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WO2025054118A1 - Réglage de la sélectivité d'une réaction au moyen d'un chauffage par induction - Google Patents

Réglage de la sélectivité d'une réaction au moyen d'un chauffage par induction Download PDF

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Publication number
WO2025054118A1
WO2025054118A1 PCT/US2024/044989 US2024044989W WO2025054118A1 WO 2025054118 A1 WO2025054118 A1 WO 2025054118A1 US 2024044989 W US2024044989 W US 2024044989W WO 2025054118 A1 WO2025054118 A1 WO 2025054118A1
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Prior art keywords
catalyst
catalyst bed
oxide
combination
bed
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English (en)
Inventor
Carlos Lizandara Pueyo
Jian-Ping Chen
Amit A GOKHALE
Erdem Sasmaz
Han Wang
Ben Ko
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BASF Corp
University of California Berkeley
University of California San Diego UCSD
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BASF Corp
University of California Berkeley
University of California San Diego UCSD
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00433—Controlling the temperature using electromagnetic heating
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00539—Pressure

Definitions

  • the present disclosure generally relates to the field of catalytic systems including a bifunctional or multifunctional catalyst bed. More specifically, it relates to a system that includes induction heating to influence the temperature of the catalyst bed.
  • a system in an embodiment, includes a reactor; and an induction heater, wherein the reactor comprises a multifunctional catalyst bed, wherein the multifunctional catalyst bed comprises a first catalyst bed and one or more additional catalyst bed(s).
  • the first catalyst bed may include a first catalyst.
  • the first catalyst may be a copper-based catalyst, a manganese-based catalyst, a zirconium based catalyst, or a combination thereof.
  • the copper-based catalyst may include copper in combination with at least one of manganese (Mn), aluminum, (Al), zirconium (Zr), chromium (Cr). zinc (Zn), or a combination thereof.
  • the manganese-based catalyst may include manganese oxide.
  • the zirconium-based catalyst may include zirconium oxide.
  • the first catalyst may include a support.
  • the one or more additional catalyst bed(s) may include a second catalyst.
  • the second catalyst may include at least one of a metal oxide, a metal, or a support.
  • the metal oxide may include a copper oxide (CuO, C112O. or CU2O3), a manganese oxide (MnO, MmCh or MnCh), an aluminum oxide (AI2O3), a zirconium oxide (Z1O2), a tantalum oxide (TazOs), a magnesium oxide (MgO), or a combination thereof.
  • the metal may include silver (Ag), cobalt (Co), copper (Cu), titanium (Ti), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), rhodium (Rh), ruthenium (Ru), zirconium (Zr). zinc (Zn), iron (Fe), or a combination thereof.
  • the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate, or a combination thereof.
  • the silicon may include fumed SiCh, SiCh gel, or a combination thereof.
  • the induction heater may include a ferromagnetic material.
  • the ferromagnetic material may include cobalt.
  • the ferromagnetic material may be impregnated with the first catalyst, the second catalyst or a combination thereof.
  • the induction heater may be configured to heat the first catalyst bed to a first average temperature and the second catalyst bed to a second average temperature.
  • the first average temperature range may be about 150°C to about 300°C
  • the second average temperature may be about 250°C to about 500°C.
  • the first average temperature and the second temperature may have a temperature difference between at least about 25°C.
  • the reactor may be configured to receive a feed of ethanol optionally mixed with an inert gas.
  • the inert gas may include nitrogen, argon or helium.
  • the first catalyst bed may be configured to perform an ethanol dehydrogenation reaction.
  • the ethanol dehydrogenation reaction may produce acetaldehyde.
  • the one or more additional catalyst bed(s) may be configured to receive ethanol and acetaldehyde.
  • a reaction in the one or more additional catalyst bed(s) may produce 1,3-butadiene.
  • the reaction may have about 15% to about 100% selectivity to a C4 product.
  • a method for converting ethanol into a C4 product includes feeding ethanol to a reactor comprising a multifunctional catalyst bed, and heating the reactor via an induction heater, wherein the multifunctional catalyst bed includes a first catalyst bed and one or more additional catalyst bed(s).
  • the first catalyst bed may include a first catalyst.
  • the first catalyst may include a copper-based catalyst, a manganese-based catalyst, a zirconium-based catalyst, or a combination thereof.
  • the copper-based catalyst may include copper in combination with at least one of manganese (Mn), aluminum, (Al), zirconium (Zr), chromium (Cr), zinc (Zn), or a combination thereof.
  • the manganese-based catalyst may include manganese oxide.
  • the zirconium- based catalyst may include zirconium oxide.
  • the first catalyst may include a support.
  • the one or more additional catalyst bed(s) may include a second catalyst.
  • the second catalyst may include at least one of a metal oxide, a metal, or a support.
  • the metal oxide may include copper oxide, manganese oxide, aluminum oxide, zirconium oxide (ZrCh). tantalum oxide (Ta20s), magnesium oxide (MgO) or a combination thereof.
  • the metal may include silver (Ag), cobalt (Co), copper (Cu), titanium (Ti), platinum (Pt), ruthenium (Ru), zirconium (Zr), zinc (Zn), iron (Fe), aluminum (Al), or a combination thereof.
  • the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof.
  • the silicon may include fumed SiCh, SiCh gel, or a combination thereof.
  • the induction heater may include a ferromagnetic material. In some embodiments, the ferromagnetic material may include cobalt. In some embodiments, the induction heater heats the first catalyst bed to a first average temperature and heats the one or more additional catalyst bed(s) to a second average temperature. In some embodiments, the first average temperature may be about 150°C to about 300°C, and the second average temperature may be about 250°C to about 500°C. In some embodiments, the method may be performed at a pressure of about 0. 1 bar to about 100 bar. [00025] In certain embodiments, the space velocity for the first catalyst bed may be about 1 (h‘ ') to about 50 (h -1 ). In certain embodiments, the space velocity for the one or more additional catalyst bed may be about 0.5 (h' 1 ) to about 50 (h -1 ).
  • FIG. 1 illustrates a process for heating multiple temperature zones using an induction heater in a single reactor.
  • FIG. 4 is a comparison of catalysts' performances for individual and tandem reactions.
  • FIG. 5 is a comparison of catalyst’s activity with induction heating and furnace heating
  • FIG. 6 is a comparison of catalyst performances in the tandem system at different WHSVs and reaction temperature of the Example.
  • FIG.7 is a graph showing changes in temperature based on amount of Co powder in bed 2 of the Example.
  • FIGs. 8a and 8b illustrate the catalyst performances in the tandem system at different reaction temperatures of bed 1 of the Example.
  • FIGs. 9a and 9b illustrate the conversion and selectivity with a furnace and comparison of single bed and tandem system, respectively, of the Example.
  • FIG. 10 represents the main reaction pathway of the ethylene butadiene reaction.
  • FIGs. l la-c show a comparison between the tandem Ostromislensky reaction with induction heating and the Lebedev process with the benchmark 4wt% Ag/4wt% ZrO2/SBA-16 catalyst with furnace heating.
  • reaction sy stems utilize a traditional furnace to heat the reactors within the system. This method of heating has several shortcomings including nonuniform heating distribution and lower catalysis selectivity.
  • the reaction may require a variety of different temperatures depending on the desired product.
  • the Ostromislensky process involves a two-step reaction to produce 1,3-butadiene from ethanol. First, ethanol undergoes dehydrogenation to form acetaldehyde, and then 1,3-butadiene is produced from ethanol and acetaldehyde.
  • using a single reactor with conventional furnace heating makes the 1,3- butadiene production inefficient.
  • an induction heater improves the selectivity and efficiency of the heating within the reactor.
  • the induction heater allows for separate reaction temperature zones to be achieved in a single reactor by adjusting the amount of the susceptors, such as ferromagnetic material, so that two-step reactions may be performed in a tandem system to increase selectivity to the desired products.
  • the present disclosure relates to a system and a method for including induction heating in a chemical reactor having a bifunctional or multifunctional catalysis bed.
  • the system and method of the present disclosure may be used with a reactor for the conversion of ethanol to a C4 product, such as 1,3-butadiene.
  • the system of the present disclosure can be applied to any system that could benefit from using multiple temperature zones within the same reactor either having one catalyst bed or a plurality of catalyst beds.
  • such systems may include converting syngas to MeOH, MeOH to DME, CO2 hydrogenation and/or a Fischer-Tropsch process.
  • the system and method as described herein provide temperature control of a multifunctional catalyst bed having multiple temperature zones. By being able to control the temperature within the multifunctional catalyst bed, it enables high selectivity to C4 products as well as higher yield and operating efficiency than previous heating methods.
  • the term “about” or “approximately” in connection with a measured quantity' refers to the normal variations in that measured quantity as expected by one of ordinary' skill in the art in making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment. In certain embodiments, the term “about” includes the recited number ⁇ 10%, such that “about 10” would include from 9 to 11.
  • the term “C4 product” refers to a hydrocarbon that includes four carbon atoms in its chemical structure, wherein the chain may be linear or branched as well as saturated or unsaturated.
  • C4 product may refer to, but is not limited to, 1,3-butadiene, butane, isobutane, but-l-ene, but-2-ene, but-l-yne, but-2-yne, isobutylene, 1,2-butadiene, vinylacetylene, diacetylene, or a combination thereof.
  • a system has been developed that includes a reactor including a multifunctional catalyst bed and an induction heater.
  • the multifunctional catalyst bed may include a first catalyst bed and one or more additional catalyst beds.
  • the multifunctional catalyst bed may include a plurality’ of catalyst beds.
  • the multifunctional catalyst bed may refer to a system having more than one catalyst bed, such as a bifunctional catalyst bed or trifunctional catalyst bed, that requires a plurality’ of different temperatures.
  • a multifunctional catalyst bed including a first catalyst bed and a second catalyst bed will be described herein.
  • reference to second catalyst bed and one or more additional catalyst bed(s) are used interchangeably herein.
  • the first catalyst bed may include a first catalyst.
  • the first catalyst may include a copper-based catalyst, a manganese-based catalyst, a zirconium-based catalyst, or a combination thereof.
  • the first catalyst may include a copper-promoted catalyst, a manganese-promoted catalyst, a zirconium-promoted catalyst, or a combination thereof.
  • the copper-based catalyst may include a supported copper catalyst, copper(II) acetlacetonate, metallic copper, copper supported on silica, copper oxide active species, a copper crystallite, a copper-manganese catalyst, copper nitrate, copper acetate, an oxidized copper cluster, copper-chromium, copper-zinc-aluminum, copper-zinc-chromium, copper chromite, copper oxide, or a combination thereof.
  • the copper-based catalyst may include copper in combination with at least one of manganese (Mn), aluminum (Al), zirconium (Zr), chromium (Cr). zinc (Zn), or a combination thereof.
  • the manganese-based catalyst may include manganese oxide.
  • the zirconium-based catalyst may include zirconium oxide.
  • the ferromagnetic material may be mixed with a catalyst, such as by being impregnated with a catalyst.
  • the catalyst may be any of the catalysts as described herein, i.e. the first catalyst and/or the second catalyst.
  • the temperature difference between the first average temperature and the second average temperature may be at least about 25°C, at least about 35°C, at least 45°C, at least about 50°C, at least about 75°C, at least about 100°C, at least about 125°C, at least about 135°C, at least about 145°C, or at least about 150°C.
  • the first average temperature may be higher than the second average temperature, while in other embodiments, the first average temperature may be lower than the second average temperature.
  • the second average temperature may be in a range about 250°C to about 500°C, about 260°C to about 490°C, about 270°C to about 480°C, about 280°C to about 470°C, about 290°C to about 460°C, about 300°C to about 450°C, about 310°C to about 440°C, about 320°C to about 430°C, about 330°C to about 420°C, about 340°C to about 410°C. about 350°C to about 400°C, about 360°C to about 390°C, about 370°C to about 380°C.
  • the feed of ethanol may include a carrier gas.
  • the carrier gas may include hydrogen
  • the carrier gas may include carbon dioxide.
  • the multifunctional catalyst bed When the system is used to convert ethanol to a C4 product, such as butadiene, the multifunctional catalyst bed includes a first catalyst bed and a second catalyst bed.
  • the first catalyst bed is configured to perform an ethanol dehydrogenation reaction. During the ethanol dehydrogenation reaction, acetaldehyde is produced.
  • the second catalyst bed is configured to receive ethanol and acetaldehyde and perform a reaction to produce at least 1.3-butadiene as a product.
  • syngas may be converted to methanol by providing a feed of syngas to be received by the first catalyst bed.
  • the feed of syngas may be mixed with one of the carrier or inert gases previously described.
  • the first catalyst bed may be configured to perform the conversion of syngas to methanol.
  • the second catalyst bed may be configured to receive methanol and any unconverted syngas. The second catalyst bed may then be configured to perform further conversion of the methanol to light olefins.
  • the first catalyst bed and the second catalyst bed are heated using an inducted heater such that the first catalyst bed and the second catalyst bed are heated to different temperatures.
  • a reaction in the second catalyst bed/one or more additional catalyst bed(s) may produce a C4 product.
  • the C4 product may include 1,3 -butadiene.
  • the reaction may have a selectivity to the C4 product of about 15% to about 100%, about 20% to about 99%, about 25% to about 95%, about 30% to about 90%, about 35% to about 85%, about 40% to about 80%, about 45% to about 75%, or about 50% to about 70%.
  • a method is provided to perform at least the ethanol dehydrogenation reaction. The method includes feeding ethanol to a reactor that includes a multifunctional catalyst bed as described herein. That is, the multifunctional catalyst bed includes a plurality' of catalyst beds.
  • the multifunctional catalyst includes a first catalyst bed, a second catalyst bed, a third catalyst bed or more as needed to perform the reaction.
  • the method may further include heating the reactor via an induction heater.
  • the reactor may include an induction reactor, a thermal reactor, a fixed bed reactor, a semi-batch reactor, a slurry reactor, or a mixed-bed reactor.
  • the first catalyst bed includes a first catalyst
  • the second catalyst bed includes a second catalyst.
  • the first catalyst and the second catalyst may be the same catalyst or may be different catalysts.
  • the first catalyst may include a metal oxide, a copper-based catalyst, a manganese-based catalyst, a zirconium-based catalyst, or a combination thereof. In other embodiments, the first catalyst may include a copper-promoted catalyst, a manganese- promoted catalyst, a zirconium-promoted catalyst, or a combination thereof.
  • the copper-based catalyst may include a supported copper catalyst, copper(II) acetlacetonate, metallic copper, copper supported on silica, copper oxide active species, a copper crystallite, a copper-manganese catalyst, copper nitrate, copper acetate, an oxidized copper cluster, copper-chromium, copper-zinc-aluminum, copper-zinc-chromium, copper chromite, copper oxide, or a combination thereof.
  • the copper-based catalyst may include copper in combination with at least one of manganese (Mn), aluminum (Al), zirconium (Zr), chromium (Cr), zinc (Zn), or a combination thereof.
  • the metal oxide may include a copper oxide (CuO, CU2O, or CU2O3), a manganese oxide (MnO, MmCh or MnCh). an aluminum oxide (AI2O3), a zirconium oxide (ZrCh), a tantalum oxide (Ta20s), a magnesium oxide (MgO), or a combination thereof.
  • the manganese-based catalyst may include manganese oxide.
  • the zirconium-based catalyst may include zirconium oxide.
  • the first catalyst may further include a support.
  • the second catalyst bed may include a second catalyst.
  • the second catalyst may include at least one of a metal oxide, a metal, or a support.
  • the metal oxide may include a copper oxide (CuO, CU2O. or CU2O3), a manganese oxide (MnO, MmCh or MnCh), an aluminum oxide (AI2O3), a zirconium oxide (ZrCh), a tantalum oxide (Ta2C>5), a magnesium oxide (MgO), or a combination thereof.
  • the metal may include at least one of silver (Ag) , cobalt (Co), copper (Cu), titanium (Ti), platinum (Pt), ruthenium (Ru), zirconium (Zr), zinc (Zn).
  • the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof.
  • the silicon may include fumed SiCh. S1O2 gel, or a combination thereof.
  • the first catalyst or the second catalyst may include a catalyst binder.
  • catalyst binders may include silica, alumina, silica-alumina, silica- titania, silica-thoria, silica-magnesia, silica-zirconia, silica-beryllia, ternary' compositions of silica with other refractory oxides, and the like.
  • other matrices may include clays, such as naturally occurring clays illustrated by montmorillonites, kaolines, bentonites, halloysites, dickites, nacrites and anauxites.
  • the first catalyst or the second catalyst may include a metal containing catalyst, a heterogenous catalyst including a platinum group metal, a heterogenous catalyst including a transition metal, or a combination thereof.
  • the induction heater includes a ferromagnetic material.
  • the ferromagnetic material includes cobalt.
  • the ferromagnetic material includes iron, nickel, or a combination thereof.
  • the cobalt is cobalt powder.
  • the ferromagnetic material may be mixed with the first catalysis and/or the second catalysis.
  • the induction heater may be supplied with about 145 watts to about 10,000 watts of power, about 200 watts to about 9,500 watts, about 250 watts to about 9,000 watts, about 300 watts to about 8,500 watts, about 350 watts to about 8,000 watts, about 400 watts to about 7,500 watts, about 450 watts to about 7,000 watts, about 500 watts to about 6,500 watts, about 550 watts to about 6,000 watts, about 600 watts to about 5,500 watts, about 650 watts to about 5,500 watts, about 700 watts to about 5,000 watts, about 750 watts to about 4,500 watts, about 800 watts to about 4,000 watts, about 850 watts to about 3,500 watts, about 900 watts to about 3,000 watts, about 950 watts to about 2,500 watts, or about 1,000 watts to about
  • the induction heater may heat the first catalyst bed to a first average temperature and may heat the second catalyst bed to a second average temperature. [00095] As described above, the heating may produce multiple average temperatures depending on the multifunctional catalyst bed used.
  • the first average temperature is about 180°C to about 275°C, about 190 °C to about 270°C, about 200 °C to about 260°C, about 210°C to about 250°C, or about 220°C to about 240°C.
  • the second average temperature is about 300°C to about 400°C, about 310°C to about 390°C, about 320°C to about 380°C, about 330°C to about 370°C, or about 340°C to about 360°C.
  • the temperature difference between the first average temperature and the second average temperature is at least about 25°C, at least about 35°C, at least about 45°C, or at least about 50°C, or about 10°C to about 150°C, about 15°C to about 125°C, about 20°C to about 100°C, or about 25°C to about 75°C.
  • the method may be performed at a pressure of about 0. 1 bar to about 100 bar, about 1 bar to about 95 bar, about 5 bar to about 90 bar, about 10 bar to about 85 bar, about 15 bar to about 80 bar, about 20 bar to about 75 bar, about 25 bar to about 70 bar, or about 35 bar to about 50 bar.
  • the first catalyst may have a first space velocity' of about 1 (h -1 ) to about 50 (h 1 ). In other embodiments, the first catalyst may have a first space velocity of about 5 (h -1 ) to about 45 (h -1 ), about 10 (h -1 ) to about 40 (h’ 1 ), about 15 (h' 1 ) to about 35 (h' 1 ), or about 20 (h -1 ) to about 30 (h -1 ).
  • the second catalyst may have a second space velocity of about 0.6 (h' 1 ) to about 50 (h' 1 ). In other embodiments, the second catalyst may have a second space velocity of about 1 (h -1 ) to about 45 (h -1 ), about 10 (h -1 ) to about 40 (h -1 ), about 15 (h -1 ) to about 35 (h -1 ), or about 20 (h -1 ) to about 30 (h -1 ).
  • the first catalyst bed includes at least about 5% to about 70% of the first catalyst as described herein.
  • the second catalyst bed includes at least about 5% to about 70% of the second catalyst as described herein.
  • FIG. 1 illustrates the schematics of the process for the heating of a multifunctional catalyst bed with multiple temperature zones with an induction heater 100 according to an embodiment of the present disclosure.
  • an ethanol and inert gas feed 105 is fed into a first catalyst bed 110.
  • the first catalyst bed contains a first catalyst that may be configured to perform an ethanol dehydrogenation reaction. After performing the first step of the ethanol dehydrogenation reaction, acetaldehyde may be produced and feed to the second catalyst bed 115.
  • the second catalyst bed 115 is also be configured to receive any remaining ethanol along with the acetaldehyde.
  • the second catalyst bed includes a second catalyst. After performing the reaction, a product of C4 is produced.
  • the first catalyst bed 110 may be heated to a first temperature range.
  • the second catalyst bed 1 15 may be heated to a second temperature range.
  • the first and second temperature ranges are achieved by heating via the induction heater 120.
  • the tandem system includes a single reactor having two catalyst beds to perform the reaction.
  • the C4 selectivity is tuned by individually controlling the reaction temperature and weight hourly space velocity (WHSV) of each catalyst bed.
  • WHSV weight hourly space velocity
  • the ethanol-acetaldehyde reaction was conducted using the commercial catalyst (BASF Cu 0582E), which contains 52% CuO on AI2O3.
  • the catalysts were prepared using incipient wetness impregnation.
  • zirconium (IV) oxynitrate hydrate Sigma- Aldrich, 99.99% trace metal basis
  • was dissolved in deionized water and added dropwise to fumed SiCh (Sigma-Aldrich, powder, 0.2-0.3 pm avg. particle size).
  • the mixture was dried overnight at room temperature, heated to 120 °C for 1 hour at a ramping rate of 5 °C/min, and then calcined at 610 °C for 6 hours at a ramping rate of 2 °C/min.
  • the SBA-16 support (ACS Material) was calcined at 700°C for 8 hours prior to the synthesis.
  • Silver nitrate (Fisher Scientific, 99.85%) and zirconyl nitrate solution (Sigma-Aldrich, 35 wt% in diluted nitric acid, > 99 % trace metals basis) were mixed in DI water and added dropwise to the calcined SBA-16 support after cooled downed to the room temperature.
  • the mixture was dried overnight and then calcined at 500 °C for 4 hours.
  • the Cu/AbOs catalyst, ZrO2/SiO2, and SiCh gel were physically mixed with Co powder (Sigma- Aldrich, 2 pm particle size, 99.8% trace metals basis) for tandem experiments with induction heating.
  • the Brunauer- Emmett-Teller (BET) surface areas and pore size distribution were determined by N2 adsorption using Micromeritics MicroActive TriStar II Plus.
  • the analysis bath temperature is -195.8 °C, and the relative pressure (P/Po) was in the range of 0 to 0.99.
  • FIG. 1 illustrates a sketch of a (a) single bed reactor for step 1 or step 2 reaction of the Ostromislensky process and (b) tandem reactor for ETB reaction with induction heating.
  • a fused quartz reactor of 7 mm I.D. x 9.5 mm O.D. (grey) insulated by ceramic fiber is inserted in a copper coil.
  • Fig. 1 illustrates a sketch of a single bed reactor for step 1 or step 2 reaction of the Ostromislensky process and (b) tandem reactor for ETB reaction with induction heating.
  • the catalyst bed contained a mixture of C11/AI2O3 and Co powder for the ethanol dehydrogenation reaction or a mixture of ZrCh/Sith and Co powder to convert ethanol and acetaldehyde mixture.
  • bed 1 had the same mixture as the single-bed configuration for the ethanol dehydrogenation reaction, while bed 2 contained a ZrO2/SiO2 catalyst and Co powder to covert ethanol and acetaldehyde produced from bed 1.
  • 316 stainless steel (SS) beads or mesh were mixed to enhance heating if specified.
  • a laser pyrometer (Micro-Epsilon, focus: 0.5 mm @ 150 mm) was connected to a PID controller (Omega) to control the reaction temperature.
  • a PID controller (Omega) to control the reaction temperature.
  • one pyrometer was used to control the temperature of bed 2, and an additional pyrometer was applied to monitor the temperature of bed 1.
  • the Cu/AhOs catalyst was reduced using a 20% H2 in N2 at a total flow rate of 25 ccm for 3 hours at 180°C prior to the reaction in both the single-bed and tandem system.
  • a comparative process using a conventional furnace heater was used with Ag/ZrO2/SBA-l 6 catalyst.
  • the catalyst activity was tested with furnace heating using a clam-shell ceramic fiber furnace (Watlow).
  • the Ag/ZrCh/SB A- 16 catalyst was first pretreated with 50 ccm N2 at 500 °C for 8 hours to remove the residual NOs" then reduced under 20% H2 in N2 with a total flow rate of 25 ccm at 325°C.
  • the amount of Co powder in each catalyst bed and the distance between bed 1 and bed 2 were adjusted accordingly. The details of the catalysts and Co amount, as well as the bed distance are described below. Additionally, four separate heating layers containing 15 mg Co powder each were placed above the first catalyst bed with 17 mm in between to pre-heat the ethanol inlet vapor to ensure the ethanol remained in gas form.
  • the XRD pattern is shown in Figure 3 of the ZrCh/SiCh catalyst indicates no diffraction patterns for ZrCh on amorphous SiCh, indicating that ZrCh is well-dispersed over the support.
  • the individual activities of C11/AI2O3 and ZrCh/SiCh catalysts, as well as tandem Ostromislenksy reaction with two catalyst beds were evaluated, as shown in Figure 4 and Table 1 below.
  • tandem system as opposed to the single ZrCh/SiCh catalyst bed, enhanced acetaldehyde selectivity to 45.1% from 3.4%. This suggests that Cu/AhCh in the tandem system effectively converted ethanol to acetaldehyde, and the residual ethanol and produced acetaldehyde were subsequently reacted in the second catalyst bed, ZrCh/SiCh, to yield 1,3-butadiene.
  • the tandem operation of two beds at distinct temperature zones significantly improved the selectivity of C4 products, affirming the potential for the Ostromislensky process to be integrated into a single reactor with induction heating.
  • Fig. 6 and Table 3 show the ethanol conversion and selectivities to C4 products at different WHSVs and reaction temperatures of the catalyst beds in the tandem system.
  • the Lebedev process involves studying reaction conditions ranging from 0.04 h' 1 to 0.474 h’ 1 .
  • the WHSV of bed 2 was reduced from 2.4 h' 1 to 0.6 h’ 1 .
  • the ZrCh/SiCh catalyst was pelletized into particles ranging from 250 pm to 425 pm in diameter to decrease the overall volume.
  • the bulk density increased from 0.3 mg/mm’ to 0.5 mg/mm 3 after palletization, resulting in almost a 50% decrease in volume.
  • Fig. 7 shows the change of Ti with the Co amount in bed 2 while T2 was controlled at 320 °C.
  • a higher Co content in bed 2 resulted in reduced overall energy consumption, leading to a weaker magnetic field and less heat generation in bed 1.
  • Ti reached 245 °C, whereas this temperature decreased to 171 °C with 200 mg of Co.
  • Fig. 8 (a) depicts the time-on-stream (TOS) data for Ti values of 171 °C, 178 °C, 215 °C, and 245 °C at a constant T2 of 320 °C.
  • TOS time-on-stream
  • the data illustrates that ethanol conversion increased with the reaction temperature.
  • Ti 245 °C
  • Fig. 8 (b) and Table 4 show- the product selectivities influenced by the bed 1 reaction temperature in the tandem system.
  • the selectivities of C4 products were 55.3%, 28.9%, 30.7%, and 58.6% at Ti of 171 °C, 178 °C, 215 °C, and 245 °C, respectively.
  • As Ti increased, the conversion of ethanol to acetaldehyde decreased. This suggests that a preferred ethanol-to-acetaldehyde ratio could be achieved at the lower Ti, resulting in higher selectivity to C4 at Ti 171 °C.
  • Co has negligible effect in the first reaction, it can participate in the second reaction and convert ethanol to acetaldehyde at temperatures of 300 °C and 350 °C, as shown in Fig. 9 (a) and Table 4.
  • the ethanol conversion and acetaldehyde selectivity increased with the reaction temperature.
  • Co affects the ethanol-to-acetaldehyde ratio over the ZrC SiCh in the tandem Ostromislensky reaction, due to its role in converting ethanol to acetaldehyde.
  • Fig. 10 shows the ETB reaction pathway, where the ethanol dehydrogenation reaction (step a) occurs separately over the Cu/AhCh catalyst in the tandem system. Since ethanol dehydration to ethylene competes with ethanol dehydrogenation reaction, a higher ethanol concentration favors ethylene production over acetaldehyde. Conversely, a lower ethanol concentration is insufficient to reduce crotonaldehyde to crotyl alcohol, causing the reactions to shift back to acetaldehyde and thus inhibiting 1,3-butadiene production. It has been reported that an ethanol-to-acetaldehyde ratio of 1 : 1 is optimal for the second step in the ETB reaction.
  • This can be achieved by applying induction heating to a tandem system, i.e., a system including a multi catalyst bed, through which the hysteresis loss from the susceptors generates heat to establish two temperature zones for the two-step reaction within a single reactor.
  • the tandem system utilizes acetaldehyde, formed during the first step of the reaction, as the intermediate for the second-step reaction. Consequently, only ethanol needs to be supplied as a feed.
  • the term “of’ may mean “comprising.”
  • a liquid dispersion of may be interpreted as “a liquid dispersion comprising.”
  • a or “an” entity refers to one or more of that entity, e.g., “a compound” refers to one or more compounds or at least one compound unless stated otherwise.
  • the terms “a” (or “an”), “one or more”, and “at least one” are used interchangeably herein.
  • the term “and/or” includes any and all combinations of one or more of the associated listed items. Additionally, as used herein, “or” means “and/or.”
  • Claims or descriptions that include “or” or “and/or” between at least one member of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary' or otherwise evident from the context.
  • the disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process.
  • the disclosure includes embodiments in which more than one, or all the group members are present in, employed in, or otherwise relevant to a given product or process.
  • the disclosure encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, and descriptive term from at least one of the listed claims is introduced into another claim.
  • any claim that is dependent on another claim can be modified to include at least one limitation found in any other claim that is dependent on the same base claim.
  • elements are presented as lists, such as, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should be understood that, in general, where the disclosure, or aspects of the disclosure, is/are referred to as comprising particular elements and/or features, embodiments of the disclosure or aspects of the disclosure consist, or consist essentially of, such elements and/or features.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un système et un procédé associé impliquant le chauffage d'un réacteur avec un dispositif de chauffage par induction. Le réacteur comprend un lit catalytique multifonctionnel avec un premier lit catalytique et un second lit catalytique, qui sont chauffés à différentes températures. Le système comprend également un dispositif de chauffage par induction qui est conçu pour chauffer les premier et second lits catalytiques.
PCT/US2024/044989 2023-09-05 2024-09-03 Réglage de la sélectivité d'une réaction au moyen d'un chauffage par induction Pending WO2025054118A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001212A1 (fr) * 1997-07-03 1999-01-14 E.I. Du Pont De Nemours And Company Reacteur catalytique a chauffage par induction
WO2003092748A1 (fr) * 2002-04-18 2003-11-13 Adh Health Products, Inc. Appareil et procede servant a de decontaminer l'air de respiration de ses substances toxiques et organismes pathogenes
US20200377365A1 (en) * 2017-12-08 2020-12-03 Haldor Topsøe A/S A process and system for reforming a hydrocarbon gas
WO2023073000A1 (fr) * 2021-10-27 2023-05-04 Totalenergies Onetech Procédé de production d'hydrogène et de carbone par décomposition catalytique non oxydante d'hydrocarbures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001212A1 (fr) * 1997-07-03 1999-01-14 E.I. Du Pont De Nemours And Company Reacteur catalytique a chauffage par induction
WO2003092748A1 (fr) * 2002-04-18 2003-11-13 Adh Health Products, Inc. Appareil et procede servant a de decontaminer l'air de respiration de ses substances toxiques et organismes pathogenes
US20200377365A1 (en) * 2017-12-08 2020-12-03 Haldor Topsøe A/S A process and system for reforming a hydrocarbon gas
WO2023073000A1 (fr) * 2021-10-27 2023-05-04 Totalenergies Onetech Procédé de production d'hydrogène et de carbone par décomposition catalytique non oxydante d'hydrocarbures

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