Molybdenum-vanadium-niobium-tellurium-iron-based oxidative dehydrogenation catalyst materials

Abstract

The present disclosure relates to oxidative dehydrogenation catalyst materials that include molybdenum, vanadium, niobium, tellurium, and iron.

Description

[0001] MOLYBDENUM- VANADIUM-NIOBIUM-TELLURIUM-IRON-BASED OXIDATIVE DEHYDROGENATION CATALYST MATERIALS

[0002] TECHNICAL FIELD

[0003] The present disclosure relates to oxidative dehydrogenation catalyst materials of alkanes such as ethane.

[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. Selective oxidation processes, such as oxidative dehydrogenation (ODH), are methods used to convert lower alkanes into olefins. 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.

[0006] SUMMARY OF INVENTION

[0007] Provided herein is a catalyst material comprising molybdenum, vanadium, niobium, tellurium, iron, and oxygen, wherein: the molar ratio of molybdenum to vanadium is from 1 :0. 10 to 1 :0.60, the molar ratio of molybdenum to niobium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to tellurium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to iron is from 1:0.20 to 1:5.00, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0008] Also provided herein is a method comprising contacting a gas mixture comprising ethane with the catalyst material described herein to form ethylene.

[0009] Also provided herein is a method comprising contacting a gas mixture comprising ethane with a catalyst mixture to form ethylene wherein the catalyst mixture comprises

[0010] (i) a first catalyst material wherein the first catalyst material is the catalyst material described herein; and

[0011] (ii) a second catalyst material comprising molybdenum, vanadium, niobium, and tellurium wherein: the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.35, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.25, and the molar ratio of molybdenum to tellurium is from 1:0.10 to 1:0.30.

[0012] BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 shows an XRD scan of Catalyst 1.1.

[0014] Figure 2 shows an XRD scan of Catalyst 1.2.

[0015] Figure 3 shows an XRD scan of Catalyst Material 2.2 before an MRU run.

[0016] Figure 4 shows an XRD scan of Catalyst Material 2.2 after an MRU run.

[0017] Figure 5 shows the ethylene conversion at different temperatures using Catalyst Material 2.2.

[0018] Figure 6 shows the ethylene conversion at different temperatures using Catalyst Material 2.3.

[0019] Figure 7 shows the ethylene selectivity at different temperatures using Catalyst Material 2.3.

[0020] Figure 8 shows a schematic representation of catalyst loading on MRU for double bed.

[0021] Figure 9 shows an XRD scan of Catalyst Material 2.3.

[0022] Figure 10 shows XRD scans of Catalyst 1.1, Catalyst 1.2, Catalyst Material 2.2, and Catalyst Material 2.3.

[0023] Figure 11 shows XRD scans of Catalyst Material 2.2 and Catalyst Material 2.3.

[0024] DESCRIPTION OF EMBODIMENTS

[0025] 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 drawings. 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 to the disclosed subject matter.

[0026] Provided herein is a catalyst material comprising molybdenum, vanadium, niobium, tellurium, iron, and oxygen, wherein: the molar ratio of molybdenum to vanadium is from 1 :0. 10 to 1 :0.60, the molar ratio of molybdenum to niobium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to tellurium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to iron is from 1:0.20 to 1:5.00, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides. In some embodiments, the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45. In some embodiments, the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.40. In some embodiments, the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.35. In some embodiments, the molar ratio of molybdenum to vanadium is 1:29, 1:31, or 1:34.

[0027] In some embodiments, the molar ratio of molybdenum to niobium is from 1 :0.10 to 1:0.30. In some embodiments, the molar ratio of molybdenum to niobium is from 1:0.15 to 1:0.25. In some embodiments, the molar ratio of molybdenum to niobium is from 1:0.15 to 1:0.20. In some embodiments, the molar ratio of molybdenum to niobium is 1:0.17 or 1:0.20.

[0028] In some embodiments, the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30. In some embodiments, the molar ratio of molybdenum to tellurium is from 1 :0.10 to 1 : 0.20. In some embodiments, the molar ratio of molybdenum to tellurium is from 1:0.15 to 1:0.20. In some embodiments, the molar ratio of molybdenum to tellurium is from 1:0.16 or 1:0.17.

[0029] In some embodiments, the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0. In some embodiments, the molar ratio of molybdenum to iron is from 1:0.50 to 1:3.3. In some embodiments, the molar ratio of molybdenum to iron is from 1:0.50 to 1:0.60. In some embodiments, the molar ratio of molybdenum to iron is from 1:2.50 to 1:3.3. In some embodiments, the molar ratio of molybdenum to iron is from 1:0.57, 1:2.97, or 1:3.13.

[0030] In some embodiments: the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.30, the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30, the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0031] In some embodiments: the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.30, the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30, the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0032] In some embodiments, the molar ratio of molybdenum to vanadium is from 1 : 0.31, the molar ratio of molybdenum to niobium is from 1:0.17, the molar ratio of molybdenum to tellurium is from 1:0.16, the molar ratio of molybdenum to iron is from 1:3.13, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0033] In some embodiments, the molar ratio of molybdenum to vanadium is from 1:0.29, the molar ratio of molybdenum to niobium is from 1:0.20, the molar ratio of molybdenum to tellurium is from 1:0.16, the molar ratio of molybdenum to iron is from 1:2.97, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0034] In some embodiments, the molar ratio of molybdenum to vanadium is from 1:0.34, the molar ratio of molybdenum to niobium is from 1:0.20, the molar ratio of molybdenum to tellurium is from 1:0.17, the molar ratio of molybdenum to iron is from 1:0.57, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

[0035] In some embodiments, the catalyst material has an amorphous content of about 20 wt. % to about 80 wt. %. In some embodiments, the catalyst material has an amorphous content of about 35 wt. % to about 65 wt. %. In some embodiments, the catalyst material has an amorphous content of about 30 wt. % to about 45 wt. %, about 30 wt. % to about 40 wt. %, or about 35 wt. % to about 40 wt. %. In some embodiments, the catalyst material has an amorphous content of about 55 wt. % to about 70 wt. %, about 55 wt. % to about 65 wt. %, or about 60 wt. % to about 65 wt. %. In some embodiments, the catalyst material has an amorphous content of about 38 wt. % or about 62 wt. %.

[0036] In some embodiments, at least a portion of the iron in the catalyst material is present as Fe(III). In some embodiments, the iron in the catalyst material is present as an iron oxide, an iron oxide hydroxide, or a combination thereof. In some embodiments, the iron in the catalyst material is present as an iron oxide hydroxide. In some embodiments, the iron in the catalyst material is present as goethite.

[0037] In some embodiments, the catalyst material has a 35% conversion temperate from about 300°C to about 400°C. In some embodiments, the catalyst material has a 35% conversion temperate from about 350°C to about 380°C. In some embodiments, the catalyst material has a 35% conversion temperate from about 355°C to about 380°C. In some embodiments, the catalyst material has a 35% conversion temperate of about 357°C, about 375°C, or about 377°C.

[0038] In some embodiments, the catalyst material has an ethylene selectivity from about 70 mol % to about 98 mol %. In some embodiments, the catalyst material has an ethylene selectivity from about 85 mol % to about 95 mol %. In some embodiments, the catalyst material has an ethylene selectivity from about 86 mol %to about 94 mol %. In some embodiments, the catalyst material has an ethylene selectivity of about 87 mol %, about 88 mol %, or about 93 mol %

[0039] In some embodiments, the catalyst material has an acetic acid selectivity of less than 2 mol %. In some embodiments, the catalyst material has an acetic acid selectivity of less than 1.5 mol %. In some embodiments, the catalyst material has an acetic acid selectivity of less than 0. 1 mol %.

[0040] Also provided herein is a method comprising contacting a gas mixture comprising ethane with the catalyst material described herein to form ethylene.

[0041] In some embodiments, the ethylene is substantial free of acetylene.

[0042] In some embodiments, the method does not produce acetic acid.

[0043] Also provided herein is a method comprising contacting a gas mixture comprising ethane with a catalyst mixture to form ethylene wherein the catalyst mixture comprises

[0044] (i) a first catalyst material wherein the first catalyst material is the catalyst material described herein; and

[0045] (ii) a second catalyst material comprising molybdenum, vanadium, niobium, and tellurium wherein: the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.35, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.25, and the molar ratio of molybdenum to tellurium is from 1:0.10 to 1:0.30.

[0046] In some embodiments, the gas mixture is contacted with the first catalyst material followed by the second catalyst material. In some embodiments, the gas mixture is contacted with the second catalyst material followed by the first catalyst material. In some embodiments, wherein the ethylene is substantial free of acetylene.

[0047] In some embodiments, the method does not produce acetic acid.

[0048] In some embodiments, the gas mixture has an hourly space velocity of from 500 h’1to 15000 h’1. In some embodiments, the gas mixture has an hourly space velocity of 500 h’ \ 1000 h’1, 1500 h’1, 2000 h’1, 2500 h’1, 3000 h’1, 3500 h’1, 4000 h’1, 4500 h’1, 5000 h’1, 5500 h’1, 6000 h’1, 6500 h’1, 7000 h’1, 7500 h’1, 8000 h’1, 8500 h’1, 9000 h’1, 9500 h’1, 10000 h’1, 10500 h'1, HOOO h’1, 11500 h1, 12000 b’1, 12500 b’1, 13000 b’1, 13500 h’1, 14000 h’1, 14500 h’1, or 15000 h’1.

[0049] In some embodiments, the weight hourly space velocity of the gas mixture is from 0.5 h’1to 15 h’1. In some embodiments, the weight hourly space velocity of the gas mixture is 0.5 h’1, 1.0 h’1, 1.5 h’1, 2.0 h’1, 2.5 h’1, 3.0 h’1, 3.5 h’1, 4.0 h’1, 4.5 h’1, 5.0 h’1, 5.5 h’1, 6.0 h’1, 6.5 h’1, 7.0 h’1, 7.5 h’1, 8.0 h’1, 8.5 h’1, 9.0 h’1, 9.5 h’1, 10 h’1, 10.5 h’1, 11 h’1, 11.5 h’1, 12 h’1, 12.5 h’1, 13 h’1, 13.5 h’1, 14 h’1, 14.5 h’1, or 15 h’1. In some embodiments, the weight hourly space velocity is calculated based on the active phase of the catalyst.

[0050] In some embodiments, the gas mixture has a temperature of from 300°C to 500°C. In some embodiments, the gas mixture has a temperature of 300°C, 350°C, 400°C, 450°C, or 500°C.

[0051] In some embodiments, the first catalyst material has a temperature of 300°C to 500°C. In some embodiments, the first catalyst material has a temperature of 300°C, 350°C, 400°C, 450°C, or 500°C.

[0052] In some embodiments, the second catalyst material has a temperature of 300°C to 500°C. In some embodiments, the second catalyst material has a temperature of 300°C, 350°C, 400°C, 450°C, or 500°C.

[0053] In some embodiments, the gas mixture has an inlet pressure of from 5 psig to 100 psig. In some embodiments, the gas mixture has an inlet pressure of 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 35 psig, 40 psig, 45 psig, 50 psig, 55 psig, 60 psig, 65 psig, 70 psig, 75 psig, 80 psig, 85 psig, 90 psig, 95 psig, or 100 psig.

[0054] In some embodiments, the linear velocity of the gas mixture is at least 4 cm / sec. In some embodiments, the linear velocity of the gas mixture is at least 5 cm / sec, at least 6 cm / sec, at least 7 cm / sec, at least 8 cm / sec, or at lest 9 cm / sec. In some embodiments, the linear velocity of the gas mixutes is 1 cm / sec to 1000 cm / sec, 2 cm / sec to 500 cm / sec, or 3 cm / sec to 300 cm / sec.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] As used herein, the term “alkane” refers to an acyclic saturated hydrocarbon. In many cases, an alkane consists of hydrogen and carbon atoms arranged in a linear structure in which all of the carbon-carbon bonds are single bonds. Alkanes have the general chemical formula C»H2»-2. In some embodiments, alkane refers to one or more of ethane, propane, butane, pentane, hexane, octane, decane and dodecane. In particular embodiments, alkane refers to ethane and propane and, in some embodiments, ethane.

[0059] As used herein, the term “alkene” refers to unsaturated hydrocarbons that contain at least one carbon-carbon double bond. In many embodiments, alkene refers to alpha olefins. In some embodiments, alkene refers to one or more of ethylene, propylene, 1- butene, butadiene, pentene, pentadiene, hexene, octene, decene and dodecene. In particular embodiments, alkene refers to ethylene and propylene and, in some embodiments, ethylene. As used herein, the term, “oxidative dehydrogenation” or “ODH” refers to processes that couple the endothermic dehydrogenation of an alkane with the strongly exothermic oxidation of hydrogen as is further described herein.

[0060] As used herein, the term “substantially free of acetylene” refers to the amount of acetylene present, if any, remaining after the ODH reaction. In many embodiments, the amount of acetylene present is undetectable using the analytical techniques described herein or zero ppm. In some embodiments. The amount of acetylene present is close to zero ppm.

[0061] As used herein, the term “STP” refers to standard temperature and pressure. In some embodiments, STP is 1 atm and 21 °C.

[0062] As used herein, the gas hourly space velocity (GHSV) in h'1can be calculated using the equation: GHSV =

[0063] Volumetric flow rate of feed, gas and / or vapor entering the reactor (or feed flow rate) at STP Volume of catlyst bed active phase

[0064] As used herein, the LHSV can be calculated using the equation:

[0065] . Mass flow rate of feed gas and / or vapor entering the reactor (or feed flow rate)

[0066] LHS V — - .

[0067] Mass of catlyst bed active phase

[0068] As used herein, the linear velocity can be calculated using the equation: Linear Velocity =

[0069] Volumetric Flow rate of feed gas and / or vapor entering the reactor at reactor temperature and reactor inlet pressure cross section area of reactor tube x void fraction of catalyst bed

[0070] EXAMPLES

[0071] Example 1 : Preparation of Catalyst 1. 1

[0072] To a vessel was charged 10 L of distilled water, this water was heated to 65°C. To this vessel was also charged 1102.0 grams of oxalic acid (C2H2O4 (s>; 12.240 mol), which dissolved quickly with stirring to form a clear, colorless solution. To the 65°C aqueous oxalic acid solution was then charged with 656.3 grams of diniobium pentoxide hydrate (Nb2O5*xH2O(s), purchased from CBMM). The weight of diniobium pentoxide hydrate was weighed assuming an 80% weight ofNb2Os with MW of 265.81 g / mol, which is 525.06 g & 1.975 mol of Nb2O5. This addition formed a white suspension. The vessel opening was rinsed with 1 L of distilled water rinsing the residual powders into the solution, producing a total volume of 11 L. The 11 L of aqueous, white suspension was left to heat and stir at 65°C for 36 hours. After the 36 hours of heating at 65°C the solution was cooled down to ambient conditions. The turbid solution of H3[NbO(C2O4)3] (aq) was clear and colorless with only small amounts of white insoluble matter at the bottom of the vessel in the absence of mixing. Once cooled to room temperature the solution can be stored for extended periods of time before use.

[0073] To another vessel was charged 6 L of distilled water, this water was heated to 60°C. 1054.6 grams of telluric acid (Te(OH)e (s>; 4.593 mol) was added to the 60°C distilled water. This dissolved easily upon stirring to form a clear and colorless solution. The vessel opening was rinsed with 1 L of distilled water in order to rinse the powders into solution producing a final volume of 7 L. The 60°C, 7 L Te(OH)e (aq) solution was cooled down to room temperature and held for the following steps.

[0074] To a jacketed glass reactor, 16 L of distilled water was added and heated using a circulation bath and silicone oil. The 16 L of distilled water was heated to 30-35°C. To the jacketed vessel was then charged 4865.0 grams of ammonium molybdate tetrahydrate ((NH4)6MO7O24*4H2O(S); 3.934 mol), which dissolved with stirring to form a turbid white solution. The vessel opening was rinsed with 1 L of distilled water to rinse any residual solids into solution, producing a total volume of 17 L.

[0075] The entire 7 L Te(OH)e solution was transferred at ambient temperature to the jacketed vessel which contained a stirred solution of (NH4)6MoO24,4H2O(aq) turbid solution at an addition rate of 412 mL / min to form a clear and colorless solution. The vessel from that contained the telluric acid was rinsed with 1 L of distilled water. The rinsing solution was transferred to the jacketed glass reactor. The MoTe solution was heated to 80°C, the pH was adjusted to 7.40-7.60 using 1680-2000 grams (calculated 1.85-2.20 L at density of 0.91 g / cm3) of 28-30% ammonium hydroxide solution. The pH 7.50 MoTe solution was stirred at 80°C for one hour, after which the pH of the MoTe solution was adjusted from 7.50 to 4.9-5.1 using 1270-1550 grams (calculated 0.69-0.84 L at density of 1.85 g / cm3) of 95-08% sulfuric acid.

[0076] The MoTe solution, now an aqueous ammonium molybtellurate ((NH4)eMo6TeO24 (aq)), was transferred to a hydrothermal reactor pre-heated to 60°C. The glass reactor was then rinsed with 2 L of distilled water. The rinsing solution was transferred to the 60°C preheated hydrothermal reactor. The 60-80°C MoTe solution was stirred via agitator inside the high-pressure hydrothermal reactor.

[0077] To a separate vessel was charged 11 L of distilled water. The water was heated to 60°C. To the water was charged 4043 grams of vanadyl sulfate hydrate (VOSO4*3.35H2O <s); 18.10 mol). The powder dissolved with vigorous stirring forming a clear, blue solution. The vessel opening was rinsed with 1 L of distilled water to rinse residual powders into solution producing a total volume of 12 L. The 60°C, 12 L VOSO4 (aq) solution was held at 60°C for additional steps.

[0078] To the ammonium molybdotellurate solution stirred in the high-pressure hydrothermal reactor at 55-65°C, was charged the entire volume of the 60°C vanadyl sulfate solution at an addition rate of 367 ml / min. The vanadyl sulfate vessel was rinsed with 2 L of distilled water. The rinsing solution was also transferred to the high-pressure hydrothermal vessel. The resulting solution was stirred for 30 minutes at 55-60°C.

[0079] After 30 minutes, the entire volume of room temperature niobium oxalate solution was transferred to the stirred reactor autoclave, 55-60°C, MoTeV solution at an addition rate of 183 mL / min to form a purple slurry. The niobium oxalate vessel was rinsed with 2 L of distilled water and the rinsing solution was also transferred to the high-pressure hydrothermal reactor. After the addition of all reagents, the reactor was heated to 160- 165°C.

[0080] The slurry inside the reactor was heated to 160-165°C, while the pressure was maintained at 95-105 psi with the use of a back-pressure regulator built into the reactor head (gas produced from the reaction was released through the back-pressure regulator). Custom heating mantles, insulation and temperature programming control were used to heat the reactor slurry to 160-165°C, without exceeding 185°C at the metal surface of the reactor. The slurry in the reactor was heated for 24-48 hours. The reaction was cooled — by removing heat and insulation — for 17-20 hours. The slurry was stirred during cool down at the same rate as the hydrothermal reaction (100 rpm).

[0081] The solids from the hydrothermal reaction were filtered and recovered. The solids separated from the mother liquor are herein referred to in this example as pre-catalyst. After the pre-catalyst was washed with water until the filtrate was almost colorless and dried at 90°C in a drying pans for 3-5 days the solids were crumbly and friable. This material, herein referred to as uncalcined catalyst in this example, was ground to 125-500 pm size range. This ground uncalcined catalyst was dried additionally in air at 250°C for 6 hours in drying boats to reduce the moisture to <2% yielding 5.9-6.3 kg of uncalcined catalyst. The uncalcined catalyst was calcined in a quartz reactor under continues nitrogen flow (1000 seem of nitrogen flow, Quartz tube supplied by Opti-Tech, 140 mm ID, 150 mm OD, 1800 mm L. Model VER-TU-QRZ-140-1800, or different supplier like ACE GLASS, or United Silica). The quartz reactor was ramped to 600°C at 1.6°C per minute and held at 600°C for 6 hours. The quartz reactor was then cooled to room temperature before the catalyst was removed. Example 2: Preparation of Catalyst 1.2

[0082] To a vessel was charged 10 L of distilled water, this water was heated to 65°C. To this vessel was also charged 1102.0 grams of oxalic acid (C2H2O4 (s>; 12.240 mol), which dissolved quickly with stirring to form a clear, colorless solution. To the 65°C aqueous oxalic acid solution was then charged with 656.3 grams of diniobium pentoxide hydrate (Nb2O5*xH2O(s), purchased from CBMM). The weight of diniobium pentoxide hydrate was weighed assuming an 80% weight ofNb2Os with MW of 265.81 g / mol, which is 525.06 g & 1.975 mol of Nb2O5. This addition formed a white suspension. The vessel opening was rinsed with 1 L of distilled water rinsing the residual powders into the solution, producing a total volume of 11 L. The 11 L of aqueous, white suspension was left to heat and stir at 65°C for 36 hours. After the 36 hours of heating at 65°C the solution was cooled down to ambient conditions. The turbid solution of H3[NbO(C2O4)3] (aq) was clear and colorless with only small amounts of white insoluble matter at the bottom of the vessel in the absence of mixing. Once cooled to room temperature the solution can be stored for extended periods of time before use.

[0083] To another vessel was charged 6 L of distilled water, this water was heated to 60°C. 1054.6 grams of telluric acid (Te(OH)e (s>; 4.593 mol) was added to the 60°C distilled water. This dissolved easily upon stirring to form a clear and colorless solution. The vessel opening was rinsed with 1 L of distilled water in order to rinse the powders into solution producing a final volume of 7 L. The 60°C, 7 L Te(OH)e (aq) solution was cooled down to room temperature and held for the following steps.

[0084] To a jacketed glass reactor, 16 L of distilled water was added and heated using a circulation bath and silicone oil. The 16 L of distilled water was heated to 30-35°C. To the jacketed vessel was then charged 4865.0 grams of ammonium molybdate tetrahydrate ((NH4)6MO7O24*4H2O(S); 3.934 mol), which dissolved with stirring to form a turbid white solution. The vessel opening was rinsed with 1 L of distilled water to rinse any residual solids into solution, producing a total volume of 17 L.

[0085] The entire 7 L Te(OH)e solution was transferred at ambient temperature to the jacketed vessel which contained a stirred solution of (NEUjeMoC^ EECkaq) turbid solution at an addition rate of 412 mL / min to form a clear and colorless solution. The vessel from that contained the telluric acid was rinsed with 1 L of distilled water. The rinsing solution was transferred to the jacketed glass reactor. The MoTe solution was heated to 80°C, the pH was adjusted to 7.40-7.60 using 1680-2000 grams (calculated 1.85-2.20 L at density of 0.91 g / cm3) of 28-30% ammonium hydroxide solution. The pH 7.50 MoTe solution was stirred at 80°C for one hour, after which the pH of the MoTe solution was adjusted from 7.50 to 4.9-5.1 using 1270-1550 grams (calculated 0.69-0.84 L at density of 1.85 g / cm3) of 95-08% sulfuric acid.

[0086] The MoTe solution, now an aqueous ammonium molybtellurate ((NH4)eMo6TeO24 <aq)), was transferred to a hydrothermal reactor pre-heated to 60°C. The glass reactor was then rinsed with 2 L of distilled water. The rinsing solution was transferred to the 60°C preheated hydrothermal reactor. The 60-80°C MoTe solution was stirred via agitator inside the high-pressure hydrothermal reactor.

[0087] To a separate glass vessel was charged 11 L of distilled water. The water was heated to 60°C. To the water was charged 4023.5 grams of vanadyl sulfate hydrate (VOSO4*3.35H2O <s); 18.10 mol). The powder dissolved with vigorous stirring forming a clear, blue solution. The vessel opening was rinsed with 1 L of distilled water to rinse residual powders into solution producing a total volume of 12 L. The 60°C, 12 L VOSO4 (aq) solution was held at 60°C for additional steps.

[0088] To the ammonium molybdotellurate solution stirred in the high-pressure hydrothermal reactor at 55-65°C, was charged the entire volume of the 60°C vanadyl sulfate solution at an addition rate of 367 ml / min. The vanadyl sulfate vessel was rinsed with 2 L of distilled water. The rinsing solution was also transferred to the high-pressure hydrothermal vessel. The resulting black solution was stirred for 30 minutes at 55-60°C.

[0089] After 30 minutes, the entire volume of room temperature niobium oxalate solution was transferred to the stirred reactor autoclave, 55-60°C, MoTeV solution at an addition rate of 183 mL / min to form a purple slurry. The niobium oxalate vessel was rinsed with 2 L of distilled water and the rinse was also transferred to the high-pressure hydrothermal reactor. After the addition of all reagents, the reactor was heated to 160-165°C.

[0090] The slurry inside the reactor was heated to 160-165°C, while the pressure was maintained at 95-105 psi with the use of a back-pressure regulator built into the reactor head (gas produced from the reaction was released through the back-pressure regulator). Custom heating mantles, insulation and temperature programming control were used to heat the reactor slurry to 160-165°C, without exceeding 185°C at the metal surface of the reactor. The slurry in the reactor was heated for 24-48 hours. The reaction was cooled — by removing heat and insulation — for 17-20 hours. The slurry was stirred during cool down at the same rate as the hydrothermal reaction (100 rpm).

[0091] The solids from the hydrothermal reaction were filtered and recovered. The solids separated from the mother liquor are herein referred to in this example as pre-catalyst. After the pre-catalyst was washed with water until the filtrate was almost colorless and dried at 90°C in a drying pans for 3-5 days the solids were crumbly and friable. This material, herein referred to as uncalcined catalyst in this example, was ground to 125-500 pm size range. This ground uncalcined catalyst was dried in drying boats to reduce the moisture to <2% yielding 5.9-6.3 kg of uncalcined catalyst. The uncalcined catalyst was calcined in a quartz reactor under nitrogen. The quartz reactor was ramped to 600°C at 1.6°C per minute and held at 600°C for 10 hours. The quartz reactor was then cooled to room temperature before removing the catalyst.

[0092] Example 3: Preparation of Catalyst Material 2, 1

[0093] Goethite was pressed and sieved. Goethite (1.4365 g) was mixed with Catalyst 1.1 (1.96 g) resulting in Catalyst Material 2. 1.

[0094] Example 4: Preparation of Catalyst Material 2,2

[0095] To a 100 mL beaker, 4.0 g of Catalyst 1. 1 or Catalyst 1.2 and 6.0 g of goethite (Fe(OH)O, CAS: 2344-49-4 (Lot#BCBQ8228V with 30-63% Fe); SIGMA-ALDRICH®) were added. About 15 mL of distilled water was added to the beaker and stirred manually. The beaker was placed in an oil bath at approximately 100°C. An overhead stirrer was installed and stirred at approximately 90 rpm until the mixture became a paste. The mixture was a mustard color. The paste was then dried in a 90°C oven overnight. Next, the dried paste was then calcined at 350°C in oven for 2.5 hours and cooled overnight to yield Catalyst Material 2.2.

[0096] Example 5: Preparation of Catalyst Material 2,3

[0097] To a 100 mL beaker, 8.0 g of Catalyst 1. 1 or Catalyst 1.2 and 2.0 g of goethite were weighed. Around 15 mL of distilled water was added to the same beaker and stirred manually. The beaker was placed in an oil bath at approximately 100°C. A overhead stirrer was installed to this beaker and stirred at approximately 85 rpm until the mixture became a paste. The mixture was a green color. The paste was then dried in a 90°C oven overnight. Next, the dried paste was then calcined at 350°C in oven for 2.5 hours and cooled overnight to yield Catalyst Material 2.3. The final catalyst material color was red.

[0098] Example 6: Preparation of Catalyst Material 2,4

[0099] Pure goethite (1.96 g) was mixed with sand to have a total volume of 3 mL. Example 7: Preparation of Catalyst Material 2,5

[0100] Catalyst 1. 1 or Catalyst 1.2 was impregnated with 40% goethite. Example 8: XRD Analysis

[0101] Powder X-Ray Diffractometry (PXRD) data was collected using a PANalytical Aeris X-ray diffractometer by SEMx Incorporated. This diffractometer instrument consisted of three basic elements: X-ray tube, sample holder, and X-ray detector. X-rays were generated in a cathode ray tube (Cu source with Ka radiation = 1.5418 A) with the resulting X-rays being directed onto the sample. As the sample and detector are rotated, the intensity of the reflected X-rays is recorded to produce characteristic X-ray spectra. When the incident X-rays reflecting off the sample satisfies the Bragg Equation (n =2d sin 0), constructive interference occurs and a peak in intensity occurs (y-axis). X-ray diffractometers were setup such that the sample rotates in the path of the X-ray beams at an angle 0, while the X-ray detector is mounted on an arm to collect the diffracted X-rays and rotates at an angle of 20 from ~5° to 70° (x-axis).

[0102] Qualitative XRD analysis and Rietveld Refinement was performed using HighScore Plus XRD analysis software. The samples were finely ground to reduce particle size and to obtain a uniform mixture. They were then loaded onto the XRD sample holder and the XRD spectrum was acquired. The Rietveld Refinement results were combined with Highscore Plus and EDS results to perform qualitative and quantitative analysis.

[0103] The weight percentage of amorphous content was determined by external standard. With an external standard phase, the instrument intensity constant, K-factor, is determined. Corundum was used as the external standard and was measured with the same instrument configuration shortly after the unknown sample was measured. The K-factor approach is described by O’Connor and Raven: 1988, Powder Diffraction, 3 (1), 2-6. For each sample, the weight percentage of the crystalline MoVOx orthorhombic phase had to be determined in order to assign weight percentages to the amorphous content. The Degree of Crystallinity (DOC) Method, based on the estimation that the total intensity of area contributed to the overall diffraction pattern by each component in the analysis, was used to determine the amount of amorphous phase. The degree of crystallinity was calculated from the total areas under the defined crystalline and amorphous components from:

[0104] DOC = Crystalline Area + Amorphous Area Where the weight fraction of the amorphous material was calculated from:

[0105] W amorphous = 1 - DOC

[0106] The Ortho-MoVOx phase contributed to the crystalline area and therefore needed to be quantified in order to determine the amorphous area. To compensate for the fact that different materials and backgrounds would have different effects, a sample of MoVTeNbOx was used to calibrate some constants needed for the DOC method. Samples containing MoVOx phases had the ortho-MoVOx phase weight percentages qualitatively determined using only two elements (Mo and V) based on the MoVTeNbOx calibration.

[0107] Ml phase content determination. The MoVOx orthorhombic phase (also referred to in literature as the Ml phase) was fitted using literature crystal structure data for a different yet crystallographically analogous compound because the orthorhombic Pba2 crystalline phase was a match. The literature crystal structure used for fitting was taken from reference: S. Ishikawa, D. Kobayashi, T. Konya, T. Murayama, N. Yasuda, M. Sadakane, W. Ueda. J. Phys. Chem. C, 119, 7195, (2015).

[0108] Comparative raw data analysis. The PXRD raw data was also analyzed using a Python code through the program Spyder. The code generated overlaid plots. It also analyzed the data by comparing the peak prominence of all the local maxima and generated a plot with peaks meeting an established threshold. Relevant catalyst peaks are highlighted in the plot with vertical lines and the range of the relative peak intensities were provided by the code.

[0109] Energy Dispersive Spectroscopy was used as elemental analysis input for XRD analysis interpretation.

[0110] XRD Analysis of Catalysts 1.1 and 1.2 and Catalyst Materials 2.2 and 2.3

[0111] The amorphous and crystalline content of Catalysts 1.1 and 1.2 as well as Catalyst Materials 2.2 and 2.3 is presented in Table 8A. Further, XRD scans of Catalysts 1.1 and 1.2 as well as Catalyst Material 2.2 are presented in Figures 1-4, respectively. Catalyst and catalyst material peaks from Figure 10 are shown in Table 8B. Catalyst material peaks from Figure 11 are showin in Table 8C. Peaks 21, 22, 24, 29, 33, 37, and 38 are attributed to geothite.

[0112] TABLE 8A

[0113] *The sample was taken before the calcination step. TABLE 8B

[0114] TABLE 8C

[0115] Example 9: ICP-MS

[0116] Inductively Coupled Plasma Mass Spectrometry (ICP-MS), sensitive enough to detect elements in ppb concentration ranges, was the analytical technique used for measuring the elemental composition of catalyst or catalyst materials. ICP-MS analysis was performed on an Agilent 7700X ICP-MS system. Liquid samples were introduced to ICP as an aerosol through a nebulizer and spray chamber. The argon plasma dried the aerosol and dissociated the sample’s molecules into atomic ions. The ions were directed towards the MS detector and were separated based on their mass-to-charge ratio and measured by a detector to produce a signal that was proportional to the ions’ concentration. Quantitative determination of atoms’ concentration in the original sample was determined with the use of an external standard calibration. The calibration curves were constructed after subtracting the reagent blank. Concentrations were given in ng / mg (wt-ppm) or pg / g (wt-ppm) units in this analysis.

[0117] Samples were prepared by placing 10 milligram (mg) of catalyst or catalyst material in 3 mb of a 6.25-35.0 molar (M) NaOH solution. The solution was then heated in an oil bath at 90°C with rigorous mixing.

[0118] ICP-MS Analysis of Catalysts 1.1. and 1.2 and Catalyst Materials 2.2 and 2.3

[0119] The ICP-MS analysis of Catalysts 1.1 and 1.2 as well as Catalyst Materials 2.2 and 2.3 is presented in Table 9A.

[0120] TABLE 9A

[0121] *The sample was taken before the calcination step.

[0122] Example 10: Calculation of Molar Ratios

[0123] The molar ratio for the synthesized catalysts and catalyst materials were calculated based on elemental analysis or based on the weight percent of the various starting materials.

[0124] Calculation of molar ratios by based on reaction starting materials (i.e. mass balance method) . When reported in this fashion, the final composition of the catalyst material was calculated under the assumption that all metal elements, which were present in the catalyst material precursors (e.g. catalyst and goethite) were present in their entirety in the final catalyst material. This method was presumed to be accurate when no additional washes, filtration, or other catalyst material purification methods were used. When stated below that the element ratios were calculated based using the mass balance method, the calculation was done based according to the following steps:

[0125] 1. The weight concentrations of the first catalyst precursor of the catalyst material MoaVbTecNbaOe was obtained via ICP-MS analysis.

[0126] 2. The weight of the metal element in the second catalyst material precursor (Fe in this case) was obtained via following equation: where CEI is weight concentration (i.e. wt.-ppm) of the corresponding metal element in the second catalyst precursor (i.e. Fe), Cox is weight concentration of the second catalyst precursor in the final formulation of the catalyst material (wt.-ppm) (i.e. FeO), MEI is molar mass in g / mol of the corresponding element, Mox is molar mass in g / mol of the second catalyst precursor.

[0127] Calculation of Molar Ratios by ICP-MS. Sample solubilization for ICP-MS analysis was done via digestion in a 50 wt. % oxalic acid solution. Calibration of the ICP- MS was performed using external standards matched to the matrix of the sample and the curves are calculated after subtracting the reagent blank. Several elements (Li Sc, Y, In, Tb and Bi) served as internal standards and were mixed continuously through online addition to monitor and compensate for signal drift. The results were generally reported as pg / g (ppmw) or pg / L (ppbv).

[0128] The below description details how molar ratios were determined by ICP-MS. Table 10A below shows the composition of the Catalyst Materia 2.2 and Catalyst Material 2.3 (synthesis described below) as determined by ICP-MS:

[0129] TABLE 10A, ICP-MS

[0130] In order to calculate the molar ratios of elements the following equation was used: fo /

[0131] ' 95.94

[0132] Where REI is the ratio number for the corresponding element (e.g., Mo, V, Nb, Te, Fe), CEI is the weight concentration (i.e. wt.-ppm) of the corresponding element, MEI is the molar mass in g / mol of the corresponding element, CMO is the weight concentration (i.e. wt.-ppm) of molybdenum (Mo) in the corresponding catalyst, 95.94 is molar mass of Mo in g / mol. Application of the above equation provides the elemental ratios of the elements in the catalyst material, whereby the ratio number for Mo in this calculation is assigned to be 1. It is well known to art that any element in the catalyst material can be assigned the ratio number of 1, which will change the ratio numbers for all the other elements. In this particular case, Mo was chosen for convenience due Mo being the most abundant element in the catalyst starting material (i.e. MoaVbTecNbaOe).

[0133] Using the method, described above, the molar ratios of elements were calculated for Catalyst 1.1 and are presented in the Table 1.1 A.

[0134] Example 11 : Microreactor Unit (MRU)

[0135] The ability of catalysts and catalyst materials described herein to participate in the oxidative dehydrogenation of ethane were tested in a microreactor unit (MRU).

[0136] The MRU included a reactor tube made from stainless-steel SWAGEEOK® Tubing, which had an outer diameter of 0.5 inches, an internal diameter of about 0.4 inches, and a length of about 15 inches. A 6-point WIKA Instruments Ltd. K-type thermocouple which had an outer diameter of 0. 125 inches was inserted axially through the center of the reactor, which was used to measure and control the temperature within the catalyst bed. A room temperature glass tight sealed condenser was located after the reactor to collect water / acidic acid condensates. The gas product flow was allowed to either vent or was directed to a gas chromatography (Agilent 6890N Gas Chromatograph, Using Chrom Perfect - Analysis, Version 6.1.10 for data evaluation) via a sampling loop.

[0137] To prepare catalyst and catalyst materials for testing in the MRU, the catalyst or catalyst material was loaded into a 1-inch round die and pressed with 8 tons of compression force for 10 to 15 seconds of dwelling time. The pressed catalyst or catalyst material was then crushed into small pieces using a mortar and pestle. The crushed catalyst or catalyst material was sieved and a particle sizes between 425 pm and 1 mm were collected to be loaded for testing on the MRU.

[0138] For MRU experiments, the catalyst bed was prepared by Method 1 or Method 2. Method 1 was employed to test catalysts and catalyst materials. Method 2 was employed to test catalyst materials

[0139] Method 1. 1.96 g of catalyst or catalyst material was physically mixed with quartz sand (50-70 mesh (0.21-0.29 mm)) such that the catalyst bed had a total volume of about 3 mb.

[0140] Method 2. Under this method, the catalyst bed consisted only of catalyst material. Further, the amount of catalyst material was determined based on the amount of catalyst used to prepare the catalyst material. Specifically, the catalyst material was loaded in an amount such that the theoretical amount of (i) catalyst or (ii) catalyst and goethite in the catalyst bed was 1.96 g. For example, if a catalyst material was prepared from 40 wt. % catalyst and 60 wt. % goethite, then 4.9 g of catalyst material would be used to prepare the catalyst bed.

[0141] For both Methods 1 and 2, the catalyst bed was loaded in the middle zone of the reactor — located between points 3 and 4 of the thermocouple — and the remaining volume of the reactor was packed with quartz sand. The load was then secured with glass wool on the top and the bottom of reactor.

[0142] For the MRU testing, a pre-mixed feed gas was fed through the reactor. The premixed feed gas entering the reactor was 36 mol % ethane, 18 mol % oxygen, and 46 mol % nitrogen. Further, the pre-mixed feed gas flow was adjusted by a calibrated mass flow controller to obtain a gas hourly space velocity (GHSV) of about 3,000 h-1, based on the catalyst or catalyst material volume in the catalyst bed as defined by Method 1 or Method 2.

[0143] The flow rate of the feed gas can be about 70 standard cubic centimeters per minute (seem) to about 80 seem. For example, the flow rate of the feed gas can be about 74.6 seem. The catalyst bed placed in the reactor tube can include the catalyst or catalyst material and a filler. With reference to the MRU’s catalyst bed, a filler refers to a material that does not participate in the oxidative dehydrogenation of ethane or have other catalytic activity, such as non-selective oxidation under the MRU test conditions. For example, the filler can be quartz sand. The ratio of catalyst or catalyst material to filler is 1: 1 (by volume). The 35% ethane conversion temperature is determined at a weight hourly space velocity (WHSV) of 2.90 h’1, with the WHSV based on the amount of catalyst or the amount of catalyst used to prepare the catalyst material, and a gas hourly space velocity (GHSV) of about 3,000 h'1. Whereby WHSV is defined as mass flow of feed gas to the reactor divided by the weight of the catalyst in the catalyst bed, GHSV is defined as volumetric flow of the reactor feed gas divided by the volume of the catalyst bed.

[0144] Typically, the inlet pressure was in the range of about 1 pound per square inch gauge (psig) to about 2.5 psig and the outlet pressure is in the range of about 0 psig to about 0.5 psig. The gas feed exiting the catalyst bed can be 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.

[0145] The gas exiting the reactor was analyzed by gas chromatography (Agilent 6890N Gas Chromatograph, Using Chrom Perfect - Analysis, Version 6.1.10 for data evaluation) to determine the percent of various hydrocarbons (e.g., ethane and ethylene) and, optionally other gases such as O2, CO2, and CO and acetylene. A catalyst or catalyst material’s 35% conversion temperature was determined as follows. Conversion of the feed gas was calculated as a mass flow rate change of ethane in the product compared to feed ethane mass flow rate using the following formula:

[0146] In the above equation, C is the percent of feed gas that has been converted from ethane to another product (i.e., ethane conversion) and X is the molar concentration of the corresponding compound in the gaseous effluent exiting the reactor at corresponding temperature. The ethane conversion was then plotted as a function of temperature to acquire a linear algebraic equation. The linear equation for ethane conversion was solved to determine the temperature in which the ethane conversion was 35% (i.e. the 35% conversion temperature)

[0147] Further, the gas exiting the reactor was 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 was determined using the following equation:

[0148] In the above equation, 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. The selectivity to ethylene was determined at the 35% conversion temperature, unless otherwise indicated. As such, after the 35% conversion temperature was determined, the above equation for selectivity was solved using the corresponding values for cthyiene, Xco2, and Xco at the 35% conversion temperature.

[0149] When reported, acetic acid production was determined by running MRU testing long enough to collect an aqueous condensate in the condenser (e.g., 1-3 days). After collecting a sample of the condensate, the sample was submitted for liquid GC analysis (Agilent 6890N Gas Chromatograph, Using Chrom Perfect - Analysis, Version 6.1.10 for data evaluation). To perform the liquid GC analysis, 300-450 mg of liquid sample was transferred to a scintillation vial. Next, 25 mg of isopropanol (IP A) was added as an internal standard. Further, 18-20 mU of distilled H2O was added to dilute the sample. Prepared samples were then transferred to GC vials and set in sequence to tested using an auto sampler. The GC analysis was a split injection method with a temperature program and FID detector. Further, a set of 3 calibration standards were run in duplicate for the relative response factor used for calculating acetic acid content in sample.

[0150] MRU Testing of Catalyst 1.1 and 1.2 and Catalyst Materials 2.2 and 2.3

[0151] Catalyst 1. 1 was loaded onto an MRU reactor according to Method 1.

[0152] Catalyst 1.2 was loaded onto an MRU reactor according to Method 1.

[0153] Catalyst Material 2. 1 was loaded onto an MRU reactor according to Method 1 but diluted with pressed Goethite.

[0154] Catalyst Material 2.2 (4.9037 g) was loaded onto an MRU according to Method 2.

[0155] Catalyst Material 2.3 was loaded onto an MRU according to Method 1.

[0156] Three mU of Catalyst Material 2.4 was loaded onto an MRU reactor.

[0157] Catalyst performance is shown in Table 11A below.

[0158] TABUE 11A a Goethite was determined to have a 15% conversion at 334°C. b Goethite was determined to have an ethylene selectivity of 51 mol % at 334°C.

[0159] Table 1 IB shows catalyst performance of Catalyst 1.1 at different temperatures. The temperature at 35% conversion was 379°C and ethylene selectivity was 94 mol %.

[0160] TABUE 11B

[0161] Table 11C shows catalyst performance of Catalyst 1.2 at different temperatures. The temperature at 35% conversion was 379°C and ethylene selectivity was 96 mol %. TABLE 11C

[0162] Table 1 ID shows catalyst performance of Catalyst Material 2. 1 at different temperatures. The temperature at 35% conversion was 377°C and ethylene selectivity was 87 mol %. Acetic acid content in the condensate was 0.25 wt%.

[0163] TABLE I IP

[0164] Table 1 IE shows catalyst performance of Catalyst Material 2.2 at different temperatures. The temperature at 35% conversion was 357°C and ethylene selectivity was 88 mol %. Figure 5 shows the ethylene conversion at different temperatures using Catalyst

[0165] Material 2.2.

[0166] TABLE HE

[0167] Table 1 IF shows catalyst performance of Catalyst Material 2.3 at different temperatures. The temperature at 35% conversion was 375°C and ethylene selectivity was 93 mol %. Acetic acid content in the condensate was 3.88 wt. %. Figure 6 shows the ethylene conversion at different temperatures using Catalyst Material 2.3. Figure 7 shows the ethylene selectivity at different temperatures using Catalyst Material 2.3. TABLE 1 IF

[0168] Table 11G shows catalyst performance of Catalyst Material 2.4 at different temperatures on the first day. TABLE 11G

[0169] Table 11H shows catalyst performance of Catalyst Material 2.4 at different temperatures on the second day.

[0170] TABLE 11H

[0171] Example 12: Double Bed Preparation

[0172] As shown in Figure 8, two different catalyst has been loaded to MRU reactor. The first bed had only PCSU8 catalyst and the second bad had 40% goethite impregnated PCSU8. Also, both catalyst has been loaded as standard mode (50% dilution with sand). Therefore, the goethite content has been treated as a part of active phase catalyst. During this study, the flow has been changed three times (74.6, 119, and 149 seem) to monitor the activity and selectivity change. Table 12A shows the performance summary of double bed which consists of Catalyst 1.2 (loaded onto an MRU reactor according to Method 1) and Catalyst Material 2.5 (loaded onto an MRU reactor according to Method 1).

[0173] TABUE 12A

[0174] OTHER EMBODIMENTS

[0175] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.

[0176] INDUSTRIAL APPLICABILITY

[0177] Catalysts materials for oxidative dehydrogenation of alkanes, such as the oxidative dehydrogenation of ethane to ethylene.

Claims

CLAIMS1. A catalyst material comprising molybdenum, vanadium, niobium, tellurium, iron, and oxygen, wherein: the molar ratio of molybdenum to vanadium is from 1 :

0. 10 to 1 :0.60, the molar ratio of molybdenum to niobium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to tellurium is from 1:0.05 to 1:0.50, the molar ratio of molybdenum to iron is from 1:0.20 to 1:5.00, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

2. The catalyst material of claim 1, wherein the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45.

3. The catalyst material of claim 1, wherein the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.40.

4. The catalyst material of any one of claims 1-3, wherein the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.30.

5. The catalyst material of any one of claims 1-3, wherein the molar ratio of molybdenum to niobium is from 1:0.15 to 1:0.25.

6. The catalyst material of any one of claims 1-5, wherein the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30.

7. The catalyst material of any one of claims 1-5, wherein the molar ratio of molybdenum to tellurium is from 1:0.10 to 1:0.20.

8. The catalyst material of any one of claims 1-7, wherein the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0.

9. The catalyst material of any one of claims 1-7, wherein the molar ratio of molybdenum to iron is from 1:0.50 to 1:3.3.

10. The catalyst material of claim 1, wherein: the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.30, the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30, the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

11. The catalyst material of claim 1, wherein: the molar ratio of molybdenum to vanadium is from 1:0.15 to 1:0.45,the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.30, the molar ratio of molybdenum to tellurium is from 1:0.07 to 1:0.30, the molar ratio of molybdenum to iron is from 1:0.35 to 1:4.0, and oxygen is present at least in an amount to satisfy the valency of any present metal oxides.

12. The catalyst material of any one of claims 1-11, wherein the catalyst material has an amorphous content of about 20 wt. % to about 80 wt. %.

13. The catalyst material of any one of claims 1-11, wherein the catalyst material has an amorphous content of about 35 wt. % to about 65 wt. %.

14. The catalyst material of any one of claims 1-11, wherein the catalyst material has an amorphous content of about 38 wt. % or about 62 wt. %.

15. The catalyst material of any one of claims 1-14, wherein at least a portion of the iron in the catalyst material is present as Fe(III).

16. The catalyst material of any one of claims 1-14, wherein the iron in the catalyst material is present as an iron oxide, an iron oxide hydroxide, or a combination thereof.

17. The catalyst material of any one of claims 1-14, wherein the iron in the catalyst material is present as goethite.

18. The catalyst material of any one of claims 1-17, wherein the catalyst material has a 35% conversion temperate from about 300°C to about 400°C.

19. The catalyst material of any one of claims 1-17, wherein the catalyst material has a 35% conversion temperate from about 350°C to about 380°C.

20. The catalyst material of any one of claims 1-17, wherein the catalyst material has a 35% conversion temperate of about 357°C, about 375°C, or about 377°C.

21. The catalyst material of any one of claims 1-20, wherein the catalyst material has an ethylene selectivity from about 70 mol % to about 98 mol %.

22. The catalyst material of any one of claims 1-20, wherein the catalyst material has an ethylene selectivity from about 85 mol % to about 95 mol %.

23. The catalyst material of any one of claims 1-20, wherein the catalyst material has an ethylene selectivity of about 87 mol %, about 88 mol %, or about 93 mol %.

24. The catalyst material of any one of claims 1-23, wherein the catalyst material has an acetic acid selectivity of less than 2 mol %.

25. The catalyst material of any one of claims 1-23, wherein the catalyst material has an acetic acid selectivity of less than 1.5 mol %.

26. The catalyst material of any one of claims 1-23, wherein the catalyst material has an acetic acid selectivity of less than 0.1 mol %.

27. A method comprising contacting a gas mixture comprising ethane with the catalyst material of any one of claims 1-26 to form ethylene.

28. The method of claim 27, wherein the ethylene is substantial free of acetylene.

29. A method comprising contacting a gas mixture comprising ethane with a catalyst mixture to form ethylene wherein the catalyst mixture comprises(i) a first catalyst material wherein the first catalyst material is the catalyst material of any one of claims 1-26; and(ii) a second catalyst material comprising molybdenum, vanadium, niobium, and tellurium wherein: the molar ratio of molybdenum to vanadium is from 1:0.25 to 1:0.35, the molar ratio of molybdenum to niobium is from 1:0.10 to 1:0.25, and the molar ratio of molybdenum to tellurium is from 1:0.10 to 1:0.30.

30. The method of claim 29, wherein the catalyst mixture has a 35% conversion temperate from about 300°C to about 400°C.

31. The method of claim 29, wherein the catalyst mixture has a 35% conversion temperate of about 370°C.

32. The method of any one of claims 29-31, wherein the catalyst mixture has an ethylene selectivity from about 80 mol % to about 98 mol %.

33. The method of any one of claims 29-31, wherein the catalyst mixture has an ethylene selectivity of about 85 mol % to about 96 mol %.

34. The method of any one of claims 29-33, wherein the catalyst mixture has an acetic acid selectivity of less than 2 mol %.

35. The method of any one of claims 29-33, wherein the catalyst mixture has an acetic acid selectivity of less than 1 mol %.

36. The method of any one of claims 29-35, wherein the gas mixture is contacted with the first catalyst material followed by the second catalyst material.

37. The method of any one of claims 29-35, wherein the gas mixture is contacted with the second catalyst material followed by the first catalyst material.

38. The method of any one of claims 29-37, wherein the ethylene is substantial free of acetylene.

39. The method of any one of claims 27-38, wherein the gas mixture has an hourly space velocity of from 500 h'1to 15000 h'1.

40. The method of any one of claims 27-39, wherein the weight hourly space velocity of the gas mixture is from 0.5 h'1to 15 h'1.

41. The method of any one of claims 27-40, wherein the gas mixture has a temperature of from 300°C to 500°C.

42. The method of any one of claims 27-41, wherein the first catalyst material has a temperature of 300°C to 500°C.

43. The method of any one of claims 27-42, wherein the second catalyst material has a temperature of 300°C to 500°C.

44. The method of any one of claims 27-43, wherein the gas mixture has an inlet pressure of from 5 psig to 100 psig.

45. The method of any one of claims 27-44, wherein the linear velocity of the gas mixture is 1 cm / sec to 1000 cm / sec, 2 cm / sec to 500 cm / sec, or 3 cm / sec to 300 cm / sec.

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