WO2024091452A1 - Procédés de conversion catalytique d'alcools en c1-c5 en mélanges d'oléfines en c2-c5 - Google Patents

Procédés de conversion catalytique d'alcools en c1-c5 en mélanges d'oléfines en c2-c5 Download PDF

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WO2024091452A1
WO2024091452A1 PCT/US2023/035708 US2023035708W WO2024091452A1 WO 2024091452 A1 WO2024091452 A1 WO 2024091452A1 US 2023035708 W US2023035708 W US 2023035708W WO 2024091452 A1 WO2024091452 A1 WO 2024091452A1
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catalyst
olefins
reactor
output stream
bed reactor
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WO2024091452A9 (fr
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Jonathan Smith
Andrew Ingram
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Gevo, Inc.
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Publication of WO2024091452A1 publication Critical patent/WO2024091452A1/fr
Publication of WO2024091452A9 publication Critical patent/WO2024091452A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Definitions

  • U.S. Pat. No. 4,302,357 relates to an activated alumina catalyst employed in a process for production of ethylene from ethanol through a dehydration reaction.
  • LHSV of ethanol is from 0.25 to 5 h' 1 and preferably from 0.5 to 3 h’ 1 .
  • the examples are carried out at 370 °C. and LHSV of 1 h’ 1 , ethylene yield is from 65 to 94%.
  • Process Economics Reviews PEP 79-3 (SRI international) of December 1979 describes the dehydration of an ethanol water (95/5 weight%) mixture on a silica-alumina catalyst in a tubular fixed bed at 315 °C-360 °C, 1.7 bar absolute and a WHSV (on ethanol) of 0.3 h.
  • the ethanol conversion is 99% and the ethylene selectivity is 94.95%.
  • the ethanol conversion is 99.6% and the ethylene selectivity is 99.3%.
  • the oligomerization of ethylene requires high pressures, generally ranging between 2-4 MPa, but lower temperatures, generally between 20 °C-200 °C.
  • the catalysts used are in most cases transition metals deposited on silica-alumina type supports, zeolites (ZSM-5) or mesoporous solids (MCM-41) described by V. Hulea et al., J. Catal., 225 (2004) and Heveling et al., J. Applied Catalysis A: General 174 (1998).
  • ZSM-5 zeolites
  • MCM-41 mesoporous solids
  • the oligomerization of ethylene to Cs+ olefins may be accomplished via a two-stage process.
  • the first stage encompasses dimerization of a purified ethylene stream to butenes, followed by second stage oligomerization of butenes to Cs+ olefins which provides the base stock for fuels after hydrogenation.
  • U.S. Pat. No. 8,552,241 relates to a process for converting ethanol in a single step to a diesel fuel base stock which includes contacting ethanol with an acid catalyst at a reaction temperature of 300 °C-500 °C.
  • the catalyst used is a 50/50 mixture of a y-alumina in combination with a commercial Axens catalyst “type IS463” marketed as an alumina-based catalyst for skeletal isomerization of C4 and C5 olefin cuts.
  • the typical single pass product distribution consisted of a hydrocarbon fraction of 40-50%, and an organic liquid phase yield of 5-20%.
  • the organic liquid phase consists of -50% olefins of which Ce olefins are the majority, and -40% has a boiling point above 150 °C, and therefore compatible with the diesel pool.
  • the 40-50% hydrocarbon gaseous phase predominately contains ethylene and ethane as well as traces of Ci, C3, C4 and C5. In this case, the yield to the organic liquid phase is relatively low with -20% having a boiling point above 150 °C.
  • the other 80% of the organic liquid and hydrocarbon fraction is a predominately ethylene and ethane as well as traces of Ci, C3, C4 and C5 and Ce olefins.
  • U.S. Pat. No. 9,840,676 relates to a process for converting ethanol in a three-step process into fuels which can be utilized as full performance or military jet or diesel fuels. However, the process begins with ethylene formation followed by trimerization to hexenes and finally oligomerization to jet and diesel fractions.
  • aspects of the current subject matter relate inter alia to systems and processes for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins.
  • process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins includes contacting an input stream comprising the one or more C1-C5 linear or branched alcohols with at least a first catalyst and a second catalyst in a single bed reactor to form an output stream.
  • the output stream including the one or more C2-C5 olefins.
  • the single bed reactor being at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.5 to about 5.0.
  • WHSV weight hourly space velocity
  • the first catalyst being a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si), to form a first mixture, and the second catalyst being a doped or undoped zeolite catalyst.
  • the single bed reactor can be a fixed bed reactor. In other embodiments, the single bed reactor can be a fluidized bed reactor.
  • contacting the input stream can further include contacting the input stream with a third catalyst in the single bed reactor.
  • the third catalyst can include a doped or undoped SiCh catalyst.
  • the C1-C5 linear or branched alcohols can be bio-based and produced by fermentative processes. In some embodiments, the C1-C5 linear or branched alcohols can be not derived from petroleum.
  • the one or more C2-C5 olefins can be present in the output stream in an amount that can be at least 80 wt. %, at least 85 wt. %, at least 90 wt. %, or at least 95 wt. %.
  • the output stream can include one or more aromatic (C7+) compounds in an amount from about 2 wt. % to about 10 wt. %. In some embodiments, the output stream can include one or more aromatic (C7+) compounds in an amount that does not exceed 10 wt. %.
  • the process can include removing at least a portion of C2 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C4 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C5 olefins from the output stream.
  • the temperature can be from about 550 °C to about 750 °C. In some embodiments, the temperature can be from about 350 °C to about 550 °C.
  • the WHSV can be from about 0.5 to about 1.0. In some embodiments, the WHSV can be from about 2.0 to about 5.0.
  • a process for converting methanol to one or more C2-C5 olefins includes contacting an input stream comprising the methanol with at least a first catalyst and a second catalyst in a single bed reactor to form an output stream.
  • the output stream including the one or more C2-C5 olefins.
  • the single bed reactor being at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.5 to about 5.0.
  • WHSV weight hourly space velocity
  • the first catalyst being a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si), and the second catalyst being a doped or undoped zeolite catalyst.
  • the single bed reactor can be a fixed bed reactor. In other embodiments, the single bed reactor can be a fluidized bed reactor.
  • contacting the input stream can further include contacting the input stream with a third catalyst in the single bed reactor.
  • the third catalyst can include a doped or undoped SiCh catalyst.
  • the C1-C5 linear or branched alcohols can be bio-based and produced by fermentative processes. In some embodiments, the C1-C5 linear or branched alcohols can be not derived from petroleum. [0024] In some embodiments, the one or more C2-C5 olefins can be present in the output stream in an amount that can be at least 80 wt. %, at least 85 wt. %, at least 90 wt. %, or at least 95 wt. %.
  • the output stream can include one or more aromatic (C7+) compounds in an amount from about 2 wt. % to about 10 wt. %. In some embodiments, the output stream can include one or more aromatic (C7+) compounds in an amount that does not exceed 10 wt. %.
  • the process can include removing at least a portion of C2 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C4 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C5 olefins from the output stream.
  • the temperature can be from about 550 °C to about 750 °C. In some embodiments, the temperature can be from about 350 °C to about 550 °C.
  • the WHSV can be from about 0.5 to about 1.0. In some embodiments, the WHSV can be from about 2.0 to about 5.0.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins includes contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a first catalyst in a stacked bed reactor at a temperature from about 350 °C to about 550 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 1.0 to about 2.0 to form a first mixture.
  • the first catalyst being a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si).
  • the process further including contacting the first mixture with at least a second catalyst in the stacked bed reactor to form an output stream that includes the one or more C2-C5 olefins, in which the second catalyst is a doped or undoped zeolite catalyst.
  • the stacked bed reactor can be a fixed bed reactor. In other embodiments, the stacked bed reactor can be a fluidized bed reactor. [0031] In some embodiments, contacting the first mixture can further include contacting the first mixture with a third catalyst in the stacked bed reactor.
  • the third catalyst can include a doped or undoped SiCh catalyst.
  • the C1-C5 linear or branched alcohols can be bio-based and produced by fermentative processes. In some embodiments, the C1-C5 linear or branched alcohols can be not derived from petroleum.
  • the one or more C2-C5 olefins can be present in the output stream in an amount that can be at least 80 wt. %, at least 85 wt. %, at least 90 wt. %, or at least 95 wt. %.
  • the output stream can include one or more aromatic (C7+) compounds in an amount from about 2 wt. % to about 10 wt. %. In some embodiments, the output stream can include one or more aromatic (C7+) compounds in an amount that does not exceed 10 wt. %.
  • the process can include removing at least a portion of C2 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C4 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C5 olefins from the output stream.
  • the temperature can be from about 550 °C to about 750 °C. In some embodiments, the temperature can be from about 350 °C to about 550 °C.
  • the WHSV can be from about 0.5 to about 1.0. In some embodiments, the WHSV can be from about 2.0 to about 5.0.
  • a process for converting methanol to one or more C2-C5 olefins includes contacting an input stream that includes the methanol with a first catalyst in a stacked bed reactor at a temperature from about 350 °C to about 550 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 1.0 to about 2.0 to form a first mixture.
  • the first catalyst comprises a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si).
  • the process further including contacting the first mixture with at least a second catalyst in the stacked bed reactor to form an output stream that includes the one or more C2-C5 olefins, in which the second catalyst is a doped or undoped zeolite catalyst.
  • the stacked bed reactor can be a fixed bed reactor. In other embodiments, the stacked bed reactor can be a fluidized bed reactor.
  • contacting the first mixture can further include contacting the first mixture with a third catalyst in the stacked bed reactor.
  • the third catalyst can include a doped or undoped SiCh catalyst.
  • the C1-C5 linear or branched alcohols can be bio-based and produced by fermentative processes. In some embodiments, the C1-C5 linear or branched alcohols can be not derived from petroleum.
  • the one or more C2-C5 olefins can be present in the output stream in an amount that can be at least 80 wt. %, at least 85 wt. %, at least 90 wt. %, or at least 95 wt. %.
  • the output stream can include one or more aromatic (C7+) compounds in an amount from about 2 wt. % to about 10 wt. %. In some embodiments, the output stream can include one or more aromatic (C7+) compounds in an amount that does not exceed 10 wt. %.
  • the process can include removing at least a portion of C2 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C4 olefins from the output stream. In some embodiments, the process can include removing at least a portion of C5 olefins from the output stream.
  • the temperature can be from about 550 °C to about 750 °C. In some embodiments, the temperature can be from about 350 °C to about 550 °C.
  • the WHSV can be from about 0.5 to about 1.0. In some embodiments, the WHSV can be from about 2.0 to about 5.0.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more Ci-C5 linear or branched alcohols with a catalyst in a reactor to form an output stream comprising the one or more C2- C5 olefins, in which the catalyst consists essentially of zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 300 °C to about 600 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 10.
  • WHSV weight hourly space velocity
  • the reactor can be a single bed reactor.
  • the single bed reactor can be a fixed bed reactor.
  • the single bed reactor can be a fluidized bed reactor.
  • the single bed reactor can be a moving bed reactor.
  • the one or more C2-C5 olefins can be present in the output stream in an amount that is from about 50 wt. % to about 99 wt. % of the total hydrocarbon products in the output stream. In some embodiments, the one or more C2-C5 olefins can be present in the output stream in an amount that is from about 85 wt. % to about 99 wt. % of the total hydrocarbon products in the output stream.
  • the boron can be present in the catalyst in an amount from about 0.01 wt. % to about 10 wt. %. In some embodiments, the boron can be present in the catalyst in an amount of at least 0.05 wt. %.
  • the phosphor can be present in the catalyst in an amount from about 0.1 wt. % to about 7 wt. %. In some embodiments, the phosphor can be present in the catalyst in an amount of at least 1.5 wt. %.
  • the zeolite can be ZSM-5 zeolite.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a single catalyst in a reactor to form an output stream that includes the one or more C2-C5 olefins.
  • the single catalyst includes zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 5.
  • the single catalyst can consist essentially of zeolite doped with boron and phosphor.
  • the reactor can be a single bed reactor.
  • the single bed reactor can be a fixed bed reactor.
  • the single bed reactor can be a fluidized bed reactor.
  • the single bed reactor can be a moving bed reactor.
  • the one or more C2-C5 olefins can be present in the output stream in an amount that is from about 50 wt. % to about 99 wt. % of the total hydrocarbon products in the output stream. In some embodiments, the one or more C2-C5 olefins can be present in the output stream in an amount that is from about 85 wt. % to about 99 wt. % of the total hydrocarbon products in the output stream.
  • the boron can be present in the catalyst in an amount from about 0.01 wt. % to about 10 wt. %. In some embodiments, the boron can be present in the catalyst in an amount of at least 0.05 wt. %.
  • the phosphor can be present in the catalyst in an amount from about 0.1 wt. % to about 7 wt. %. In some embodiments, the phosphor can be present in the catalyst in an amount of at least 1.5 wt. %.
  • the zeolite can be a ZSM-5 zeolite.
  • the process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a catalyst in a reactor to form an output stream that includes the one or more C2-C5 olefins.
  • the catalyst consists essentially of ZSM-5 zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 350 °C to about 475 °C, a gauge pressure from 0 to about 5 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 10.
  • the boron is present in the catalyst in an amount from about 0.05 wt. % to about 5 wt. %, and the phosphor is present in the catalyst in an amount from about 0.2 wt. % to about 7 wt. %.
  • FIG. 1 shows an example process concept for an on-purpose propylene configuration of a single fixed bed reactor system with closed-loop recycle of C2, C4, and C5 olefins, consistent with implementations of the current subject matter;
  • FIG. 2 is a graph illustrating the data results of Example 10.
  • FIG. 3 is a graph illustrating the date results of Example 11.
  • FIG. 4 is a graph illustrating the data results of Example 12.
  • Oxygenate refers to compounds which include oxygen in their chemical structure. Examples of oxygenates include, but are not limited to water, alcohols, esters, and ethers.
  • WHSV weight hourly space velocity and is defined as the weight of the feed flowing per unit weight of the catalyst per hour.
  • “Aromatics” or “aromatic compounds” as used herein refer to cyclic organic carbon compounds consisting of six or more carbons (e.g. benzene, etc.).
  • Trace amounts” or “trace levels” as used herein refer to levels less than 2%. In some embodiments, trace amounts or trace levels can refer to levels less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.1%, from about 0.1% to about 1.8%, or from about 1% to about 1.5%.
  • Single stage transformation refers to processes which occur within a single reactor system.
  • alcohols may be converted to an olefinic mixture including primarily C2-C7 olefins with low levels of aromatic compounds.
  • the processes provide paths towards economical ways to convert alcohols, e.g. ethanol, to base stocks for the production of fuels. Further, the processes described herein can be performed at lower pressures and higher temperatures with higher yields of olefins in comparison to previously available approaches.
  • the processes may include a single stage transformation of an aqueous bioalcohol feedstock derived from biomass into a higher molecular weight olefinic mixture, which can easily be oligomerized in high yield to C10+ hydrocarbons or diesel fractions.
  • the single-stage reactor or two-stage reactor configurations use specific catalytic systems, which make it possible to minimize the production of aromatic compounds and therefore maximize production of middle distillates.
  • Processes described in WO 2021/067294 convert C2-C5 alcohols efficiently and economically as a base stock for fuels. Conversion of C2-C5 alcohols to the desired fuel product precursors (e.g., C3-C7 olefins) in high yields reduces processing costs.
  • aspects of the subject matter disclosed herein improve on earlier approaches by, inter alia, providing processes in which a two-catalyst system is used to convert C2-C5 linear or branched alcohols to C2-C7 olefins in high yield with low levels of aromatics at competitive costs.
  • processes for the direct conversion of bio-based C1-C5 alcohols to olefinic mixtures (e.g., C2-C5) with low levels of aromatics may be carried out in a single fixed bed reactor.
  • the C2-C5 olefins can be easily oligomerized to base stocks used in the production of fuels in high yields.
  • the processes described herein can be carried out in a single bed reactor. In other embodiments, the processes described herein can be carried out in a single stacked bed reactor.
  • alcohols e.g. methanol or ethanol
  • olefinic mixtures e.g., C2-C5
  • the resulting C2- C5 olefinic mixture is suitable for oligomerization into either gasoline, jet, or diesel fuel cuts at relatively low temperatures and pressures depending upon the oligomerization catalyst selected.
  • the single bed reactor or stacked bed reactor can be defined as a fixed bed reactor, whereas in other embodiments, a fluidized bed reactor may be used.
  • a catalytic process consistent with the present disclosure includes alcohol dehydration followed by a skeletal carbon build-up and subsequent “cracking” resulting in high yields to low molecular weight olefins (e.g., C2-C5).
  • the catalyst mixture can result in a C2-C5 olefinic mixture providing access to low molecular weight olefins in yields with good carbon accountability as defined by moles of carbon fed into the system as ethanol versus moles of carbon out of the system incorporated in the C2-C5 olefinic mixture.
  • recycle streams of specific olefins e.g., C2-C5
  • desirable olefins such as propylene, butenes, or mixtures thereof.
  • the mixture of olefins are suitable for oligomerization to either gasoline, jet, or diesel fuel cuts at relatively low temperatures and pressures depending upon the oligomerization catalyst selected.
  • C2-C5 alcohols are dehydrated in a single unit operation, at between 300 °C-500 °C in the presence of a dehydration catalyst, resulting in production of the C2-C5 olefin along with water.
  • the water is removed, and the C2-C5 olefin is further processed/purified to remove unreacted C2-C5 alcohols and/or impurities prior to conversion to chemicals and/or fuels.
  • the approach to converting C4 or C5 alcohols to chemicals and/or fuels utilize discrete unit operations to accomplish i) dehydration to the C4 or C5 olefin, ii) olefin purification to remove oxygenates and/or unreacted alcohols, and iii) oligomerization to unsaturated Jet and/or Diesel fuel precursors.
  • industrial processes convert methanol, primarily derived from coal, to olefins via a mesoporous catalyst (e.g., SAPO-34, etc.) to olefins in a single step with olefin recycle.
  • a mesoporous catalyst e.g., SAPO-34, etc.
  • a concept which simultaneously dehydrates, oligomerizes, and cracks C1-C5 alcohols or mixtures thereof in one reactor is challenging due to higher temperatures required for complete dehydration (e.g., from about 300 °C to about 500 °C), and large amounts of water present.
  • Implementation of a single unit operation capable of simultaneously dehydrating, oligomerizing, and cracking olefins derived from C1-C5 alcohol dehydration requires that catalysts employed be able to withstand high temperatures along with large amounts of water and other oxygenates.
  • An exemplary single reaction step encompasses i) dehydration, ii) oligomerization to C4+ olefins, iii) skeletal rearrangement, and iv) cracking to primarily propylene along with minor amounts of C4+ olefins and aromatics.
  • This catalyst combination in a single fixed bed reactor accomplishes i) dehydration, ii) oligomerization to C4+ olefins, iii) skeletal rearrangement, and iv) cracking that results in longer catalyst time on stream (ToS), improved hydrothermal stability, and improved selectivity to olefins with lesser amounts of saturates and aromatics.
  • ToS catalyst time on stream
  • the present systems and processes may optionally include the recycle of one or more specific olefin fractions (e.g., C2+C4+C5 or C2+C5, etc.) in a closed- loop process configuration, while co-feeding the C1-C5 alcohols.
  • one or more specific olefin fractions e.g., C2+C4+C5 or C2+C5, etc.
  • This can result in the maximization of on-purpose yields to selected olefins.
  • the recycle of the C2+C4+C5 olefin fraction in combination with co-feeding C1-C5 alcohols using the present system and processes provided herein unpredictably resulted in an on-purpose propylene carbon yield exceeding 80 wt. %.
  • An exemplary single-step reaction can encompass i) in-situ dehydration, ii) oligomerization to C3+ olefins, iii) skeletal rearrangement, and iv) cracking to C2-C5 olefins along with formation of minor amounts of C5+ olefins and aromatics. Recycling the olefin fraction of choice can therefore enable on-purpose olefin production for chemicals and/or fuels production.
  • the process according to the invention implements a scheme that includes a “single” stage transformation of an aqueous C1-C5 bio-alcohols feedstock obtained from biomass into primarily C2-C5 olefinic mixture, which may be separated to isolate key low molecular weight olefins used throughout the industry as chemical building blocks, or may be easily oligomerized in high yield to C10+ hydrocarbons or diesel fraction.
  • the two stage or single stage configuration using specific catalytic systems makes it possible to minimize the production of aromatic compounds and therefore maximize production of middle distillates, which constitutes both an asset for the ethanol refiner and an advantage from the standpoint of lasting development.
  • International patent application WO 2010/097175A1 relates to the direct conversion of alcohols and oxygenates via a two-stage process in which both the first and second stage reactors in series have a commercially available type ZSM-5 zeolite catalyst added (Zeolyst CBV-28014).
  • the first reactor is brought to a temperature of 460 °C, and the temperature of the second reactor to 320 °C. After temperatures have stabilized the feed consisting of 86% methanol, 9% isopropanol, and 5% water is initiated.
  • the final liquid product is preferably hydrogenated to give gasoline cuts, or oligomerized according to conventional processes to give mixtures of gasoline, kerosene, and diesel.
  • Conversion of C1-C5 alcohols to the desired fuel product, or fuel product precursors (e.g., C2-C5 olefins) as in the case of C1-C5 alcohols, or mixtures thereof, in a single fixed bed reactor configuration, can reduce processing costs.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins is provided.
  • the process includes: contacting an input stream comprising the one or more C1-C5 linear or branched alcohols with at least a first catalyst and a second catalyst in a single bed reactor to form an output stream comprising the one or more C2-C5 olefins, the single bed reactor being at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) of about 0.5 to about 5.0.
  • WHSV weight hourly space velocity
  • Exemplary catalyst combinations, physically mixed within the single-fixed bed reactor, for C2-C5 olefin formation can include one part (e.g., a first catalyst) doped zeolites such as crystalline silicates of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or a dealuminated crystalline silicate of the group ZSM5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or a phosphorus and/or boron modified crystalline silicate of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or molecular
  • Additional additives for mixing with doped zeolites consist of SiO2 supports doped with metal dopants including iron (Fe), strontium (Sr), cobalt (Co), nickel (Ni), lanthanum (La), chromium (Cr), zirconium (Zr), ruthenium (Ru), molybdenum (Mo), iridium (Ir), magnesium (Mg), tungsten (W), copper (Cu), manganese (Mn), vanadium (V,) zinc (Zn), titanium (Ti), rhodium (Rh), rhenium (Re), gallium (Ga), palladium (Pd), silver (Ag), indium (In).
  • metal dopants including iron (Fe), strontium (Sr), cobalt (Co), nickel (Ni), lanthanum (La), chromium (Cr), zirconium (Zr), ruthenium (Ru), molybdenum (Mo), iridium (Ir), magnesium (M
  • a second part of the catalyst mixture can include a silicated, zirconated, titanated, niobium, or fluorinated y-alumina.
  • the aforementioned exemplary catalyst combination efficiently dehydrates the C1-C5 alcohols to their respective olefins, while the doped zeolite results in the oligomerization and cracking to C2-C5 olefins with lesser amounts of saturates and aromatics in comparison to literature reports utilizing a single component zeolite catalyst or metal oxide catalyst.
  • the following representative example(s) relate to converting C1-C5 alcohols, or mixtures thereof, to primarily propylene and butenes in > 85 wt. % carbon yields along with lesser amounts of C5+ olefins and aromatics (BTX) via a single unit operation with quantitative C1-C5 alcohol conversion. Furthermore, desirable carbon accountability is achieved as further indicated by no detection of carbon monoxide or carbon dioxide along with trace amounts of methane. Unreacted olefin fractions (e.g., C2-C5 olefins) may be separated and recycled resulting in the on-purpose formation in high yield and carbon accountability to the desired olefin.
  • C2-C5 olefins may be separated and recycled resulting in the on-purpose formation in high yield and carbon accountability to the desired olefin.
  • Granular or extruded catalyst(s) can be used for the reactions described herein.
  • granular or extruded catalyst(s) can have a particle size of greater than at least about 0.05 mm, about 0.1 mm or greater, or from about 0.05 mm to about 2.5 mm, including all the subranges in between.
  • granular or extruded catalysts(s) can have a particle size from about 0.4 to about 2.0 mm.
  • This disclosure describes a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins.
  • the process includes: contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with at least a first catalyst and a second catalyst in a single bed reactor to form an output stream that includes the one or more C2-C5 olefins, in which the single bed reactor is at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.5 to about 5.0, where the first catalyst includes a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si); and the second catalyst includes a doped or undoped zeolite catalyst.
  • Zr zirconium
  • Ti titanium
  • This disclosure also describes a process for converting methanol to one or more C2-C5 olefins.
  • the process includes contacting an input stream that includes the methanol with at least a first catalyst and a second catalyst in a single bed reactor to form an output stream comprising the one or more C2-C5 olefins.
  • the single bed reactor operates at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.5 to about 5.0
  • the first catalyst includes a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si).
  • the second catalyst includes a doped or undoped zeolite catalyst.
  • This disclosure also provides a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins.
  • the process can include: contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a first catalyst in a stacked bed reactor to form an output stream that includes the one or more C2-C5 olefins.
  • the stacked bed reactor is at a temperature from about 350 °C to about 550 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 1.0 to about 2.0
  • the first catalyst includes a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si).
  • the process further includes contacting the first mixture with at least a second catalyst, where the second catalyst includes a doped or undoped zeolite catalyst.
  • This disclosure also provides a process for converting methanol to one or more C2-C5 olefins.
  • the process includes contacting an input stream that includes the methanol with a first catalyst in a stacked bed reactor to form a first mixture.
  • the stacked bed reactor is at a temperature from about 350 °C to about 550 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 1.0 to about 2.0.
  • the first catalyst includes a doped or undoped alumina catalyst including, in neutral or ionic form, one or more of zirconium (Zr), titanium (Ti), tungsten (W), or silicon (Si), to form a first mixture.
  • the first mixture is then contacted with at least a second catalyst to form an output stream that includes the one or more C2-C5 olefins, and the second catalyst includes a doped or undoped zeolite catalyst.
  • contacting the input stream or first mixture further includes contacting the input stream or first mixture with a third catalyst.
  • the third catalyst may be a doped or undoped SiCh catalyst.
  • the reactor may be a fixed bed reactor, and/or a fluidized bed reactor.
  • Suitable C1-C5 linear or branched alcohols include those which are bio-based and produced by fermentative processes, and those which are not derived from petroleum.
  • the C2-C5 olefins may be present in an amount that is at least 80 wt. % of the output stream.
  • the C2-C5 olefins may be present in an amount from 80 wt. % 99 wt.
  • the C2-C5 olefins may be present in an amount that is at least 85 wt. % of the output stream.
  • the C2-C5 olefins may be present in an amount that is at least 90 wt. % of the output stream.
  • the C2-C5 olefins may be present in an amount that is at least 95 wt. % weight percent.
  • the processes disclosed herein may further include removing at least a portion of the C2 olefins from the output stream.
  • the processes may include removing at least a portion of the C4 olefins from the output stream.
  • the processes may include removing at least a portion of the C5 olefins from the output stream.
  • the reactor may be operated at a temperature from about 350 °C to about 550 °C, including all the subranges in between.
  • the reactor may be operated at a temperature from about 550 °C to about 750 °C, including all the subranges in between.
  • the reactor may be operated at a WHSV from about 0.5 to about 1.0, including all the subranges in between.
  • the reactor may be operated at a WHSV from about 2.0 to about 5.0, including all the subranges in between.
  • the reactor may be a fixed bed reactor.
  • the reactor may be a fluidized bed reactor.
  • the disclosure also describes a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system.
  • these disclosed processes use a system having only one catalyst.
  • the use of a single catalyst system can be desirable in a variety of instances, for example, when some portion of unconverted C1-C5 linear or branched alcohols and related oxygenates are acceptable in the output stream, or when the catalyst is continuously regenerated during operation, which can be implemented in, for example, fluidized bed or moving bed reactors.
  • the one or more C1-C5 linear or branched alcohols can be one or more C1-C5 linear or branched monohydric alcohols.
  • Conversion of C1-C5 alcohols to the desired fuel product, or fuel product precursors (e.g., C2-C5 olefins) as in the case of C1-C5 alcohols, or mixtures thereof with a single catalyst system can, for example, reduce processing costs and simplify and optimize the conversion process that would not otherwise be possible with a two-catalyst system.
  • the single catalyst system includes only one catalyst, such as doped zeolite.
  • the only one catalyst is not a doped or undoped alumina catalyst.
  • the zeolite can be zeolite doped with boron and phosphor.
  • Non-limited examples of zeolites olefin formation can include one part (e.g., a first catalyst) doped zeolites such as crystalline silicates of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10, or a dealuminated crystalline silicate of the group ZSM5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10.
  • a first catalyst doped zeolites such as crystalline silicates of the group ZSM-5 (MFI or BEA frameworks), CHA, FER, FAU, MWW, MOR, EUO, MFS, ZSM-48, MTT or TON having Si/Al higher than 10.
  • doped zeolites such as crystalline silicates of
  • the ZSM-5 zeolite when the zeolite is a ZSM-5 zeolite, can have a Si/AhOs ratio from about 20 to about 300. In certain embodiments, the ZSM-5 zeolite can have a Si/AhOs ratio from about 50 to about 150.
  • the single catalyst system includes only zeolite doped with boron and phosphor.
  • boron increases the stability of the phosphor during time on stream (TOS), while also maintaining selectivity. That is, the presence of boron in such instances can minimize the production of saturates and aromatics in the output stream.
  • Boron and phosphor can be present within the single catalyst system at a variety of different concentrations.
  • the boron can be present in the single catalyst system in amount from about 0.01 wt. % to about 10 wt. %, including all the subranges in between.
  • the boron can be present in the single catalyst system in an amount from about 0.05 wt. % to about 5 wt. %, including all the subranges in between.
  • the boron can be present in the single catalyst system in an amount from about 0.05 wt. % to about 3 wt. %, including all the subranges in between.
  • the boron can be present in the single catalyst system in an amount of at least 0.05 wt. %. In some embodiments, the phosphor can be present in the single catalyst system in amount from about 0.1 wt. % to about 7 wt. %, including all the subranges in between. In certain embodiments, the phosphor can be present in the single catalyst system in an amount from about 1.5 wt. % to about 6 wt. %, including all the subranges in between. In one embodiment, the phosphor can be present in the single catalyst system in an amount of at least 3 wt. %. In certain embodiments, the boron can be present in the single catalyst system in amount from about 0.5 wt. % to about 3 wt. %, and the phosphor can be present in the single catalyst system in an amount from about 2 wt. % to 6 wt. %.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a catalyst in a reactor to form an output stream comprising the one or more C2-C5 olefins, in which the catalyst consists essentially of zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 300 °C to about 600 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 10.
  • WHSV weight hourly space velocity
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a single catalyst in a reactor to form an output stream that includes the one or more C2-C5 olefins.
  • the single catalyst includes zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 350 °C to about 750 °C, a gauge pressure from 0 to about 30 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 5.0.
  • the single catalyst consists essentially of zeolite doped with boron and phosphor.
  • the process can include, after contacting the input stream with the catalyst in the reactor, regenerating the catalyst.
  • the regeneration of the catalyst can be carried out by purging any gaseous or liquid hydrocarbons or oxygenates from the reactor and then introducing air and/or oxygen optionally diluted with inert gas or steam to combust any solid carbon deposits on the catalyst.
  • the process can include, a system whereby the catalyst is circulated between a reactor in which it is contacted with the input stream and a regeneration reactor in which is it contacted with air and/or oxygen optionally diluted with inert gas or steam to combust any solid carbon deposits on the catalyst.
  • the process can further include contacting another input stream that includes the one or more C1-C5 linear or branched alcohols with the regenerated catalyst (e.g., the catalyst post-regeneration) in the reactor to form another output stream comprising one or more C2-C5 olefins.
  • the regenerated catalyst can have a lower concentration of boron, phosphor, or both compared to the catalyst prior to regeneration.
  • the reactor can be operated at a temperature from about 300 °C to about 750 °C, including all the subranges in between.
  • the reactor can be operated at a temperature from about 350 °C to about 700 °C, including all the subranges in between.
  • the reactor can be operated at a temperature from about 300 °C to about 600 °C.
  • the reactor can be operated at a gauge pressure from 0 to about 30 bar, including all the subranges in between.
  • the reactor can be operated at a gauge pressure from 0 to about 5 bar, including all the subranges in between.
  • the reactor can be operated at a gauge pressure of about 6 or lower.
  • the reactor can be operated at a WHSV from about 0.1 to about 10, including all the subranges in between.
  • the reactor can be operated at a WHSV from about 0.25 to about 10, including all the subranges in between.
  • the reactor can be operated at a WHSV from about 0.25 to about 5, including all the subranges in between.
  • the reactor can be operated at a WHSV from about 1 to about 10, including all the subranges 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.
  • the C2-C5 olefins can be present in the output stream in an amount that is at least 50 wt. % of the total hydrocarbon products in the output stream.
  • the total hydrocarbon products in the output stream does include any water that can be present in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount from about 50 wt. % to about 85 wt. %, including all the subranges in between, of the total hydrocarbon products in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount from about 50 wt. % to about 99 wt.
  • the C2-C5 olefins can be present in the output stream in an amount from about 70 wt. % to about 99 wt. %, including all the subranges in between, of the total hydrocarbon products in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount from about 85 % wt. to about 99 wt. %, including all the subranges in between, of the total hydrocarbon products in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount that is at least 85 wt. % of the total hydrocarbon products in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount that is at least 90 wt. % of the total hydrocarbon products in the output stream.
  • the C2-C5 olefins can be present in the output stream in an amount that is at least 95 wt. % of the total hydrocarbon products in the output stream.
  • the processes disclosed herein can further include removing at least a portion of the C2 olefins from the output stream.
  • the processes can include removing at least a portion of the C3 olefins from the output stream.
  • the processes can include removing at least a portion of the C4 olefins from the output stream.
  • the processes can include removing at least a portion of the C5 olefins from the output stream.
  • a process for converting one or more C1-C5 linear or branched alcohols to one or more C2-C5 olefins using a single catalyst system can include contacting an input stream that includes the one or more C1-C5 linear or branched alcohols with a catalyst in a reactor to form an output stream that includes the one or more C2-C5 olefins.
  • the catalyst consists essentially of ZSM-5 zeolite doped with boron and phosphor.
  • the reactor is at a temperature from about 350 °C to about 475 °C, a gauge pressure from 0 to about 5 bar, and a weight hourly space velocity (WHSV) from about 0.25 to about 10.
  • the boron is present in the catalyst in an amount from about 0.05 wt. % to about 5 wt. %, and the phosphor is present in the catalyst in an amount from about 0.2 wt. % to about 7 wt. %.
  • Alcohol (i.e., C1-C5) conversion to C2-C5 olefins was carried out at 300 °C-500 °C, via fixed bed reactors, containing specified catalyst(s), and flowing preheated (160 °C) vaporized alcohol in a downward flow over the fixed catalyst bed while co-feeding nitrogen at atmospheric pressure or under moderate pressures (i.e., 0-30 bar).
  • the flow rate of alcohol was controlled by Teledyne Model 500D syringe pumps, and the flow rates were adjusted to obtain the targeted olefin WHSV (weight hourly space velocity).
  • the internal reaction temperature was maintained constant via a Lindberg Blue M furnace as manufactured by Thermo-Scientific.
  • Alcohol conversion and selectivity was calculated by analysis of the liquid phase reactor effluent by GC for organic and water content, online GC analysis of noncondensed hydrocarbons (i.e., C2-C5 olefins), and on-line thermal conductivity detector for quantitation of CO, CO2 and CH4 relative to nitrogen as internal standard.
  • C2-C5 olefins noncondensed hydrocarbons
  • on-line thermal conductivity detector for quantitation of CO, CO2 and CH4 relative to nitrogen as internal standard.
  • Zr-y- Alumina catalyst was prepared by incipient wetness technique as described.
  • the precursor metal salts (Sigma Aldrich): 2.64g Zirconium (IV) oxynitrate hydrate was dissolved in deionized water (14.9 mL). Upon salt dissolution, the solution was added in dropwise fashion to 15g y-alumina support. The resulting mixed metal oxide was manually mixed to assure complete wetting, and the resulting impregnated catalyst was dried at 160 °C for 1 hr, and afterwards calcined at 500 °C for 4 hrs.
  • Boron and Phosphor impregnated zeolite catalyst was prepared by incipient wetness technique as described. 0.78g phosphoric acid (85%) and 0.96g boric acid (99+%) was dissolved in deionized water (7.4 mL). Upon heating and dissolution, the solution was added in dropwise fashion to 6g ZSM-5 zeolite support (i.e., Zeolyst type CBV-5524 H + ). The resulting impregnated catalyst was dried at 160 °C for 1 hr, and afterwards calcined at 550 °C for 3-15 hrs.
  • FIG. 1 shows a single stage reactor system 1000. As shown in the figure, an input 100, such as hydrous ethanol (92%) may be fed into a fixed bed reactor 300, to produce an output 200, such as a C2-C5 olefin mixture having the final output given in Table 4 above.
  • an input 100 such as hydrous ethanol (92%) may be fed into a fixed bed reactor 300, to produce an output 200, such as a C2-C5 olefin mixture having the final output given in Table 4 above.
  • recycle streams Rl, R2, and R3 may recycle C2, C4, and C5 olefins respectively, back into the input 100 to be fed back into the fixed bed reactor 300.
  • Wastewater 400 may also be produced in situ by the fixed bed reactor 300, via dehydration of ethanol to ethylene, and thus condensed and removed as part of the output 200.
  • Example 7 Simultaneous dehydration, dimerization, skeletal rearrangement, and cracking of C1-C5 bio-based or petro-based alcohols and mixtures thereof to C2-C7 olefins
  • the purpose of this example is to provide data illustrating the conversion of C1-C5 bio-based or petro-based alcohols to C2-C7 olefinic mixtures, having low levels of aromatic compounds. Details of the reactor set up and resulting effluent stream, as well as yield data, are provided below.
  • Catalyst Zirconated (4.0 wt%) y-Alumina.
  • Example 10 Repeated use of Boron and Phosphor Doped Zeolite with Zr-alumina
  • Admixed catalyst was subjected to 24 hours time on stream, then repeatedly regenerated and resubjected to reaction conditions.
  • Example 11 Impact of Boron and Phosphor Loading on Catalytic Activity and Stability
  • Catalysts were subjected to 24 hours time on stream, then repeatedly regenerated and resubjected to reaction conditions.
  • the data shown in FIG. 4 illustrates ethylene conversion over repeated uses of a phosphor doped zeolite.
  • the exemplary cycles with the boron and phosphor doped zeolite (Example 10) are more stable than the exemplary cycles with the phosphor doped zeolite (example 12).
  • the presence of boron can allow for greater C2 conversion over longer times on stream, which can also provide for more consistent catalytic activity.

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Abstract

L'invention concerne des procédés de conversion d'un ou de plusieurs alcools en C1-C5 linéaires ou ramifiés en une ou plusieurs oléfines en C2-C5. Dans un mode de réalisation donné à titre d'exemple, le procédé peut être un procédé en une seule étape pour la conversion directe d'alcools en C1-C5 en mélanges oléfiniques (par exemple, C2-C5) mis en œuvre dans un réacteur à l'aide d'un catalyseur qui comprend une zéolite dopée avec du bore et du phosphore. L'invention concerne également des systèmes pour mettre en œuvre ces procédés.
PCT/US2023/035708 2022-10-27 2023-10-23 Procédés de conversion catalytique d'alcools en c1-c5 en mélanges d'oléfines en c2-c5 WO2024091452A1 (fr)

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US4049573A (en) * 1976-02-05 1977-09-20 Mobil Oil Corporation Zeolite catalyst containing oxide of boron or magnesium
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WO2010097175A1 (fr) 2009-02-26 2010-09-02 Eni S.P.A. Procédé de conversion directe de composés oxygénés en hydrocarbures liquides ayant une teneur en composés aromatiques réduite
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