds may be impregnated with the same one or more catalysts. In other aspects, one or more catalyst beds of the first reactor may be impregnated with one or more first catalysts, and one or more catalyst beds of the second reactor may be impregnated with one or more second catalysts different from the first catalyst.

[0140] The following specific examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention as defined by the appended claims.

[0141] Example Example 1: Reactor Setup The conversion of bio-oil, fatty acids / esters, or mixtures thereof (optionally co-feeded with C1-C5 alcohols and / or water) to C2-C5 olefins and aromatic compounds is carried out at a temperature of 300°C to 600°C via a fixed-bed reactor comprising one or more specific catalysts. Preheated (180°C) bio-oil, fatty acids / esters, or mixtures thereof, with or without C1-C5 alcohols and / or water as co-feed, is flowed downwards through a fixed catalyst bed while nitrogen is co-fed at atmospheric pressure or at a moderate pressure (i.e., 0-30 bar). The flow rate of the bio-oil, fatty acids / esters, or mixtures thereof (optionally co-feeded with C1-C5 alcohols and / or water) is controlled by a Teledyne 500D injection pump and adjusted to obtain the target olefin heavy hourly space velocity (WHSV). The internal reaction temperature is maintained constant via a Lindberg Blue M furnace manufactured by Thermo-Scientific. The conversion and selectivity of bio-oil, fatty acids / esters, or mixtures thereof were calculated by analyzing the organic matter and water content of the liquid-phase reactor effluent using gas chromatography (GC), analyzing non-condensable hydrocarbons (i.e., C2-C5 olefins) using online gas chromatography, and quantitatively analyzing CO and CO2 relative to nitrogen as an internal standard using an online thermal conductivity detector. Therefore, passing the vaporized stream of corn oil through a catalyst combination in a single fixed-bed reactor between 460°C and 500°C resulted in the formation of C2-C5 olefins and aromatic compounds in high yields.

[0142] Example 2: Preparation of Catalyst Preparation of Boron and / or Phosphorus Impregnated ZSM-5 Zeolite Catalyst: As described, the boron and phosphorus impregnated zeolite catalyst was prepared using the incipientwetness technique. 0.83 g of phosphoric acid (85%) and 0.94 g of boric acid were dissolved in deionized water (7.2 mL). After dissolution, the solution was added dropwise to 6 g of ZSM-5 zeolite support (i.e., Clariant H-CZP-90E). The resulting impregnated catalyst was dried at 160 °C for 1 hour and then calcined at 550 °C for 3 hours.

[0143] Preparation of the impregnated Zr-γ-alumina catalyst (nominal Zr metal 5 wt%): As described, the Zr-γ-alumina catalyst was prepared using a pre-wetting technique. Precursor metal salt (Sigma Aldrich): 2.64 g of zirconium oxynitrate (IV) hydrate was dissolved in deionized water (14.9 mL). After the salt was dissolved, the solution was added dropwise to 15 g of γ-alumina support. The resulting mixed metal oxide was manually mixed to ensure complete wetting, and the resulting impregnated catalyst was dried at 160 °C for 1 hour and then calcined at 500 °C for 4 hours.

[0144] Example 3: Single-stage reactor—food-grade corn oil feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 460°C in reactor, corn oil flow rate = 0.30 mL / min, weight hourly space velocity = 3.35 (based on corn oil), nitrogen = 10 mL / min, pressure = 0 bar; catalyst—zirconate-modified (4.0 wt%) γ-alumina physically mixed with doped ZSM-5 zeolite.

[0145] Composition of the effluent from a single-pass reactor and the corresponding total weight percentage (Table 2A shows the gas phase and Table 2B shows the liquid phase).

[0146] Table 2A:

[0147] Table 2B:

[0148] As shown in the figure, the gaseous phase contains about 58% olefins, and the liquid phase contains about 67% aromatics.

[0149] Example 4: Single-stage reactor—food-grade corn oil + deionized water feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 480°C in reactor, corn oil flow rate = 0.20 mL / min, deionized (DI) water flow rate = 0.10 mL / min; weight hourly space velocity = 4.43 (based on corn oil), nitrogen = 10 mL / min, pressure = 0 bar; catalyst—boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0150] The composition of the single-pass reactor effluent and the corresponding total weight percentage are as a percentage of the corn oil feed mass (Table 3A shows the gas phase and Table 3B shows the liquid phase).

[0151] Table 3A (33% of the corn oil feed mass was converted in the gas phase), CO2 / CO ratio not measured:

[0152] Table 3B (67% of the corn oil feed mass was converted in liquid phase):

[0153] As shown in the figure, the gaseous phase contains about 75% olefins, and the liquid phase contains about 65% aromatics.

[0154] Example 5: Single-stage reactor – food-grade corn oil + ethanol + deionized water feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 480°C in reactor, corn oil flow rate = 0.10 mL / min, ethanol / deionized water (50 / 50) flow rate = 0.20 mL / min; weight hourly space velocity = 4.35 (based on corn oil + ethanol), nitrogen = 10 mL / min, P = 0 bar; catalyst—boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0155] The composition of the single-pass reactor effluent and the corresponding total weight percentage as a percentage of the corn oil feed mass (Table 4A shows the gas phase and Table 4B shows the liquid phase).

[0156] Table 4A (Gas phase = 46% corn oil + ethanol feed mass), trace amounts of CO2 / CO were detected:

[0157] Table 4B (Liquid phase = 54% corn oil + ethanol feed mass):

[0158] As shown in the figure, the gaseous phase contains about 80% olefins, and the liquid phase contains about 75% aromatics.

[0159] Example 6: Single-stage reactor (feed of food-grade corn oil, ethanol, and deionized water) Single-stage reactor configuration: Reaction conditions: feed preheater = 180℃, reactor T = 485℃ in reactor, corn oil flow rate = 0.03 mL / min, ethanol / deionized water (50 / 50) flow rate = 0.12 mL / min; weight hourly space velocity = 2.29 (based on corn oil + ethanol), nitrogen = 10 mL / min, P = 0 bar; catalyst—boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0160] The composition of the single-pass reactor effluent and the corresponding total weight percentage are as a percentage of the corn oil feed mass (Table 5A shows the gas phase and Table 5B shows the liquid phase).

[0161] Table 5A (Gas phase = 43% corn oil + ethanol feed mass), CO2 / CO ratio not measured:

[0162] Table 5B (Liquid phase = 57% corn oil + ethanol feed mass):

[0163] As shown in the figure, the gaseous phase contains about 80% olefins, and the liquid phase contains about 80% aromatics.

[0164] Example 7: Single-stage reactor – food-grade corn oil + ethanol feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 480°C in reactor, corn oil flow rate = 0.10 mL / min, ethanol (100%) flow rate = 0.12 mL / min; weight hourly space velocity = 4.52 (based on corn oil + ethanol), nitrogen = 10 mL / min, pressure = 0 bar; catalyst - boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0165] The composition of the single-pass reactor effluent (gas phase "Table 6A" and liquid phase "Table 6B") and the corresponding total weight percentage are presented as a percentage of the corn oil feed mass.

[0166] Table 6A (Gas phase = 54% corn oil + ethanol feed mass), CO2 / CO ratio not measured:

[0167] Table 6B (Liquid phase = 46% corn oil + ethanol feed mass):

[0168] As shown in the figure, the gaseous phase contains about 80% olefins, and the liquid phase contains about 70% aromatics.

[0169] Example 8: Single-stage reactor (distilled corn oil + ethanol + deionized water feed) Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 485°C in reactor, distilled corn oil flow rate = 0.03 mL / min, ethanol / deionized water (65 / 35%) flow rate = 0.15 mL / min; weight hourly space velocity = 2.16 (based on corn oil + ethanol), nitrogen = 10 mL / min, pressure = 0 bar; catalyst - boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0170] The composition of the single-pass reactor effluent and the corresponding total weight percentage as a percentage of the corn oil feed mass (Table 7A shows the gas phase and Table 7B shows the liquid phase).

[0171] Table 7A (Gas phase = 58% distilled corn oil + ethanol feed mass), CO2 / CO ratio not measured:

[0172] Table 7B (Liquid phase = 42% corn oil + ethanol feed mass):

[0173] As shown in the figure, the gaseous phase contains about 80% olefins, and the liquid phase contains about 80% aromatics.

[0174] Example 9: Single-stage reactor – canola oil + deionized water feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180°C, reactor T = 480°C in reactor, canola oil flow rate = 0.20 mL / min, deionized water flow rate = 0.10 mL / min; weight hourly space velocity = 4.43 (based on canola oil), nitrogen = 10 mL / min, pressure = 0 bar; catalyst - boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0175] The composition of the single-pass reactor effluent and the corresponding total weight percentage are as a percentage of the mass of canola oil + water feed (Table 8A shows the gas phase and Table 8B shows the liquid phase).

[0176] Table 8A (Gas phase = 33% rapeseed oil + deionized water feed mass), CO2 / CO ratio not measured:

[0177] Table 8B (Liquid phase = 67% rapeseed oil + deionized water feed mass):

[0178] As shown in the figure, the gaseous phase contains about 75% olefins, and the liquid phase contains about 75% aromatics.

[0179] Example 10: Single-stage reactor – Canola oil + ethanol + deionized water feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180℃, reactor T = 480℃ in reactor, rapeseed oil flow rate = 0.10 mL / min, ethanol / deionized water (50 / 50%) flow rate = 0.20 mL / min; weight hourly space velocity = 4.35 (based on rapeseed oil + ethanol), nitrogen = 10 mL / min, pressure = 0 bar; catalyst - boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90).

[0180] The composition of the single-pass reactor effluent and the corresponding total weight percentage are as a percentage of the mass of canola oil + ethanol / water feed (Table 9A shows the gas phase and Table 9B shows the liquid phase).

[0181] Table 9A (Gas phase = 43% rapeseed oil + ethanol / water feed mass), CO2 / CO ratio not measured:

[0182] Table 9B (Liquid phase = 57% rapeseed oil + ethanol / water feed mass), CO2 / CO ratio not measured:

[0183] As shown in the figure, the gaseous phase contains about 75% olefins, and the liquid phase contains about 80% aromatics.

[0184] Example 11: Single-stage reactor – coconut oil + ethanol + deionized water feed Single-stage reactor configuration: Reaction conditions: feed preheater = 180℃, reactor T = 450℃ in reactor, coconut oil flow rate = 0.10 mL / min, ethanol / deionized water (65 / 35%) flow rate = 0.15 mL / min; weight hourly space velocity = 3.36 (based on coconut oil + ethanol), nitrogen = 10 mL / min, pressure = 0 bar; catalyst - boron / phosphorus doped ZSM-5 zeolite (SiO2 / AlO3 ratio = 90) + Zr doped γ-alumina.

[0185] The composition of the single-pass reactor effluent and the corresponding total weight percentage are as a percentage of the coconut oil + ethanol / water feed mass (Table 10 shows the gas phase, and the liquid phase was not analyzed).

[0186] Table 10 (Gas phase = 45% coconut oil + ethanol / water feed mass), CO2 / CO not measured:

[0187] As shown in the figure, the content of the gaseous olefins is approximately 75%.

[0188] Although various exemplary aspects have been described above, numerous changes may be made to these aspects without departing from the teachings herein. For example, in alternative aspects, the order of the method steps described herein may generally be altered, and in other alternative aspects, one or more method steps may be skipped entirely. Optional features of the various system and method aspects may be included in some aspects but not in others. Therefore, the foregoing description is provided primarily for illustrative purposes and should not be construed as limiting the scope of the claims.

[0189] The embodiments and illustrations contained herein are shown by way of example and not limitation, and specific aspects of the subject matter can be practiced. As mentioned, other aspects can be utilized and derived from them, allowing for structural and logical substitutions and changes without departing from the scope of this disclosure. For convenience, these aspects of the subject matter of the invention may be referred to individually or collectively as “inventions” herein, and are not intended to actively limit the scope of this application to any single invention or inventive concept (if multiple inventions or inventive concepts are actually disclosed). Thus, although specific aspects have been shown and described herein, any arrangement aimed at achieving the same purpose may replace the specific aspects shown. This disclosure is intended to cover any and all modifications or variations of the various aspects. Those skilled in the art will understand, upon reading the foregoing description, combinations of the foregoing aspects and other aspects not specifically described herein. The term “based on” as used herein and in the claims is intended to mean “at least partially based on,” such that features or elements not listed are also permitted.

[0190] The subject matter described herein can be embodied in systems, apparatus, methods, and / or articles according to desired configurations. The aspects set forth in the foregoing description do not represent all aspects consistent with the subject matter described herein. Rather, they are merely some instances of aspects consistent with the subject matter. Although some variations have been described in detail herein, other modifications or additions are possible. Specifically, additional features and / or variations may be provided in addition to the features set forth herein. For example, the aspects described herein may be for various combinations and sub-combinations of the disclosed features and / or combinations and sub-combinations of several other features disclosed herein. Furthermore, the logical flows depicted in the figures and / or described herein do not necessarily require the specific order or sequence shown to achieve the desired results. Other aspects are within the scope of the appended claims.

Claims

1. A method for producing one or more olefins, the method comprising: In at least one reactor, an input stream is contacted with one or more catalysts to form an output stream containing the one or more olefins, the input stream containing one or more bio-oils, and a first catalyst of the one or more catalysts containing a first zeolite and one or more first dopants; The at least one reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of about 1 to about 10 bar, and a duration of about 0.5 h. -1 approximately 10 hours -1 Heavy space velocity (WHSV).

2. The method according to claim 1, wherein the at least one reactor comprises two or more beds.

3. The method of claim 1, wherein the at least one reactor comprises one or more catalyst beds, and wherein the method further comprises impregnating at least one of the one or more catalyst beds with the first catalyst and the second catalyst.

4. The method of claim 2, wherein the two or more catalyst beds are stacked relative to each other within a single reactor.

5. The method according to claim 1, wherein the at least one reactor is a single-bed reactor.

6. The method according to claim 5, wherein the single-bed reactor is a fixed-bed reactor.

7. The method according to claim 5, wherein the single-bed reactor is a fluidized bed reactor.

8. The method according to claim 5, wherein the single-bed reactor is a moving-bed reactor.

9. The method according to any one of claims 1 to 8, wherein the one or more olefins comprise C2-C5 olefins.

10. The method of claim 9, wherein the one or more olefins comprises a primary first olefin, wherein the primary first olefin is propylene.

11. The method according to any one of claims 9 to 10, wherein the one or more olefins further comprise ethylene.

12. The method of claim 9, wherein the amount of one or more C2-C5 olefins present in the output stream is about 65% to about 85% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

13. The method of claim 12, wherein the amount of the one or more C2-C5 olefins present in the output stream is about 75% to about 80% by weight based on the hydrocarbon products in the output stream.

14. The method according to any one of claims 1 to 13, wherein the output stream further comprises one or more aromatic compounds.

15. The method of claim 14, wherein the amount of the one or more aromatic compounds present in the output stream is about 65% to about 80% by weight based on the output stream.

16. The method according to any one of claims 1 to 15, wherein the one or more dopants comprise boron, phosphorus, or a combination thereof.

17. The method of claim 16, wherein boron is present in the first catalyst in an amount of about 0.5% by weight to about 3% by weight.

18. The method of claim 16, wherein the amount of boron present in the first catalyst is at least about 2 by weight.

19. The method of claim 16, wherein phosphorus is present in the first catalyst in an amount of about 1% to about 5% by weight.

20. The method of claim 16, wherein phosphorus is present in the first catalyst in an amount of at least about 3 by weight.

21. The method according to any one of claims 1 to 20, wherein the first zeolite comprises ZSM-5 zeolite.

22. The method according to any one of claims 1 to 21, wherein the output stream further comprises saturated hydrocarbons, wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 20% by weight based on the output stream.

23. The method of claim 22, wherein the total amount of saturated hydrocarbons present in the output stream is from about 5% to about 15% by weight.

24. The method of claim 22, wherein the total amount of saturated hydrocarbons present in the output stream is from about 5% to about 10% by weight.

25. The method according to any one of claims 1 to 24, wherein the method further comprises: Before contacting the input stream with the at least one catalyst, the input stream is combined with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols.

26. The method of claim 25, wherein the one or more C1-C5 alcohols comprise ethanol.

27. The method according to any one of claims 25 to 26, wherein the one or more C1-C5 alcohols comprise methanol.

28. The method according to any one of claims 25 to 27, wherein the one or more C1-C5 alcohols comprise isobutanol.

29. The method according to any one of claims 25 to 28, wherein the one or more C1-C5 alcohols comprise a mixture of at least C4 alcohols, a mixture of C5 alcohols, or a mixture of C4 alcohols and C5 alcohols.

30. The method according to any one of claims 1 to 29, wherein the one or more bio-oils are produced by a fermentation process.

31. The method according to any one of claims 1 to 30, the method further comprising removing at least a portion of the C2 olefin from the output stream.

32. The method according to any one of claims 1 to 31, the method further comprising removing at least a portion of the C4 olefin from the output stream.

33. The method according to any one of claims 1 to 32, the method further comprising removing at least a portion of the C5 olefin from the output stream.

34. The method according to any one of claims 1 to 33, the method further comprising removing at least a portion of the aromatic compound from the output stream.

35. The method according to any one of claims 1 to 34, wherein the temperature is about 350°C to about 500°C.

36. The method of claim 35, wherein the temperature is about 450°C to about 500°C.

37. The method according to any one of claims 1 to 36, wherein the weight hourly space velocity is about 2.0 h. -1 To approximately 5.0h -1 .

38. The method of claim 37, wherein the weight hourly space velocity is about 3.0 h. -1 To approximately 5.0h -1 .

39. The method according to any one of claims 1 to 38, wherein the second catalyst in the one or more catalysts comprises a second zeolite and one or more second dopants.

40. The method of claim 39, wherein the first zeolite and the second zeolite are the same or different, and wherein one or more first dopants and one or more second dopants are the same or different.

41. The method according to any one of claims 1 to 38, wherein the second catalyst in one or more catalysts comprises a doped or undoped alumina catalyst.

42. The method of claim 41, wherein the doped alumina catalyst comprises zirconium, titanium, tungsten, silicon, fluorine, or any combination thereof in neutral or ionic form.

43. The method according to any one of claims 1 to 38, wherein the second catalyst in one or more catalysts comprises silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, silica-alumina catalyst, or any combination thereof.

44. A method for producing one or more olefins, the method comprising: In a single reactor, the input stream is contacted with at least a first catalyst and a second catalyst to form an output stream containing one or more olefins, the input stream containing one or more bio-oils, and the single reactor is subjected to a temperature of about 300°C to about 600°C, a gauge pressure of 1 to about 10 bar, and a time of about 0.5 h. -1 approximately 10 hours -1 The weight hourly space velocity (WHSV), The first catalyst comprises a first zeolite and one or more first dopants.

45. The method of claim 44, wherein the second catalyst comprises a second zeolite and one or more second dopants.

46. ​​The method of claim 45, wherein the first zeolite and the second zeolite are the same or different, and wherein one or more first dopants and one or more second dopants are the same or different.

47. The method of claim 44, wherein the second catalyst comprises a doped or undoped alumina catalyst.

48. The method of claim 47, wherein the doped alumina catalyst comprises zirconium, titanium, tungsten, silicon, fluorine, or any combination thereof in neutral or ionic form.

49. The method of claim 47, wherein the second catalyst comprises silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, aluminosilicate catalyst, or any combination thereof.

50. The method according to any one of claims 44 to 49, wherein the single reactor comprises one or more catalyst beds, and wherein the method further comprises impregnating at least one of the one or more catalyst beds with the first catalyst and the second catalyst.

51. The method of claim 50, wherein the one or more catalyst beds are stacked relative to each other within the single reactor.

52. The method according to any one of claims 44 to 51, wherein the method further comprises: One or more first dopants are added to the first catalyst before the input stream is brought into contact.

53. The method according to any one of claims 44 to 52, wherein the method further comprises: One or more second dopants are added to the second catalyst before the input stream is brought into contact.

54. The method according to any one of claims 44 to 53, wherein the one or more olefins comprise C2-C5 olefins.

55. The method of claim 54, wherein the C2-C5 olefin comprises a primary first olefin, wherein the primary first olefin is propylene.

56. The method according to any one of claims 54 to 55, wherein the C2-C5 olefin comprises ethylene.

57. The method according to any one of claims 54 to 56, wherein the C2-C5 olefin is present in the output stream in an amount of about 65% to about 85% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

58. The method of claim 57, wherein the C2-C5 olefin is present in the output stream in an amount of about 75% to about 80% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

59. The method according to any one of claims 44 to 58, wherein the output stream further comprises one or more aromatic compounds.

60. The method of claim 59, wherein the amount of the one or more aromatic compounds present in the output stream is about 65% to about 80% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

61. The method according to any one of claims 44 to 60, wherein the one or more first dopants comprise boron, phosphorus, or a combination thereof.

62. The method of claim 61, wherein boron is present in the first catalyst in an amount of about 0.5% by weight to about 3% by weight.

63. The method of claim 61, wherein the amount of boron present in the catalyst is at least about 2 by weight.

64. The method of claim 61, wherein phosphorus is present in the catalyst in an amount of about 1% to about 5% by weight.

65. The method of claim 61, wherein phosphorus is present in the catalyst in an amount of at least about 3 by weight.

66. The method according to any one of claims 44 to 58, wherein the first zeolite comprises ZSM-5 zeolite.

67. The method according to any one of claims 44 to 66, wherein the output stream further comprises saturated hydrocarbons, wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 20% by weight based on the output stream.

68. The method of claim 67, wherein the total amount of saturated hydrocarbons present in the output stream is from about 5% to about 15% by weight.

69. The method of claim 67, wherein the total amount of saturated hydrocarbons present in the output stream is from about 5% to about 10% by weight.

70. The method according to any one of claims 44 to 69, wherein the method further comprises: Before contacting the input stream with the first catalyst, the input stream is combined with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols.

71. The method of claim 70, wherein the one or more C1-C5 alcohols comprise ethanol.

72. The method according to any one of claims 70 to 71, wherein the one or more C1-C5 alcohols comprise methanol.

73. The method according to any one of claims 70 to 72, wherein the one or more C1-C5 alcohols comprise isobutanol.

74. The method according to any one of claims 70 to 73, wherein the one or more C1-C5 alcohols comprise a mixture of at least C4 alcohols, a mixture of at least C5 alcohols, or a mixture of at least C4 alcohols and C5 alcohols.

75. The method according to any one of claims 44 to 74, wherein one or more bio-oils are produced by a fermentation process.

76. The method according to any one of claims 44 to 75, the method further comprising removing at least a portion of the C2 olefin from the output stream.

77. The method according to any one of claims 44 to 76, the method further comprising removing at least a portion of the C4 olefin from the output stream.

78. The method according to any one of claims 44 to 77, the method further comprising removing at least a portion of the C5 olefin from the output stream.

79. The method according to any one of claims 44 to 78, the method further comprising removing at least a portion of the aromatic compound from the output stream.

80. The method according to any one of claims 44 to 79, wherein the temperature is about 350°C to about 500°C.

81. The method of claim 80, wherein the temperature is about 450°C to about 500°C.

82. The method according to any one of claims 44 to 81, wherein the weight hourly space velocity is about 2.0 h. -1 To approximately 5.0h -1 .

83. The method of claim 82, wherein the weight hourly space velocity is about 3.0 h. -1 To approximately 5.0h -1 .

84. A method for producing one or more olefins, the method comprising: The input stream is contacted in at least one reactor with at least a first catalyst and a second catalyst to form an output stream containing one or more olefins, the input stream containing one or more bio-oils, the first catalyst containing zeolite and two dopants, and the second catalyst containing doped or undoped alumina catalyst. The at least one reactor is subjected to a temperature of about 450°C to about 500°C, a gauge pressure of about 1 to about 2 bar, and a duration of about 2.0 h. -1 To approximately 5.0h -1 Heavy space velocity (WHSV).

85. The method of claim 84, wherein the first dopant of the two dopants comprises boron and the second dopant comprises phosphorus, wherein the boron is present in the first catalyst at an amount of at least about 2% by weight and the phosphorus is present in the catalyst at an amount of at least about 3% by weight.

86. The method according to any one of claims 84 to 85, wherein the zeolite comprises ZSM-5 zeolite.

87. The method according to any one of claims 84 to 86, wherein the doped alumina catalyst comprises silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, undoped zeolite, aluminosilicate catalyst, or any combination thereof.

88. The method according to any one of claims 84 to 87, wherein the method further comprises: Before contacting the input stream with the first and second catalysts, the input stream is combined with water, one or more C1-C5 alcohols, or water and one or more C1-C5 alcohols.

89. The systems, methods, and compositions described herein.

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