Catalyst materials for oxidative dehydrogenation

Abstract

A catalyst material and method for making the catalyst material are provided. An exemplary catalyst material includes 15 wt.% to 99 wt.% of a catalyst having the formula: MoaVb(M1)c(M2)dOx, and 1 wt.% to 45 wt.% of a bismuth-containing compound. In this formula, M1 is Bi, Te, Sb, or a mixture thereof; M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral. The values a, b, c, and d are determined based on the amount of each starting material used to form the catalyst. The catalyst material has a PXRD pattern including peaks at 2θ values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Kα radiation.

Description

[0001] CATALYST MATERIALS FOR OXIDATIVE DEHYDROGENATION

[0002] TECHNICAL FIELD

[0003] The present disclosure relates generally to catalyst materials for oxidative dehydrogenation (ODH) of alkanes such as ethane. The catalyst material includes a catalyst containing molybdenum (Mo); vanadium (V); one or more of bismuth (Bi), tellurium (Te), and antimony (Sb); one or both of tantalum (Ta) and niobium (Nb); oxygen (O); and a bismuth-containing compound.

[0004] BACKGROUND ART

[0005] Olefins like ethylene, propylene, and butylene, are basic building blocks for a variety of commercially valuable polymers. Since naturally occurring sources of olefins do not exist in commercial quantities, polymer producers rely on methods for converting the more abundant lower alkanes into olefins. One such method for commercial scale producers is steam cracking, a highly endothermic process where steam-diluted hydrocarbons are subjected very briefly to a temperature of at least 600°C. The fuel demand to produce the required temperature and the need for equipment that can withstand that temperature add significantly to the overall cost. In addition, the high temperature promotes the formation of coke, which accumulates within the system, resulting in the need for costly periodic reactor shutdowns for maintenance and coke removal.

[0006] Selective oxidation processes, such as oxidative dehydrogenation (ODH), are an alternative to steam cracking that are exothermic and produce little or no coke. In ODH, a lower alkane, such as ethane, is mixed with oxygen in the presence of a catalyst and optionally an inert diluent, such as carbon dioxide or nitrogen or steam, which may be performed at temperatures as low as 300°C, to produce the corresponding alkene. Various other oxidation products may be produced in this process, including carbon dioxide and acetic acid, among others. However, ODH suffers from lower conversion rates when compared to steam cracking, a fact that when combined with lower selectivity may have prevented ODH from achieving widespread commercial implementation. There is a need for a catalyst material for an ODH of ethane process with high ethylene selectivity, activity, and longevity.

[0007] SUMMARY OF INVENTION

[0008] The present disclosure provides a catalyst material comprising 15 wt.% to 99 wt.% of a catalyst and 1 wt.% to 45 wt.% of a bismuth-containing compound. The catalyst comprises the formula MoaVb(Mi)c(M2)dOx wherein Mi is Bi, Te, Sb, or a mixture thereof; M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst. The catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0009] In some embodiments, the bismuth-containing compound is provided by combining the catalyst with at least one reactive bismuth compound.

[0010] In some embodiments, the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate. In some embodiments, the at least one reactive bismuth compound comprises bismuth hydroxide.

[0011] In some embodiments, a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range from 5 : 1 to 15: 1.

[0012] In some embodiments, the bismuth-containing compound comprises bismuth molybdate, Bi2(MC>4)3.

[0013] In some embodiments, the catalyst material comprises 40 wt.% to 50 wt.% of the catalyst, as determined by Rietveld analysis of the PXRD pattern.

[0014] In some embodiments, the catalyst material comprises 5 wt.% to 20 wt.% of the bisumuth-containing compound, as determined by Rietveld analysis of the PXRD pattern.

[0015] In some embodiments, the catalyst material further comprises 1 wt.% to 80 wt.% of an inert carrier material.

[0016] In some embodiments, the catalyst material comprises 30 wt.% to 70 wt.% of the catalyst; 20 wt.% to 60 wt.% of the inert carrier material; and 2 wt.% to 15 wt.% of the bismuth-containing compound.

[0017] In some embodiments, b is 0.2 to 0.4; c is 0.01 to 0.07; and d is 0.01 to 0.07.

[0018] In some embodiments, the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbTecNbaOx, and MoaVbSbcTaaOx. In some embodiments, the catalyst as a formula MoaVbBicNbaOx.

[0019] In some embodiments, the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or Mo1V0.20-0.40Sb0.01-0.07Ta0.01-0.07Ox.

[0020] In some embodiments, the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05 Nbo.o40x, or Mo1V0.30Sb0.05Ta0.05Ox. In some embodiments, the values of a, b, c, and d are further determined by elemental analysis.

[0021] In some embodiments, the inert carrier material comprises precipitated synthetic silica, fumed synthetic silica, silica-alumina, a-alumina, y-alumina, titania, silicon carbide, MgAl spinel, an aluminate compound, an aluminosilicate compound, a zeolite, zirconia, doped zirconia, boron nitride, cerium oxide, doped cerium oxide, a perovskite, steel, or a combination thereof. In an aspect, the inert carrier material comprises a-alumina.

[0022] In some embodiments, the PXRD pattern further comprises peaks at 20 values of 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, and 22.1° ± 0.2°.

[0023] In some embodiments, the catalyst material has a pore volume between 0.01 cm3 / g and 0.25 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett- Joyner- Halenda (BJH) model. In some embodiments, the catalyst material has a pore volume between 0.01 cm3 / g and 0.1 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett- Joyner-Halenda (BJH) model.

[0024] In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area between 2 m2 / g and 10 m2 / g, as determined by a nitrogen physisorption analysis. In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area between 4 m2 / g and 6 m2 / g, as determined by a nitrogen physisorption analysis.

[0025] In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area of 5 m2 / g as determined by a nitrogen physisorption analysis and a pore volume of 0.02 cm3 / g as determined by a nitrogen physisorption analysis with a Barrett-Joyner- Halenda (BJH) model.

[0026] In some embodiments, the catalyst material is a non-porous pellet.

[0027] The present disclosure also provides a method for preparing a catalyst material. The method comprises combining a first mixture comprising a catalyst described herein, and a reactive bismuth compound described herein, with a liquid medium to form a second mixture; and heating the second mixture to form the catalyst material.

[0028] In some embodiments, the first mixture comprises the catalyst and the reactive bismuth compound in a weight ratio from about 5: 1 to about 15: 1, catalystreactive bismuth compound. In some embodiments, the first mixture comprises the catalyst and the reactive bismuth compound in a weight ratio from about 5: 1 to about 10: 1, catalystreactive bismuth compound.

[0029] In some embodiments, the liquid medium comprises water. In some embodiments, the first mixture further comprises an inert carrier material. In some embodiments, the inert carrier material comprises a-alumina.

[0030] In some embodiments, the first mixture further comprises a binder.

[0031] In some embodiments, the method further comprises calcining the catalyst material to provide a calcined catalyst material.

[0032] In some embodiments, the first mixture comprises: 1 wt.% to 50 wt.% of the catalyst; 1 wt.% to 90 wt.% of the inert carrier material; 1 wt.% to 20 wt.% of the reactive bismuth compound; and up to 10 wt.% of one or more binders other than water.

[0033] In some embodiments, the binder comprises one or more of: a liquid binder selected from the group consisting of water, oil, sodium silicate, and a polybutadiene emulsion; an organic binder selected from the group consisting of starch, lignosulfonate, cellulose, cellulose-derived powders, microcrystalline cellulose powder, polyethylene glycol, polyvinyl acetate, polyvinyl alcohol, poly(acrylic acid), other synthetic polymers, and a modified-starch brewery byproduct; and an inorganic binder selected from the group consisting of bentonite, cement, clay and lime, sodium silicate, calcium aluminate, calcium silicate composite powder, alumina silicate, Fuller’s earth, and fly ash chemically activated with alkaline materials.

[0034] In some embodiments, the binder comprises polyethylene glycol, poly(acrylic acid), and polyvinyl alcohol.

[0035] In some embodiments, the method further comprises adding a lubricant to the first mixture. In some embodiments, the lubricant is selected from the group consisting of graphite, hexagonal boron nitride, calcium carbonate, a fatty acid, and a fatty acid salt.

[0036] In some embodiments, the method further comprises extruding, pressing, 3D- printing, spheronizing, or casting the catalyst material to produce a formed catalyst material. In an aspect, the method comprises pressing the catalyst material to form pellets.

[0037] In some embodiments, the method comprises heating the second mixture at a temperature of 60°C to 120°C until the water is substantially evaporated.

[0038] In some embodiments, the method further comprises drying the second mixture at a temperature of 60°C to 120°C for a drying time between 1 hour and 48 hours.

[0039] The present disclosure also provides a process for oxidative dehydrogenation of ethane. The process comprises contacting a gaseous feed comprising ethane and oxygen with a catalyst material described herein in a reactor to produce an effluent comprising ethylene. In some embodiments, the catalyst material has an increased selectivity to one or both of ethylene and acetic acid at equivalent ethane conversion as compared to the selectivity of the catalyst.

[0040] In some embodiments, the catalyst material has an increased ethane conversion at an oxygen conversion of greater than 95% as compared to the ethane conversion of the catalyst.

[0041] BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 shows a powder X-ray diffraction (PXRD) pattern of Catalyst Example 1 prior to calcination (bottom) and after calcination (top).

[0043] Figure 2 shows an overlay of PXRD patterns of Comparative Catalyst Material 1-C after calcination, alpha alumina, and Catalyst Example 1.

[0044] Figure 3 shows an overlay of PXRD patterns of Catalyst Material Example 1-E, prepared bismuth molybdate, alpha alumina, and Catalyst Example 1.

[0045] Figure 4A shows an overlay of PXRD patterns for Comparative Catalyst Material 1- C and Catalyst Material Example 1-E and Figure 4B shows the overlay zoomed in on 5-30 29 (°).

[0046] Figure 5 shows an overlay of PXRD patterns for Comparative Catalyst Material 4-C, alpha alumina, and Catalyst Example 4.

[0047] Figure 6 shows an overlay of PXRD patterns for Catalyst Material Example 4-E, prepared bismuth molybdate, alpha alumina, and Catalyst Example 4.

[0048] Figure 7A shows an overlay of Comparative Catalyst Material 4-C and Catalyst Material Example 4-E and Figure 7B shows the overlay zoomed in on 5-30 20 (°).

[0049] Figure 8 shows scanning electron microscopy (SEM) images of Comparative Catalyst Material 4-C.

[0050] Figure 9 shows SEM images of Catalyst Material Example 4-E.

[0051] Figure 10 shows a PXRD of pulverized and sintered Catalyst Material 5-E.

[0052] Figure 11 shows a flowchart of mass balance method 400 used for analyzing catalyst material performance.

[0053] Figure 12 shows a plot of ethane conversion over time on stream for Catalyst Material Example 1-E and Comparative Catalyst Material 1-C.

[0054] DESCRIPTION OF EMBODIMENTS

[0055] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying figures. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims

[0056] Selective oxidation (SO) is generally used in oxidative dehydrogenation (ODH) reactions to form alpha-olefins from corresponding alkanes, such as to form ethylene from ethane. Embodiments described herein provide a catalyst material for the ODH process.

[0057] For the ODH of ethane, it is desired to have good selectivity toward high-value products (e.g., ethylene, acetic acid), while minimizing production of over-oxidized byproducts such as CO and CO2. Many previously disclosed ODH catalysts have shown high activity for the oxidative dehydrogenation of ethane, but often suffer from insufficient selectivity to ethylene and can lack the long-term stability required for continual operation at industrial process conditions.

[0058] Provided herein is an oxidative dehydrogenation catalyst material that includes a catalyst and a bismuth-containing compound. The catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation. In some embodiments, the PXRD pattern of the catalyst material further includes peaks at 20 values of 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, and 22.1° ± 0.2°.

[0059] The catalyst materials disclosed herein, which includes a bismuth-containing compound, were found to have improved ethylene selectivity and stability compared to catalysts and catalyst materials that do not include the bismuth-containing compound. The enhanced selectivity and stability of the catalyst materials disclosed herein can allow for improvement of a continuous catalyst process by providing high selectivity toward ethylene for an extended period, minimizing the production of over oxidized by-products.

[0060] As used herein, the term “catalyst material” refers to a material that includes an active catalyst that can promote the oxidative dehydrogenation of ethane to ethylene, for example, a catalyst on a support or a catalyst formulated with a carrier. The catalyst material may be substantially comprised of the catalyst. The catalyst material can be a plurality of particles or a formed catalyst material. Non-limiting examples of formed catalyst materials include extruded catalyst materials, 3D-printed catalyst materials, spheronized catalyst materials, pressed catalyst materials, and cast catalyst materials. Non-limiting examples of pressed and cast catalyst materials include pellets, such as tablets, ovals, and spherical particles. Binder may be useful to aid in forming the catalyst material. Catalyst material formation may also include optional workup steps such as: debinding, calcining / sintering, and / or activating / pre-treatment. Workup steps may be introduced to prepare the catalyst to be loaded into a reactor and produce an expected productivity and mitigate any unexpected thermal runaways during startup.

[0061] As used herein, the term “catalyst” refers to the active catalyst portion of a catalyst material that can promote oxidative dehydrogenation, such as the oxidative dehydrogenation of ethane to ethylene. The catalyst may be processed in further steps to form a catalyst material. The catalyst material may also be processed in further steps to form a final catalyst material.

[0062] The catalyst included in the catalyst material of the present disclosure includes molybdenum (Mo), vanadium (V), Mi, M2, and oxygen (O). Mi includes bismuth (Bi), tellurium (Te), antimony (Sb), or a mixture thereof. M2 includes tantalum (Ta), niobium (Nb), or a mixture thereof.

[0063] The catalyst of the present disclosure is represented by the formula MoaVb(Mi)c(M2)dOx. In some embodiments, the catalyst has the formula MoaVbBicTaaOx, MoaVbTecNbdOx, or MoaVbSbcTaaOx. In some embodiments, the catalyst has the formula MoaVbBicNbaOx, or Moa bSbcNbaOx,

[0064] In each of these formulations, a is 1.0, and x refers to the number of oxygen atoms necessary to render the catalyst electrically neutral. The skilled person will appreciate that oxygen-containing species may also be adsorbed or trapped by the catalyst.

[0065] The values of a, b, c, and d may refer to the values based on the amount of each starting material used to form the catalyst, such as for example, by the method of preparing a catalyst described later herein. The values of a, b, c, d may also refer to values measured by elemental analysis, for example by inductively coupled plasma mass spectroscopy (ICP- MS), neutron activation analysis (NAA), X-ray fluorescence (XRF), ion chromatography mass spectrometry (IC-MS), proton induced X-ray emission (PIXE), or energy-dispersive X-ray spectroscopy (EDX). In the alternative, if specified, the values a, b, c, and d may only refer to the values determined by elemental analysis, for example by ICP-MS, NAA, XRF, IC-MS, PIXE, or EDX. The catalyst formula with respect to the ratios of values a, b, c, and d can be selected to affect the activity, selectivity, purity, and stability of the catalyst.

[0066] In some embodiments, b is 0.01 to 0.5. In some embodiments, b is 0.01 to 0.4. In some embodiments, b is 0.01 to 0.3. In some embodiments, b is 0.1 to 0.5. In some embodiments, b is 0.1 to 0.4. In some embodiments, b is 0.1 to 0.3. In some embodiments, b is 0.2 to 0.5. In some embodiments, b is 0.2 to 0.4. In some embodiments, b is 0.20 to 0.35. In some embodiments, b is 0.3 to 0.4. In some embodiments, b is 0.30 to 0.35. In some embodiments, b is 0.25 to 0.35. In some embodiments, b is 0.3. In some embodiments, b is 0.25. In some embodiments, b is 0.26. In some embodiments, b is 0.27. In some embodiments, b is 0.32. In some embodiments, b is 0.33. In some embodiments, b is 0.34.

[0067] In some embodiments, c is 0.005 to 0.2. In some embodiments, c is 0.01 to 0.2. In some embodiments, c is 0.01 to 0.1. In some embodiments, c is 0.01 to 0.09. In some embodiments, c is 0.01 to 0.07. In some embodiments, c is 0.02 to 0.1. In some embodiments, c is 0.02 to 0.09. In some embodiments, c is 0.02 to 0.07. In some embodiments, c is 0.03 to 0.1. In some embodiments, c is 0.03 to 0.09. In some embodiments, c is 0.03 to 0.07. In some embodiments, c is 0.04 to 0.07. In some embodiments, c is 0.04 to 0.06. In some embodiments, c is 0.06. In some embodiments, c is 0.05. In some embodiments, c is 0.04.

[0068] In some embodiments, d is 0.005 to 0.1. In some embodiments, d is 0.01 to 0.1. In some embodiments, d is 0.01 to 0.09. In some embodiments, d is 0.01 to 0.07. In some embodiments, d is 0.01 to 0.05. In some embodiments, d is 0.01 to 0.04. In some embodiments, d is 0.02 to 0.1. In some embodiments, d is 0.02 to 0.09. In some embodiments, d is 0.02 to 0.07. In some embodiments, d is 0.02 to 0.05. In some embodiments, d is 0.02 to 0.04. In some embodiments, d is 0.03 to 0.06. In some embodiments, d is 0.03 to 0.05. In some embodiments, d is 0.03. In some embodiments, d is 0.04. In some embodiments, d is 0.05.

[0069] In some embodiments, the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or Mo1V0.20-0.40Sb0.01-0.07Ta0.01-0.07Ox.

[0070] In some embodiments, the values of a, b, c, and d are determined based on the amount of each starting material used to form the catalyst. For example, the values of a, b, c, and d are determined based on the amount (molar equivalents) of each Mo, V, Mi, and M2 compound used in a hydrothermal synthesis reaction to prepare the catalyst. In some embodiments, the catalyst has the formula Mo1V0.31Bi0.05M0.05Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.31Bi0.05Nb0.05Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.33Bi0.05M0.04Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.33Bi0.05Ta0.04Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.30Te0.05 Nbo.o40x, wherein the formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst has the formula Mo1V0.30Sb0.05Ta0.05Ox, wherein the formula is determined based on the amount of each starting material used to form the catalyst.

[0071] In some embodiments, the values of a, b, c, and d are determined by elemental analysis, for example, EDX, ICP-MS, or both. In some embodiments, the values of a, b, c, and d are determined by elemental analysis, such as by energy-dispersive X-ray spectroscopy (EDX). In some embodiments, the catalyst has a formula selected from Mo1V0.26Bi0.06Ta0.03Ox, Mo1V0.32Bi0.04Ta0.03Ox, Mo1V0.33Bi0.05Ta0.04Ox, Mo1V0.33Bi0.06Ta0.04Ox, and Mo1V0.26Bi0.05Ta0.05Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.32Bi0.04Ta0.03Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.33Bi0.05Ta0.04Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.26Bi0.06Ta0.03Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.33Bi0.06Ta0.04Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.26Bi0.05Ta0.05Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.32Bi0.04Ta0.03Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.30Te0.05 Nbo.o40x, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.30Sb0.05Ta0.05Ox, wherein the formula is determined by EDX. In some embodiments, the catalyst has the formula Mo1V0.33Bi0.05Ta0.04Ox, wherein the formula is determined by EDX.

[0072] In some embodiments, the values of a, b, c, and d determined by EDX match the values of a, b, c, and d determined based on the amount of each starting material within 0.05, 0.04, 0.02, or 0.01.

[0073] In some embodiments, the catalyst material includes 15 wt.% to 99 wt.% of the catalyst. In some embodiments, the catalyst material includes 30 wt.% to 70 wt.% of the catalyst. In some embodiments, the catalyst material includes 40 wt.% to 60 wt.% of the catalyst, such as 50 wt.%. In some embodiments, the catalyst material includes 40 wt.% of the catalyst, 41 wt.% of the catalyst, 42 wt.% of the catalyst, 43 wt.% of the catalyst, 44 wt.% of the catalyst, 45 wt.% of the catalyst, 46 wt.% of the catalyst, 47 wt.% of the catalyst, 48 wt.% of the catalyst, 49 wt.% of the catalyst, 50 wt.% of the catalyst, 51 wt.% of the catalyst, 52 wt.% of the catalyst, 53 wt.% of the catalyst, 54 wt.% of the catalyst, 55 wt.% of the catalyst, 56 wt.% of the catalyst, 57 wt.% of the catalyst, 58 wt.% of the catalyst, 59 wt.% of the catalyst, or 60 wt.% of the catalyst.

[0074] The catalyst material disclosed herein also includes a bismuth-containing compound. In some embodiments, the bismuth-containing compound is provided by combining the catalyst with at least one reactive bismuth compound. In some embodiments, the combining is performed by contacting (for example, mixing and / or grinding) the catalyst with the at least one reactive bismuth compound. In some embodiments, the combining is performed by wet mixing or dry mixing. In some embodiments, the dry mixing further comprises granulation. In some embodiments, the granulation comprises adding water during high shear mixing. Granulation can provide small beads of blended materials. In some embodiments, the combining further comprises heating the mixture of the catalyst and the at least one reactive bismuth compound.

[0075] A “reactive bismuth compound”, as used herein, refers to a bismuth compound that, when combined with the catalyst, is capable of reacting to form a bismuth-containing compound as a reaction product. In some embodiments, a portion of the reactive bismuth compound reacts when combined with the catalyst to provide the bismuth-containing compound of the catalyst material. In some embodiments, substantially all of the reactive bismuth compound reacts when combined with the catalyst to provide the bismuth- containing compound of the catalyst material. In some embodiments, the bismuth- containing compound includes bismuth molybdate, Bi2(MO4)3. In some embodiments, bismuth molybdate may be identified and / or quantified by Reitveld refinement of PXRD data.

[0076] In some embodiments, the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate. As used herein, the term “bismuth carbonate” includes basic carbonates of bismuth and oxide -carbonates (subcarbonates) of bismuth. Examples of a bismuth carbonate include bismuth carbonate basic or bismuth subcarbonate ((BiO^CCh). In some embodiments, the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, and bismuth carbonate. In some embodiments, the at least one reactive bismuth compound includes bismuth hydroxide. In some embodiments, a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range of from 1: 1 to 50: 1, 2: 1 to 30: 1, 2: 1 to 20: 1, 3: 1 to 50: 1, 3: 1 to 30: 1, 3: 1 to 20: 1, 3: 1 to 15: 1, 5: 1 to 15: 1, 5: 1 to 10: 1, or 10: 1 to 15: 1, catalyst: at least one reactive bismuth compound. In some embodiments, a weight ratio of the catalyst to the at least one reactive bismuth compound is 10: 1 catalystat least one reactive bismuth compound. The weight ratio of the catalyst to the at least one reactive bismuth compound can be selected to optimize catalyst activity.

[0077] In some embodiments, the catalyst material includes 1 wt.% to 45 wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 1 wt.% to 30 wt. %, 1 wt.% to 20 wt.%, 2 wt.% to 15 wt.%, 5 wt.% to 25 wt.%, 5 wt.% to 20 wt.%, 5 wt.% to 15 wt.%, or 5 wt.% to 10 wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 1 wt.%, 2 wt.%, 3 wt.%, 4 wt. %, 5 wt. %, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt. %, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, or 20 wt.% of the bismuth-containing compound.

[0078] In some embodiments, the catalyst material further includes an inert carrier material. In some embodiments, the catalyst material includes 1 wt.% to 90 wt.% of the inert carrier material. In some embodiments, the catalyst material includes 5 wt.% to 90 wt.% of the inert carrier material. In some embodiments, the catalyst material comprises 1 wt.% to 80 wt.%, 10 wt.% to 70 wt.%, 20 wt.% to 60 wt.%, or 30 wt.% to 50 wt.% of the inert carrier material. In some embodiments, the catalyst material includes 35 wt.% to 50 wt.% of the inert carrier material. In some embodiments, the catalyst material includes 35 wt.% to 45 wt.% of the inert carrier material. In some embodiments, the catalyst material includes 45 wt.% to 50 wt.% of the inert carrier material.

[0079] Some inert carrier materials are particularly suitable for the catalyst material, for example, they are chemically compatible (for example, there is no substantial impact on ethylene selectivity or there is an improvement to ethylene selectivity). Other inert materials may be less compatible, meaning they may lead to substantial reduction of catalyst material performance, for example, ethylene selectivity. Consequently, the inert carrier material should be selected based on both short-term and longer-term catalysis material performance testing. In some embodiments, there is an emphasis on long-term testing showing no loss of selectivity with time on stream (for example, TOS of >48 hours). As used herein, “time on stream (TOS)” refers to the time the catalyst material spends in the ODH process without interruption. In some embodiments, the inert carrier material includes at least one of precipitated synthetic silica, fumed synthetic silica, silica-alumina, a-alumina, y-alumina, titania, silicon carbide, MgAl spinel, an aluminate compound, an aluminosilicate compound, a zeolite, zirconia, doped zirconia (for example, 18% WCh-ZrCh or yttria-stabilized ZrCh), boron nitride, cerium oxide, doped cerium oxide (for example, cerium oxide doped with one or more rare earth elements), a perovskite (for example, CaTiCh), steel, or a combination thereof. In some embodiments, the inert carrier material is selected from the group consisting of precipitated synthetic silica, fumed synthetic silica, silica-alumina, a-alumina, and anatase titania. In some embodiments, the inert carrier material includes a-alumina.

[0080] In some embodiments, the catalyst material includes 15 wt.% to 99 wt.% of the catalyst, and 1 wt.% to 45 wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 30 wt.% to 70 wt.% of the catalyst, 20 wt.% to 60 wt.% of the inert carrier material, and 2 wt.% to 15 wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 50 wt.% of the catalyst, 40 wt.% of the inert carrier material, and 5 wt.% tolO wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 50 wt.% of the catalyst, 35 wt.% of the inert carrier material, and 5 wt.% to 15 wt.% of the bismuth-containing compound. In some embodiments, the catalyst material includes 45 wt.% of the catalyst, 40 wt.% of the inert carrier material, and 15 wt.% of the bismuth containing compound.

[0081] In some embodiments, the catalyst material has a powder X-ray diffraction (PXRD) pattern includes peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation, and further includes peaks at 20 values of 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, and 22.1° ± 0.2°.

[0082] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least five powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 12.7° ± 0.2°, 13.9° ± 0.2°, 22.1° ± 0.2°, 23.3° ± 0.2°, 25.1° ± 0.2°, 25.7° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 39.0° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, 62.8° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0083] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least five powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 13.9° ± 0.2°, 21.2° ± 0.2°, 25.1° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, and 62.8° ± 0.2°, wherein the PXRD patern is obtained using Cu Ka radiation.

[0084] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least ten powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 12.7° ± 0.2°, 13.9° ± 0.2°, 21.2° ± 0.2°, 23.3° ± 0.2°, 25.1° ± 0.2°, 25.7° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 39.0° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, and 62.8° ± 0.2°, wherein the PXRD patern is obtained using Cu Ka radiation.

[0085] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least ten powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 13.9° ± 0.2°, 21.2° ± 0.2°, 25.1° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, and 62.8° ± 0.2°, wherein the PXRD patern is obtained using Cu Ka radiation.

[0086] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least fifteen powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 12.7° ± 0.2°, 13.9° ± 0.2°, 22.1° ± 0.2°, 23.3° ± 0.2°, 25.1° ± 0.2°, 25.7° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 39.0° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, and 62.8° ± 0.2°, wherein the PXRD patern is obtained using Cu Ka radiation.

[0087] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least fifteen powder X-ray diffraction peaks (20 degrees) chosen from 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, 13.9° ± 0.2°, 22.2° ± 0.2°, 25.1° ± 0.2°, 26.1° ± 0.2°, 26.7 ± 0.2°, 27.1° ± 0.2°, 28.1° ± 0.2°, 31.3° ± 0.2°, 35.2° ± 0.2°, 45.3° ± 0.2°, 48.5° ± 0.2°, 49.5° ± 0.2°, 51.1° ± 0.2°, 53.4 ± 0.2°, 54.9° ± 0.2°, 56.4° ± 0.2°, 57.6° ± 0.2°, and 62.8° ± 0.2°, wherein the PXRD patern is obtained using Cu Ka radiation. In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, and at least five powder X-ray diffraction peaks (20 degrees) chosen from 7.8 ± 0.2°, 22.2 ± 0.2°, 26.7 ± 0.2°, 27.1 ± 0.2°, 35.2 ± 0.2°, 45.3 ± 0.2°, and 48.5 ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0088] In some embodiments, the catalyst material is characterized by having powder X-ray diffraction peaks (20 degrees) at 7.8 ± 0.2°, 12.6° ± 0.2°, 18.0° ± 0.2°, 22.2 ± 0.2°, 27.1 ± 0.2°, 27.9° ± 0.2°, 35.2 ± 0.2°, and 45.3 ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0089] In some embodiments, the PXRD includes peaks (20 degrees) corresponding to MoOs, which may be unreacted MoOs.

[0090] In some embodiments, the catalyst material has an axial crush strength between 50 N and 195 N as measured using ASTM D4149-22. In some embodiments, the catalyst material has an axial crush strength between 100 N and 170 N as measured using ASTM D4149-22. In some embodiments, the catalyst material has an axial crush strength between 160 N and 170 N as measured using ASTM D4149-22.

[0091] In some embodiments, the catalyst material has a radial crush strength between 80 N and 120 N as measured using ASTM D4149-22. In some embodiments, the catalyst material has a radial crush strength between 90 N and 110 N as measured using ASTM D4149-22. In some embodiments, the catalyst material has a radial crush strength between 95 N and 105 N as measured using ASTM D4149-22.

[0092] In some embodiments, the catalyst material has a bulk density between 1.2 g / cm3and 1.7 g / cm3as measured using ASTM D3766. In some embodiments the catalyst has a bulk density between 1.4 g / cm3and 1.6 g / cm3as measured using ASTM D3766. In some embodiments, the catalyst material has a bulk density between 1.500 g / cm3and 1.570 g / cm3as measured using ASTM D3766.

[0093] In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area as determined by nitrogen physisorption analysis between 2 m2 / g and 10 m2 / g, between 3 m2 / g and 10 m2 / g, between 4 m2 / g and 8 m2 / g, between 4 m2 / g and 6 m2 / g, between 4 m2 / g and 5 m2 / g, or between 5 m2 / g and 6 m2 / g. In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area as determined by nitrogen physisorption analysis of 5 m2 / g.

[0094] In some embodiments, the catalyst material has a pore volume as determined by nitrogen physisorption analysis with a Barrett-Joyner-Halenda (BJH) model of from 0.01 cm3 / g to 0.25 cm3 / g. In some embodiments, the catalyst material has a pore volume as determined by nitrogen physisorption analysis with a BJH model from 0.02 to 0.2 cm3 / g. In some embodiments, the catalyst material has a pore volume as determined by nitrogen physisorption analysis with a BJH model from 0.05 cm3 / g to 0.2 cm3 / g, from 0.05 cm3 / g to 0.15 cm3 / g, or from 0.05 cm3 / g to 0. 1 cm3 / g. In some embodiments, the catalyst has a pore volume as determined by nitrogen physisorption analysis with a BJH model of 0.02 cm3 / g, 0.03 cm3 / g, 0.04 cm3 / g, 0.05 cm3 / g, 0.0.6 cm3 / g, 0.07 cm3 / g, 0.08 cm3 / g, 0.09 cm3 / g, or 0.10 cm3 / g.

[0095] In some embodiments, the catalyst material is a pellet having a BET surface area of 5 m2 / g and a pore volume of 0.02 cm3 / g, indicative of a non-porous pellet.

[0096] In some embodiments, the catalyst material has a drop strength of at least 80% pellets staying intact when measured using ASTM D8353-20. In some embodiments, the catalyst material has a drop strength of at least 85% pellets staying intact when measured by ASTM D8353-20. In some embodiments, the catalyst material has a drop strength of at least 90% pellets staying intact when measured using ASTM D8353-20. In some embodiments, the catalyst material has a drop strength of at least 95% pellets staying intact when measured using ASTM D8353-20.

[0097] Also provided herein is a catalyst material prepared from a catalyst including the formula MoaVb(Mi)c(M2)aOx, wherein Mi, M2, a, b, c, d, and x are as defined herein; and a reactive bismuth compound. In some embodiments, the catalyst material is prepared from 15 wt.% to 99 wt.% of the catalyst and 1 wt.% to 30 wt.% of the reactive bismuth compound.

[0098] Also provided herein is a method for preparing a catalyst material including combining a first mixture comprising: a catalyst including the formula MoaVb(Mi)c(M2)dOx; wherein Mi, M2, a, b, c, d, and x are as defined herein, and a reactive bismuth compound as described herein, with a liquid medium to form a second mixture; and heating the second mixture to form the catalyst material.

[0099] The Catalyst

[0100] The catalysts described herein and suitable for use in the catalyst materials disclosed herein may be prepared by any suitable means. For example, the catalyst can be prepared by a hydrothermal synthesis reaction. Examples of catalyst suitable for the catalyst materials of the present disclosure are described in PCT / IB2024 / 052374 and PCT / IB2024 / 052375. In some embodiments, the catalyst is prepared by forming a slurry and heating a slurry including metal oxides; one or more of a bismuth compound, an antimony compound, and a tellurium compound; one or both of an oxide of tantalum and an oxide of niobium; a reducing agent; and water. As used herein, the term “slurry” refers to a mixture of solids in a liquid, and includes a suspension, a paste (that is, the mixture is viscous such that it cannot freely move), or a colloidal solution. As used herein, “water” may refer to deionized water, distilled water, and the like. In some embodiments, the water is distilled water. In some embodiments, the water is distilled, deionized water. In some embodiments, the water may include higher levels of contaminants without harming the catalyst.

[0101] In some embodiments, the metal oxides include an oxide of molybdenum, an oxide of vanadium. In some embodiments, the oxide of molybdenum is MoOs. In some embodiments, the oxide of vanadium is V2O5. In some embodiments, the oxide of vanadium is VO2. In some embodiments, the oxide of tantalum, when present, is Ta2Ch XH2O, and the oxide of niobium, when present, is Nb2Os XH2O.

[0102] In some embodiments, the catalyst contains bismuth, and the bismuth compound used to prepare the catalyst includes bismuth oxide, bismuth hydroxide, or a bismuth carbonate. In some embodiments, the bismuth compound is bismuth hydroxide. In some embodiments, the catalyst contains antimony, and the antimony compound includes an oxide of antimony, an antimony acetate, or an antimony ethoxide. In some embodiments, the antimony compound is an oxide of antimony. In some embodiments, the catalyst contains tellurium, and the tellurium compound includes tellurium dioxide (TeCh).

[0103] The slurry can include one reducing agent, or two or more reducing agents. In some embodiments, the slurry includes one or more reducing agents. In some embodiments, the slurry includes no more than one reducing agent.

[0104] Any suitable reducing agent may be included in the slurry in the method of preparing the catalyst. As used herein, the term “reducing agent” refers to a chemical substance that is capable of reducing an oxidation state of one or more of the metals of the metal oxides or the bismuth compound in the slurry. Suitable reducing agents to facilitate the reaction include reducing agents that are prone to decomposition or oxidation during the reaction process. In some embodiments, grinding, wet milling, dry milling, or crushing the reducing agent is used for controlled size modification of the reducing agent.

[0105] In some embodiments, the reducing agent includes an alcohol, a carboxylic acid, an ester, or a metal oxide. In some embodiments, the reducing agent includes an alcohol, a carboxylic acid, or an ester. Suitable examples of alcohol reducing agents include but are not limited to ethanol, methanol, reducing sugars, and polyols such as glycol and glycerol. Suitable examples of carboxylic acid reducing agents include but are not limited to oxalic acid, formic acid, acetic acid, and citric acid. Suitable examples of ester reducing agents include but are not limited to ethyl acetate, dimethyl carbonate, dimethyl oxalate, and diethyl oxalate.

[0106] The catalyst may be formed by using a ratio of water to metal oxides between 0.1 mL water per gram of metal oxides and 10 mb water per gram of metal oxides, such as between 0.1 mL water per gram of metal oxides and 5 mL water per gram of metal oxides, between 0.1 mL water per gram of metal oxides and 4 mL water per gram of metal oxides, between 0.1 mL water per gram of metal oxides and 3 mL water per gram of metal oxides, between 0.1 mL water per gram of metal oxides and 2 mL water per gram of metal oxides, or between 0.1 mL water per gram of metal oxides and 1 mL water per gram of metal oxides.

[0107] The phrase “ratio of water to metal oxides” as used herein refers to the ratio of water used in the slurry to the total mass of metal oxides used in the slurry, which includes an oxide of molybdenum; an oxide of vanadium; one or both of an oxide of tantalum and an oxide of niobium; and, some embodiments, MoO2 or VO2. For example, a slurry comprising 2.7 mL of water, 5.3673 g of MoOs, 1.0419 g V2O5, and 0.4255 of Ta2C>5 xFLO would include 6.8347 g of total metal oxides and provide a ratio of water to metal oxides of 0.395.

[0108] The method to form the catalyst may include a ratio of water in the slurry to amount of catalyst formed between 0.1 mL water per gram of catalyst and 10 mL water per gram of catalyst. As used herein, the phrase “water in the slurry” refers to the amount of water used to form the slurry for the hydrothermal synthesis reaction and does not include water that is not consumed or contaminated during the reaction or water that is used after the reaction. For example, “water in the slurry” does not include water present in the hydrothermal synthesis vessel for heat transfer and / or to maintain a humid atmosphere, or water that is used to wash the catalyst. As used herein, “catalyst formed” refers to the amount of catalyst solid obtained from the catalyst synthesis after drying the catalyst.

[0109] The slurry can be heated by ramping a temperature of the slurry and subsequently holding a temperature of the slurry. The ramping of the temperature can be used to avoid surface boiling of the slurry. The expression “ramping a temperature”, as used herein, refers to changing from an initial temperature to a final temperature over a time. For example, the temperature of the slurry may be ramped from an initial temperature of room temperature to a final temperature greater than room temperature over the course of a specified number of hours. The final temperature may be the holding temperature. The term “room temperature” as used herein refers to a temperature between 15°C and 28°C. The term “holding temperature”, as used herein, refers to the temperature at which the reaction vessel is held, which can be measured by the ambient temperature of the oven the reaction vessel was placed in. In some embodiments, the slurry is heated by ramping a temperature from ambient to a temperature between 100°C and 200°C over a ramping time between 2 hours and 48 hours; and holding the temperature at a holding temperature between 100°C and 200°C for a holding time between 12 hours and 160 hours. In some embodiments, the slurry is heated by ramping a temperature from ambient to a temperature between 100°C and 200°C over a ramping time between 2 hours and 48 hours; and holding the temperature at a holding temperature between 100°C and 200°C for a holding time between 12 hours and 120 hours. In some embodiments, the slurry is heated by ramping a temperature from ambient to a temperature between 150°C and 200°C over a ramping time between 2 hours and 24 hours; and holding the temperature at a holding temperature between 150°C and 200°C for a holding time between 24 hours and 60 hours.

[0110] The catalyst can be washed with water until the fdtrate is colorless. The catalyst can be dried, for example, at temperatures below 100°C by any suitable drying method.

[0111] The catalyst used to prepare the catalyst materials disclosed herein may be calcined. The skilled person will be familiar with calcination and suitable methods for calcining the catalyst. In some embodiments, the catalyst is calcined by placing the catalyst in a furnace under an oxygen-free environment; ramping a temperature of the furnace from ambient to a temperature between 500°C and 620°C over a ramping time between 2 hours and 10 hours; and holding the temperature of the furnace at a holding temperature between 500°C and 620°C for a holding time between 1 hour and 10 hours. For example, the catalyst is calcined by placing the catalyst in a furnace; ramping a temperature of the furnace from ambient to a temperature of 600°C over a ramping time of 6 hours; and holding the temperature of the furnace at a holding temperature of 600°C for a holding time of 2 hours. As used herein, an “oxygen-free environment” refers to an environment having a molecular oxygen content below 10 ppm. For example, the furnace may be under an inert atmosphere, such as a purified nitrogen atmosphere or a purified argon atmosphere, or the furnace may be under a CO2 and / or steam atmosphere.

[0112] The Catalyst Material

[0113] The method of preparing the catalyst materials disclosed herein includes combining a first mixture comprising: a catalyst including the formula MoaVb(Mi)c(M2)dOx; wherein Mi, M2, a, b, c, d, and x are as defined herein, and a reactive bismuth compound as described herein, with a liquid medium to form a second mixture; and heating the second mixture to form the catalyst material.

[0114] In some embodiments, the first mixture includes the catalyst and the reactive bismuth compound in a weight ratio from 1: 1 to 50: 1 2: 1 to 30: 1, 2: 1 to 20: 1, 3: 1 to 50: 1, 3: I to 30: 1, 3: I to 20: 1, 3: I to 15:1, 5:1 to 15: 1, 5: 1 to 10: 1, 10: l to 15: 1, or 10: 1 catalyst: reactive bismuth compound. In some embodiments, the first mixture includes the catalyst and the reactive bismuth compound in a weight ratio from 5: 1 to 15: 1 catalyst: reactive bismuth compound. In some embodiments, the first mixture includes the catalyst and the reactive bismuth compound in a weight ratio of 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, or 10: 1, catalyst: reactive bismuth compound. The reactive bismuth compound may refer to a single reactive bismuth compound or a combination of two or more reactive bismuth compounds.

[0115] In some embodiments, the first mixture includes 15 wt.% to 99 wt.% of the catalyst. In some embodiments, the first mixture includes 30 wt.% to 70 wt.% of the catalyst. In some embodiments, first mixture includes 40 wt.% to 60 wt.% of the catalyst, such as about 50 wt.%. In some embodiments, the first mixture includes 40 wt.% of the catalyst, 41 wt.% of the catalyst, 42 wt.% of the catalyst, 43 wt.% of the catalyst, 44 wt.% of the catalyst, 45 wt.% of the catalyst, 46 wt.% of the catalyst, 47 wt.% of the catalyst, 48 wt.% of the catalyst, 49 wt.% of the catalyst, 50 wt.% of the catalyst, 51 wt.% of the catalyst, 52 wt.% of the catalyst, 53 wt.% of the catalyst, 54 wt.% of the catalyst, 55 wt.% of the catalyst, 56 wt.% of the catalyst, 57 wt.% of the catalyst, 58 wt.% of the catalyst, 59 wt.% of the catalyst, or 60 wt.% of the catalyst.

[0116] In some embodiments, the first mixture includes 1 wt.% to 30 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 1 wt.% to 20 wt.%, 2 wt.% to 15 wt.%, 5 wt.% to 15 wt.%, or 5 wt.% to 10 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 5 wt. %, 6 wt. %, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, or 15 wt.% of the reactive bismuth compound.

[0117] In some embodiments, the first mixture includes 15 wt.% to 99 wt.% of the catalyst and 1 wt.% to 30 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 1 wt.% to 50 wt.% of the catalyst and 5 wt.% to 10 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 45 wt.% to 55 wt.% of the catalyst and 5 wt.% to 15 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 50 wt.% of the catalyst, and 5 wt.% to 10 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 50 wt.% of the catalyst and 5 wt.% of the reactive bismuth compound. In some embodiments, the first mixture includes 50 wt.% of the catalyst and 10 wt.% of the reactive bismuth compound.

[0118] In some embodiments, the first mixture further includes an inert carrier material. In some embodiments, the first mixture includes 1 wt.% to 90 wt.%, of the inert carrier material. In some embodiments, the first mixture includes 1 wt.% to 80 wt.%, 10 wt.% to 70 wt.%, 20 wt.% to 60 wt.%, or 30 wt.% to 50 wt.% of the inert carrier material. In some embodiments, the first mixture includes 35 wt.% to 50 wt.% of the inert carrier material. In some embodiments, the first mixture includes 35 wt.% to 45 wt.% of the inert carrier material. In some embodiments, the first mixture includes 45 wt.% to 50 wt.% of the inert carrier material.

[0119] In some embodiments, the first mixture further includes a binder. Suitable binders include liquid binders, organic binders, inorganic binders, or combinations thereof. Examples of liquid binders include but are not limited to water, oil, sodium silicate, and a polybutadiene emulsion. Examples of organic binders include but are not limited to starch, lignosulfonate, cellulose, cellulose-derived powders (e.g., PERIDUR®), microcrystalline cellulose powder (e.g., AVICEL®), polyethylene glycol, polyvinyl acetate, polyvinyl alcohol (e.g., MOWIOL® 8-88), poly(acrylic acid), other synthetic polymers (e.g., ALCOTAC®), and a modified-starch brewery byproduct (e.g., Brewex). In some embodiments, the starch is com starch. Examples of inorganic binders include but are not limited to bentonite, cement, clay and lime, sodium silicate, calcium aluminate, calcium silicate composite powder, alumina silicate, Fuller’s earth, and fly ash chemically activated with alkaline materials.

[0120] In some embodiments, the binder comprises one or more of a liquid binder, an organic binder, and an inorganic binder. In some embodiments, the binder comprises water and at least one of a binder other than water. In some embodiments, the binder comprises polyethylene glycol, poly(acrylic acid), and polyvinyl alcohol. In some embodiments, the first mixture includes 0.1 wt.% to 30 wt.%, 0.5 wt.% to 20 wt.%, or 1 wt.% to 10 wt.% of one or more binders other than water. In some embodiments, the first mixture includes up to 10 wt.% of one or more binders other than water. In some embodiments, the first mixture includes up to 5 wt.% of one or more binders other than water. In some embodiments, the second mixture includes 1 wt.% to 99 wt.%, 20 wt.% to 95 wt.%, 50 wt.% to 95 wt.%, or 70 wt.% to 90 wt.% of the liquid medium. In some embodiments, the second mixture includes 75 wt.% to 85 wt.% of the liquid medium. The liquid medium can include one or more liquids suitable for mixing and / or binding the first mixture. In some embodiments, the liquid medium includes a liquid binder. For example, the liquid medium includes water, oil, sodium silicate dissolved in water, a polybutadiene emulsion, or a combination thereof. In some embodiments, the liquid medium includes water.

[0121] In some embodiments, the method further includes adding a lubricant to the first mixture. In some embodiments, the lubricant is selected from the group consisting of graphite, hexagonal boron nitride, calcium carbonate, a fatty acid, and a fatty acid salt. In some embodiments, the fatty acid is stearic acid. In some embodiments, the fatty acid salt is calcium stearate, sodium stearate, or a combination thereof. In some embodiments, the lubricant is a binder as disclosed herein.

[0122] In some embodiments, the method further includes extruding, pressing, 3D-printing, spheronizing, or casting the catalyst material to produce a formed catalyst material. In some embodiments, the method includes pressing the catalyst material to form pellets.

[0123] In some embodiments, the method further includes heating the second mixture until the liquid medium is substantially evaporated. In some embodiments, wherein the liquid medium includes water, the method includes heating the second mixture at a temperature of about 60°C to about 120°C until the water is substantially evaporated. In some embodiments, the method further includes drying the second mixture at a temperature of about 60°C to about 120°C for a drying time between 1 hour and 48 hours. For example, the second mixture is dried at about 90°C for a drying time between about 16 hours and about 20 hours.

[0124] In some embodiments, the method further includes calcining the catalyst material to provide a calcined catalyst material. In some embodiments, the calcining includes: placing the catalyst material in a furnace under an oxygen-containing environment; ramping a temperature of the furnace from ambient to a temperature between 300°C and 500°C over a ramping time between 30 minutes and 4 hours; allowing the temperature of the furnace to cool to ambient temperature; placing the furnace under an oxygen-free environment; ramping a temperature of the furnace from ambient to a temperature between 500°C and 700°C over a ramping time between 30 minutes and 4 hours; and allowing the temperature of the furnace to cool to ambient temperature. The ramping of the temperature can be used to avoid surface boiling of the reaction mixture.

[0125] As used herein, the term “temperature of the furnace” refers to the external surface temperature of the calcining vessel. As used herein, an “oxygen-free environment” refers to an environment having a molecular oxygen content below 10 ppm. For example, the furnace is under an inert atmosphere, such as a purified nitrogen atmosphere or a purified argon atmosphere, or the furnace is under a CO2 and / or steam atmosphere.

[0126] The catalyst materials prepared from the methods disclosed herein include a catalyst and a bismuth-containing compound, and have a powder X-ray diffraction (PXRD) pattern including peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation. Further properties of the catalyst material prepared from the methods disclosed herein are described earlier herein.

[0127] The catalyst materials disclosed herein may be suitable as catalyst in oxidative dehydrogenation reactions. Also provided herein is a process for the oxidative dehydrogenation of ethane using the catalyst materials disclosed herein. As used herein, the term “oxidative dehydrogenation” or “ODH” refers to processes that couple the endothermic dehydrogenation of an alkane (CnH2n+2) with the strongly exothermic oxidation of hydrogen as is further described herein to form, amongst other things, alpha-olefins. In some embodiments, the alkane is one or more of ethane, propane, butane, pentane, hexane, octane, decane, and dodecane. In some embodiments, the alkane is ethane or propane. In some embodiments, the alkane is ethane. Fortesting catalysts, the ODH reactions herein are assumed to be referring to the ODH of ethane.

[0128] The process includes contacting a gaseous feed comprising ethane and oxygen with a catalyst material described herein in a reactor to produce an effluent comprising ethylene. The catalysts provided herein can be used for the oxidative hydrogenation of ethane to form ethylene and other value-added products. In some embodiments, the value-added products comprise one or both of ethylene and acetic acid.

[0129] In some embodiments, the catalyst material has an increased selectivity to one or both of ethylene and acetic acid at equivalent ethane conversion as compared to the selectivity of the catalyst. For example, when measured at the same level of ethane conversion, the catalyst material has an increased selectivity to one or both of ethylene and acetic acid compared to the selectivity of the catalyst.

[0130] In some embodiments, the catalyst material has an increased ethane conversion at an oxygen conversion of greater than 95% as compared to the ethane conversion of the catalyst (that is, as compared to the ethane conversion of the same catalyst material without the bismuth-containing compound at an oxygen conversion of greater than 95%) at a given ethane conversion temperature. In some embodiments, the catalyst material has a gradual improvement in ethane conversion when left on stream at greater than 60% ethane conversion at a given ethane conversion temperature, while maintaining good ethylene selectivity. In some embodiments, the catalyst material maintains an ethane conversion of greater than 60% for about 1 day, about 2 days, or about 3 days on stream.

[0131] The ethane conversion temperature can be determined using a microreactor unit. For example, in a microreactor unit, the 45% ethane conversion temperature of a catalyst can be determined by passing a feed gas over a catalyst bed in a reactor tube. The MRU reactor tube has an outer diameter of 0.5 inches and an internal diameter of 0.4 inches and length of 15 inches. For example, the reactor tube can be stainless-steel SWAGELOK® Tubing with a wall thickness of 0.049 inches. The feed gas can include ethane and oxygen having a molar ratio of 70:30 to 90: 10. For example, the feed gas can include ethane and oxygen having a molar ratio of 82: 18. Alternatively, the feed gas can include ethane, oxygen, and nitrogen. The molar ratio of ethane to oxygen to nitrogen can be 18:8:74 to 54: 18:28. For example, the molar ratio of ethane to oxygen to nitrogen can be 20: 10:70. The flow rate of the feed gas can be 70 standard cubic centimeters per minute (seem) to 80 seem. For example, the flow rate of the feed gas can be 75 seem (e.g., 74.6 seem). The catalyst bed consists of the oxidative dehydrogenation catalyst and a filler, such as quartz sand, 1 : 0.5 to 1 :3 volume ratio, with the total weight for the oxidative dehydrogenation catalyst being 1.96 to 2.00 g. Any remaining space in the reactor tube (e.g., below or above the catalyst bed) is packed with an additional filler, such as quartz sand. The 45% ethane conversion temperature is determined at a weight hourly space velocity (WHSV) of 3.57 h-1, with the WHSV based on the weight of catalyst in the sample, and a gas hourly space velocity (GHSV) of 2,000 to 5,000 h-1. As used herein, the expression “weight hourly space velocity” refers to the weight flow of the total feed gas divided by the weight of the catalyst. Typically, the inlet pressure is in the range of 1 pound per square inch gauge (psig) to 2.5 psig and the outlet pressure is in the range of 0 psig to 0.5 psig. The gas feed exiting the catalyst bed is analyzed by gas chromatography to determine the percent of various hydrocarbons (e.g., ethane and ethylene), and optionally other gases such as O2, CO2, and CO.

[0132] Conversion of the ethane feed gas to products by the ODH process can be calculated as a volume flow rate change of ethane in the product compared to feed ethane mass flow rate using the following formula: In Equation 1, C is the percent (molar percent) of ethane feed gas that has been converted from ethane to another product (that is, ethane conversion) and X is the molar concentration of the corresponding compound in the gaseous effluent exiting the reactor at corresponding temperature.

[0133] Furthermore, the gas exiting the reactor can be analyzed by gas chromatography to determine catalyst or catalyst material selectivity to ethylene (i.e., the percentage on a molar basis of ethane that forms ethylene). Selectivity to ethylene can be determined using the following equation:

[0134] In Equation 2, SEthyiene is the selectivity to ethylene and X is the molar concentration of the corresponding compound in the gaseous effluent exiting the reactor at corresponding temperature. As used herein, the phrase “selectivity to ethylene” refers to the percentage on a molar basis of converted or reacted ethane that forms ethylene.

[0135] In some embodiments, the gaseous feed contains ethane in a range of about 10 mol% to about 50 mol%, about 10 mol% to about 30 mol%, or about 20 mol%. In some embodiments, the gaseous feed further comprises oxygen in a range of about 1 mol% to about 40 mol%, about 1 mol% to about 25 mol%, or about 10 mol%. In some embodiments, the gaseous feed further comprises a diluent in a range of about 50 mol% to about 90 mol%, about 60 mol% to about 80 mol%, or about 70 mol%. In some embodiments, the diluent is selected from N2, CO2, H2O, methane, Ar, or a combination thereof. In some embodiments, the diluent comprises nitrogen. In some embodiments, the gaseous feed comprises about 20 mol% ethane, about 10 mol% oxygen, and about 70 mol% nitrogen.

[0136] In some embodiments, a reaction inlet pressure for the ODH process is in a range of about 0 psig to about 150 psig, or about 10 psig to about 30 psig. In some embodiments, the ODH process is carried out under about 20 psig to about 25 psig nitrogen.

[0137] In some embodiments, the operating temperature of the ODH process is in a range of about 275°C to about 500°C, about 350°C to about 450°C, or about 400°C to about 440°C.

[0138] In some embodiments, the gas hourly space velocity (GHSV) is in the range of about 1,000 h'1to about 30,000 h’1, or about 2,000 to about 5,000 h’1. GHSV (gas hourly space velocity) is defined as volumetric flow of the reactor feed gas divided by the volume of the catalyst bed. As used herein, the term “volume of the catalyst bed” refers to the volume occupied by catalyst particles, optional diluent particles, and any void spaces within the catalyst bed. For GHSV values of Catalyst Materials, the catalyst bed is treated as catalyst only (not including support) where an assumption was made that the total volume of the catalyst material measured when multiplied by the wt.% of catalyst is the volume of the catalyst. The GHSV can be calculated based off the measured volume of the pressed particles (before mixing with quartz sand) and varies depending on each catalyst or catalyst material bulk density. For catalyst materials discussed herein, the GHSV reported is for the catalyst only, where an assumption was made that the total volume of the catalyst material measured when multiplied by the wt.% of catalyst is the volume of the catalyst.

[0139] In some embodiments, the weight hourly space velocity (WHSV) is in a range of about 1 h'1to about 30 h’1, or about 2 h'1to about 6 h’1. For example, the WHSV is about 5.46 h’1. As used herein, “WHSV” refers to a ratio of weight flow rate of total feed to the weight of catalyst in the catalyst bed.

[0140] In some embodiments, the linear space velocity of the gaseous feed is in a range of about 1 cm / s to about 500 cm / s. As used herein, the linear velocity in cm / sec can be calculated using the equation:

[0141] Volumetric Flow rate of feed gas and / or vapor entering the reactorT, at reactor temperature and reactor inlet pressure

[0142] Linear Velocity = - - - - - — - - - - - - — — cross section area of reactor tube x void fraction of catalyst bed

[0143] Void fraction of catalyst bed is the fraction of volume of the void in catalyst bed active phase measured experimentally.

[0144] Ethylene provided by ODH of ethane using the catalyst materials and processes described herein can subsequently be converted into a variety of products. For example, ethylene can be converted to very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene dichloride, ethylene oxide, ethylbenzene, linear alcohols, vinyl acetate, alkanes, alpha olefins (e.g., 1-hexene and 1 -octene), various hydrocarbon-based fuels, ethanol and the like. These products can then be further processed using methods well known to one of ordinary skill in the art to obtain other valuable chemicals and consumer products.

[0145] In some embodiments, ethylene provided by the ODH process described herein is converted to polyethylene. In some embodiments, the polyethylene is very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

[0146] Other than in the operating examples or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, etc. used in the specification and claims are to be understood as modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties, which the present disclosure desires to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0147] As used in this disclosure, the term “substantially” refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

[0148] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0149] In addition, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

[0150] EXAMPLES

[0151] Reagents and Equipment

[0152] Molybdenum(VI) oxide (MoOs, >99.5% purity), vanadium(V) oxide (V2O5, >98% purity), tellurium dioxide (TeCh) and oxalic acid dihydrate (>99% purity) were purchased from Sigma-Aldrich. Tantalum pentoxide hydrate (Ta2C>5 xFLO) was purchased from BassTech International. Niobium pentoxide hydrate was purchased from Companhia Brasileria.

[0153] Bismuth(III) hydroxide (technical grade) and a-alumina (99.9%, <1.0 pm particles) were purchased from Thermo Fisher Scientific. Polyethylene glycol) (Mwabout 1000), poly(vinyl alcohol) (MOWIOL® 8-88, Mwabout 67,000), graphite flakes (synthetic, <20 pm particles) and poly(acrylic acid) (Mvabout 1,250,000) were purchased from Sigma- Aldrich. All reagents were used as is without any further purification. All water that was used was distilled water.

[0154] Power X-ray diffraction (PXRD) experiments were performed using a PANalytical Empyrean powder X-ray diffractometer equipped with a monochromated Cu Ka X-ray source. Data was acquired between 3 - 80° 20 at a scan rate of l° / min. Data was analyzed using PANalytical HighScore software Version 4.8.

[0155] Scanning electron microscopy (SEM) images were collected using a JEOL JSM- IT300LV InTouchScope scanning electron microscope. Samples were collected under high vacuum at xl5,000 magnification. Catalyst metal compositions can be determined by energy dispersive x-ray spectroscopy (EDX). EDX was conducted on the SEM equipment using an Ultim Max 65 large area Analytical Silicon Drift Detector on the widest possible sample area at 50x magnification. The scan was conducted at 25 kV accelerating voltage and analysis was done using AnalysisStation provided by JEOL. EDX was used to determine the elemental composition of the samples by scanning the widest area of the sample possible, approximately 2.8 mm x 2. 1 mm.

[0156] In the examples that follow, comparative catalyst materials prepared without the addition of the reactive bismuth compound are indicated by a -C label and catalyst material examples according to the present disclosure are indicated by -E in the label. Preparation of Catalyst Example 1 (MoVTaBiOx)

[0157] Catalyst Example 1 was prepared with solid reagents listed in Table 1. The solid reagents were added to a blender and mixed for 1 minute to blend and pulverize. The solid mixture was then transferred a 40 mb glass bottle, after which 8.0 mb of the distilled water solvent was used to rinse the grinder and transfer the residual solids to the bottle. The sample was stirred lightly with a glass stir rod to form a thick orange slurry and another 2.8 mb of water was then used to rinse sample stuck to the stir rod back into the bottle. Table 1. Amounts of Reagents Used to Prepare Catalyst Example 1. The bottle was then placed in a glass lined steel autoclave, and water was filled around the bottle to the level of the slurry to help with heat transfer and to maintain a humid atmosphere in the vessel (~20 mL of water). The autoclave was then sealed and placed in an oven to heat from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then turned off to cool back to ambient over 3 - 4 hours. After the reaction, the sample was a deep purple hard solid. The sample was scraped from the bottle onto filter paper in a vacuum filtration set-up and was washed with distilled water, with the filtrate being a deep blue color. The sample was washed until the filtrate from the sample was nearly colorless, then was left to dry on the filter paper to obtain 29.4870 g of shiny purple-black powdered solid.

[0158] Most of the sample (24.6823 g) was then calcined in a tubular autoclave under N2 flow (3.9 cm / min linear velocity at STP) for 8 hours at 80°C, after which it was heated to 600°C over 6 hours, held at 600°C for 2 hours, then the furnace was turned off and the samples cooled back to ambient conditions over approximately 12 hours. After calcination, the sample was a deep purple-black powder. The mass of the sample after calcining was 23.3152 g.

[0159] Powder X-ray diffraction (PXRD) analysis was conducted on the sample of Catalyst Example 1 before and after calcination (Figure 1). By PXRD, both samples were characterized as a doped molybdenum vanadium oxide phase known in the art as Ml. Before calcination, the sample was characterized with a minor impurity of MoOs, which converted into the desired phase after calcination.

[0160] The catalyst formula for catalyst Example 1 was determined by EDX to be Mo1V0.33Bi0.05Ta0.04Ox.

[0161] Preparation of Comparative Catalyst Material 1-C

[0162] A mixture was prepared including calcined catalyst Example 1 (10.0671 g), a- alumina (10.0771 g), poly(acrylic acid) (0.0199 g) and water (100 mL) and stirred overnight in a beaker to disperse. This mixture was then vacuum filtered and left to dry. The filter cake was then transferred back into the beaker along with polyethylene glycol) 1000 (0.3912 g), MOWIOL® 8-88 (0.6008 g), poly(acrylic acid) (0.0163 g) and water (90 mL), and stirred while heating at 85°C until the water had evaporated. The sample was then placed in an oven at 90°C overnight to dry completely.

[0163] After drying, the sample was lightly pulverized using a mortar and pestle, sieved to obtain particles between 250 pm and 500 pm in size. 1 wt.% of graphite flakes were then added to the sieved particles and the mixture was shaken in a closed container to disperse. The graphite coated particles were pelleted using a Dott Bonapace model CPR-6 automatic pellet press to obtain cylindrical pellets with approximately 5 mm length and 3 mm diameter.

[0164] The pellets were placed in a quartz boat and heated first under dry air (1.8 cm / min linear velocity at STP) at a rate of 1.0°C / min to 400°C, held at 400°C for 1 hour, then heating was stopped and the furnace was left to cool back to ambient conditions over approximately 12 hours. Following the air treatment, the atmosphere was then purged with dry nitrogen (3.9 cm / min linear velocity at STP) for 8 hours, then under the same nitrogen flow, heated at a rate of 1.6°C / min to 600°C, held at 600°C for 2 hours, then heating was stopped and the furnace was left to cool back to ambient conditions over approximately 12 hours. After the calcination / sintering procedure, the pellets mass was reduced by 5.28%.

[0165] As shown in Figure 2, PXRD was collected on comparative catalyst material 1-C following this procedure and showed that the sample was a mixture of the catalytically active Ml phase and a-alumina with a minor impurity of y-alumina.

[0166] Preparation of Example Catalyst Material 1-E

[0167] A mixture was prepared including calcined catalyst Example 1 (3.8232 g), a- alumina (3.0462 g), bismuth(III) hydroxide (0.8645 g), poly(acrylic acid) (0.0078 g), poly(ethylene glycol) 1000 (0.1614 g), MOWIOL® 8-88 (0.2739 g), and water (50 mL). The mixture was stirred while heating at 80°C until the water had evaporated. The sample was then placed in an oven at 90°C overnight to dry completely.

[0168] After drying, the sample was lightly pulverized using a mortar and pestle, and sieved to obtain particles between 250 pm and 500 pm in size. Graphite flakes (1 wt.%) were then added to the sieved particles and the mixture was shaken in a closed container to disperse. The graphite coated particles were then pelleted using a Dott Bonapace model CPR-6 automatic pellet press to obtain cylindrical pellets with approximately 5 mm length and 3 mm diameter.

[0169] The pellets were placed in a quartz boat and heated first under dry air (1.8 cm / min linear velocity at STP) at a rate of 1.0°C / min to 400°C, held at 400°C for 1 hour, then heating was stopped and the furnace was left to cool back to ambient conditions over approximately 12 hours. Following the air treatment, the atmosphere was then purged with dry nitrogen (3.9 cm / min linear velocity at STP) for 8 hours, then under the same nitrogen flow, heated at a rate of 1.6°C / min to 600°C, held at 600°C for 2 hours, then heating was stopped and the furnace was left to cool back to ambient conditions over approximately 12 hours. After the calcination / sintering procedure, the mass of the pellets was reduced by 5.53%.

[0170] As shown in Figure 3, PXRD was collected on catalyst material Example 1-E following this procedure and indicated that the bismuth(III) hydroxide had reacted with some molybdenum components, and the catalyst was a mixture of the catalytically active Ml phase, Bi2(MC>4)3 (see preparation described herein), and a-alumina at an approximate weight ratio of 30 / 15 / 55, respectively, by crude Rietveld refinement.

[0171] Bismuth molybdate (Bi2(MC>4)3) was quantified by Rietveld refinement using HighScore Plus software version 4.8 produced by Malvern Panalytical. Crystal structures used for fitting and refining the PXRD patterns can be found in, for example, the Inorganic Crystal Structure Database, the International Centre for Diffraction Data.

[0172] Figure 4A shows an overlay of the PXRD patterns of comparative catalyst material 1-C (bottom) and catalyst material Example 1-E (top) and Figure 4B is the PXRD overlay of Figure 4A zoomed in on 5-30 20°. In Figure 4B, peaks at 12.6°, 18.0°, 27.9°, and 29.1° are attributed to bismuth molybdate.

[0173] Preparation of Catalyst Examples 2 (MoVTaBiOx, uncalcined) and 3 (MoVTaBiOx, calcined)

[0174] The solids listed in Table 2 were weighed out and added together in a blender, then blended for 3 - 4 minutes in approximately 1 minute intervals, shaking and knocking down the solids in the blender between intervals. The powdery orange solid mixture was then added to a 100 mb disposable glass vial and 20 mb of water was added. An additional 3 mb of water was used to rinse the blender and added into the vial, then the mixture was stirred with a glass stir rod to form a viscous orange slurry.

[0175] Table 2, Amounts of Reagents Used to Prepare Catalyst Examples 2 and 3,

[0176] This mixture was then placed in a steel autoclave, and water was filled around the vial to assist with heat transfer and to maintain a humid atmosphere inside the vessel. The autoclave was then sealed and placed in a programmable oven to heat from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then the oven was turned off and allowed to passively cool back to ambient temperature. The damp purple solid product was removed from the vial, stirred in distilled deionized water (~50 mL) and fdtered by vacuum fdtration, producing a deep blue filtrate. The solid was washed until the filtrate was colorless, then was dried in an oven at 90°C overnight.

[0177] A portion of this dried sample was set aside (catalyst Example 2), while a 28.7285 g subsample was calcined under nitrogen flow (3.9 cm / min linear velocity at STP) in a tubular quartz furnace, first by heating the sample for 8 hours at 60°C to purge the furnace with nitrogen, then heating at 1.6°C / min to 600°C, holding at 600°C for 2 hours, then allowing the furnace to cool back to room temperature passively under nitrogen flow. After calcination the sample (catalyst Example 3) remained a deep purple color and the mass was 27.8612 g, or 3.02% mass loss.

[0178] Preparation of Example Catalyst Materials 2-E, 3-E1, and 3-E2

[0179] Example catalyst material 2-E was prepared with catalyst Example 2 and 10% bismuth hydroxide. Example catalyst materials 3 -El and 3-E2 were prepared with catalyst Example 3. Example 3-E1 was prepared with 5 wt.% bismuth hydroxide, and Example 3-E2 was prepared with 10 wt.% bismuth hydroxide.

[0180] For each catalyst material preparation, the catalyst sample was added to a 600 mL beaker along with a-alumina, bismuth hydroxide, polyethylene glycol (weight average molecular weight = 1000), poly(vinyl alcohol) (MOWIOL 8-88), poly(acrylic acid), and water (Table 3).

[0181] Table 3, Amounts of reagents used to prepare Example catalyst materials 2-E, 3 -El, and 3-E2, Each mixture was stirred while heating open in the air at 90°C to evaporate the water, then was dried overnight in an oven at 90°C. After drying, each sample was lightly pulverized using a mortar and pestle, then particles were sieved to obtain granules between 250 and 500 pm. Graphite flakes (1 wt.%) was then added to the sieved particles and pellets with approximate dimensions of 3 mm diameter and 8 mm length were formed using an automated pellet press (Dott Bonapace model CPR-6).

[0182] These pellets were heated in a tubular quartz furnace under dry air flow (1.8 cm / min linear velocity at STP) from room temperature to 400°C at a rate of l°C / min, held at 400°C for 1 hour, then heating was stopped and the furnace was left passively cool back to ambient under air flow. After cooling, the gas flow was changed to nitrogen (3.9 cm / min linear velocity at STP), and after 8 hours of purging, the furnace was heated from room temperature to 600°C at a rate of 1 ,6°C / min, held at 600°C for 2 hours, then the heating was stopped and the furnace was left to cool back to room temperature passively under nitrogen flow.

[0183] Preparation of Catalyst Example 4 (MoVNbTeOx)

[0184] Catalyst Example 4 was prepared using the same procedure as catalyst Examples 2 and 3 using the reagents listed in Table 4.

[0185] Table 4, Amounts of Reagents Used to Prepare Catalyst Example 4,

[0186] After calcination, mass loss of 2.45% was observed. Deep purple-black solid (32.2259g) was obtained.

[0187] Preparation of Comparative Catalyst Material 4-C and Example Catalyst Material 4-E

[0188] Comparative catalyst material 4-C and Example catalyst material 4-E were prepared using calcined catalyst Example 4, and the reagents listed in Table 5. Table 5, Amounts of Reagents Used to Prepare Catalyst Material Examples 4-C and 4-E,

[0189] Figure 5 shows a PXRD pattern of comparative catalyst material 4-C overlaid with the PXRD patterns for alpha alumina and catalyst example 4. Figure 6 shows a PXRD pattern of catalyst material example 4-E overlaid with the PXRD patterns for catalyst example 4, alpha alumina, and bismuth molybdate (prepared as described herein).

[0190] Atomic composition of the catalyst phase for both comparative Catalyst Material 4- C and Catalyst Material 4-E, determined by EDS and normalized to molybdenum, was found to be Mo1V0.32Nb0.03Te0.04Ox. Alumina composition was found to be 53.4 wt.% for sample 10A and 52.2 wt.% for 10B.

[0191] Figure 7A shows an overlay of comparative catalyst material 4-C and catalyst material example 4-E and Figure 7B is the PXRD overlay of Figure 7A zoomed in on 5-30 20°. In Figure 7B, peaks at 12.6°, 18.0°, 27.9°, and 29.1° are attributed to bismuth molybdate.

[0192] Figure 8 shows scanning electron microscopy (SEM) images of comparative catalyst material 4-C and Figure 9 shows SEM images of catalyst material 4-E.

[0193] Preparation of Catalyst Example 5

[0194] Catalyst Example 5 was prepared using a larger scale reaction that omitted the solid grinding step. All solids listed in Table 6 were added to a 1.8 L PTFE beaker and stirred with an overhead stirrer for 45 minutes to form an orange slurry. The beaker was then placed in a 2 L steel autoclave and 50 mb of water was fdled around the outside of the PTFE beaker in order to maintain 100% relative humidity inside the vessel. The vessel was then sealed and placed in an oven to heat from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then heating was stopped and the vessel was cooled back to room temperature over approximately 6 hours. The vessel was then vented in a fume hood, and the dark purple solid was transferred into a 3 L beaker. Water (I L) was added to the beaker, and the mixture was stirred with an overhead stirrer overnight. The purple slurry was then filtered by vacuum filtration and washed with a further 3 L of water in 1 L portions, then dried in an oven at 90°C for 24 hours and 813.27 g of dry catalyst was obtained.

[0195] Table 6, Amounts of Reagents Used to Prepare Slurry for Catalyst Example 5,

[0196] The dry Catalyst Example 5 was calcined in a tubular quartz furnace under nitrogen flow (3.9 cm / min linear velocity at STP). After sufficient time was given for the furnace to purge with nitrogen (~8 hours), the furnace was heated from room temperature to 600°C at 1.6°C / min, held at 600°C for 2 hours, then the heating was stopped, and the sample was allowed to cool back to room temperature over approximately 12 hours. Preparation of Catalyst Material 5-E

[0197] Calcined Catalyst Example 5 (333.3 g), alpha alumina (300.0 g) and bismuth(III) hydroxide (33.3 g) were added to the bowl of an Eirich EL-1 laboratory mixer fitted with a Z-type rotor. The bowl was tilted to 20°, and the rotor tip speed was adjusted to 25 m / s. The solids were mixed dry for 440 s, after which 165 mb of water was slowly added through the top port over 2 minutes using an addition funnel while still mixing at 25 m / s tip speed. After full addition of water, the mixing continued for 1 minute, then mixing was stopped. This resulted in the formation of wet microgranules which were transferred to a steel pan to dry in an oven at 90°C overnight. After removing from the oven, the granules were sieved to obtain particle size between 180 - 500 pm. Oversized and undersized granules would be retained and recycled back into the granulation process. Generally, 60 - 80% of granules in the desired size range were obtained. Granules of the correct size had 1 wt.% graphite flakes added, and were shaken to disperse. The mixture was then fed into an automatic pellet press (Dott Bonapace CPR-6) to obtain pressed cylindrical pellets with approximate dimensions of 3 mm diameter and 4.5 mm length. The pellets were then sintered in a two-step procedure in the CCF. Firstly, under air flow (1.9 cm / min linear velocity at STP), the pellets were heated to 400°C at 1.0°C / min, held at 400°C for 1 hour, then cooled to room temperature over approximately 8 hours. The furnace was then purged with nitrogen for 8 hours flow (3.9 cm / min linear velocity at STP), after which it was heated to 600°C at a rate of 1.6°C / min, then heating was stopped, and the furnace was cooled to room temperature over approximately 12 hours. The PXRD for sintered pellets of catalyst material 5-E following this procedure is shown in Figure 10.

[0198] Pellets of Catalyst material Example 5-E were tested for crush strength (ASTM D4179-22), envelope density (ASTM D3766), bulk density (ASTM D3766), and drop strength (ASTM D8353-20). Nitrogen gas physisorption analysis was measured on a single pellet. The average envelope density of the pellets was found to be 2.69 g / cm3. Average axial crush strength was measured to be 165 N, and average radial crush strength was measured to be 101 N. Bulk density was found to be 1.512 g / cm3as loaded, and 1.556 g / cm3after tapping. Drop strength results were 95% of pellets intact. The BET surface area of the pellet was determined to be 5 m2 / g and the pore volume was found to be 0.02 cm3 / g, suggesting a non-porous pellet. Catalyst Material Testing

[0199] The catalyst materials described herein were tested for their ability to catalyze the oxidative dehydrogenation (ODH) of ethane using a microreactor unit (MRU). The MRU has a reactor tube made from stainless-steel SWAGELOK® Tubing, which had an outer diameter of 0.5 inches (1.27 cm), an internal diameter of about 0.4 inches (1.02 cm), and a length of about 13.4-15 inches (34.0 - 38.1 cm). Experimental temperatures of the MRU are measured using a 6-point WIKA Instruments Ltd. K-type thermocouple, which had an outer diameter of 0. 125 inches (0.318 cm) and was inserted through the reactor. The 6-point thermocouple is used to measure and control the temperature within the catalyst bed. A room temperature stainless steel condenser is located after the reactor to collect water / acetic acid condensates. The gas product flow was allowed to either vent or was directed to an Agilent 8890 “hot gas” Gas Chromatograph (HGGC) during times when product gas analysis was required.

[0200] The samples were pressed into pellets using a steel die and hydraulic press, then the pellet was pulverized and particle sizes of 425 - 710 pm were sieved out for loading into the MRU. Approximately 4 g of sample was placed in the reactor under a target gas flow rate of 150 seem (WHSV = 1.79 h'1) and a target pressure of 23 psig. Once the catalyst bed was loaded into the reactor and connected to the MRU equipment, the testing was conducted as described herein. The catalyst bed was loaded in the middle zone of the reactor and the remaining volume of the reactor was packed with quartz sand to produce the catalyst bed volume of 6 mL to ensure the catalyst volume was sufficient to cover the thermocouple area. The reactor loading was then secured with glass wool on both the top and the bottom of the reactor. Quartz sand was added to produce the catalyst bed volume of 6 mL to ensure the catalyst volume was sufficient to cover the thermocouple area.

[0201] The target gas feed composition was 20 mol% ethane, 10 mol% oxygen and 70 mol% nitrogen for all testing, which corresponds to an ethane:oxygen mol ratio of 1:0.5. Gas composition was determined by gas chromatography (GC) using an Agilent 6890N Gas Chromatograph, and analyzed using Chrom Perfect - Analysis, Version 6.1. 10 for data evaluation. Samples were left on stream at temperature between 380°C and 420°C until data appeared to equilibrate, which was approximately 5 days.

[0202] For the MRU experiments, the mol. % ethane conversion temperature is determined at the WHSV of 3.57 h-1, and a gas hourly space velocity (GHSV) in the range of 2,000 to 5,000 h-1. The gaseous product exiting the catalyst bed is directed to vent during runs. When the gaseous product is to be analyzed, it is momentarily redirected to a gas chromatography unit to determine the percent of ethane, ethylene, O2, CO2, CO, and, optionally, acetic acid. The gas exiting the reactor was analyzed by gas chromatography

[0203] Conversion (C) of the ethane feed gas was calculated as a volume flow rate change of ethane in the product compared to feed ethane mass flow rate using the following formula:

[0204] Eq. l

[0205] In Eq. 1, X is the molar concentration of the corresponding compound in the gaseous effluent exiting the reactor at corresponding temperature.

[0206] The gas exiting the reactor was analyzed by GC to determine catalyst or catalyst material selectivity to ethylene (i.e., the percentage on a molar basis of ethane that forms ethylene). Selectivity to ethylene (SEthyiene) was determined using the following equation:

[0207] In the above equation 2, SEthyiene is the selectivity to ethylene and X is the molar concentration of the corresponding compound in the gaseous effluent exiting the reactor at corresponding temperature. In order to close the mass balance for ODH experiments based on GC analysis of non-condensable products, an assumption was made that that all non-condensable gaseous products behave as ideal gases. The ideal gas equation of state is accurate in prediction of gas mixture behavior at operating pressure close to 1 atm -absolute. For the ODH experiments, the product gas samples were collected and injected to a lab GC at operating pressure close to 1 atm absolute. Therefore, the ideal gas behavior assumption is expected to generate accurate prediction of the gas mixture behavior. The bulk chemical reactions shown in Table 7 were assumed in order to calculate formed amounts of condensable products. The reactions in Table 7 were used for the purpose of stoichiometrically-balanced mass balance calculations and not to represent the actual chemical reactions occurring in the ODH reaction.

[0208] Table 7, Bulk Chemical Reactions Assumed for Mass Balance Methodology.

[0209] “ As a result, the corresponding amount of water per mole of produced acetic acid and ethylene will be reduced. For example, 1 mole of acetic acid and 4 moles of ethylene would give 5 moles of water, when produced by reacting ethane and oxygen, but the same amount of both compounds would result in 2 moles of water for the same compounds to be produced by reaction of ethane and CO2. This results in 3 moles less water produced to make these compounds for each 2 moles of CO2 being consumed. These will be subtracted in the mass balance.

[0210] Based on reactions shown in Table 7, Method 400 shown in Figure 11 was used in

[0211] MS Excel XX. A GRG Nonlinear solving method was used with the objective of setting the absolute deviation of estimated and measured oxygen from the reactor to zero by modifying the acetic acid output in the solver.

[0212] In step 402, the total molar flow of C2 (ethane) into the reactor is calculated using equation 3:

[0213] F2Total = 100000*FTotal* (CEthane + 0.5 * CcO2) / 22.4 Eq. 3 wherein F2Totai is the total molar flow of C2 into the reactor, [ pmol / min ]; Frotai is the total feed flow to reactor (including all diluents), [seem]; CEthane is the molar fraction of ethane in total feed; Cco2 is the molar fraction of CO2 in total feed; and 22.4 is the molar volume at STP, [1 / mol],

[0214] In step 404, the molar flow of all reactive compounds in product effluent from the reactor is calculated excluding inert diluents.

[0215] The total molar flow of acetic acid in the product, [mmol / min] (FAAOUI) is estimated by Equation 4:

[0216] FAAOUI=y (first estimate: y = 1 [mmol / min]) Eq. 4

[0217] The total molar flows of C2 in non-condensable compounds in the reactor product is calculated using Equation 5 :

[0218] F2outx=F2Total * (Cxout / ( SCxout)) * ((F2Total - FAAout) / F2Total) Eq. 5 wherein F2outx is the total molar flow of C2 of x, [mmol / min]; Cxout is the molar fraction of x in the reactor product; and x is Ethane, Ethylene, CO2 or CO.

[0219] The total molar flow of O2 from the reactor is calculated using the following algorithm:

[0220] If F20UTC02 - (100000*FTotai*(0.5*Cco2) / 22.4)) > 0 then use Equation 6:

[0221] F02out = ( I 00000*FTotal* (0.5 * CO2) / 22.4)) - 0.5 * F2outethane - 3.5 * F2OUTCO2- 2.5*

[0222] F2outCO - 1.5* FoutAAout Eq. 6

[0223] If F20UTC02 - (100000*FTotai*(0.5*Cco2) / 22.4)) < 0 then use Equation 7:

[0224] F02out = (100000*FTotal*(0.5*Co2) / 22.4)) - 0.5* F2outethane + ABS(3.5* F2OUTCO2)

[0225] - 2.5* F2outco - 1.5* FoutAAout Eq. 7

[0226] The total molar flow of H2O from the reactor is calculated using Equation 8: FffiOoutx = FH2O + F2outethane - 3 * F2OUTCO2- 3 *F2outCO - FAAout Eq. 8

[0227] In step 406, the molar fractions of all reactive compounds in the product effluent from the reactor are calculated on the dry (water free) basis, using FAAout from step 404.

[0228] The molar fraction of acetic acid in the product is calculated using Equation 9: CAAoutcalc=FAAout / (FAAout + SFxout + Fo2out) Eq. 9

[0229] The molar fraction of C2 in ethane, ethylene, CO2 and CO in the product is calculated using Equation 10:

[0230] Cxoutcalc=F2outx / (FAAout + SFxout + Fo2out) Eq. 10

[0231] The molar fraction of oxygen in the product is calculated using Equation 11 :

[0232] Co2outcalc=Fo2out / (FAAout + SFxout + Fo2out) Eq. 11 In step 408, the absolute deviation of estimated and measured O2 in the noncondensable product from the reactor is calculated using Equation 12:

[0233] D02 = Co2outcalc - (C02 / (CEthane +CEthylne + 0.5*CcO2 + 0.5Cco+ C02) * (I - CAAoutcalc)) Eq. 12

[0234] As shown in step 410, if D02 is less than 10'4, proceed to step 412. If D02 is not less than 10'4, return to step 404 and repeat. On the repeated steps, FAAout = y (wherein y = new estimate [mmol / min]) is changed, and the steps are repeated to determine whether D02 is closer to the target in step 410.

[0235] In step 412, ethane conversion is calculated using Equation 13: and selectivity toward each product is calculated using Equation 14: wherein CxoutCalc=CEthyleneoutCalc, CAAoutCalc, 0.5 * CcO2outCalc Or 0.5 * CcOOutcalc.

[0236] Summary of Catalyst Material Performance

[0237] After 5 days of equilibration time, there was a significant difference in the performance of catalyst material example 1-E compared to comparative 1-C (which does not include the bismuth-containing compound because it was not prepared with a reactive bismuth compound). The catalyst material prepared using bismuth hydroxide (example 1-E) showed a slight reduction in activity, but greatly improved selectivity to value added products in the ethane ODH reaction, particularly ethylene, at equivalent levels of ethane conversion (Table 8).

[0238] Table 8, Comparison of Examples 1-C and 1-E at Equivalent Ethane Conversion

[0239] Moreover, due to the higher selectivity for example 1-E, the temperature could be further increased to achieve greater levels of ethane conversion while still maintaining high selectivity to value added products over multiple days without loss in performance, achieving ethane conversion of 61.4% at oxygen conversion over 95%, as shown in Figure 12. A linear fit was added to example 1-C in Figure 12 to show the gradual loss of performance from 5 to 12 days on stream. Example 1-C could only achieve ethane conversion of 58.1% before being oxygen depleted, showing greater output is achievable with the bismuth hydroxide additive under equivalent product flow while still maintaining high selectivity to value added products, as shown in Tables 9 and 10.

[0240] Table 9, Comparison of Comparative Catalyst Material 1-C and Example Catalyst Material 1-E at Oxygen Conversion >95% Table 10. Comparison of Comparative Catalyst Material 1-C and Example Catalyst Material

[0241] 1-E by Molar Reactor Input and Output Rates

[0242] Overall, the results for comparative catalyst material 1-C and Example catalyst material 1-E show that the addition of bismuth(III) hydroxide to the catalyst formed a catalyst material having greatly improved selectivity to value added products, and reduced selectivity to COx by-products. Without being bound by any particular theory, it is believed that the reactive bismuth compound (e.g., the bismuth hydroxide) acts as a promoter by reacting with the catalyst, and / or with impurities produced during catalyst synthesis, to allow for an increase in molar output of valuable products while reducing the molar output of waste COx at high ethane and oxygen conversion in the ODH process.

[0243] The data for examples 2-E, 3-E1, and 3-E2 shown in Table 11 indicates that a catalyst material prepared with 5 wt.% of the bismuth hydroxide (Example 3 -El) has similar beneficial properties as a catalyst material prepared with 10 wt.% of the bismuth hydroxide (Example 3-E2).The data also shows that pre -calcination of the catalyst prior to addition of the bismuth hydroxide provides a catalyst material that has similar activity and selectivity as compared to catalyst materials prepared using uncalcined catalyst in the formulation step (Example 2-E).

[0244] Table 11. Comparison of Examples 2-E1, 3 -El, and 3-E2 at Equivalent Ethane Conversion

[0245] The data for comparative catalyst material 4-C and Example catalyst material 4-E shown in Table 12 indicates that a catalyst material prepared with an MoVNbTeOx catalyst and 5 wt.% of the bismuth hydroxide (Example 4-E) has a similar beneficial effect as seen for the MoVTaBiOx examples. Example 4-E had showed improved ethylene selectivity and reduced acetic acid selectivity at comparable conversion levels to comparative 4-C (prepared without bismuth hydroxide).

[0246] Table 12, Comparison of Comparative Catalyst Material 4-C and Example Catalyst Material 4-E at Equivalent Ethane Conversion Synthesis of Bismuth Molybdate

[0247] Bismuth molybdate was prepared by adding bismuth hydroxide (4.9992 g) and molybdenum(VI) oxide (7. 1769 g) along with PEG 1000 (0.4631 g) in a beaker and stirring in 10 m of water, then evaporating in an oven at 40°C overnight. The next day, another 3 m of water was added to the blend, the sample was again stirred, then placed into an oven again at 90°C overnight to dry. The dry powder was then compressed into a pellet using a 3 cm die in a hydraulic press at 10 metric tons for 1 minute. The pellet was then heated in a tubular quartz furnace under dry air flow (1.8 cm / min linear velocity at STP) from room temperature to 400°C at a rate of l°C / min, held at 400°C for 1 hour, then heating was stopped and the furnace was left passively cool back to ambient under air flow. After cooling, the gas flow was changed to nitrogen (3.9 cm / min linear velocity at STP), and after 8 hours of purging, the furnace was heated from room temperature to 600°C at a rate of 1.6°C / min, held at 600°C for 2 hours, then the heating was stopped and the furnace was left to cool back to room temperature passively under nitrogen flow.

[0248] Catalyst Performance for Bismuth Molybdate

[0249] Table 13 summarizes the catalytic testing data for three trials with the synthesized bismuth molybdate, carried out in a similar manner to the other Examples described herein. Table 13, Catalyst Performance of Synthesized Bismuth Molybdate

[0250] The data shown in Table 13 shows that the bismuth molybdate alone is essentially inactive as a catalyst for ethane ODH. Without being bound by any particular theory, it is believed that while bismuth molybdate is essentially inert as an ethane ODH catalyst, the reaction of the reactive bismuth compound with impurities in the catalyst to form bismuth molybdate may passivate impurities in the ODH process, which would otherwise be active as ethane oxidation catalysts.

[0251] Non-limiting embodiments of the present disclosure include the following:

[0252] Embodiment A. A catalyst material comprising: 15 wt.% to 99 wt.% of a catalyst comprising the formula: MoaVb(Ml)c(M2)dOx wherein: Ml is Bi, Te, Sb, or a mixture thereof; M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and 1 wt.% to 45 wt.% of a bismuth-containing compound; wherein the catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0253] Embodiment B. The catalyst material of Embodiment A, wherein the bismuth- containing compound is provided by combining the catalyst with at least one reactive bismuth compound.

[0254] Embodiment C. The catalyst material of Embodiment B, wherein the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

[0255] Embodiment D. The catalyst material of Embodiment B or C, wherein the at least one reactive bismuth compound comprises bismuth hydroxide.

[0256] Embodiment E. The catalyst material of Embodiment B, C, or D, wherein a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range from 5 : 1 to 15: 1.

[0257] Embodiment F. The catalyst material Embodiment A, B, C, D, or E, wherein the bismuth-containing compound comprises bismuth molybdate, Bi2(MO4)3.

[0258] Embodiment G. The catalyst material of Embodiment A, B, C, D, E, or F, comprising 40 wt.% to 50 wt.% of the catalyst, as determined by Rietveld analysis of the PXRD pattern.

[0259] Embodiment H. The catalyst material of Embodiment A, B, C, D, E, F, or G, comprising 5 wt.% to 20 wt.% of the bismuth-containing compound, as determined by Rietveld analysis of the PXRD pattern.

[0260] Embodiment I. The catalyst material of Embodiment A, B, C, D, E, F, G, or H, further comprising 1 wt.% to 80 wt.% of an inert carrier material.

[0261] Embodiment J. The catalyst material Embodiment I comprising: 30 wt.% to 70 wt.% of the catalyst; 20 wt.% to 60 wt.% of the inert carrier material; and 2 wt.% to 15 wt.% of the bismuth-containing compound.

[0262] Embodiment K. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, or J, wherein: b is 0.2 to 0.4; c is 0.01 to 0.07; and d is 0.01 to 0.07. Embodiment L. The catalyst material Embodiment A, B, C, D, E, F, G, H, I, J, or K, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbBicNbdOx, MoaVbTecNbdOx, and MoaVbSbcTadOx.

[0263] Embodiment M. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, or

[0264] K, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTadOx, MoaVbTecNbdOx, and MoaVbSbcTadOx.

[0265] Embodiment N. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, or J, wherein the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01- o.o7Nbo.oi-o.o70x, or Mo1V0.20-0.40Sb0.01-0.07Ta0.01-0.07Ox.

[0266] Embodiment O. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, or J, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05 Nb0.04Ox, or Mo1V0.30Sb0.05Ta0.05Ox.

[0267] Embodiment P. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K,

[0268] L, M, N, or O, wherein the values of a, b, c, and d are further determined by elemental analysis.

[0269] Embodiment Q. The catalyst material of Embodiment I, J, K, L, M, N, O, or P, wherein the inert carrier material comprises precipitated synthetic silica, fumed synthetic silica, silica-alumina, a-alumina, y-alumina, titania, silicon carbide, MgAl spinel, an aluminate compound, an aluminosilicate compound, a zeolite, zirconia, doped zirconia, boron nitride, cerium oxide, doped cerium oxide, a perovskite, steel, or a combination thereof.

[0270] Embodiment R. The catalyst material of Embodiment I, J, K, L, M, N, O, or P, wherein the inert carrier material comprises a-alumina.

[0271] Embodiment S. The catalyst material of A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, or R, wherein the PXRD pattern further comprises peaks at 20 values of 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, and 22.1° ± 0.2°.

[0272] Embodiment T. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S, having a pore volume between 0.01 cm3 / g and 0.25 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett-Joyner-Halenda (BJH) model.

[0273] Embodiment U. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S, having a pore volume between 0.01 cm3 / g and 0.1 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett-Joyner-Halenda (BJH) model. Embodiment V. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, or U, having a Brunauer-Emmett-Teller (BET) surface area between 2 m2 / g and 10 m2 / g, as determined by a nitrogen physisorption analysis.

[0274] Embodiment W. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J,

[0275] K, L, M, N, O, P, Q, R, S, T, or U, having a Brunauer-Emmett-Teller (BET) surface area between 4 m2 / g and 6 m2 / g, as determined by a nitrogen physisorption analysis.

[0276] Embodiment X. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K,

[0277] L, M, N, O, P, Q, R, or S, having a Brunauer-Emmett-Teller (BET) surface area of 5 m2 / g as determined by a nitrogen physisorption analysis and a pore volume of 0.02 cm3 / g as determined by a nitrogen physisorption analysis with a Barrett-Joyner-Halenda (BJH) model.

[0278] Embodiment Y. The catalyst material of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S, wherein the catalyst material is a non-porous pellet.

[0279] Embodiment Z. A method for preparing a catalyst material comprising: combining a first mixture comprising: a catalyst comprising the formula: MoaVb(Ml)c(M2)dOx wherein: Ml is Bi, Te, Sb, or a mixture thereof; M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and a reactive bismuth compound; with a liquid medium to form a second mixture; and heating the second mixture to form the catalyst material.

[0280] Embodiment AA. The method according to Embodiment Z, wherein the reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

[0281] Embodiment AB. The method according Embodiment Z or AA, wherein the reactive bismuth compound comprises bismuth hydroxide.

[0282] Embodiment AC. The method according to Embodiment Z, AA, or AB, wherein the first mixture comprises the catalyst and the reactive bismuth compound in a weight ratio from 5: 1 to 15: 1, catalystat least one reactive bismuth compound.

[0283] Embodiment AD. The method according to Embodiment Z, AA, or AB, wherein the first mixture comprised the catalyst and the reactive bismuth compound in a weight ratio from 5: 1 to 10: 1, catalystat least one reactive bismuth compound. Embodiment AE. The method according Embodiment Z, AA, AB, AC, or AD, wherein the liquid medium comprises water.

[0284] Embodiment AF. The method according Embodiment Z, AA, AB, AC, AD, or AE, wherein the first mixture further comprises an inert carrier material.

[0285] Embodiment AG. The method according to Embodiment AF, wherein the first mixture comprises: 1 wt.% to 50 wt.% of the catalyst; 1 wt.% to 90 wt.% of the inert carrier material; 1 wt.% to 20 wt.% of the reactive bismuth compound; and up to 10 wt.% of one or more binders other than water.

[0286] Embodiment AH. The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, or AG, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTadOx, MoaVbTecNbdOx, and MoaVbSbcTaaOx.

[0287] Embodiment AE The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, or AG, wherein the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or Mo1V0.20-0.40Sb0.01-0.07Ta0.01-0.07Ox.

[0288] Embodiment AJ. The method according to Z, AA, AB, AC, AD, AE, AF, or AG, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05Nb0.04, Ox or Mo1V0.30Sb0.05Ta0.05Ox.

[0289] Embodiment AK. The method according to Embodiment AF, AG, AH, Al, or AJ, wherein the inert carrier material comprises a-alumina.

[0290] Embodiment AL. The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, AG, AH, Al, AJ, or AK, wherein the first mixture further comprises a binder, the binder comprising one or more of polyethylene glycol, poly(acrylic acid), and polyvinyl alcohol.

[0291] Embodiment AM. The method according to Embodiment AE, AF, AG, AH, Al, AJ, AK, or AL, comprising heating the second mixture at a temperature of about 60°C to about 120°C until the water is substantially evaporated.

[0292] Embodiment AN. The method according Embodiment AM, further comprising drying the second mixture at a temperature of 60°C to 120°C for a drying time between 1 hour and 48 hours.

[0293] Embodiment AO. The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, AG, AH, Al, AJ, AK, AL, AM, or AN, further comprising adding a lubricant to the first mixture. Embodiment AP. The method according to Embodiment AO, wherein the lubricant is selected from the group consisting of graphite, hexagonal boron nitride, calcium carbonate, a fatty acid, and a fatty acid salt.

[0294] Embodiment AQ. The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, AG, AH, Al, AJ, AK, AL, AM, AN, AO, or AP, further comprising extruding, pressing, 3D-printing, spheronizing, or casting the catalyst material to produce a formed catalyst material.

[0295] Embodiment AR. The method according to Embodiment AQ, comprising pressing the catalyst material to form pellets.

[0296] Embodiment AS. The method according to Embodiment Z, AA, AB, AC, AD, AE, AF, AG, AH, Al, AJ, AK, AL, AM, AN, AO, AP, AQ, or AR, further comprising calcining the catalyst material to provide a calcined catalyst material.

[0297] Embodiment AT. A process for oxidative dehydrogenation of ethane, the process comprising contacting a gaseous feed comprising ethane and oxygen with a catalyst material in a reactor to produce an effluent comprising ethylene, wherein the catalyst material comprises: 15 wt.% to 99 wt.% of a catalyst comprising the formula: MoaVb(Ml)c(M2)dOx wherein: Ml is Bi, Te, Sb, or a mixture thereof; M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and 1 wt.% to 30 wt.% of a bismuth-containing compound; wherein the catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

[0298] Embodiment AU. The process of Embodiment AT, wherein the bismuth-containing compound is provided by combining the catalyst with at least one reactive bismuth compound prior to contacting the gaseous feed with the catalyst material.

[0299] Embodiment AV. The process of Embodiment AU, wherein the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

[0300] Embodiment AW. The process of Embodiment AU or AV, wherein the at least one reactive bismuth compound is bismuth hydroxide. Embodiment AX. The process of Embodiment AU, AV, or AW, wherein a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range from about 5: 1 to about 15: 1.

[0301] Embodiment AY. The process of Embodiment AT, AU, AV, AW, or AX, wherein the bismuth-containing compound comprises bismuth molybdate, Bi2(MC>4)3.

[0302] Embodiment AZ. The process of Embodiment AT, AU, AV, AW, AX, or AY, wherein the catalyst material further comprises 1 wt.% to 80 wt.% of an inert carrier material.

[0303] Embodiment AAA. The process of Embodiment AT, AU, AV, AW, AX, AY, or AZ, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbTecNbdOx, and MoaVbSbcTaaOx.

[0304] Embodiment AAB. The process of Embodiment AT, AU, AV, AW, AX, AY, AZ, or AAA, wherein the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, M01V0.20- o.4oTeo.o 1-0.07Nb0.01-0.07Ox, or Mo 1 Vo.2o-o.4oSbo.o i-o.o7Tao.o i-o.o?Ox.

[0305] Embodiment AAC. The process of Embodiment AT, AU, AV, AW, AX, AY, AZ, or AAA, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05Nb0.04Ox, or Mo1V0.30Sb0.05Ta0.05Ox.

[0306] Embodiment AAD. The process of Embodiment AZ, AAA, AAB, or AAC, wherein the inert carrier material comprises a-alumina.

[0307] Embodiment AAE. The process of Embodiment AT, AU, AV, AW, AX, AY, AZ, AAA, AAB, AAC, or AAD, wherein the catalyst material has an increased selectivity to one or both of ethylene and acetic acid at equivalent ethane conversion as compared to the selectivity of the catalyst.

[0308] Embodiment AAF. The process of Embodiment AT, AU, AV, AW, AX, AY, AZ, AAA, AAB, AAC, AAD, or AAE, wherein the catalyst material has an increased ethane conversion at an oxygen conversion of greater than 95% as compared to the ethane conversion of the catalyst.

[0309] Embodiment AAG. The process of Embodiment AT, AU, AV, AW, AX, AY, AZ, AAA, AAB, AAC, AAD, AAE, or AAF, further comprising converting the ethylene to a product.

[0310] Embodiment AAH. The process of Embodiment AAG, wherein the product is a polyethylene is selected from very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE). Other implementations are also within the scope of the following claims.

[0311] INDUSTRIAL APPLICABILITY

[0312] Catalyst materials for oxidative dehydrogenation of alkanes, such as the oxidative dehydrogenation of ethane to ethylene.

Claims

CLAIMS1. A catalyst material comprising:15 wt.% to 99 wt.% of a catalyst comprising the formula: oaVb( l)c( 2)dOx wherein:Mi is Bi, Te, Sb, or a mixture thereof;M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and1 wt.% to 45 wt.% of a bismuth-containing compound; wherein the catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

2. The catalyst material of claim 1, wherein the bismuth-containing compound is provided by combining the catalyst with at least one reactive bismuth compound.

3. The catalyst material of claim 2, wherein the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

4. The catalyst material of claim 2 or 3, wherein the at least one reactive bismuth compound comprises bismuth hydroxide.

5. The catalyst material of any one of claims 2 to 4, wherein a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range from 5 : 1 to 15: 1.

6. The catalyst material of any one of claims 1 to 5, wherein the bismuth-containing compound comprises bismuth molybdate, Bi2(MC>4)3.

7. The catalyst material of any one of claims 1 to 6, comprising 40 wt.% to 50 wt.% of the catalyst, as determined by Rietveld analysis of the PXRD pattern.

8. The catalyst material of any one of claims 1 to 7, comprising 5 wt.% to 20 wt.% of the bismuth-containing compound, as determined by Rietveld analysis of the PXRD pattern.

9. The catalyst material of any one of claims 1 to 8, further comprising 1 wt.% to 80 wt.% of an inert carrier material.

10. The catalyst material of claim 9, comprising:30 wt.% to 70 wt.% of the catalyst;20 wt.% to 60 wt.% of the inert carrier material; and2 wt.% tol5 wt.% of the bismuth-containing compound.

11. The catalyst material of any one of claims 1 to 10, wherein: b is 0.2 to 0.4; c is 0.01 to 0.07; and d is 0.01 to 0.07.

12. The catalyst material of any one of claims 1 to 11, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbBicNbaOx MoaVbTecNbaOx, and MoaVbSbcTaaOx.

13. The catalyst material of any one of claims 1 to 11, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbTecNbaOx, and MoaVbSbcTaaOx.

14. The catalyst material of any one of claims 1 to 10, wherein the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or M01V0.20- o.4oSbo.oi-o.o7Tao.oi-o.o70x.

15. The catalyst material of any one of claims 1 to 10, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05 Nbo.o40x, or Mo1V0.30Sb0.05Ta0.05Ox.

16. The catalyst material of any one of claims 1 to 15, wherein the values of a, b, c, and d are further determined by elemental analysis.

17. The catalyst material of any one of claims 9 to 16, wherein the inert carrier material comprises precipitated synthetic silica, fumed synthetic silica, silica-alumina, a-alumina, y- alumina, titania, silicon carbide, MgAl spinel, an aluminate compound, an aluminosilicate compound, a zeolite, zirconia, doped zirconia, boron nitride, cerium oxide, doped cerium oxide, a perovskite, steel, or a combination thereof.

18. The catalyst material of any one of claims 9 to 16, wherein the inert carrier material comprises a-alumina.

19. The catalyst material of any one of claims 1 to 18, wherein the PXRD pattern further comprises peaks at 20 values of 6.5° ± 0.2°, 7.8° ± 0.2°, 8.9° ± 0.2°, 10.4° ± 0.2°, and 22.1° ± 0.2°.

20. The catalyst material of any one of claims 1 to 19, having a pore volume between 0.01 cm3 / g and 0.25 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett-Joyner-Halenda (BJH) model.

21. The catalyst material of any one of claims 1 to 19, having a pore volume between 0.01 cm3 / g and 0.1 cm3 / g, as determined by a nitrogen physisorption analysis with a Barrett- Joyner-Halenda (BJH) model.

22. The catalyst material of any one of claims 1 to 21, having a Brunauer-Emmett-Teller (BET) surface area between 2 m2 / g and 10 m2 / g, as determined by a nitrogen physisorption analysis.

23. The catalyst material of any one of claims 1 to 21, having a Brunauer-Emmett-Teller (BET) surface area between 4 m2 / g and 6 m2 / g, as determined by a nitrogen physisorption analysis.

24. The catalyst material of any one of claims 1 to 19, having a Brunauer-Emmett-Teller (BET) surface area of 5 m2 / g as determined by a nitrogen physisorption analysis and a pore volume of 0.02 cm3 / g as determined by a nitrogen physisorption analysis with a Barrett- Joyner-Halenda (BJH) model.

25. The catalyst material of any one of claims 1 to 19, wherein the catalyst material is a non-porous pellet.

26. A method for preparing a catalyst material comprising: combining a first mixture comprising: a catalyst comprising the formula:MOaVb(Ml)c(M2)dOx wherein:Mi is Bi, Te, Sb, or a mixture thereof;M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; and x is the number of oxygen atoms necessary to render the catalyst electrically neutral;wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and a reactive bismuth compound; with a liquid medium to form a second mixture; and heating the second mixture to form the catalyst material.

27. The method according to claim 26, wherein the reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

28. The method according to claim 26 or 27, wherein the reactive bismuth compound comprises bismuth hydroxide.

29. The method according to any one of claims 26 to 28, wherein the first mixture comprises the catalyst and the reactive bismuth compound in a weight ratio from 5: 1 to 15: 1, catalystreactive bismuth compound.

30. The method according to any one of claims 26 to 28, wherein the first mixture comprised the catalyst and the reactive bismuth compound in a weight ratio from 5: 1 to 10: 1, catalystreactive bismuth compound.

31. The method according to any one of claims 26 to 30, wherein the liquid medium comprises water.

32. The method according to any one of claims 26 to 31, wherein the first mixture further comprises an inert carrier material.

33. The method according to claim 32, wherein the first mixture comprises:1 wt.% to 50 wt.% of the catalyst;1 wt.% to 90 wt.% of the inert carrier material;1 wt.% to 20 wt.% of the reactive bismuth compound; and up to 10 wt.% of one or more binders other than water.

34. The method according to any one of claims 26 to 33, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbTecNbaOx, and MoaVbSbcTaaOx.

35. The method according to any one of claims 26 to 33, wherein the catalyst has the formula Mo1V0.20-0.40Bi0.01-0.07Ta0.01-0.07Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or M01V0.20- o.4oSbo.oi-o.o7Tao.oi-o.o70x.

36. The method according to any one of claims 26 to 33, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05 Nbo.04, Ox or Mo1V0.30Sb0.05Ta0.05Ox.

37. The method according to any one of claims 32 to 36, wherein the inert carrier material comprises a-alumina.

38. The method according to any one of claims 26 to 37, wherein the first mixture further comprises a binder, the binder comprising one or more of polyethylene glycol, poly(acrylic acid), and polyvinyl alcohol.

39. The method according to any one of claims 31 to 38, comprising heating the second mixture at a temperature of 60°C to 120°C until the water is substantially evaporated.

40. The method according to claim 39, further comprising drying the second mixture at a temperature of about 60°C to about 120°C for a drying time between 1 hour and 48 hours.

41. The method according to any one of claims 26 to 40, further comprising adding a lubricant to the first mixture.

42. The method according to claim 41, wherein the lubricant is selected from the group consisting of graphite, hexagonal boron nitride, calcium carbonate, a fatty acid, and a fatty acid salt.

43. The method according to any one of claims 26 to 42, further comprising extruding, pressing, 3D-printing, spheronizing, or casting the catalyst material to produce a formed catalyst material.

44. The method according to claim 43, comprising pressing the catalyst material to form pellets.

45. The method according to any one of claims 26 to 44, further comprising calcining the catalyst material to provide a calcined catalyst material.

46. A process for oxidative dehydrogenation of ethane, the process comprising contacting a gaseous feed comprising ethane and oxygen with a catalyst material in a reactor to produce an effluent comprising ethylene, wherein the catalyst material comprises:15 wt.% to 99 wt.% of a catalyst comprising the formula:MOaVb(Ml)c(M2)dOx wherein:Mi is Bi, Te, Sb, or a mixture thereof;M2 is Ta, Nb, or a mixture thereof; a is 1.0; b is 0.01 to 0.5; c is 0.005 to 0.2; d is 0.005 to 0.1; andx is the number of oxygen atoms necessary to render the catalyst electrically neutral; wherein a, b, c, and d are determined based on the amount of each starting material used to form the catalyst; and1 wt.% to 30 wt.% of a bismuth-containing compound; wherein the catalyst material has a powder X-ray diffraction (PXRD) pattern comprising peaks at 20 values of 12.6° ± 0.2°, 18.0° ± 0.2°, 27.9° ± 0.2°, and 29.1° ± 0.2°, wherein the PXRD pattern is obtained using Cu Ka radiation.

47. The process of claim 46, wherein the bismuth-containing compound is provided by combining the catalyst with at least one reactive bismuth compound prior to contacting the gaseous feed with the catalyst material.

48. The process of claim 47, wherein the at least one reactive bismuth compound is selected from the group consisting of bismuth hydroxide, bismuth oxide, bismuth carbonate, bismuth subcarbonate, bismuth acetate, bismuth nitrate, a hydrate of bismuth nitrate, bismuth subnitrate, and bismuth subsalicylate.

49. The process of claim 47 or 48, wherein the at least one reactive bismuth compound is bismuth hydroxide.

50. The process of any one of claims 47 to 49, wherein a weight ratio of the catalyst to the at least one reactive bismuth compound is in a range from 5 : 1 to 15: 1.

51. The process of any one of claims 47 to 50, wherein the bismuth-containing compound comprises bismuth molybdate, Bi2(MO4)3.

52. The process of any one of claims 46 to 51, wherein the catalyst material further comprises al wt.% to 80 wt.% of an inert carrier material.

53. The process of any one of claim 46 to 52, wherein the catalyst has a formula selected from the group consisting of MoaVbBicTaaOx, MoaVbTecNbdOx, and MoaVbSbcTaaOx.

54. The process of any one of claims 46 to 53, wherein the catalyst has the formulaMo i Vo.2o-o.4oBio.o i-o.cnTao.o i-o.o?Ox, Mo1V0.20-0.40Te0.01-0.07Nb0.01-0.07Ox, or Mo 1 V o.2o-o.4oSbo.oi- o.o7Tao.oi-o.o70x.

55. The process of any one of claims 46 to 53, wherein the catalyst has the formula Mo1V0.31Bi0.05Ta0.05Ox, Mo1V0.30Te0.05 Nbo.o40x, or Mo1V0.30Sb0.05Ta0.05Ox.

56. The process of any one of claims 52 to 55, wherein the inert carrier material comprises a-alumina.

57. The process of any one of claims 46 to 56, wherein the catalyst material has an increased selectivity to one or both of ethylene and acetic acid at equivalent ethane conversion as compared to the selectivity of the catalyst.

58. The process of any one of claims 46 to 57, wherein the catalyst material has an increased ethane conversion at an oxygen conversion of greater than 95% as compared to the ethane conversion of the catalyst.

59. The process of claim any one of claims 46 to 58, further comprising converting the ethylene to a product.

60. The process of claim 59, wherein the product is a polyethylene is selected from very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

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