WO2025054118A1 - Tuning reaction selectivity with induction heating - Google Patents

Abstract

Disclosed herein is a system and method that has been developed that includes heating a reactor with an induction heater. The reactor includes a multifunctional catalyst bed with a first catalyst bed and a second catalyst bed, which are heated to different temperatures. The system also includes an induction heater that is configured to heat the first and second catalyst beds.

Description

TUNING REACTION SELECTIVITY WITH INDUCTION HEATING

CROSS REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to U.S. Provisional Patent Application No. 63/536,555 filed on September 5, 2023. The entire content of which is incorporated in its entirety.

FIELD OF INVENTION

[0002] 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.

BACKGROUND

[0003] The utilization of renewable biomass as an alternative resource has received great attention to relieve the reliance on fossil fuels, which can lead to the emission of greenhouse gases causing climate change. Additionally, process heating from the combustion of fossil fuels in many industrial applications is also one of the largest sources of greenhouse gas emissions. For example, ethanol dehydrogenation is such a process that is used to produce acetaldehyde but is highly endothermic requiring high temperatures to increase the conversion efficiency. However, the current state of the art has uneven temperature distribution in the catalyst bed.

[0004] Moreover, current heating strategies for reaction systems typically include a traditional furnace, such that approximately 50% of the heat supplied by a traditional furnace may be utilized. Furnace heating also lacks the ability' to control reaction temperatures of multiple temperature zones. Thus, reaction steps with different temperatures need to be separated into individual processes.

[0005] Therefore, there is a need in the art to develop a system having a more efficient use of the heating supplied to a reactor in combination with a multifunctional catalyst bed within a single reactor having multiple temperature ranges.

SUMMARY

[0006] In an embodiment, a system is provided. The system 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). [0007] In some embodiments, the first catalyst bed may include a first catalyst. In some embodiments, the first catalyst may be a copper-based catalyst, a manganese-based catalyst, a zirconium based catalyst, or a combination thereof.

[0008] In certain embodiments, 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.

[0009] In certain embodiments, the manganese-based catalyst may include manganese oxide. [00010] In certain embodiments, the zirconium-based catalyst may include zirconium oxide. [00011] In some embodiments, the first catalyst may include a support.

[00012] In some embodiments, the one or more additional catalyst bed(s) may include a second catalyst. In certain embodiments, the second catalyst may include at least one of a metal oxide, a metal, or a support.

[00013] In certain embodiments, 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. In certain embodiments, 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. In certain embodiments, the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate, or a combination thereof.

[00014] In certain embodiments, the silicon may include fumed SiCh, SiCh gel, or a combination thereof.

[00015] In certain embodiments, the induction heater may include a ferromagnetic material. In certain embodiments, the ferromagnetic material may include cobalt. In certain embodiments, the ferromagnetic material may be impregnated with the first catalyst, the second catalyst or a combination thereof.

[00016] In certain embodiments, 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.

[00017] In certain embodiments, the first average temperature range may be about 150°C to about 300°C, and the second average temperature may be about 250°C to about 500°C. In certain embodiments, the first average temperature and the second temperature may have a temperature difference between at least about 25°C.

[00018] In certain embodiments, the reactor may be configured to receive a feed of ethanol optionally mixed with an inert gas. In some embodiments, the inert gas may include nitrogen, argon or helium. [00019] In certain embodiments, the first catalyst bed may be configured to perform an ethanol dehydrogenation reaction. In some embodiments, the ethanol dehydrogenation reaction may produce acetaldehyde.

[00020] In certain embodiments, the one or more additional catalyst bed(s) may be configured to receive ethanol and acetaldehyde. In some embodiments, a reaction in the one or more additional catalyst bed(s) may produce 1,3-butadiene. In certain embodiments, the reaction may have about 15% to about 100% selectivity to a C4 product.

[00021] In another embodiment, a method for converting ethanol into a C4 product is provided. The method 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).

[00022] In some embodiments, the first catalyst bed may include a first catalyst. In some embodiments, the first catalyst may include a copper-based catalyst, a manganese-based catalyst, a zirconium-based catalyst, or a combination thereof. In some embodiments, 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. In some embodiments, the manganese-based catalyst may include manganese oxide. In some embodiments, the zirconium- based catalyst may include zirconium oxide.

[00023] In some embodiments, the first catalyst may include a support. In some embodiments, the one or more additional catalyst bed(s) may include a second catalyst. In some embodiments, the second catalyst may include at least one of a metal oxide, a metal, or a support. In certain embodiments, the metal oxide may include copper oxide, manganese oxide, aluminum oxide, zirconium oxide (ZrCh). tantalum oxide (Ta20s), magnesium oxide (MgO) or a combination thereof. In certain embodiments, 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. In certain embodiments, the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof. In some embodiments, the silicon may include fumed SiCh, SiCh gel, or a combination thereof.

[00024] In certain embodiments, 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).

BRIEF DESCRIPTION OF DRAWINGS

[00026] The disclosure described herein is illustrated by way of example and not by way of limitation in the accompanying figures.

[00027] FIG. 1 illustrates a process for heating multiple temperature zones using an induction heater in a single reactor.

[00028] FIG. 2 a-b illustrates the packing of a single-bed reactor and a tandem reactor with induction heating, respectively.

[00029] FIG. 3 is an XRD pattern of the ZrCh/SiCh catalyst.

[00030] FIG. 4 is a comparison of catalysts' performances for individual and tandem reactions.

[00031] FIG. 5 is a comparison of catalyst’s activity with induction heating and furnace heating

(F) with ethanol and acetaldehyde co-feed (8.2% in N2) at 350 °C.

[00032] FIG. 6 is a comparison of catalyst performances in the tandem system at different WHSVs and reaction temperature of the Example.

[00033] FIG.7 is a graph showing changes in temperature based on amount of Co powder in bed 2 of the Example.

[00034] FIGs. 8a and 8b illustrate the catalyst performances in the tandem system at different reaction temperatures of bed 1 of the Example.

[00035] FIGs. 9a and 9b illustrate the conversion and selectivity with a furnace and comparison of single bed and tandem system, respectively, of the Example.

[00036] FIG. 10 represents the main reaction pathway of the ethylene butadiene reaction.

[00037] 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.

DETAILED DESCRIPTION

[00038] Current 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. In some reaction systems, the reaction may require a variety of different temperatures depending on the desired product. For example, 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. However, because different temperature and catalyst requirements are needed for each step, using a single reactor with conventional furnace heating makes the 1,3- butadiene production inefficient. In such a system, effective heating is needed to achieve higher selectivity of the catalysis. It has been found that including an induction heater improves the selectivity and efficiency of the heating within the reactor. For example, 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.

[00039] 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. For example, 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. In other embodiments, 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. For example, 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.

[00040] Reference throughout this specification to ’‘one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. In addition, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.”

[00041] As used herein, the singular forms “a,” “an,” and “the” include plural references unless the context clearly indicates otherwise. Thus, for example, reference to “a sample” includes a single sample as well as more than one sample.

[00042] As used herein, 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. [00043] As used herein, 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. For example, a “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.

[00044] In an embodiment of the present disclosure, 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. In other embodiments, the multifunctional catalyst bed may include a plurality’ of catalyst beds. As understood herein, 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. For simplicity’ of the present disclosure, a multifunctional catalyst bed including a first catalyst bed and a second catalyst bed will be described herein. Thus, reference to second catalyst bed and one or more additional catalyst bed(s) are used interchangeably herein.

[00045] In some embodiments, the first catalyst bed may include a first catalyst. In some embodiments, the first catalyst may include 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.

[00046] In some embodiments, 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.

[00047] In some embodiments, 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.

[00048] In some embodiments, the manganese-based catalyst may include manganese oxide. In some embodiments, the zirconium-based catalyst may include zirconium oxide.

[00049] In some embodiments, the first catalyst may further include a support.

[00050] In some embodiments, the one or more additional catalyst bed(s)/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. [00051] In some embodiments, 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.

[00052] In some embodiments, the metal may include at least one of silver (Ag) , cobalt (Co), copper (Cu), titanium (Ti), platinum (Pt), ruthenium (Ru), zirconium (Zr), zinc (Zn). iron (Fe), aluminum (Al), or a combination thereof.

[00053] In some embodiments, the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate, or a combination thereof. In some embodiments, the silicon may include fumed SiCh. S1O2 gel, or a combination thereof.

[00054] In some embodiments, the first catalyst or the second catalyst may include a catalyst binder. In some embodiments, catalyst binders may include silica, alumina, silica-alumina, zirconia-alumina, silica-titania, silica-thoria, silica-magnesia, silica-zirconia, silica-beryllia, ternary compositions of silica with other refractory oxides, and the like. In some embodiments, other matrices may include clays, such as naturally occurring clays illustrated by montmorillonites, kaolines, bentonites, halloysites, dickites, nacrites and anauxites.

[00055] In some embodiments, the first catalyst or the second catalyst may include a metalcontaining catalyst, a heterogenous catalyst including a platinum group metal, a heterogenous catalyst including a transition metal, an alkali metal or earth alkali metal or a combination thereof. [00056] It is understood to one of the skill in the art that the system may include a plurality of catalyst beds in which a plurality of catalysts can be used. The plurality of catalysts may be selected from the first catalyst and the second catalyst as described herein. In other embodiments, the plurality of catalysts may include any catalyst as known in the art depending on the reaction and the reaction system. In some embodiments, the catalysts may be the same catalysts, or they may be different catalysts.

[00057] In some embodiments, the induction heater of the system includes a ferromagnetic material.

[00058] In some embodiments, the ferromagnetic material may include cobalt, iron, nickel, their alloys, their oxides, carbides, steel, and stainless steel. In some embodiments, the ferromagnetic material includes cobalt. In some embodiments, the cobalt is cobalt powder.

[00059] In other embodiments, 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.

[00060] In some embodiments, the reactor may include an induction reactor, athermal reactor, a fixed-bed reactor, a semi-batch reactor, a slurry reactor, or a mixed-bed reactor. [00061] In some embodiments, the induction heater may be supplied with about 145 watts to about 435 watts of power, about 150 watts to about 420 watts, about 155 watts to about 415 watts, about 160 watts to about 410 watts, about 165 watts to about 405 watts, about 170 watts to about 400 watts, about 175 watts to about 395 watts, about 180 watts to about 390 watts, about 185 watts to about 385 watts, about 190 watts to about 380 watts, about 195 watts to about 375 watts, about 200 watts to about 370 watts, about 205 watts to about 365 watts, about 210 watts to about 360 watts, about 215 watts to about 355 watts, about 220 watts to about 350 watts, about 225 watts to about 345 watts, about 230 watts to about 340 watts, about 235 watts to about 335 watts, about 240 watts to about 330 watts, about 245 watts to about 325 watts, about 250 watts to about 320 watts, about 255 watts to about 315 watts, about 260 watts to about 310 watts, about 265 watts to about 305 watts, about 270 watts to about 300 watts, about 275 watts to about 295 watts, or about 280 watts to about 290 watts.

[00062] In some embodiments, the induction heater may be configured to heat the first catalyst bed to a first average temperature and the second catalyst bed (or one or more additional catalyst beds) to a second average temperature. In other embodiments, the induction heater may be configured to heat the multifunctional catalyst bed to at least two different temperatures. In yet other embodiments, the induction heater may be configured to heat the multifunctional catalyst bed to a first average temperature, a second average temperature, a third average temperature and so on. In some embodiments, 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. In some embodiments, 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.

[00063] In some embodiments, the first average temperature may be in a range of about 150°C to about 300 °C, about 160°C to about 290°C, about 170°C to about 280°C. about 180°C to about 270°C, about 190°C to about 260°C, about 200°C to about 250°C, about 210°C to about 240°C, about 220°C to about 230°C.

[00064] In some embodiments, 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.

[00065] In some embodiments, the system may be used to convert ethanol to butadiene, as will be described herein. In such embodiments, the reactor may be configured to receive a feed of ethanol and an inert gas. In some embodiments, the inert gas may include nitrogen. In other embodiments, the inert gas may include nitrogen, argon, helium, or a combination thereof.

[00066] In some embodiments, the feed of ethanol may include a carrier gas.

[00067] In some embodiments, the carrier gas may include hydrogen.

[00068] In some embodiments, the carrier gas may include carbon dioxide.

[00069] 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.

[00070] In other embodiments of the system, additional reactions may be performed. For example, syngas may be converted to methanol by providing a feed of syngas to be received by the first catalyst bed. In some embodiments, the feed of syngas may be mixed with one of the carrier or inert gases previously described.

[00071] In such an embodiment where the syngas is being converted, the first catalyst bed may be configured to perform the conversion of syngas to methanol. In some embodiments, 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. As described above, 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.

[00072] In other embodiments, a different reaction may be performed in the system. The different reactions may include the conversion of methanol to dimethyl ether (DME), the hydrogenation of carbon dioxide, a Fischer-Tropsch process, or a combination thereof.

[00073] In some embodiments, a reaction in the second catalyst bed/one or more additional catalyst bed(s) may produce a C4 product. In some embodiments, the C4 product may include 1,3 -butadiene.

[00074] In some embodiments, a reaction in the second catalyst bed may produce dimethyl ether. In some embodiments, a reaction in the second catalyst bed may facilitate the hydrogenation of carbon dioxide.

[00075] In some embodiments, 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%. [00076] In another embodiment, 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. For example, the multifunctional catalyst includes a first catalyst bed, a second catalyst bed, a third catalyst bed or more as needed to perform the reaction. For simplicity', a multifunctional catalyst bed having two catalyst beds (i.e., a first catalyst bed and a second catalyst bed) will be described herein, but it is understood that more than two catalyst beds can be included. The method may further include heating the reactor via an induction heater.

[00077] In some embodiments, 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.

[00078] In some embodiments, the first catalyst bed includes a first catalyst, while 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.

[00079] In some embodiments, 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.

[00080] In some embodiments, 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.

[00081] In some embodiments, 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.

[00082] In some embodiments, 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.

[00083] In some embodiments, the manganese-based catalyst may include manganese oxide. In some embodiments, the zirconium-based catalyst may include zirconium oxide.

[00084] In some embodiments, the first catalyst may further include a support.

[00085] In some embodiments, 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. [00086] In some embodiments, 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.

[00087] In some embodiments, the metal may include at least one of silver (Ag) , cobalt (Co), copper (Cu), titanium (Ti), platinum (Pt), ruthenium (Ru), zirconium (Zr), zinc (Zn). iron (Fe), chromium (Cr), nickel (Ni), palladium (Pd), rhodium (Rh), or a combination thereof.

[00088] In some embodiments, the support may include silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof. In some embodiments, the silicon may include fumed SiCh. S1O2 gel, or a combination thereof.

[00089] In some embodiments, the first catalyst or the second catalyst may include a catalyst binder. In some embodiments, 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. In some embodiments, other matrices may include clays, such as naturally occurring clays illustrated by montmorillonites, kaolines, bentonites, halloysites, dickites, nacrites and anauxites.

[00090] In some embodiments, 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.

[00091] In some embodiments, the induction heater includes a ferromagnetic material. In some embodiments, the ferromagnetic material includes cobalt. In other embodiments, the ferromagnetic material includes iron, nickel, or a combination thereof. In some embodiments, the cobalt is cobalt powder.

[00092] In some embodiments, the ferromagnetic material may be mixed with the first catalysis and/or the second catalysis.

[00093] In some embodiments, 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 2,000 watts.

[00094] In some embodiments of the method, 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.

[00096] In some embodiments, 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.

[00097] In some embodiments, 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.

[00098] In some embodiments, 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.

[00099] In some embodiments, 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.

[000100] In some embodiments, 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).

[000101] In some embodiments, 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).

[000102] In some embodiments, the first catalyst bed includes at least about 5% to about 70% of the first catalyst as described herein. In some embodiments, the second catalyst bed includes at least about 5% to about 70% of the second catalyst as described herein.

[000103] Referring to Fig. 1, 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. As can be seen in the Figure, 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.

Examples

[000104] The following examples are set forth to assist in understanding the invention and should not, of course, be construed as specifically limiting the invention described and claimed herein. Such variations of the invention, including the substitution of all equivalents now known or later developed, which would be within the purview of those skilled in the art, and changes in formulation or minor changes in experimental design, are to be considered to fall within the scope of the invention incorporated herein.

[000105] A study was conducted to investigate the Ostromislensky process for the ethanol-to- butadiene (ETB) reaction using induction heating in a tandem system. As understood, 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. By operating the catalyst beds at 171 °C and 320 °C, an ethanol conversion of 62.0% and C4 selectivity of 55.3% over a commercial Cu catalyst for bed 1 and a ZrO^SiCh catalyst for bed 2 at a WHSV of 0.6 h’¹. At the same space velocity, the ethanol conversion and C4 selectivity’ of 52% and 44.9% were achieved, respectively, using the benchmark Ag/ZrO2/SBA-16 catalyst, indicating that the induction heating can improve the catalyst behavior under lower reaction temperatures. Thus, this study supports that implementing induction heating in a tandem system can effectively establish dual temperature zones inside a single reactor, improving production efficiency for a multi-step reaction.

Method

Materials and catalysis synthesis

[000106] The ethanol-acetaldehyde reaction was conducted using the commercial catalyst (BASF Cu 0582E), which contains 52% CuO on AI2O3. The second reaction, ethanol and acetaldehyde to 1,3-butadiene, was carried out over 4 wt% ZrCh and 4 wt% Ag supported on SiCh and SBA-16. The catalysts were prepared using incipient wetness impregnation. To prepare the catalyst, 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. for the Ag/ZrO2/SBA-16 catalyst, 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 (Davisil Grade 636) were physically mixed with Co powder (Sigma- Aldrich, 2 pm particle size, 99.8% trace metals basis) for tandem experiments with induction heating.

Catalyst Characterization and activity testing,

[000107] X-ray Diffraction (XRD) measurements were performed using a Rigaku Ultima III equipped with a Cu Ka X-ray generator operating at 30 kV and 40 mA. The samples were scanned at a rate of 2°C/min between 20° and 90°C using a wavelength of X = 1.5405 A. 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.

[000108] The induction heating reaction system (Ambrell EASYHEAT 0224), equipped with a water-to-air heat exchanger (FLOWMAX- 115), is utilized to heat up the catalytic bed. The system operates at a stable frequency of 227 kHz during the heating process. Figure 2 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. In the single bed, Fig. 2a, 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. In the tandem reactor for the Ostromislensky process of Fig. 2b, 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. Additionally, 316 stainless steel (SS) beads or mesh were mixed to enhance heating if specified. For the single bed system, a laser pyrometer (Micro-Epsilon, focus: 0.5 mm @ 150 mm) was connected to a PID controller (Omega) to control the reaction temperature. In the tandem system, one pyrometer was used to control the temperature of bed 2, and an additional pyrometer was applied to monitor the temperature of bed 1.

[000109] 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. To provide the desired reaction temperatures, 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.

[000110] Pure ethanol was fed through a liquid pump (New Era NE-4000) and vaporized in an evaporator at 180 °C. N2 was used as the carrier gas to achieve 5% - 10% ethanol at different WHSVs. The effluent gas was analyzed using an SRI gas chromatography (GC) equipped with Hayesep D columns, a Moleseive 5A column, a WAX column, and an alumina column. The experimental measurement error from the GC reading is within +/- 5%. The conversion of ethanol or ethanol acetaldehyde co-feed (X), product selectivity (Si, where i is 1,3-butadiene, acetaldehyde, butene isomers, ethylene, propylene, acetone), and carbon balance (CB) were calculated as follows:

Results and Discussion

Tandem Activity

[000111] 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.

Table 1

[000112] Initially, the activities of the C11/AI2O3 and ZrCh/SiCh catalysts mixed with Co powders were individually tested in induction heater single-bed systems with 10% EtOH in N2. The ethanol conversion over C11/AI2O3 catalyst reached 52.3% with a selectivity of 79.1% for acetaldehyde (AA) at 217°C after a steady state was established following 10 hours. The ZrO2/SiO2 catalyst produced significant side products, including ethylene, propylene, diethyl ether, and liquid products, with an 84.3% ethanol conversion at 350°C. The selectivity of 1,3-butadiene was only 1.7% over the ZrO2/SiO2 catalyst, suggesting its limited ability to produce the desired product in the absence of acetaldehyde. Instead, ZrO2/SiO2 catalyst can facilitate the ethanol dehydration reactions to produce ethylene and diethyl ether.

[000113] The tandem Ostromislensky reaction was performed with sequentially stacked C11/AI2O3 and ZrO2/SiO2 catalysts operated at Ti = 217°C and T2 = 350°C, respectively. Acetaldehyde produced from the first bed was combined with unconverted ethanol feed and further processed to yield 1.3-butadiene in the second bed. As shown in Figure 4 and Table I, ethanol conversion reached 65.9%, with selectivities to C4 products at 29.9%. The selectivity for 1,3- butadiene increased to 20.5%, up from 1.7% in the single bed system, while selectivity to butene isomers reached 9.1%. a large improvement from 1%. The 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.

[000114] To investigate the impact of ZrO2/SiO2 during the Ostromislensky process, ethanol and acetaldehyde were co-fed in a molar ratio of 1:1.8 in both conventional furnace heating and induction heating. As shown in Fig. 5 and Table 2, the ethanol conversions were 9.5 % and 33.3 % with furnace heating and induction heating, respectively. While the ethanol conversion was notably higher with induction heating compared to furnace heating, the selectivity to C4 products remained similar at 90.7% and 96.3% for furnace heating and induction heating, respectively. This observation is consistent with previous results in the ethanol dehydrogenation reaction, where the conversion improved with induction heating while the selectivities remained similar due to the quick compensation of heat loss and the close contact between the catalyst and the heating elements.

Table 2

Tuning, 1,3-butadiene production in tandem reaction

[000115] 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. Three experiments were conducted to investigate the impact of the WHSV and reaction temperatures of the tandem system on ethanol conversion and C4 selectivities. In experiments A and B. where the WHSVs of beds 1 and 2 were set at 1.2 h'¹ and 2.4 h’¹, respectively, it was observed that lower reaction temperatures (Ti = 180 °C, T2 = 300 °C) notably enhanced selectivities to both 1,3- butadiene and butene isomers compared to higher reaction temperatures (Ti = 217 °C, T2 = 350 °C). The ethanol conversion in experiment A decreased to 35.5% at higher temperatures compared to 65.6% in experiment B due to the endothermic reactions of both steps. At Ti = 180 °C, the production of acetaldehyde was lower in bed 1 compared to Ti = 217 °C. The reduced amount of acetaldehyde was effectively consumed in the second reaction step, resulting in a higher selectivity for 1,3-butadiene compared to the reaction at Ti = 217 °C and T2 = 350 °C. A higher ethanol-to- acetaldehyde ratio was achieved at Ti = 180 °C in bed 1, benefiting the second-step reaction and improving the 1,3-butadiene selectivity. Additionally, adjustments to the WHSV can impact product selectivities. In experiment C, at temperatures of Ti = 210 °C and T2 = 350 °C, increasing the WHSV of bed 1 from 1.2 h'¹ to 2.4 h'¹ reduced the contact time of the reactants, resulting in decreased acetaldehyde production. This led to a decline in acetaldehyde selectivity from 43.5% to 38.7% and an increase in 1,3-butadiene selectivity from 23.6% to 33.6% within the temperature range of 210 °C - 217 °C. Table 3

[000116] The Lebedev process involves studying reaction conditions ranging from 0.04 h'¹ to 0.474 h’¹. To improve ethanol conversion and C4 selectivity by efficiently converting acetaldehyde produced in the first step, the WHSV of bed 2 was reduced from 2.4 h'¹ to 0.6 h’¹. Additionally, 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/mm³ 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. Specifically, when 100 mg of Co was used in bed 2, Ti reached 245 °C, whereas this temperature decreased to 171 °C with 200 mg of Co. The power required to achieve T2 = 320 °C was 930 W with 200 mg of Co, but decreased to 100 W with 100 mg of Co.

[000117] 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. The data illustrates that ethanol conversion increased with the reaction temperature. However, at the highest temperature (Ti = 245 °C), the more severe C11/AI2O3 sintering led to faster deactivation compared to the other reaction temperatures. 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. The presence of a high amount of Co within bed 2 at Ti = 171 °C also played a role in tuning the ethanol conversion and C4 selectivities. Although 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. 9 (b) shows that the addition of Co in bed 2 caused the 1 : 1 ethanol-to-acetaldehyde ratio to shift to a lower temperature range of 155 C and 175 C, while the temperature range was around 215 C and 235 °C in the single catalyst bed. Therefore, rather than requiring a high reaction temperature for bed 1, a relatively low Ti in the tandem system can be beneficial for 1,3-butadiene production.

Table 4

[000118] 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.

Comparison between the Ostromislensky process with induction heatins and the Lebedev process with furnace heating

[000119] The tandem Ostromislensky reaction with induction heating was compared to the benchmark 4wt% Ag/4wi% ZrO2/SBA-16 catalyst in the Lebedev process. The SBA-16 support is chosen over fumed SiCh in the Lebedev process because of its large surface area for Ag dispersion. The BET surface area of 4wi% Ag/4\\ t%ZrO2/SBA- l 6 is 400.67 m²/g, which is higher than the 196.98 m²/g of 4wt% ZrCh/SiCh (Table 5). After the catalyst was reduced before the reaction, metallic Ag sites were observed (Fig. 3). As shown in Fig. 11 (a) and Table 6, it is evident that the tandem system with induction heating demonstrated improved conversion and selectivities to C4 products. Fig. 11 (b) and (c) show higher ethanol conversion and product selectivities within a 20 h reaction when using the tandem induction heating system. Fluctuations in the conversion and selectivity observed with furnace heating were attributed to the motor movement of the liquid pump due to the low ethanol feeding rate. While the Lebedev process with furnace heating achieved 52% ethanol conversion and 44.9% selectivity to C4 products, the tandem Ostromislensky reaction with induction heating achieved 62.9% ethanol conversion and 55.3% selectivity to C4 products. Akhade et al. reported that the 4wt%Ag/4wt% ZrO2/SBA-16 catalyst can achieve a 94.3% ethanol conversion and 69% 1,3 -butadiene selectivity with a 24% ethanol/N2 inlet at WHSV of 0.23 h'¹ within TOS of 6 h. This higher ethanol conversion and 1,3-butadiene selectivity' compared to our work is attributed to the larger ethanol concentration and lower WHSV. The improvement of the conversion and C4 production with the tandem induction heating system underscores the advantages of individual control of the two-step reaction in one reactor, providing an effective method to produce the desired products without the need for complicated catalyst synthesis.

Table 5

Table 6

Conclusion

[000120] The study supports that 1,3-butadiene could be synthesized from ethanol through the tandem Ostromislensky reaction in a single reactor. It is also believed that operating each step at its optimal temperature could reduce energy consumption, minimize the production of byproducts, and improve the selectivity of C4 productions, including both 1,3-butadiene and butene isomers. 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.

[000121] From this work, it has shown that the ethanol conversion of 62.9% acetaldehyde selectivity' of 37.5%, and high C4 products’ selectivity of 55.3% can be achieved while consuming nine times less power at temperatures Ti = 171°C and T2 = 320°C. The tandem Ostromislensky reaction with induction heating surpasses the Lebedev process using the benchmark Ag/ZrO2/SBA-16 catalyst, significantly improving the C4 selectivity by providing the required temperature for each reaction step. Additionally, both catalysts in each reaction are scalable, showing the potential of the tandem system with induction heating to be scaled up for industrial applications. The use of induction heating in the ETB tandem reaction enables two temperature zones inside one reactor and individual control of reaction temperatures and WHS Vs for the first time, representing a breakthrough technology that can be extended to the application of cascade reactions inside one reactor.

[000122] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[000123] As used herein, the term “of’ may mean “comprising.” For example, “a liquid dispersion of’ may be interpreted as “a liquid dispersion comprising.”

[000124] As used herein, “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. As such, the terms “a” (or “an”), “one or more”, and “at least one” are used interchangeably herein. [000125] As used 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.”

[000126] 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.

[000127] Furthermore, 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. For example, 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. Where 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. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. Where ranges are given (such as, e.g.. from [X] to [Y]). endpoints (such as. e.g., [X] and [Y] in the phrase “from [X] to [Y]”) are included unless otherwise indicated. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary' skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

Claims

What is claimed is:

1. A system comprising: 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).

2. The system of claim 1, wherein the first catalyst bed comprises a first catalyst.

3. The system of claim 2, wherein the first catalyst comprises a copper-based catalyst, a manganese-based catalyst, a zirconium based catalyst, or a combination thereof.

4. The system of claim 3, wherein 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.

5. The system of claim 3, wherein the manganese-based catalyst comprises manganese oxide.

6. The system of claim 3, wherein the zirconium-based catalyst comprises zirconium oxide.

7. The system of any one of claims 2-6, wherein the first catalyst comprises a support.

8. The system of any one of claims 1- 7, wherein the one or more additional catalyst bed(s) comprises a second catalyst.

9. The system of claim 8, wherein the second catalyst comprises at least one of a metal oxide, a metal, or a support.

10. The system of claim 9, wherein the metal oxide comprises 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.

11. The system of claim 9, wherein the metal comprises 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.

12. The system of claim 9, wherein the support comprises silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof.

13. The system of claim 12, wherein the silicon comprises fumed SiCh, SiCh gel, or a combination thereof.

14. The system of any of the preceding claims, wherein the induction heater comprises a ferromagnetic material.

15. The system of claim 14. wherein the ferromagnetic material comprises cobalt, iron, nickel, their alloys, their oxides, carbides, steel, and stainless steel.

16. The system of claim 14, wherein the ferromagnetic material is impregnated with the first catalyst, the second catalyst or a combination thereof.

17. The system of any of the preceding claims, wherein the induction heater is configured to heat the first catalyst bed to a first average temperature and the second catalyst bed to a second average temperature.

18. The system of claim 17, wherein the first average temperature range is about 150°C to about 300°C, and the second average temperature is about 250°C to about 500°C.

19. The system of claim 17 or 18. wherein the first average temperature and the second temperature have a temperature difference between at least about 25°C.

20. The system of any of the preceding claims, wherein the reactor is configured to receive a feed of ethanol optionally mixed with an inert gas.

21. The system of claim 20, wherein the inert gas comprises nitrogen, argon, or helium.

22. The system of any of the preceding claims, wherein the first catalyst bed is configured to perform an ethanol dehydrogenation reaction.

23. The system of claim 22, wherein the ethanol dehydrogenation reaction produces acetaldehyde.

24. The system of claim 23, wherein the one or more additional catalyst bed(s) is configured to receive ethanol and acetaldehyde.

25. The system of claim 24. wherein a reaction in the one or more additional catalyst bed(s) produces 1,3-butadiene.

26. The system of claim 22, wherein the ethanol dehydrogenation reaction has about 15% to about 100% selectivity to a C4 product.

27. A method for converting ethanol into a C4 product comprising: feeding ethanol to a reactor comprising a multifunctional catalyst bed, and heating the reactor via an induction heater. wherein the multifunctional catalyst bed comprises a first catalyst bed and one or more additional catalyst bed(s).

28. The method of claim 27, wherein the first catalyst bed comprises a first catalyst.

29. The method of claim 28, wherein the first catalyst comprises a copper-based catalyst, a manganese-based catalyst, a zirconium-based catalyst, or a combination thereof.

30. The method of claim 29, wherein the copper-based catalyst comprises copper in combination with at least one of manganese (Mn), aluminum, (Al), zirconium (Zr), chromium (Cr), zinc (Zn), or a combination thereof.

31. The method of claim 29, wherein the manganese-based catalyst comprises manganese oxide.

32. The method of claim 29, wherein the zirconium-based catalyst comprises zirconium oxide.

33. The method of any one of claims 28-32, wherein the first catalyst comprises a support.

34. The method of any one of claims 27- 33, wherein the one or more additional catalyst bed(s) comprises a second catalyst.

35. The method of claim 34, wherein the second catalyst comprises at least one of a metal oxide, a metal, or a support.

36. The method of claim 35, wherein the metal oxide comprises copper oxide, manganese oxide, aluminum oxide, zirconium oxide (ZrCh), tantalum oxide (Ta20s), magnesium oxide (MgO) or a combination thereof.

37. The method of claim 35, wherein the metal comprises silver (Ag), cobalt (Co), copper (Cu), titanium (Ti), platinum (Pt), ruthenium (Ru), zirconium (Zr). zinc (Zn), iron (Fe), aluminum (Al), or a combination thereof.

38. The method of claim 35, wherein the support comprises silicon, carbon, aluminum oxide, aluminosilicate, borosilicate, magnesium silicate or a combination thereof.

39. The method of claim 38, wherein the silicon comprises fumed SiCh, SiCh gel, or a combination thereof.

40. The method of claim any one of claims 27-39, wherein the induction heater comprises a ferromagnetic material.

41. The method of claim 40, wherein the ferromagnetic material comprises cobalt.

42. The method of any one of claims 27-41, wherein 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.

43. The method of claim 42, wherein the first average temperature is about 150°C to about 300°C, and the second average temperature is about 250°C to about 500°C.

44. The method of any one of claims 27-43, wherein the method is performed at a pressure of about 0. 1 bar to about 100 bar.

45. The method of any one of claims 27-44, wherein space velocity for the first catalyst bed is about 1 (h ¹) to about 50 (h ¹).

46. The method of any one of claims 27-45, wherein space velocity for the one or more additional catalyst bed is about 0.5 (h'¹) to about 50 (h^-1).