Systems and methods for catalytic conversion of c1-c5 alcohols to c2-c5 olefin mixtures

Abstract

The present invention provides methods for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins. In one exemplary aspect, the methods can be a single-stage process for direct conversion of C1-C5 alcohols to olefinic mixtures (e.g., C2-C5) using a catalyst comprising a zeolite doped with at least one or more metal dopants in a reactor. The present invention also provides systems for performing these methods.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 603,330, filed November 28, 2023, and U.S. Provisional Patent Application No. 63 / 627,521, filed January 31, 2024, each entitled “Systems and Processes for Catalytic Conversion of C1-C5 Alcohols to C2-C5 Olefin Mixtures”, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0002] The present invention relates to systems and methods for the catalytic conversion of C1-C5 alcohols, and more specifically, to catalytic methods leading to the direct conversion of bio-based C1-C5 alcohols into mixtures of alkenes (e.g., C2-C5). Background Technology

[0003] There is a growing demand for the use of biomass to partially replace petroleum resources in the synthesis of fuels. Therefore, the use of bioethanol as a base feedstock for fuel synthesis is of great interest. The fundamental reaction in the process of converting ethanol into a base feedstock for fuel is the dehydration of ethanol, followed by ethylene oligomerization.

[0004] In most ethanol dehydration methods, ethanol conversion is almost complete. Improving C2-selectivity while maintaining high ethanol conversion is important for increasing method efficiency and saving on costly downstream separation / purification steps. It is well known that dehydration readily occurs on acidic solids at temperatures above 300°C. The reaction products are primarily water and ethylene, with ethylene obtained with selectivity up to 96+%. The most commonly used catalysts are high-purity γ-alumina, silica-alumina, unprocessed zeolites (e.g., ZSM-5), or zeolites modified by steam heating. Furthermore, the presence of water in the ethanol feed can limit catalyst surface deactivation.

[0005] Oligopolymerization of ethylene requires high pressure, typically between 2 and 4 MPa, but lower temperatures, usually between 20°C and 200°C. The catalysts used are, in most cases, transition metals deposited on silica-alumina supports, zeolites (ZSM-5), or mesoporous solids (MCM-41). However, direct oligopolymerization of ethylene results in a relatively small amount (~40% of the highest reported level) of C. 10+ Or diesel fraction. Alternatively, ethylene can be oligomerized into C... 8+ Olefins can be produced via a two-stage process. The first stage involves dimerizing purified ethylene streams into butene, followed by a second stage that oligomerizes the butene into C4.8+ Olefins, after hydrogenation, provide a basic feedstock for fuels.

[0006] Therefore, there is still a need for improved, efficient, and cost-effective catalytic methods that lead to the direct conversion of bio-based alcohols into mixtures of alkenes. Summary of the Invention

[0007] A particular aspect of the subject matter of this invention relates to systems and methods for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins.

[0008] This invention discloses an exemplary method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins. In one exemplary aspect, the method includes contacting an input stream with a catalyst in a reactor to form an output stream, the input stream comprising the one or more C1-C5 linear or branched alcohols, and the output stream comprising the one or more C2-C5 olefins. The catalyst comprises a zeolite and one or more metal dopants, wherein the one or more metal dopants include one or more first metal dopants, one or more second metal dopants, or both. The reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 0 to about 30 bar, and for about 0.25 h. -1 approximately 35 hours -1 Heavy space velocity (WHSV).

[0009] In some aspects, the method may include adding one or more metal dopants to the catalyst before contacting the input stream.

[0010] In some aspects, the 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.

[0011] In some aspects, the amount of the one or more C2-C5 olefins in the output stream may not exceed about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream. In a particular aspect, the amount of the one or more C2-C5 olefins in the output stream may be from about 70% by weight to about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream. In other aspects, the amount of the one or more C2-C5 olefins in the output stream may be from about 85% by weight to about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream.

[0012] In some aspects, the catalyst may further comprise one or more non-metallic dopants. In a particular aspect, the one or more non-metallic dopants may comprise boron, phosphorus, or combinations thereof. In one aspect, the amount of boron present in the catalyst may be from about 0.01 wt% to about 10 wt%. In another aspect, the amount of boron present in the catalyst may be at least 0.05 wt%. In one aspect, the amount of phosphorus present in the catalyst may be from about 0.1 wt% to about 7 wt%. In another aspect, the amount of phosphorus present in the catalyst may be at least 1.5 wt%.

[0013] In some respects, the zeolite may include ZSM-5 zeolite.

[0014] In some respects, the zeolite may include MFI zeolite, BEA zeolite, FER zeolite, CHA zeolite, FAU zeolite, or any combination thereof.

[0015] In some aspects, the output stream may include saturated hydrocarbons, wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 25% 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 3% by weight to about 25% by weight. In other aspects, the total amount of saturated hydrocarbons present in the output stream may be from about 3% by weight to about 15% by weight.

[0016] In some aspects, the amount of the one or more first metal dopants in the catalyst may not exceed about 2% by weight. In a particular aspect, the amount of the one or more first metal dopants in the catalyst may be from about 0.01% by weight to about 2% by weight. In other aspects, the amount of the one or more first metal dopants in the catalyst may be from about 0.01% by weight to about 0.2% by weight. In one aspect, the amount of the one or more first metal dopants in the catalyst may be at least about 0.05% by weight.

[0017] In some aspects, the amount of the one or more second metal dopants in the catalyst may not exceed about 2% by weight. In a particular aspect, the amount of the one or more second metal dopants in the catalyst may be from about 0.01% by weight to about 2% by weight. In other aspects, the amount of the one or more second metal dopants in the catalyst may be from about 0.01% by weight to about 0.2% by weight. In one aspect, the amount of the one or more second metal dopants in the catalyst may be at least about 0.05% by weight.

[0018] In some respects, the C1-C5 linear or branched alcohols may be biologically based and produced through fermentation processes. In other respects, the C1-C5 linear or branched alcohols may not be derived from petroleum.

[0019] In some aspects, the method may include removing at least a portion of the C2 olefins from the output stream.

[0020] In some aspects, the method may include removing at least a portion of the C4 olefins from the output stream.

[0021] In some aspects, the method may include removing at least a portion of the C5 olefins from the output stream.

[0022] In some aspects, the temperature can be from about 550°C to about 600°C. In other aspects, the temperature can be from about 350°C to about 550°C.

[0023] In some respects, the WHSV can be approximately 0.5h. -1 From approximately 1.0h -1 In other respects, the WHSV can be approximately 2.0h. -1 To approximately 5.0h -1 .

[0024] In some aspects, the one or more first metal dopants may include sodium, potassium, lithium, or any combination thereof. In one aspect, the one or more first metal dopants may be sodium.

[0025] In some respects, the one or more second metal dopants may include magnesium, calcium, strontium, barium, or any combination thereof.

[0026] In some aspects, the catalyst may include one or more other dopants. The other dopants may include sulfur, scandium, yttrium, selenium, iron, manganese, tellurium, or any combination thereof. In a particular aspect, the amount of the one or more other dopants in the catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more other dopants in the catalyst may be from about 0.05% by weight to about 1% by weight. In one aspect, the amount of the one or more other dopants in the catalyst may be from about 0.05% by weight to about 0.5% by weight. In another aspect, the amount of the one or more other dopants in the catalyst may be at least about 0.25% by weight.

[0027] In another exemplary method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 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, the input stream comprising the one or more C1-C5 linear or branched alcohols. The output stream comprises the one or more C2-C5 olefins. The single reactor is operated at a temperature of about 350°C to about 750°C, a gauge pressure of 0 to about 30 bar, and for about 0.5 h. -1 To approximately 35.0h -1 The weight space velocity (WHSV). The second catalyst comprises zeolite and one or more metal dopants, wherein the one or more metal dopants include one or more first metal dopants, one or more second metal dopants, or both.

[0028] In some aspects, the first catalyst may comprise a doped or undoped alumina catalyst. In one aspect, the doped alumina catalyst may comprise zirconium, titanium, tungsten, silicon, or any combination thereof in neutral or ionic form.

[0029] In some aspects, the single reactor may include one or more catalyst beds, and the method may include impregnating at least one of the one or more catalyst beds with the first catalyst and the second catalyst. In one aspect, two of the one or more catalyst beds may be stacked relative to each other within the single reactor.

[0030] In some aspects, the single reactor may include two or more catalyst beds, wherein the method may include impregnating a first catalyst bed with at least a first catalyst and impregnating a second catalyst bed with at least a second catalyst. In one aspect, the two or more catalyst beds may be stacked relative to each other within the single reactor. In a particular aspect, contacting the input stream with at least a first catalyst and a second catalyst may include contacting the input stream with the first catalyst bed before contacting the second catalyst bed. In one aspect, the method may include introducing one or more additional input streams downstream of the first catalyst bed into the reactor.

[0031] In some respects, the first catalyst bed may not need to be impregnated with the second catalyst.

[0032] In some respects, the second catalyst bed may not need to be impregnated with the first catalyst.

[0033] In some aspects, the first catalyst may include 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.

[0034] In some aspects, the first catalyst may include undoped γ-alumina, zirconate-treated γ-alumina, or both.

[0035] In some aspects, the method may include adding the one or more metal dopants to the second catalyst before contacting the input stream.

[0036] In some aspects, the amount of the one or more C2-C5 olefins in the output stream may not exceed about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream. In a particular aspect, the amount of the one or more C2-C5 olefins in the output stream may be from about 70% by weight to about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream. In other aspects, the amount of the one or more C2-C5 olefins in the output stream may be from about 85% by weight to about 98% by weight of the total amount of unsaturated hydrocarbons present in the output stream.

[0037] In some aspects, the second catalyst may include one or more non-metallic dopants. The one or more non-metallic dopants may include boron, phosphorus, or combinations thereof. In a particular aspect, the amount of boron present in the catalyst may be from about 0.01 wt% to about 10 wt%. In another aspect, the amount of boron present in the catalyst may be at least 0.05 wt%. In a particular aspect, the amount of phosphorus present in the catalyst may be from about 0.1 wt% to about 7 wt%. In another aspect, the amount of phosphorus present in the catalyst may be at least 1.5 wt%.

[0038] In some respects, the zeolite may include ZSM-5 zeolite.

[0039] In some respects, the zeolite may include MFI zeolite, BEA zeolite, FER zeolite, CHA zeolite, FAU zeolite, or any combination thereof.

[0040] In some aspects, the output stream may include saturated hydrocarbons, wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 25% by weight based on the output stream. In a particular aspect, the total amount of saturated hydrocarbons present in the output stream is about 3% by weight to about 25% by weight. In other aspects, the total amount of saturated hydrocarbons present in the output stream is about 3% by weight to about 15% by weight.

[0041] In some aspects, the amount of the one or more first metal dopants in the second catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more first metal dopants in the second catalyst may be from about 0.01% by weight to about 2% by weight. In one aspect, the amount of the one or more first metal dopants in the second catalyst may be from about 0.01% by weight to about 0.2% by weight. In another aspect, the amount of the one or more first metal dopants in the second catalyst may be at least about 0.05% by weight.

[0042] In some aspects, the amount of the one or more second metal dopants in the second catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more second metal dopants in the second catalyst may be from about 0.01% by weight to about 2% by weight. In one aspect, the amount of the one or more second metal dopants in the second catalyst may be from about 0.01% by weight to about 0.2% by weight. In another aspect, the amount of the one or more second metal dopants in the second catalyst may be at least about 0.05% by weight.

[0043] In some respects, the C1-C5 linear or branched alcohols may be biologically based and produced through fermentation processes. In other respects, the C1-C5 linear or branched alcohols may not be derived from petroleum.

[0044] In some aspects, the method may include removing at least a portion of the C2 olefins from the output stream.

[0045] In some aspects, the method may include removing at least a portion of the C4 olefins from the output stream.

[0046] In some aspects, the method may include removing at least a portion of the C5 olefins from the output stream.

[0047] In some aspects, the temperature can be from about 550°C to about 600°C. In other aspects, the temperature can be from about 350°C to about 550°C.

[0048] In some respects, the WHSV can be approximately 0.5h. -1 From approximately 1.0h -1 In other respects, the WHSV can be approximately 2.0h. -1 To approximately 5.0h -1 .

[0049] In some aspects, the one or more first metal dopants may include sodium, potassium, lithium, or any combination thereof. In one aspect, the one or more first metal dopants may be sodium.

[0050] In some respects, the one or more second metal dopants may include magnesium, calcium, strontium, barium, or any combination thereof.

[0051] In some aspects, the second catalyst may include one or more other dopants. The other dopants may include sulfur, scandium, yttrium, selenium, iron, manganese, tellurium, or any combination thereof. In a particular aspect, the amount of the one or more other dopants in the second catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more other dopants in the second catalyst may be from about 0.05% by weight to about 1% by weight. In one aspect, the amount of the one or more other dopants in the second catalyst may be from about 0.05% by weight to about 0.5% by weight. In another aspect, the amount of the one or more other dopants in the second catalyst may be at least about 0.25% by weight.

[0052] 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 subject matter of the invention disclosed herein. Specifically, all combinations of the claimed subject matter of this disclosure are considered part of the subject matter of the invention 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

[0053] 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 description, help to explain some principles related to the disclosed aspects. In the drawings: Figure 1 An exemplary method concept for a reactor system for on-purpose propylene configuration is shown, the reactor system having closed-loop recycling of C2 olefins, C4 olefins and C5 olefins, consistent with the implementation of the subject matter of the present invention.

[0054] Where feasible, similar reference figures represent similar structures, features, or elements. Detailed Implementation

[0055] In the following description, specific details are set forth in order to provide a thorough understanding of the 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 variations thereof (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.

[0056] 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."

[0057] 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.

[0058] "Oxygen-containing compounds" are compounds whose chemical structure includes oxygen. Examples of oxygen-containing compounds include, but are not limited to, water, alcohols, esters, and ethers.

[0059] "WHSV (Weight Time Space Velocity)" refers to 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 a quantity of less than 2%. In some respects, trace or trace level may refer to a level of 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] It should be understood that the embodiments and aspects described herein are for illustrative purposes only, and various modifications or variations thereof will be suggested by those skilled in the art and will be included within the spirit and scope of this application and the appended claims. All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety for all purposes.

[0067] The aspects of the subject matter disclosed herein improve upon earlier conversion methods by specifically providing a method using a catalyst system doped with Group 1A metals (e.g., sodium, potassium, or lithium) and / or Group 2A metals (e.g., magnesium, calcium, strontium, or barium) to convert C1-C5 linear or branched alcohols into C2-C7 olefins with low saturated hydrocarbon content at competitive cost and in high yields. According to this disclosure, the method for the direct conversion of bio-based C1-C5 alcohols into olefin mixtures (e.g., C2-C5) with low saturated hydrocarbon content 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.

[0068] One or more C1-C5 linear or branched alcohols may include one or more C1-C5 linear alcohols or one or more C1-C5 branched alcohols, or both. In some aspects, the one or more linear or branched alcohols include methanol, ethanol, or combinations thereof. In certain aspects, the one or more linear or branched alcohols do not include methanol.

[0069] In some respects, the C1-C5 linear or branched alcohols may be biologically based and produced through fermentation processes. In other respects, the C1-C5 linear or branched alcohols are not derived from petroleum.

[0070] 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, or a moving bed). In other aspects, the methods described herein can be carried out in a single stacked-bed reactor. For example, in a particular aspect, alcohols (e.g., methanol or ethanol) 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 obtain a cut fraction for gasoline, jet fuel, or diesel fuel, 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.

[0071] Systems and methods for the catalytic conversion of C1-C5 alcohols are provided. Typically, the catalytic methods according to this disclosure involve alcohol dehydration, followed by skeletal carbon construction and subsequent “cracking” to produce low molecular weight olefins (e.g., C2-C5) in high yields. Furthermore, such catalytic methods can produce low contents of saturated hydrocarbons (e.g., no more than 20% by weight, based on the output stream, for a given conversion of one or more alcohols to their respective olefins and such respective olefins to other hydrocarbons). In other words, for example, adding one or more Group 1A and / or Group 2A metal dopants to a BP-doped zeolite results in a relatively low content of saturated hydrocarbons under the same conversion conditions compared to BP-doped zeolite without said one or more Group 1A and / or Group 2A metal dopants (e.g., 10% vs. 15% saturated hydrocarbon content, respectively, in the case where one or more alcohols are completely or nearly completely converted to their respective olefins and 60% of such respective olefins are converted to other hydrocarbons). In this single-stage process, the catalyst mixture can produce a C2-C5 olefin mixture to provide low molecular weight olefins in yields with good carbon balance, defined as the ratio of the number of carbon moles fed into the system as alcohol to the number of carbon moles added to the C2-C5 olefin mixture leaving the system. Furthermore, the use of a recycle stream of specific olefins (e.g., C2-C5) advantageously maximizes the ability to purposefully form desired olefins (e.g., propylene, butene, or mixtures thereof). In some aspects, the olefin mixture is 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.

[0072] Typically, most C2-C5 alcohols are dehydrated in a single unit operation at 300°C–500°C in the presence of a dehydration catalyst, resulting in the corresponding C2-C5 olefins and water. The water is removed, and the C2-C5 olefins are further processed / purified to remove unreacted C2-C5 alcohols and / or impurities before conversion to chemicals and / or fuels. The classic method for converting ethanol (C2 alcohols) to chemicals and / or fuels utilizes discrete unit operations to achieve i) dehydration to ethylene, ii) ethylene purification followed by dimerization to butene, iii) optionally, olefin metathesis or cracking to propylene, iv) butene oligomerization to unsaturated jet fuel precursors and / or diesel fuel precursors, or v) direct oligomerization of ethylene to unsaturated jet fuel precursors and / or diesel fuel precursors. Similarly, methods for converting C3, C4, or C5 alcohols into chemicals and / or fuels utilize discrete unit operations to accomplish i) dehydration to the corresponding olefins, ii) olefin purification to remove oxygen-containing compounds and / or unreacted alcohols, iv) optionally, olefin metathesis or cracking to adjust the olefin distribution, and / or iii) oligomerization to unsaturated jet fuel precursors and / or diesel fuel precursors. In contrast to methanol, industrial methods convert methanol, primarily derived from coal, into olefins in a single step with olefin recycling via porous catalysts (e.g., SAPO-34, etc.).

[0073] Due to the high temperatures required for complete dehydration (e.g., approximately 300°C to approximately 500°C), the presence of large amounts of water, and when C 2+ The extreme endothermic reaction encountered during alcohol dehydration presents a challenge to the concept of simultaneously dehydrating, oligomerizing, and cracking C1-C5 alcohols or mixtures thereof in a single reactor. Implementing a single-unit operation capable of simultaneously dehydrating, oligomerizing, and cracking olefins derived from the dehydration of C1-C5 alcohols requires catalysts that can withstand high temperatures and large amounts of water and other oxygen-containing substances.

[0074] To address these challenges and to define the methods for converting C1-C5 alcohols into viable feedstocks for high-yield fuel production, methods have been developed that enable the high-yield conversion of C1-C5 alcohols into a mixture of C2-C5 olefins via a single unit operation (e.g., in a single reactor or a single reactor section, without intermediate separation). This mixture of C2-C5 olefins 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, lower capital investment, less energy consumption, and increased productivity.

[0075] Therefore, according to this disclosure, the conversion of methanol and / or mixtures of methanol with C2-C5 alcohols is carried out in a similar manner to convert to a mixture of C2-C5 olefins in high yield and carbon balance. An exemplary single reaction step includes i) dehydration, ii) oligomerization to C2-C5 olefins. 4+ iii) skeletal rearrangement, and iv) cracking to produce mainly propylene and C 4+ Olefins and small amounts of saturated hydrocarbons. Thus, a stream of vaporized methanol and / or ethanol is passed through a single fixed catalyst bed at approximately 300°C to approximately 450°C to produce a C2-C5 olefin mixture, the single fixed catalyst bed comprising a physical mixture optionally comprising a first portion in combination with a second portion, the first portion being a first portion of silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, and the second portion being a second portion of doped zeolite (e.g., zeolite doped with boron, phosphorus, and Group 1A metals (e.g., sodium, potassium, or lithium) and / or Group 2A metals (e.g., magnesium, calcium, strontium, or barium), or zeolite doped with Group 1A metals (e.g., sodium, potassium, or lithium) and / or Group 2A metals (e.g., magnesium, calcium, strontium, or barium)). The C2-C5 olefin mixture can be separated for sale, or oligomerized "as is" as a primary jet fuel and / or diesel fuel after the removal of condensate. This catalyst combination in a single fixed-bed reactor accomplished i) dehydration, ii) oligomerization to C 4+ Olefins, iii) skeletal rearrangement, and iv) cracking lead to longer catalyst time on stream (ToS), improved hydrothermal stability, improved selectivity for olefins, and fewer saturated hydrocarbons and aromatics.

[0076] Furthermore, the systems and methods of the present invention may optionally include, in a closed-loop process configuration, the recycling of one or more specific olefin fractions (e.g., C2+C4+C5 or C2+C5, etc.) while co-feeding C1-C5 alcohols. This can lead to maximization of the desired yield of the selected olefins. For example, by using the systems and methods of the present invention provided herein, the recycling of the C2+C4+C5 olefin fraction in combination with co-feeding C1-C5 alcohols unexpectedly results in a desired propylene carbon yield that may exceed 80% by weight. Selective recycling of the C2+C5 olefin fraction can result in a combined carbon yield of the desired propylene and butene that exceeds 80% by weight. Furthermore, the recycling of the C4+C5 olefin fraction can result in a combined carbon yield of the desired ethylene and propylene that exceeds 80% by weight. Exemplary single-step reactions may include i) in-situ dehydration, ii) oligomerization to C 3+ iii) skeletal rearrangement, and iv) cracking into C2-C5 alkenes and the formation of small amounts of C 5+Olefins and aromatic compounds. Therefore, the recycled olefin fraction can achieve the desired olefin production for chemical and / or fuel production.

[0077] Unlike the conversion of ethylene, the conversion of propylene and other higher molecular weight olefins (C60-C50) involves... 4+ Oligopolymerization can be readily achieved on a wide range of catalysts, both zeolite and non-zeolite. This disclosure enables the conversion of C1-C5 alcohols into olefin mixtures primarily comprising C2-C5 olefins and low contents of saturated hydrocarbons in a single-stage reactor configuration or a two-stage reactor configuration in series. This provides a pathway to an economical method for converting C1-C5 alcohols into base feedstocks for chemicals and / or fuels. The method according to the invention includes a scheme comprising the “single”-stage conversion of a biomass-derived aqueous C1-C5 bioethanol feedstock into a predominantly C2-C5 olefin mixture, which can be separated to isolate key low-molecular-weight olefins used as chemical building blocks throughout the industry, or can be readily oligopolymerized in high yields to C2-C5 olefins. 10+ Hydrocarbon or diesel fractions. The use of two-stage or single-stage configurations of specific catalytic systems allows for the minimization of aromatic compound production, thereby maximizing the production of middle distillates. This constitutes an asset for ethanol refineries and is also an advantage from a sustainability perspective.

[0078] In cases where C1-C5 alcohols or mixtures thereof are in a single reactor configuration, converting C1-C5 alcohols to desired fuel products or fuel product precursors (e.g., C2-C5 olefins) can reduce processing costs. In one aspect, a method is provided for converting one or more linear or branched C1-C5 alcohols to one or more C2-C5 olefins. In some aspects, the method comprises a single catalyst system (e.g., a doped zeolite), while in other aspects, the method comprises two or more catalyst systems (e.g., a dehydration catalyst and a doped zeolite).

[0079] In one aspect, the method may include: contacting an input stream with a catalyst in a reactor to form an output stream, the input stream comprising one or more C1-C5 linear or branched alcohols, the output stream having one or more C2-C5 olefins, wherein the reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 0 to about 30 bar, and for about 0.25 h. -1 approximately 35 hours -1 The heavy space velocity (WHSV) is measured. The catalyst comprises zeolite and one or more metal dopants, wherein the one or more metal dopants include one or more first metal dopants, one or more second metal dopants, or both. In a particular aspect, the method may further include adding the one or more metal dopants to the catalyst prior to contacting the input stream.

[0080] The production of zeolite types A, X, and Y is typically carried out by mixing and heating sodium aluminate and sodium silicate solutions, thereby forming a sodium aluminosilicate gel. This silica and alumina-containing compound enters the liquid phase, from which the zeolite crystallizes. Thus, the crude crystalline zeolite containing the primary alkali metal can subsequently be converted to an intermediate ammonium form and then calcined at 500-550°C to remove the ammonium counterion, thus yielding its final hydrogen form. In the case of Group 1A metals (e.g., Na, K, Li), the residual alkali metal cation content from the synthesis of the primary zeolite (as previously stated) should be in an amount that will not effectively deactivate the catalyst (e.g., less than or equal to 500 ppm). Commercially produced hydrogen-form zeolites (e.g., Clariant, Zeolyst, etc.) are typically used in cracking, isomerization, and alcohol-to-olefin chemistry, and have a residual sodium content of less than or equal to 0.05% by weight (e.g., 500 ppm). Higher residual sodium content (e.g., >2500 ppm) and other Group 1A metals (e.g., Li, K, etc.) can severely deactivate the zeolite catalysts, making them unacceptable for chemistry requiring highly acidic catalytic activity.

[0081] To this end, the inventors unexpectedly discovered that subsequent impregnation of doped zeolites (e.g., doped with boron and phosphorus) with low amounts of Group 1A metals (e.g., Na < 2000 ppm, K < 2000 ppm, and / or Li < 1000 ppm) resulted in improved C1-C5 alcohol-to-olefin selectivity, as observed by the following: lower (~15%) aliphatic (e.g., saturated hydrocarbon) and aromatic compounds compared to doped zeolites without subsequent Group 1A or Group 2A impregnation. The ability to minimize the formation of aliphatic and aromatic compounds, thereby achieving improved olefin content from alcohols, simplifies downstream separation of enriched olefin streams into individual C2-C5 olefins, or allows enriched C2-C5 olefin streams to be readily oligomerized into fuels in a single unit operation.

[0082] 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 group having a Si / Al ratio greater than 10, or dealuminated crystalline silicates of the ZSM-5 (MFI framework or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON group having a Si / Al ratio greater than 10, or molecular sieves of the silica-alumina phosphate type of the AEL group.

[0083] Zeolites doped with one or more metal dopants are also referred to herein as metal-doped zeolites. Non-limiting examples of one or more metal dopants (e.g., Group 1A and / or Group 2A 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 particular aspects, 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.

[0084] 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 lithium.

[0085] In some aspects, the metal-doped zeolite may be further doped with one or more non-metallic dopants. Non-limiting examples of non-metallic dopants include boron, phosphorus, or any combination thereof. In one aspect, the one or more non-metallic dopants include only boron and phosphorus.

[0086] In certain aspects, the catalyst may comprise a zeolite doped with one or more first metal dopants and one or more nonmetal dopants. In some aspects, the catalyst may comprise a zeolite doped with sodium, lithium, potassium, or any combination thereof, and boron, phosphorus, or both. 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.

[0087] Boron and phosphorus can be present in the catalyst in various amounts. In some aspects, the amount of boron in the catalyst can be from about 0.01 wt% to about 10 wt%, including all sub-ranges therein. In a particular aspect, the amount of boron in the catalyst can be from about 0.05 wt% to about 5 wt%, including all sub-ranges therein. In a particular aspect, the amount of boron in the catalyst can be from about 0.05 wt% to about 3 wt%, including all sub-ranges therein. In one aspect, the amount of boron in the catalyst can be at least 0.05 wt%. In some aspects, the amount of phosphorus in the catalyst can be from about 0.1 wt% to about 7 wt%, including all sub-ranges therein. In a particular aspect, the amount of phosphorus in the catalyst can be from about 1.5 wt% to about 6 wt%, including all sub-ranges therein. In one aspect, the amount of phosphorus in the catalyst can be at least 3 wt%. In a particular aspect, the amount of boron in the catalyst can be from about 0.5 wt% to about 3 wt%, and the amount of phosphorus in the catalyst can be from about 2 wt% to 6 wt%.

[0088] In some aspects, the metal-doped zeolite, with or without a non-metallic dopant, may be further doped with additional dopant, also referred to as other dopant. In one aspect, the zeolite is doped with one or more metallic dopant, one or more non-metallic dopant, and one or more additional dopant. In another aspect, the zeolite is doped with one or more metallic dopant and one or more other dopant. Non-limiting examples of additional dopant include iron, tellurium, selenium, cobalt, nickel, lanthanum, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0089] In another aspect, such as in the case of C1-C5 alcohols or mixtures thereof in a single reactor configuration, two or more catalysts may be implemented for converting C1-C5 alcohols into desired fuel products or fuel product precursors (e.g., C2-C5 olefins). In some aspects, the method includes contacting an input stream with at least a first and a second catalyst in a single reactor to form an output stream, the input stream comprising one or more C1-C5 linear or branched alcohols, the output stream having one or more C2-C5 olefins, wherein the single reactor is operated at a temperature of about 300°C to about 750°C, a gauge pressure of 0 to about 30 bar, and for about 0.5 h. -1 To approximately 35.0h -1The second catalyst comprises a zeolite and one or more metal dopants, wherein the one or more metal dopants include one or more first metal dopants, one or more second metal 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 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.

[0090] Exemplary catalyst combinations that can be used in two or more catalyst systems and methods of the invention described herein include, for example, a catalyst mixture physically mixed in a single-bed reactor for C2-C5 olefin formation, said catalyst mixture may include a portion (e.g., a first catalyst or dehydration catalyst) of silicate-modified γ-alumina, zirconate-modified γ-alumina, titanate-modified γ-alumina, niobium-modified γ-alumina, or fluorinated γ-alumina, undoped γ-alumina, zeolite (undoped or doped), silica-alumina catalyst, solid acid, or any combination thereof. A second portion of said catalyst mixture (e.g., a second catalyst) may include metal-doped zeolite. In some aspects, the first catalyst may include undoped γ-alumina, zirconate-modified γ-alumina, or both, and the second catalyst may include zeolite doped with sodium, potassium, or lithium, or any combination thereof. In some aspects, the first catalyst may include undoped γ-alumina, zirconate-modified γ-alumina, or both, and the second catalyst may include zeolite doped with magnesium, calcium, strontium, barium, or any combination thereof. In one aspect, the first catalyst may include a doped or undoped alumina catalyst.

[0091] 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 group having a Si / Al ratio greater than 10, or dealuminated crystalline silicates of the ZSM-5 (MFI framework or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON group having a Si / Al ratio greater than 10, or molecular sieves of the silica-alumina phosphate type of the AEL group.

[0092] Non-limiting examples of one or more metal dopants (e.g., Group 1A and / or Group 2A 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.

[0093] 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 lithium.

[0094] In certain aspects, the catalyst may comprise a zeolite doped with one or more metal dopants and one or more non-metal dopants. In some aspects, the catalyst may comprise a zeolite doped with sodium, lithium, potassium, or any combination thereof; and boron, phosphorus, or both. 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.

[0095] Boron and phosphorus can be present in the catalyst in various amounts. In some aspects, the amount of boron in the catalyst can be from about 0.01 wt% to about 10 wt%, including all sub-ranges therein. In a particular aspect, the amount of boron in the catalyst can be from about 0.05 wt% to about 5 wt%, including all sub-ranges therein. In a particular aspect, the amount of boron in the catalyst can be from about 0.05 wt% to about 3 wt%, including all sub-ranges therein. In one aspect, the amount of boron in the catalyst can be at least 0.05 wt%. In some aspects, the amount of phosphorus in the catalyst can be from about 0.1 wt% to about 7 wt%, including all sub-ranges therein. In a particular aspect, the amount of phosphorus in the catalyst can be from about 1.5 wt% to about 6 wt%, including all sub-ranges therein. In one aspect, the amount of phosphorus in the catalyst can be at least 3 wt%. In a particular aspect, the amount of boron in the catalyst can be from about 0.5 wt% to about 3 wt%, and the amount of phosphorus in the catalyst can be from about 2 wt% to 6 wt%.

[0096] In some aspects, the metal-doped zeolite, with or without a non-metallic dopant, may be further doped with additional dopant, also referred to as other dopant. In one aspect, the zeolite is doped with one or more metallic dopant, one or more non-metallic dopant, and one or more additional dopant. In another aspect, the zeolite is doped with one or more metallic dopant and one or more other dopant. Non-limiting examples of additional dopant include iron, tellurium, selenium, cobalt, nickel, lanthanum, chromium, zirconium, ruthenium, molybdenum, iridium, tungsten, copper, manganese, vanadium, zinc, titanium, rhodium, rhenium, gallium, palladium, silver, indium, or any combination thereof.

[0097] 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 about 0.05 mm to about 2.5 mm, including all subranges in between. In one aspect, the one or more catalysts, either particulate or extruded, may have a particle size of about 0.4 to about 2.0 mm.

[0098] In a particular aspect, the method includes: contacting an input stream with at least a first catalyst and a second catalyst in a single-bed reactor to form an output stream, the input stream comprising one or more C1-C5 linear or branched alcohols, and the output stream comprising one or more C2-C5 olefins, wherein the single-bed reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 0 to about 30 bar, and a weight hourly space velocity (WHSV) of about 0.5 to about 35.0, wherein the first catalyst comprises a doped or undoped alumina catalyst comprising one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si) in neutral or ionic form; and the second catalyst comprises a metal-doped zeolite catalyst. Furthermore, the two catalysts can be mixed together in the single-bed reactor. We unexpectedly found that this dual-catalyst system provides a longer run time (ToS) between catalyst regenerations due to the ability of the alumina catalyst component to maintain near-quantitative alcohol conversion compared to the zeolite component, as the alumina component is far less prone to deactivation due to coke formation. In the single-catalyst system, unconverted alcohols were detected in the reactor effluent within 100 hours of ToS, compared to the dual-catalyst system which has been shown to detect trace levels of ethanol in the reactor effluent over >800 hours of ToS.

[0099] In other respects, a method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins may include: contacting an input stream with a first catalyst in a stacked bed reactor to form a first mixture comprising the one or more C2-C5 olefins, the input stream comprising the one or more C1-C5 linear or branched alcohols. The stacked bed reactor is operated at a temperature of about 350°C to about 550°C, a gauge pressure of 0 to about 30 bar, and a weight hourly space velocity (WHSV) of about 1.0 to about 2.0, and the first catalyst comprises a doped or undoped alumina catalyst comprising one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si) in neutral or ionic form. The method further comprises contacting the first mixture with at least a second catalyst, wherein the second catalyst comprises a metal-doped zeolite catalyst to produce the output stream comprising the one or more C2-C5 olefins. 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.

[0100] Regarding the output stream, the presence of the C2-C5 olefins may be at least 80% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. The presence of the C2-C5 olefins may be about 70% to about 99% by weight, about 70% to about 98% by weight, or about 85% to about 98% by weight, including all subranges within this range, based on the total amount of unsaturated hydrocarbons present in the output stream. The presence of the C2-C5 olefins may be at least 85% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. The presence of the C2-C5 olefins may be at least 90% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. The presence of the C2-C5 olefins may be at least 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream. Further regarding the output stream, the methods disclosed herein may further include removing at least a portion of the C2 olefins 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.

[0101] In some aspects, the one or more unsaturated hydrocarbons present in the output stream may comprise one or more low-carbon-intensity unsaturated hydrocarbons. In one aspect, all of the said unsaturated hydrocarbons may be low-carbon-intensity unsaturated hydrocarbons. As used herein, "low-carbon intensity" when used to modify unsaturated hydrocarbons (e.g., one or more unsaturated hydrocarbons) means that the carbon intensity is at least about 50% lower than that of its petroleum equivalent.

[0102] 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 that of its petroleum equivalent.

[0103] 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.

[0104] 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 25% by weight. In another aspect, the total amount of saturated hydrocarbons present in the output stream does not exceed about 20% by weight. In other aspects, the total amount of saturated hydrocarbons present in the output stream can be from about 3% by weight to about 25% by weight, or from about 3% by weight to about 15% by weight, including all subranges in between.

[0105] Regarding the reactor, the reactor can operate at temperatures from about 300°C to about 600°C, including all sub-ranges therebetween. The reactor can also operate at temperatures from about 350°C to about 550°C, including all sub-ranges therebetween. The reactor can operate for about 0.25 hours. -1 To approximately 35.0h -1 The reactor operates at WHSV, including all sub-ranges in between. The reactor can operate for approximately 0.25 hours. -1 Up to 10h -1 or about 0.5h -1 To approximately 5.0h -1 Approximately 5 hours -1 From approximately 10.0h -1 The reactor operates under WHSV conditions, 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.

[0106] This disclosure also describes methods for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system. In other words, these disclosed methods use a system with only one catalyst. The use of a single catalyst system may be desirable in various situations, such as when the output stream can accept some portion of unconverted C1-C5 linear or branched alcohols 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. In some aspects, the one or more C1-C5 linear or branched alcohols may be one or more C1-C5 linear or branched monohydric alcohols.

[0107] In the case of C1-C5 alcohols or mixtures thereof, converting C1-C5 alcohols to desired fuel products or fuel product precursors (e.g., C2-C5 olefins) using a single catalyst system can, for example, reduce processing costs and simplify and optimize the conversion method, which would be impossible with a dual catalyst system. In these methods, the single catalyst system comprises only one catalyst, such as a zeolite. In some aspects, the single catalyst is not a doped or undoped alumina catalyst. In particular, the zeolite may be a zeolite doped with one or more metal dopants (e.g., one or more Group 1A metals or one or more Group 2A metals) and optionally further doped with one or more non-metal dopants (e.g., boron, phosphorus, both).

[0108] In one aspect, a catalyst may comprise a zeolite and one or more metal dopants, wherein the one or more metal dopants include one or more first metal dopants (e.g., sodium, potassium, lithium, or any combination thereof). In another aspect, the catalyst may comprise a zeolite and one or more first metal dopants, wherein the one or more first metal dopants include sodium, potassium, lithium, or any combination thereof, and one or more nonmetal dopants, wherein the one or more nonmetal dopants include boron, phosphorus, or a combination thereof.

[0109] Alternatively or additionally, the one or more metal dopants may include one or more second metal 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 second metal dopants, wherein the one or more second metal dopants comprise calcium, magnesium, strontium, or any combination thereof. In another aspect, the catalyst may comprise zeolite, one or more second metal dopants, and one or more non-metal dopants, wherein the one or more second metal dopants comprise magnesium, calcium, strontium, or barium, or any combination thereof, and wherein the one or more non-metal dopants comprise boron, phosphorus, or a combination thereof.

[0110] In some aspects, the one or more metal dopants comprise only one or more Group 1A metals (e.g., one or more first metal dopants). In other aspects, the one or more metal dopants comprise only one or more Group 2A metals (e.g., one or more second metal dopants). In still other aspects, the one or more metal dopants may comprise a combination of one or more Group 1A metals and one or more Group 2A metals.

[0111] Non-limiting examples of zeolites used for olefin formation may include doped zeolites, such as crystalline silicates of the group ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON having a Si / Al ratio greater than 10, or dealuminated crystalline silicates of the group ZSM-5 (MFI or BEA framework), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT, or TON having a Si / Al ratio greater than 10. In some aspects, when the zeolite is a ZSM-5 zeolite, the ZSM-5 zeolite may have a Si / Al2O3 ratio of about 20 to about 300. In certain aspects, the ZSM-5 zeolite may have a Si / Al2O3 ratio of about 50 to about 150.

[0112] In some aspects, the single catalyst system comprises only: zeolites doped with boron and phosphorus; zeolites doped with boron and phosphorus, as well as Group 1A metals (e.g., sodium, potassium, lithium) and / or Group 2A metals (e.g., magnesium, calcium, strontium, or barium); or zeolites doped with Group 1A metals (e.g., sodium, potassium, lithium) and / or Group 2A metals (e.g., magnesium, calcium, strontium, or barium). Not bound by a single theory, it is believed that the presence of boron increases the stability of phosphorus within the zeolite framework, resulting in extended operating times (ToS) while maintaining selectivity. For example, compared to <400 hours ToS for phosphorus-doped zeolites alone, boron / phosphorus-doped zeolites maintain >800 hours ToS while maintaining good ethylene conversion and olefin selectivity. Furthermore, in this case, the presence of boron can minimize the production of saturated hydrocarbons and aromatic compounds in the output stream.

[0113] Not bound by a single theory, it is further believed that the presence of one or more Group 1A and / or Group 2A metals (e.g., between 0.01 wt% and 2 wt%) in combination with boron / phosphorus dopants within the zeolite further increases the stability of the boron / phosphorus zeolite, resulting in a prolonged run time (ToS), while maintaining selectivity due to the additional neutralization of residual strong acid sites within the zeolite framework that were not initially modified by boron and / or phosphorus impregnation. The ability to effectively titrate residual strong acid sites within the zeolite framework that were not initially modified by boron and phosphorus impregnation improves selectivity, as demonstrated by the reduction in saturated hydrocarbon levels and the prolonged ToS. Furthermore, the titration of these strong acid sites can be accomplished by simultaneous co-impregnation of boron, phosphorus, and one or more Group 1A and / or Group 2A metals. In this case, the presence of one or more Group 1A and / or Group 2A metals can further minimize the production of saturated hydrocarbons and aromatic compounds in the output stream compared to boron and phosphorus-doped zeolites.

[0114] The one or more first metal dopants can be present in the catalyst at various concentrations. In some aspects, the amount of the one or more first metal dopants in the catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more first metal dopants in the catalyst may be about 0.01% by weight to about 2% by weight, or about 0.01% by weight to about 0.2% by weight. In one aspect, the amount of the one or more first metal dopants in the catalyst may be at least about 0.05% by weight. It is also considered that the amount of the one or more first metal dopants in the catalyst does not fall outside any of these ranges. Further considered that the amount of the one or more first metal dopants in the catalyst may be between any of these ranges.

[0115] The one or more second metal dopants can be present in the catalyst at various concentrations. In some aspects, the amount of the one or more second metal dopants in the catalyst may not exceed about 2% by weight. In other aspects, the amount of the one or more second metal dopants in the catalyst may be about 0.01% by weight to about 2% by weight, or about 0.01% by weight to about 0.2% by weight. In one aspect, the amount of the one or more second metal dopants in the catalyst may be at least about 0.05% by weight. It is also considered that the amount of the one or more second metal dopants in the catalyst does not fall outside any of these ranges. Further considered that the amount of the one or more second metal dopants in the catalyst may be between any of these ranges.

[0116] In one exemplary aspect, a method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins using a single catalyst system may include contacting an input stream with a catalyst in a reactor to form an output stream, the input stream comprising the one or more C1-C5 linear or branched alcohols, and the output stream comprising the one or more C2-C5 olefins, wherein the catalyst is substantially composed of a zeolite doped with boron and phosphorus and one or more metal dopants (e.g., Group 1A metals, Group 2A metals, or any combination thereof). The reactor is operated at a temperature of about 300°C to about 600°C, a gauge pressure of 0 to about 30 bar, and for about 0.25 h. -1 approximately 35 hours -1 Heavy space velocity (WHSV).

[0117] In some aspects, the method may include regenerating the catalyst after contacting the input stream with the catalyst in the 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 to burn off any solid carbon deposits on the catalyst, wherein the air and / or oxygen is optionally diluted with an inert gas or vapor. In some aspects, the method may include a system in which the catalyst is circulated between a reactor and a regeneration reactor, wherein the catalyst is contacted with the input stream in the reactor, and wherein the catalyst is contacted with air and / or oxygen in the regeneration reactor to burn off any solid carbon deposits on the catalyst, wherein the air and / or oxygen is optionally diluted with an inert gas or vapor.

[0118] 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, the other input stream comprising one or more C1-C5 linear or branched alcohols, and the other output stream comprising one or more C2-C5 olefins. 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.

[0119] Regarding the reactor, the reactor can operate at temperatures from about 300°C to about 600°C, including all sub-ranges therebetween. The reactor can operate at temperatures from about 300°C to about 550°C, including all sub-ranges therebetween. The reactor can operate at temperatures from about 300°C to about 500°C. The reactor can operate at gauge pressures from 0 to about 30 bar, including all sub-ranges therebetween. The reactor can operate at gauge pressures from 0 to about 5 bar, including all sub-ranges therebetween. The reactor can operate at gauge pressures of about 6 bar or lower. The reactor can operate for about 0.1 hours. -1approximately 35 hours -1 The reactor operates at WHSV, including all sub-ranges in between. The reactor can operate for approximately 0.25 hours. -1 approximately 10 hours -1 The reactor operates at WHSV, including all sub-ranges in between. The reactor can operate for approximately 0.25 hours. -1 approximately 5 hours -1 The reactor operates under WHSV conditions, including all sub-ranges in between. The reactor can operate for approximately 1 hour. -1 approximately 10 hours -1 The reactor operates under WHSV conditions, 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.

[0120] Further regarding the output stream, the methods disclosed herein may further include removing at least a portion of the C2 olefins from the output stream. The method may include removing at least a portion of the C3 olefins 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.

[0121] In one exemplary aspect, a method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins using a single catalyst system may include contacting an input stream with a catalyst in a reactor to form an output stream, the input stream comprising the one or more C1-C5 linear or branched alcohols, and the output stream comprising the one or more C2-C5 olefins. The catalyst is substantially composed of a zeolite (e.g., ZSM-5 zeolite) doped with boron and phosphorus and Group 1A metals (e.g., sodium, lithium, potassium, or any combination thereof). The reactor is operated at a temperature of about 350°C to about 475°C, a gauge pressure of 0 to about 5 bar, and a time of about 0.25 h⁻¹. -1 approximately 10 hours -1 The weight hourly space velocity (WHSV) of the catalyst. The amount of boron present in the catalyst is from about 0.05 wt% to about 5 wt%, the amount of phosphorus present in the catalyst is from about 0.2 wt% to about 7 wt%, and the amount of the Group 1A metal present in the catalyst is from 0.01 wt% to about 2 wt%.

[0122] Group 1A metals, Group 2A metals, or both can be impregnated into a single or corresponding catalyst bed by any suitable means, for example, by incipient wetness or classical ion exchange methods.

[0123] Figure 1An exemplary reactor system 1000 is illustrated. As shown, input 100, such as one or more C1-C5 linear or branched alcohols, can be fed into reactor 300 to produce output 200, such as a mixture of C2-C5 olefins. 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. Wastewater 400 can also be generated in situ via ethanol dehydration to ethylene through fixed-bed reactor 300, thus being condensed and removed as part of output 200.

[0124] 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, a single catalyst bed (not shown) of reactor 300 can be impregnated with two or more catalysts to form a mixed catalyst bed.

[0125] In other aspects, reactor 300 may include two or more catalyst beds (e.g., 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 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; and the second catalyst bed may include zeolite doped with at least one or more metal dopants (e.g., one or more Group 1A metals, one or more Group 2A metals, or both). The metal-doped zeolite of the second catalyst bed may be further doped with at least one or more non-metal dopants (e.g., boron, phosphorus, or both). Alternatively or additionally, the metal-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.

[0126] 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.

[0127] In aspects where the reactor comprises two or more catalyst beds, the reactor may have staged input feeds. In these aspects, for example, the reactor may be a multistage reactor (e.g., an adiabatic multistage reactor) having multiple inputs (e.g., at least a first input feed and a second input feed), at least a first reaction stage and a second reaction stage, wherein the first reaction stage is upstream of the second reaction stage. The first reaction stage comprises a first reactor bed, and the second reaction stage comprises a second reactor bed. In use, the first input feed may be fed into a first end (e.g., the inlet) of the adiabatic multistage reactor and subsequently contact the first reactor bed to produce a first reaction mixture. A second input feed may be introduced into the adiabatic multistage reactor downstream of the first reaction stage, and it then mixes with the first reaction mixture to produce a first effluent having a different composition relative to the first reaction mixture. The first effluent may then subsequently contact the second reactor bed to produce a second reaction mixture. This second reaction mixture may then be discharged from the reactor, or in other cases, to a subsequent reaction stage of the reactor (e.g., a third reaction stage).

[0128] In some respects, no external heat is added to the adiabatic multistage reactor during and between each reaction stage. The phrase "external heat" refers to heat supplied to the adiabatic multistage reactor that is not otherwise generated by the chemical reactions within the reactor, nor by any input feed (e.g., a first, second, or third input feed). Alternatively or additionally, no heat is removed from the adiabatic multistage reactor during and between each reaction stage.

[0129] The first input feed may include one or more first oxygen-containing compounds. For the purposes of this disclosure, an "oxygen-containing compound" is a hydrocarbon that contains oxygen as part of its chemical structure. Non-limiting examples of first oxygen-containing compounds include one or more C... 2+Alcohols, such as ethanol, one or more ethers, one or more esters, and the like. In some aspects, the one or more first oxygen-containing compounds do not include methanol. In some aspects, the one or more first oxygen-containing compounds may contain the same oxygen-containing compound, while in other aspects, the one or more first oxygen-containing compounds may contain a mixture of different oxygen-containing compounds. For example, in some aspects, the one or more first oxygen-containing compounds may contain a dominant first oxygen-containing compound, such as ethanol. In such aspects, the one or more first oxygen-containing compounds may also include one or more other oxygen-containing compounds, such as methanol, propanol, one or more esters, and / or one or more ethers. A dominant first oxygen-containing compound, as used herein, may be present in the one or more first oxygen-containing compounds at a higher weight percentage than any other individual oxygen-containing compound, for example, at an amount of at least 25% by weight, at least 50% by weight, or at least 75% by weight based on the one or more first oxygen-containing compounds. In some aspects, the primary first oxygen-containing compound may be present in an amount of 25% to 99% by weight, 25% to 90% by weight, 50% to 99% by weight, or 75% to 99% by weight, based on the one or more first oxygen-containing compounds. Further consideration is that the primary first oxygen-containing compound may be present in an amount between any of these ranges.

[0130] The second input feed comprises one or more second oxygen-containing materials, so named because they are second oxygen-containing materials introduced into the reactor at the second stage or catalyst bed. Non-limiting examples of second oxygen-containing materials include one or more C... 2+Alcohols, such as ethanol, one or more ethers, one or more esters, and the like. In some aspects, the one or more second oxygen-containing compounds do not include methanol. In some aspects, the one or more second oxygen-containing compounds may contain the same oxygen-containing compound, while in other aspects, the one or more second oxygen-containing compounds may contain a mixture of different oxygen-containing compounds. For example, in some aspects, the one or more second oxygen-containing compounds may contain a dominant second oxygen-containing compound, such as ethanol. A “dominant second oxygen-containing compound” as used herein may be present in the one or more second oxygen-containing compounds at a higher weight percentage than any other single oxygen-containing compound, for example, at least 25% by weight, at least 50% by weight, or at least 75% by weight based on the one or more second oxygen-containing compounds. In some aspects, the dominant second oxygen-containing compound may be present in an amount from 25% by weight to 99% by weight based on the one or more second oxygen-containing compounds, in an amount from 25% by weight to 90% by weight based on the one or more second oxygen-containing compounds, in an amount from 50% by weight to 99% by weight based on the one or more second oxygen-containing compounds, or in an amount from 75% by weight to 99% by weight based on the one or more second oxygen-containing compounds. Furthermore, the primary second oxygen-containing compound can be present in amounts between any of these ranges.

[0131] 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, and the like). 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 designs). Alternatively or additionally, the first reactor and the second reactor may operate under the same process conditions (e.g., temperature, pressure, WHSV, and the like). 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.

[0132] 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.

[0133] Example Example 1: Reactor Setup The conversion of alcohols (i.e., C1-C5) to C2-C5 olefins was carried out in a fixed-bed reactor at 300-500°C, the reactor comprising one or more specific catalysts, with preheated (160°C) vaporized alcohols flowing downwards through a fixed catalyst bed, co-fed with nitrogen at atmospheric pressure or at moderate pressure (i.e., 0-30 bar). The flow rate of the alcohols was controlled by a Teledyne 500D syringe pump, and the flow rate was adjusted to obtain the WHSV (weight hourly space velocity) of the target olefins. The internal reaction temperature was kept constant via a Lindberg Blue M furnace manufactured by Thermo-Scientific. The alcohol conversion and selectivity were calculated by analyzing the organic matter and water content of the liquid-phase reactor effluent via GC, by online GC analysis of non-condensable hydrocarbons (i.e., C2-C5 olefins), and by online thermal conductivity detectors for quantitative analysis of CO, CO2, and CH4 relative to nitrogen as an internal standard. Therefore, passing the vaporized stream of C1-C5 alcohols through a catalyst combination in a single fixed-bed reactor at 350°C-450°C induces the formation of C2-C5 olefins in high yields.

[0134] Example 2: Preparation of ZSM-5 zeolite catalyst impregnated with boron / phosphorus and sodium (1.5% boron, 3% phosphorus, 0.13% sodium) As described, a boron, phosphorus, and sodium-impregnated zeolite catalyst was prepared using a pre-wetting technique. 0.57 g of phosphoric acid (85%), 0.43 g of boric acid (99+%), and 0.0238 g of sodium nitrate were dissolved in deionized water (3.7 mL). After heating and dissolution, the solution was added dropwise to 5 g of ZSM-5 zeolite support (i.e., Zeolyst type CBV-5524 H). + The resulting impregnated catalyst was dried at 160°C for 1 hour, and then calcined at 550°C for 3-15 hours.

[0135] Example 3: Single-stage reactor Single-stage reactor configuration: Reaction conditions: T = 445℃, WHSV = 4.9 (based on ethanol), P = 0 bar in the reactor; Catalyst - Siralox 5 / 320 (5.0 wt% silica) γ-alumina (0.625 g) physically mixed with B / P / Na (1.5% / 3.0% / 0.12%) doped ZSM-5 zeolite (2.5 g).

[0136] Table 1. Composition of effluent from a single-pass reactor and its corresponding weight percentage.

[0137] Ethylene conversion rate: ~62% (mass yield).

[0138] Example 4: Single-stage reactor Single-stage reactor configuration: Reaction conditions: T = 445℃, WHSV = 4.9 (based on ethanol), P = 0 bar in the reactor; Catalyst - a physical mixture of high-purity γ-alumina (Clariant 100-4, 0.625 g) and ZSM-5 zeolite (2.5 g) doped with B / P / Na (1.5% / 3.0% / 0.12%).

[0139] Table 2. Composition of effluent from a single-pass reactor and its corresponding weight percentage.

[0140] Ethylene conversion rate ~66% (mass yield, MS 305) Example 5: Single-stage reactor Single-stage reactor configuration: Reaction conditions: T = 445℃, WHSV = 4.9 (based on ethanol), P = 0 bar in the reactor; Catalyst - a physical mixture of high-purity γ-alumina (Clariant 100-4, 0.625 g) and B / P / K (1.5% / 3.0% / 0.18%) doped ZSM-5 zeolite (2.5 g).

[0141] Table 3. Composition of effluent from a single-pass reactor and its corresponding weight percentage.

[0142] Ethylene conversion rate ~60% (mass yield).

[0143] Comparative Example 6: Single-stage reactor Single-stage reactor configuration: Reaction conditions: T = 445℃, WHSV = 4.9 (based on ethanol), P = 0 bar in the reactor; Catalyst - Siralox 5 / 320 (5.0 wt% silica) γ-alumina (0.625 g) and Na-doped (0.27 wt%) ZSM-5 zeolite (2.5 g) are physically mixed.

[0144] Table 4. Composition of effluent from a single-pass reactor and its corresponding weight percentage.

[0145] Ethylene conversion rate: ~77% (mass yield).

[0146] Comparative Example 7: Single-stage reactor Single-stage reactor configuration: Reaction conditions: T = 445℃, WHSV = 4.9 (based on ethanol), P = 0 bar in the reactor; Catalyst - a physical mixture of high-purity γ-alumina (Clariant 100-4, 0.625 g) and B / P (1.5% / 3%) doped ZSM-5 zeolite (2.5 g).

[0147] Table 5. Composition of effluent from a single-pass reactor and its corresponding weight percentage.

[0148] Ethylene conversion rate ~64% (mass yield) (JS265).

[0149] Example 8: Olefin Selectivity The data shown in Table 6 below illustrate that, at the selected run-time (ToS) and ethylene conversion, improved propylene selectivity and a smaller total C2-C5 saturated hydrocarbons were achieved for Examples 4, 5, and 7 above.

[0150] Table 6

[0151] Although various exemplary embodiments have been described above, numerous modifications may be made to these embodiments without departing from the teachings herein. For example, in alternative embodiments, the order in which the method steps described may be performed may be altered, and in other alternative embodiments, one or more method steps may be skipped entirely. Optional features of various system and method embodiments may be included in some embodiments 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.

[0152] The embodiments and illustrations contained herein are shown by way of example and not limitation, and specific implementations of the subject matter can be practiced. As mentioned, other implementations can be utilized and derived therefrom, allowing for structural and logical substitutions and changes without departing from the scope of this disclosure. For convenience, these implementations 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). Therefore, although specific embodiments have been shown and described herein, any arrangement intended to achieve the same purpose may replace the specific embodiments shown. This disclosure is intended to cover any and all adjustments or variations of the various implementations. Those skilled in the art will understand, upon reading the foregoing description, combinations of the above-described embodiments and other embodiments 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.

[0153] The subject matter described herein can be embodied in systems, apparatus, methods, and / or articles according to desired configurations. The embodiments set forth in the foregoing description do not represent all embodiments consistent with the subject matter described herein. Rather, they are merely some examples of embodiments 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 embodiments described herein may be for various combinations and sub-combinations of the disclosed features, and / or combinations and sub-combinations of some other features disclosed herein. Furthermore, the logical flows depicted in the drawings and / or described herein do not necessarily require the specific order or sequence shown to achieve the desired results. Other embodiments are within the scope of the appended claims.

Claims

1. A method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins, the method comprising: In a reactor, an input stream is contacted with a catalyst to form an output stream, the input stream comprising one or more C1-C5 linear or branched alcohols, the output stream comprising one or more C2-C5 olefins, the catalyst comprising zeolite and one or more metal dopants, the one or more metal dopants comprising one or more first metal dopants, one or more second metal dopants, or both. The reactor is located at a temperature of approximately 300°C to approximately 600°C, a gauge pressure of 0 to approximately 30 bar, and a time of approximately 0.25 h. -1 approximately 35 h -1 Heavy space velocity (WHSV).

2. The method according to claim 1 or claim 2, further comprising adding the one or more metal dopants to the catalyst prior to contacting the input stream.

3. The method according to claim 1, wherein the reactor is a single-bed reactor.

4. The method according to claim 3, wherein the single-bed reactor is a fixed-bed reactor.

5. The method according to claim 3, wherein the single-bed reactor is a fluidized bed reactor.

6. The method according to claim 3, wherein the single-bed reactor is a moving-bed reactor.

7. The method according to any one of the preceding claims, wherein the amount of the one or more C2-C5 olefins present in the output stream does not exceed about 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

8. The method of claim 7, wherein the amount of one or more C2-C5 olefins present in the output stream is from about 70% by weight to about 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

9. The method of claim 7, wherein the amount of one or more C2-C5 olefins present in the output stream is about 85% to about 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

10. The method according to any one of the preceding claims, wherein the catalyst further comprises one or more non-metallic dopants.

11. The method of claim 10, wherein the one or more nonmetallic dopants comprise boron, phosphorus, or a combination thereof.

12. The method of claim 11, wherein boron is present in the catalyst in an amount of about 0.01% by weight to about 10% by weight.

13. The method of claim 11, wherein boron is present in the catalyst in an amount of at least 0.05% by weight.

14. The method of claim 11, wherein phosphorus is present in the catalyst in an amount of about 0.1% by weight to about 7% by weight.

15. The method of claim 11, wherein phosphorus is present in the catalyst in an amount of at least 1.5% by weight.

16. The method according to any one of the preceding claims, wherein the zeolite comprises ZSM-5 zeolite.

17. The method according to any one of claims 1 to 15, wherein the zeolite comprises MFI zeolite, BEA zeolite, FER zeolite, CHA zeolite, FAU zeolite, or any combination thereof.

18. The method according to any one of the preceding claims, wherein the output stream comprises saturated hydrocarbons, and wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 25% by weight based on the output stream.

19. The method of claim 18, wherein the total amount of saturated hydrocarbons present in the output stream is from about 3% by weight to about 25% by weight.

20. The method of claim 18, wherein the total amount of saturated hydrocarbons present in the output stream is from about 3% to about 15% by weight.

21. The method according to any one of the preceding claims, wherein the one or more first metal dopants are present in the catalyst in an amount not exceeding about 2 by weight.

22. The method of claim 21, wherein the one or more first metal dopants are present in the catalyst in an amount of about 0.01% by weight to about 2% by weight.

23. The method of claim 21, wherein the one or more first metal dopants are present in the catalyst in an amount of about 0.01% by weight to about 0.2% by weight.

24. The method of claim 21, wherein the one or more first metal dopants are present in the catalyst in an amount of at least about 0.05% by weight.

25. The method according to any one of the preceding claims, wherein the one or more second metal dopants are present in the catalyst in an amount not exceeding about 2 by weight.

26. The method of claim 25, wherein the one or more second metal dopants are present in the catalyst in an amount of about 0.01% by weight to about 2% by weight.

27. The method of claim 25, wherein the one or more second metal dopants are present in the catalyst in an amount of about 0.01% by weight to about 0.2% by weight.

28. The method of claim 25, wherein the one or more second metal dopants are present in the catalyst in an amount of at least about 0.05% by weight.

29. The method according to any one of the preceding claims, wherein the C1-C5 linear or branched alcohol is biologically based and produced by a fermentation process.

30. The method according to any one of the preceding claims, wherein the C1-C5 linear or branched alcohol is not derived from petroleum.

31. The method according to any one of the preceding claims, 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 the preceding claims, 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 the preceding claims, 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 the preceding claims, wherein the temperature is about 550°C to about 600°C.

35. The method of claim 34, wherein the temperature is from about 350°C to about 550°C.

36. The method according to any one of the preceding claims, wherein the WHSV is about 0.5 h. -1 From approximately 1.0h -1 .

37. The method of claim 36, wherein the WHSV is about 2.0 h. -1 To approximately 5.0 h -1 .

38. The method according to any one of the preceding claims, wherein the one or more first metal dopants comprise sodium, potassium, lithium, or any combination thereof.

39. The method of claim 38, wherein one or more first metal dopants are sodium.

40. The method according to any one of the preceding claims, wherein the one or more second metal dopants comprise magnesium, calcium, strontium, barium, or any combination thereof.

41. The method according to any one of the preceding claims, wherein the catalyst comprises one or more other dopants, the one or more other dopants comprising sulfur, scandium, yttrium, selenium, iron, manganese, tellurium, or any combination thereof.

42. The method of claim 41, wherein the amount of the one or more other dopants present in the catalyst does not exceed about 2 by weight.

43. The method of claim 41, wherein the one or more other dopants are present in the catalyst in an amount of about 0.05% by weight to about 1% by weight.

44. The method of claim 41, wherein the one or more other dopants are present in the catalyst in an amount of about 0.05% by weight to about 0.5% by weight.

45. The method of claim 41, wherein the one or more other dopants are present in the catalyst in an amount of at least about 0.25% by weight.

46. ​​A method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 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, the input stream comprising one or more C1-C5 linear or branched alcohols, and the output stream comprising one or more C2-C5 olefins, the single reactor being operated at a temperature of about 350°C to about 750°C, a gauge pressure of 0 to about 30 bar, and for about 0.5 h. -1 To approximately 35.0 h -1 The weight hourly space velocity (WHSV), The second catalyst comprises zeolite and one or more metal dopants, wherein the one or more metal dopants comprise one or more first metal dopants, one or more second metal dopants, or both.

47. The method of claim 46, wherein the first catalyst comprises a doped or undoped alumina catalyst.

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

49. The method according to any one of claims 46 to 48, wherein the single reactor comprises one or more catalyst beds, wherein the method further comprises impregnating at least one of the one or more catalyst beds with the first catalyst and the second catalyst.

50. The method of claim 49, wherein two of the one or more catalyst beds are stacked relative to each other within the single reactor.

51. The method according to any one of claims 46 to 48, wherein the single reactor comprises two or more catalyst beds, wherein the method further comprises, The first catalyst bed in one of the two or more catalyst beds is impregnated with at least the first catalyst, and The second catalyst bed is impregnated with at least the second catalyst.

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

53. The method of claim 51 or 52, wherein contacting the input stream with at least the first catalyst and the second catalyst comprises contacting the input stream with the first catalyst bed before contacting the second catalyst bed.

54. The method of claim 53, further comprising introducing one or more additional input streams into the reactor downstream of the first catalyst bed.

55. The method according to any one of claims 51 to 54, wherein the first catalyst bed does not contain the second catalyst.

56. The method according to any one of claims 51 to 55, wherein the second catalyst bed does not contain the first catalyst.

57. The method according to any one of claims 46 to 56, wherein the first 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, silica-alumina catalyst, or any combination thereof.

58. The method according to any one of claims 46 to 56, wherein the first catalyst comprises undoped γ-alumina, zirconate-treated γ-alumina, or both.

59. The method according to any one of claims 46 to 58, the method further comprising adding the one or more metal dopants to the second catalyst prior to contacting the input stream.

60. The method according to any one of claims 46 to 59, wherein the amount of one or more C2-C5 olefins present in the output stream does not exceed about 98 by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

61. The method of claim 60, wherein the amount of one or more C2-C5 olefins present in the output stream is from about 70% by weight to about 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

62. The method of claim 60, wherein the amount of one or more C2-C5 olefins present in the output stream is from about 85% by weight to about 98% by weight based on the total amount of unsaturated hydrocarbons present in the output stream.

63. The method according to any one of claims 46 to 62, wherein the second catalyst further comprises one or more non-metallic dopants.

64. The method of claim 63, wherein the one or more nonmetallic dopants comprise boron, phosphorus, or a combination thereof.

65. The method of claim 64, wherein boron is present in the catalyst in an amount of about 0.01% by weight to about 10% by weight.

66. The method of claim 64, wherein boron is present in the catalyst in an amount of at least 0.05 wt%.

67. The method of claim 64, wherein phosphorus is present in the catalyst in an amount of about 0.1% by weight to about 7% by weight.

68. The method of claim 64, wherein phosphorus is present in the catalyst in an amount of at least 1.5% by weight.

69. The method according to any one of claims 46 to 68, wherein the zeolite comprises ZSM-5 zeolite.

70. The method according to any one of claims 46 to 68, wherein the zeolite comprises MFI zeolite, BEA zeolite, FER zeolite, CHA zeolite, FAU zeolite, or any combination thereof.

71. The method according to any one of claims 46 to 70, wherein the output stream comprises saturated hydrocarbons, and wherein the total amount of saturated hydrocarbons present in the output stream does not exceed about 25% by weight based on the output stream.

72. The method of claim 71, wherein the total amount of saturated hydrocarbons present in the output stream is from about 3% by weight to about 25% by weight.

73. The method of claim 71, wherein the total amount of saturated hydrocarbons present in the output stream is from about 3% to about 15% by weight.

74. The method according to any one of claims 46 to 73, wherein the one or more first metal dopants are present in the second catalyst in an amount not exceeding about 2 by weight.

75. The method of claim 74, wherein the one or more first metal dopants are present in the second catalyst in an amount of about 0.01% by weight to about 2% by weight.

76. The method of claim 74, wherein the one or more first metal dopants are present in the second catalyst in an amount of about 0.01 wt% to about 0.2 wt%.

77. The method of claim 74, wherein the one or more first metal dopants are present in the second catalyst in an amount of at least about 0.05 wt%.

78. The method according to any one of claims 46 to 77, wherein the one or more second metal dopants are present in the second catalyst in an amount not exceeding about 2 by weight.

79. The method of claim 78, wherein the one or more second metal dopants are present in the second catalyst in an amount of about 0.01% by weight to about 2% by weight.

80. The method of claim 78, wherein the one or more second metal dopants are present in the second catalyst in an amount of about 0.01 wt% to about 0.2 wt%.

81. The method of claim 78, wherein the one or more second metal dopants are present in the second catalyst in an amount of at least about 0.05% by weight.

82. The method according to any one of claims 46 to 81, wherein the C1-C5 linear or branched alcohol is biologically based and produced by a fermentation process.

83. The method according to any one of claims 46 to 81, wherein the C1-C5 linear or branched alcohol is not derived from petroleum.

84. The method according to any one of claims 46 to 83, the method further comprising removing at least a portion of the C2 olefin from the output stream.

85. The method according to any one of claims 46 to 84, the method further comprising removing at least a portion of the C4 olefin from the output stream.

86. The method according to any one of claims 46 to 85, the method further comprising removing at least a portion of the C5 olefin from the output stream.

87. The method according to any one of claims 46 to 86, wherein the temperature is about 550°C to about 600°C.

88. The method of claim 87, wherein the temperature is from about 350°C to about 550°C.

89. The method according to any one of claims 46 to 88, wherein the WHSV is about 0.5 h. -1 From approximately 1.0h -1 .

90. The method of claim 89, wherein the WHSV is about 2.0 h. -1 To approximately 5.0 h -1 .

91. The method according to any one of claims 46 to 90, wherein the one or more first metal dopants comprise sodium, potassium, lithium, or any combination thereof.

92. The method of claim 91, wherein one or more first metal dopants are sodium.

93. The method according to any one of claims 46 to 92, wherein the one or more second metal dopants comprise magnesium, calcium, strontium, barium, or any combination thereof.

94. The method according to any one of claims 46 to 92, wherein the second catalyst comprises one or more other dopants, the other dopants comprising sulfur, scandium, yttrium, selenium, iron, manganese, tellurium, or any combination thereof.

95. The method of claim 94, wherein the amount of the one or more other dopants present in the second catalyst does not exceed about 2 by weight.

96. The method of claim 94, wherein the one or more other dopants are present in the second catalyst in an amount of about 0.05% by weight to about 1% by weight.

97. The method of claim 94, wherein the one or more other dopants are present in the catalyst in an amount of about 0.05% by weight to about 0.5% by weight.

98. The method of claim 94, wherein the one or more other dopants are present in the second catalyst in an amount of at least about 0.25% by weight.

99. A method for converting one or more C1-C5 linear or branched alcohols into one or more C2-C5 olefins, the method comprising: In a reactor, an input stream is contacted with a catalyst to form an output stream, the input stream comprising one or more C1-C5 linear or branched alcohols, the output stream comprising one or more C2-C5 olefins, the catalyst being substantially composed of zeolite and one or more metal dopants, the one or more metal dopants comprising one or more first metal dopants, one or more second metal dopants, or both. The reactor is located at a temperature of approximately 300°C to approximately 600°C, a gauge pressure of 0 to approximately 30 bar, and a time of approximately 0.25 h. -1 approximately 35 h -1 Heavy space velocity (WHSV).

100. The systems, methods and compositions described herein.

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