Acidified dehydration catalyst

Abstract

A catalyst and a method for producing the catalyst are provided. An exemplary catalyst is of the formula: Mo a V b Bi c M d O x This formula includes: In this formula, M is Ta or Nb, 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 required to make the catalyst electrically neutral. The values ​​of a, b, c, and d are determined based on the amount of each starting material used to form the catalyst. The catalysts provided herein may be suitable as catalysts in oxidative dehydrogenation reactions, such as the oxidative dehydrogenation of ethane.

Description

[Technical Field]

[0001] This disclosure generally relates to catalysts and catalytic materials for the oxidative dehydrogenation (ODH) of alkanes such as ethane. More specifically, the catalysts disclosed herein include molybdenum (Mo), vanadium (V), bismuth (Bi), tantalum (Ta), or niobium (Nb), or both, and oxygen (O). [Background technology]

[0002] Olefins such as ethylene, propylene, and butylene are fundamental building blocks of a variety of commercially valuable polymers. Since naturally occurring sources of olefins do not exist in commercial quantities, polymer producers rely on methods to convert more abundant lower alkanes into olefins. The method chosen by commercial-scale producers today is steam cracking. Steam cracking is a highly endothermic process that exposes hydrocarbons diluted with steam to temperatures of at least 600°C for a short period. The fuel demand to generate the required temperature and the need for equipment capable of withstanding that temperature significantly increases the overall cost. Furthermore, the high temperature promotes coke formation, which accumulates in the system, requiring costly periodic reactor shutdowns for maintenance and coke removal.

[0003] Selective oxidation processes, such as oxidative dehydrogenation (ODH), are exothermic alternatives to vapor cracking, producing little to no coke. In ODH, lower alkanes, such as ethane, are mixed with oxygen in the presence of a catalyst and optionally an inert diluent (e.g., carbon dioxide, nitrogen, or vapor), and reacted at a relatively low temperature of 300°C to produce the corresponding alkene. This process can produce a variety of other oxidation products, particularly carbon dioxide and acetic acid. ODH suffers from a lower conversion rate compared to vapor cracking, and this, combined with its low selectivity, may be hindering its commercial adoption. Catalysts for ethane ODH processes with high ethylene selectivity, activity, and long lifetime are needed. [Overview of the project]

[0004] Provided herein is a catalyst having the formula Mo 0.32 , 0.05 , 0.05 ,

[0006] , 0.31 , 0.31 , 0.33 , 0.05 , 0.03 , 0.31 , 0.32 , 0.05 , x , 0.04 , 0.05 , , x , , x , 0.06 , 0.04 , x , x , 0.05 V b Bi c M d O x where M is Ta or Nb or a mixture thereof, a is 1.0, b is from 0.01 to 0.5, c is from 0.005 to 0.2, d is from 0.005 to 0.1, and x is the number of oxygen atoms necessary to electrically neutralize the catalyst, and the values of a, b, c, and d are determined based on the amounts of each starting material used to form the catalyst. In some embodiments, the values of a, b, c, and d are also determined by elemental analysis.

[0005] In some embodiments, b is from 0.2 to 0.4, c is from as 0.01 to 0.07, and d is from 0.01 to 0.07. In some embodiments, b is from 0.30 to 0.35, c is from 0.04 to 0.05, and d is from 0.03 to 0.05. In some embodiments, b is from 0.2 to 0.3, c is from 0.05 to 0.07, and d is from 0.02 to 0.04. In some embodiments, b is from 0.3 to 0.4, c is from 0.05 to 0.07, and d is from 0.03 to 0.05.

[0006] In some embodiments, the catalyst is Mo1V 0.31 Bi 0.04 M 0.05 O x 0.31 Bi 0.05 M 0.05 O x 、Mo1V 0.31 Bi M 0.05 O<000;、Mo1V 0.32 Bi 0.05 M 0.05 O x 、Mo1V 0.32 Bi<000002;M 0.03 O x 、Mo1V 0.33Bi 0.05 M 0.04 O x Mo1V 0.26 Bi 0.06 M 0.03 O x Mo1V 0.33 Bi 0.06 M 0.04 O x , and Mo1V 0.26 Bi 0.05 M 0.05 O x It has an expression that is selected from.

[0007] In some embodiments, the catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x Mo1V 0.33 Bi 0.06 Ta 0.04 O x , and Mo1V 0.26 Bi 0.05 Ta 0.05 O x It has an expression that is selected from.

[0008] In some embodiments, the catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.05 Ta 0.05 O x , and Mo1V 0.26 Bi 0.06 Ta 0.03 O xhaving a formula selected from, the formula being determined by energy dispersive X-ray spectroscopy (EDX).

[0009] In some embodiments, the pore volume of the catalyst determined by nitrogen physisorption analysis using the Barrett-Joyner-Halenda (BJH) model is 0.02 cm 3 / g to 0.25 cm 3 / g.

[0010] In some embodiments, the pore volume of the catalyst determined by nitrogen physisorption analysis using the Barrett-Joyner-Halenda (BJH) model is 0.1 cm 3 / g to 0.2 cm 3 / g.

[0011] In some embodiments, the catalyst has a Brunauer-Emmett-Teller (BET) surface area of 5 m 2 / g to 60 m 2 / g determined by nitrogen physisorption analysis.

[0012] In some embodiments, the catalyst has a Brunauer-Emmett-Teller (BET) surface area of 10 m 2 / g to 25 m 2 / g determined by nitrogen physisorption analysis.

[0013] The present disclosure also provides a catalyst material.In some embodiments, the catalyst material includes the catalyst described herein and a catalyst support or carrier.In some embodiments, the catalyst support or carrier is selected from the group consisting of precipitated synthetic silica, fumed synthetic silica, silica-alumina, α-alumina, γ-alumina, titania, WO3-ZrO2, silicon carbide, MgAl spinel, calcium aluminate, zirconia, and boron nitride.In some embodiments, the catalyst support or carrier is α-alumina.

[0014] In some embodiments, the catalyst has at least 90% ethylene selectivity at an ethane conversion rate of at least 45% in the oxidative dehydrogenation reaction of ethane.

[0015] In some embodiments, the catalyst has a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane. In some embodiments, the catalyst has a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

[0016] In some embodiments, the catalyst material has at least 90% ethylene selectivity at an ethane conversion rate of at least 45% in the oxidative dehydrogenation reaction of ethane. In some embodiments, the catalyst material has a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane. In some embodiments, the catalyst material has a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

[0017] The present disclosure also provides a method for preparing a catalyst. The method includes forming a slurry containing a metal oxide, a bismuth compound, a reducing agent, and water, and heating the slurry to form a catalyst. Examples of the metal oxide include molybdenum oxide, vanadium oxide, and tantalum oxide or niobium oxide or both. Examples of the bismuth compound include bismuth oxide, bismuth hydroxide, or bismuth carbonate.

[0018] In some embodiments, the ratio of water in the slurry to the amount of the formed catalyst is in the range between 0.1 mL of water per gram of catalyst and 10 mL of water per gram of catalyst. In some embodiments, the ratio of water in the slurry to the amount of the formed catalyst is in the range between 0.2 mL of water per gram of catalyst and 1 mL of water per gram of catalyst.

[0019] In some embodiments, the slurry has a water-to-metal oxide ratio ranging from 0.2 mL of water per gram of metal oxide to 0.6 mL of water per gram of metal oxide. In some embodiments, the slurry has a water-to-metal oxide ratio ranging from 0.3 mL of water per gram of metal oxide to 0.5 mL of water per gram of metal oxide.

[0020] In some embodiments, the molybdenum oxide is MoO3.

[0021] In some embodiments, the vanadium oxide is V2O5.

[0022] In some embodiments, if tantalum oxide is present, it is Ta2O5·xH2O, and if niobium oxide is present, it is Nb2O5·xH2O.

[0023] In some embodiments, the bismuth compound is bismuth hydroxide.

[0024] In some embodiments, the method further includes grinding, wet milling, dry milling, or crushing the metal oxide and bismuth compound. In some embodiments, the method further includes grinding, wet milling, dry milling, or crushing the reducing agent.

[0025] In some embodiments, the reducing agent comprises an alcohol, a carboxylic acid, or an ester. In some embodiments, the reducing agent is oxalic acid. In some embodiments, the slurry comprises one or less reducing agents.

[0026] In some embodiments, the method includes heating the slurry by increasing the temperature from ambient temperature to a temperature of 100°C to 200°C over a heating-up time of 2 hours to 48 hours, and maintaining the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 hours to 160 hours.

[0027] In some embodiments, the method includes heating the slurry by increasing the temperature from ambient temperature to a temperature of 100°C to 200°C over a heating-up time of 2 hours to 48 hours, and maintaining the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 hours to 120 hours.

[0028] In some embodiments, the method further includes washing the catalyst with water.

[0029] In some embodiments, the method further includes firing the catalyst to form a fired catalyst. In some embodiments, the method includes firing the catalyst by disposing the catalyst in a furnace in an oxygen-free environment, increasing the temperature of the furnace from ambient temperature to a temperature of 500°C to 620°C over a heating-up time of 2 hours to 10 hours, and maintaining the temperature of the furnace at a holding temperature of 500°C to 620°C for a holding time of 1 hour to 10 hours.

[0030] In some embodiments, the metal oxide and the bismuth compound each have a particle size distribution in the range of 0.5 μm to 250 μm.

[0031] In some embodiments, the ratio of the total amount of water used to prepare the catalyst is in the range between 0.2 mL of water per gram of catalyst and 25 mL of water per gram of catalyst.

[0032] The present disclosure also provides a process for oxidative dehydrogenation of ethane. The process includes contacting a gaseous feed comprising ethane and oxygen with a catalyst in a reactor to produce an effluent comprising ethylene, the catalyst having the formula Mo a V b Bic M d O x has a, where M is Ta or Nb or a mixture thereof, a is 1.0, b is from 0.01 to 0.5, c is from 0.005 to 0.2, d is from 0.005 to 0.1, and x is the number of oxygen atoms necessary to render the catalyst electrically neutral, and a, b, c, and d are determined based on the amounts of each starting material used to form the catalyst. In some embodiments, the values of a, b, c, and d are also determined by elemental analysis.

[0033] In some embodiments, the catalyst has a formula selected from 0.31 Bi 0.04 M<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​0.26 Bi 0.06 Ta 0.03 O x 、 Mo1V 0.31 Bi 0.06 Ta 0.01 O x 、 Mo1V 0.33 Bi 0.06 Ta 0.04 O x 、 and Mo1V 0.26 Bi 0.05 Ta 0.05 O x and has a formula selected from the following.

[0034] In some embodiments, the catalyst is included in a catalyst material, and the catalyst material includes a catalyst support or carrier. In some embodiments, the catalyst support or carrier is α-alumina.

[0035] In some embodiments, the oxidative dehydrogenation process of ethane has a 45% ethane conversion temperature in the range of 300°C to 420°C. In some embodiments, the oxidative dehydrogenation process of ethane has a 45% ethane conversion temperature in the range of 350°C to 400°C.

[0036] In some embodiments, the oxidative dehydrogenation process of ethane further includes converting ethane to a product. In some embodiments, the product is polyethylene selected from ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

Brief Description of the Drawings

[0037] [Figure 1] Powder X-ray diffraction (PXRD) pattern of Comparative Sample 1C. [Figure 2] PXRD pattern of Example 2E. [Figure 3] PXRD pattern of Example 3E. <关于专利文本的翻译,需要注意的是,专利文本通常具有专业性和准确性要求,因此在翻译过程中需要严格遵循相关的术语和规范。对于一些特定的化学元素、化合物、技术术语等,应尽量使用准确的专业词汇进行翻译。同时,要保持原文的逻辑结构和表达顺序,确保翻译后的文本能够准确传达原文的含义。]] [Figure 4] PXRD pattern of Example 4E. [Figure 5] This is a superposition of PXRD patterns of unfired, fired, and pelletized and fired Example 5E. [Figure 6] This is the PXRD pattern for Example 6E. [Figure 7] This is the PXRD pattern for Example 7E. [Figure 8] This is a superimposition of the PXRD patterns of Example 8E before and after firing. [Figure 9] This is a superimposition of the PXRD patterns of Example 9E before and after firing. [Figure 10] This is the PXRD pattern of Example 11E before firing. [Figure 11] The scanning electron microscope (SEM) image of Example 2E is shown. [Figure 12] The SEM image of Example 4E is shown. [Figure 13] The SEM image of Example 5E is shown. [Figure 14] The SEM image of Example 11E is shown. [Figure 15] The Barrett-Joyner-Halenda (BJH) plot of pore volume for Example 9E is shown. [Figure 16] This is a plot of nitrogen physicoadsorption for Example 9E. [Figure 17] This is a plot of the ethane conversion rate (%) for comparative sample 1C and example 4E. [Figure 18] This is a plot of the selectivity for ethylene production in comparative sample 1C and example 4E. [Figure 19] This is a plot of the long-term ODH performance of catalyst 5E (pellet form). [Modes for carrying out the invention]

[0038] Hereinafter, specific embodiments of the disclosed subject matter will be described in detail, examples of which are partially shown in the accompanying drawings. The disclosed subject matter will be described in conjunction with the enumerated claims, but it will be understood that the illustrated subject matter is not intended to limit the claims.

[0039] Selective oxidation (SO) is commonly used in oxidative dehydrogenation (ODH) reactions to produce alpha-olefins from corresponding alkanes, such as ethylene from ethane. Provided in this disclosure are oxidative dehydrogenation catalysts comprising molybdenum (Mo), vanadium (V), bismuth (Bi), tantalum (Ta), or niobium (Nb), or both, and oxygen. The disclosure also provides a method for synthesizing bismuth-doped catalysts according to this disclosure, for use, for example, in ODH processes.

[0040] In the method for preparing the catalysts provided herein, catalyst precursor powders are mixed, for example, by grinding, and then used in a hydrothermal synthesis process to form the catalyst. Conventional ODH catalysts have contained tellurium or antimony as dopants. However, bismuth is less toxic than tellurium or antimony. Furthermore, in the embodiments of the catalysts described herein, bismuth-doped catalysts combine high activity in the oxidative dehydrogenation of ethane with high ethylene selectivity.

[0041] Furthermore, in the embodiments of the catalyst preparation method described herein, a smaller amount of water is used, and the amount of heavy metal-contaminated waste generated during synthesis is significantly reduced.

[0042] Furthermore, the method provided herein does not require the complex mixing or grinding steps reported in conventional synthesis procedures for the relevant MoVNbTe oxides. The method provided herein achieves significant cost reductions and simplification compared to previously reported synthesis procedures.

[0043] As used herein, the term “catalyst” generally refers to the active portion of a catalytic material capable of promoting oxidative dehydrogenation, such as the oxidative dehydrogenation of ethane to ethylene. The catalyst may be further processed to form a catalytic material. The catalytic material may also be further processed to form a final catalytic material.

[0044] The catalyst provided herein is of the formula Mo a V bBi c M d O x It is represented by the formula, where M is Ta or Nb or a mixture thereof. In some embodiments, the catalyst is Mo a V b Bi c Ta d O x , and Mo a V b Bi c Nb d O x The formula has a selection from the following. The values ​​a, b, c, and d may refer to values ​​based on the amount of each starting material used to form the catalyst, for example, values ​​based on the respective amounts of metal oxides and bismuth compounds added to the slurry to prepare the catalyst. The values ​​a, b, c, and d may also refer to values ​​measured by elemental analysis such as inductively coupled plasma mass spectrometry (ICP-MS), neutron activation spectrometry (NAA), X-ray fluorescence spectrometry (XRF), ion chromatography-mass spectrometry (IC-MS), proton-excited X-ray spectrometry (PIXE), and energy-dispersive X-ray spectrometry (EDX). Alternatively, if specified, the values ​​a, b, c, and d may refer only to values ​​determined by elemental analysis such as ICP-MS, NAA, XRF, IC-MS, PIXE, or EDX.

[0045] The catalytic chemical formula can be selected in relation to the ratios of values ​​a, b, c, and d to affect the catalytic activity, selectivity, purity, and stability. In some embodiments, the value of d is minimized to reduce costs while maintaining good catalytic performance.

[0046] In some embodiments, a is 1.0.

[0047] 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 0.25 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 0.3. 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.

[0048] 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 0.06. In some embodiments, c is 0.06. In some embodiments, c is 0.05. In some embodiments, c is 0.04.

[0049] In some embodiments, d is 0.005 to 0.1. In some embodiments, d is 0.01 to 0.10. 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 0.05. In some embodiments, d is 0.03. In some embodiments, d is 0.04. In some embodiments, d is 0.05.

[0050] Each catalyst formulation according to this disclosure contains an amount of oxygen sufficient to electrically neutralize the catalyst. Those skilled in the art will understand that oxygen-containing species can also be adsorbed or captured by the catalyst.

[0051] In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the values ​​of a, b, c, and d as described herein. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the following properties: a is 1.0, b is 0.01 to 0.5, c is 0.005 to 0.2, and d is 0.005 to 0.1. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the following properties: a is 1.0, b is 0.2-0.4, c is 0.01-0.07, and d is 0.01-0.07. In some embodiments, the catalyst is of the formula Mo a Vb Bi c Ta d O x The formula has the following properties: a is 1.0, b is 0.2-0.4, c is 0.01-0.07, and d is 0.01-0.05. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the following properties: a is 1.0, b is 0.2-0.4, c is 0.04-0.06, and d is 0.03-0.05. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the following properties: a is 1.0, b is 0.3-0.4, c is 0.03-0.08, and d is 0.03-0.06. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has a coefficient of 1.0, b is 0.2-0.4, c is 0.04-0.06, and d is 0.02-0.05. In some embodiments, the catalyst is of the formula Mo a V b Bi c Ta d O x The formula has the following values: a = 1.0, b = 0.30 to 0.35, c = 0.04 to 0.06, and d = 0.03 to 0.05.

[0052] In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has the values ​​of a, b, c, and d as described herein. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O xThe formula has the following properties: a is 1.0, b is 0.01 to 0.5, c is 0.005 to 0.2, and d is 0.005 to 0.1. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has the following properties: a is 1.0, b is 0.2-0.4, c is 0.01-0.07, and d is 0.01-0.07. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has the following properties: a is 1.0, b is 0.1 to 0.5, c is 0.01 to 0.1, and d is 0.05 to 0.1. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has a coefficient of 1.0, b is 0.2-0.4, c is 0.04-0.06, and d is 0.02-0.05. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has the following values: a is 1.0, b is 0.30-0.40, c is 0.03-0.8, and d is 0.03-0.06. In some embodiments, the catalyst is of the formula Mo a V b Bi c Nb d O x The formula has the following characteristics, where a is 1.0, b is 0.30-0.35, c is 0.04-0.05, and d is 0.03-0.05.

[0053] 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 respective amounts (molar equivalents) of the metal oxide and bismuth compound added to the slurry. In some embodiments, the catalyst is of the formula Mo1V 0.31 Bi 0.05 M 0.05The catalyst has O, and this formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst is of the formula Mo1V 0.31 Bi 0.05 Ta 0.05 The catalyst has O, and this formula is determined based on the amount of each starting material used to form the catalyst. In some embodiments, the catalyst is of the formula Mo1V 0.31 Bi 0.05 Nb 0.05 It contains O, and this formula is determined based on the amount of each starting material used to form the catalyst.

[0054] In some embodiments, the values ​​of a, b, c, and d are determined by elemental analysis such as energy-dispersive X-ray spectroscopy (EDX). In some embodiments, the catalyst is Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.33 Bi 0.06 Ta 0.04 O x , and Mo1V 0.26 Bi 0.05 Ta 0.05 O x The catalyst has a formula selected from, which is determined by EDX. In some embodiments, the catalyst has a formula Mo1V 0.32 Bi 0.04 Ta 0.03 O x It has the formula Mo1V, which is determined by EDX. In some embodiments, the catalyst is of the formula Mo1V 0.33 Bi 0.05 Ta 0.04 O x It has the formula Mo1V, which is determined by EDX. In some embodiments, the catalyst is of the formula Mo1V 0.26 Bi 0.06 Ta 0.03 O xIt has the formula Mo1V, which is determined by EDX. In some embodiments, the catalyst is of the formula Mo1V 0.33 Bi 0.06 Ta 0.04 O x It has the formula Mo1V, which is determined by EDX. In some embodiments, the catalyst is of the formula Mo1V 0.26 Bi 0.05 Ta 0.05 O x It has the formula Mo1V, which is determined by EDX. In some embodiments, the catalyst is of the formula Mo1V 0.32 Bi 0.04 Ta 0.03 O x This formula has a value that is determined by EDX.

[0055] In some embodiments, the catalyst is located at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, and 31.3°±0.2°. The PXRD pattern is characterized by having at least five powder X-ray diffraction peaks (2θ) selected from °, 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°, and is obtained using CuKα radiation.

[0056] In some embodiments, the catalyst is located at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±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°, 29.1°±0.2°, 31.3°±0.2°, and 35.2°±0.2°. The PXRD pattern is characterized by having at least five powder X-ray diffraction peaks (2θ) selected from 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°, and is obtained using CuKα radiation.

[0057] In some embodiments, the catalyst is located at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, and 31.3°±0.2°. The PXRD pattern is characterized by having at least 10 powder X-ray diffraction peaks (2θ degrees) selected from 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°, and is obtained using CuKα radiation.

[0058] In some embodiments, the catalyst is located at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±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°, 29.1°±0.2°, 31.3°±0.2°, 35.2°±0.2°, The PXRD pattern is characterized by having at least 10 powder X-ray diffraction peaks (2θ degrees) selected from 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°, and is obtained using CuKα radiation.

[0059] In some embodiments, the catalyst is at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, The PXRD pattern is characterized by having at least 15 powder X-ray diffraction peaks (2θ degrees) selected from 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°, and is obtained using CuKα radiation.

[0060] In some embodiments, the catalyst is located at 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±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°, 29.1°±0.2°, 31.3°±0.2°, 35.2°±0.2°, The PXRD pattern is characterized by having at least 15 powder X-ray diffraction peaks (2θ degrees) selected from 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°, and is obtained using CuKα radiation.

[0061] In some embodiments, the catalyst is characterized by having at least five powder X-ray diffraction peaks (2θ degrees) selected from 7.8±0.2°, 22.2±0.2°, 26.7±0.2°, 27.1±0.2°, 29.1±0.2°, 35.2±0.2°, 45.3±0.2°, and 48.5±0.2°, and the PXRD pattern is obtained using CuKα radiation.

[0062] In some embodiments, the catalyst is characterized by having powder X-ray diffraction peaks (2θ degrees) at 7.8±0.2°, 22.2±0.2°, 27.1±0.2°, 35.2±0.2°, and 45.3±0.2°, and the PXRD pattern is obtained using CuKα radiation.

[0063] In some embodiments, the PXRD includes a peak (2θ degrees) corresponding to MoO3 that may be unreacted.

[0064] In some embodiments, the catalyst has a Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis of 5 m². 2 / g~60m 2 / g, 5m 2 / g~50m 2 / g, 5m 2 / g~40m 2 / g, 5m 2 / g~30m 2 / g, 5m 2 / g~25m 2 / g, 5m 2 / g~20m 2 / g, 5m 2 / g~15m 2 / g, or 5m 2 / g~10m 2 The value is / g. In some embodiments, the catalyst has a BET surface area determined by nitrogen physicoadsorption analysis of 10 m². 2 / g~40m 2 / g, 10m 2 / g~30m 2 / g, 10m 2 / g~25m 2 / g, or 10m 2 / g~20m 2 The value is / g. In some embodiments, the catalyst is calcined and the BET surface area, determined by nitrogen physicoadsorption analysis, is 10 m². 2 / g, 11m 2 / g, 12m 2 / g, 13m 2 / g, 14m 2 / g, 15m 2 / g, 16m 2 / g, 17m 2 / g, 18m 2 / g, 19m 2 / g, or 20m 2 The value is / g. In some embodiments, the catalyst is uncalcined, and the BET surface area determined by nitrogen physicoadsorption analysis is 50m². 2 / g, 51m 2 / g, 52m 2 / g, 53m 2 / g, 54m 2 / g, 55m 2 / g, 56m 2 / g, 57m 2 / g, 58m 2 / g, 59m 2 / g, or 60m 2 It is / g.

[0065] In some embodiments, the catalyst has a pore volume of 0.02 cm³, as determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda (BJH) model. 3 / g~0.25cm 3 The value is / g. In some embodiments, the catalyst has a pore volume of 0.02–0.2 cm³, as determined by nitrogen physicoadsorption analysis using the BJH model. 3 The value is / g. In some embodiments, the catalyst has a pore volume of 0.05 cm³, as determined by nitrogen physicoadsorption analysis using the BJH model. 3 / g~0.2cm 3 / g, 0.05cm 3 / g~0.15cm 3 / g, or 0.05cm 3 / g~0.1cm 3 The value is / g. In some embodiments, the catalyst has a pore volume of 0.02 cm³, as determined by nitrogen physicoadsorption analysis using the BJH model. 3 / g, 0.03cm 3 / g, 0.04cm 3 / g, 0.05cm 3 / g, 0.06cm 3 / g, 0.07cm 3 / g, 0.08cm 3 / g, 0.09cm 3 / g, 0.1cm 3 / g, 0.11cm 3 / g, 0.12cm 3 / g, 0.13cm 3 / g, 0.14cm 3 / g, 0.15cm 3 / g, 0.16cm 3 / g, 0.17cm 3 / g, 0.18cm 3 / g, 0.19cm 3 / g, or 0.2cm 3 It is / g.

[0066] In some embodiments, the catalyst is Mo a V b Bi c Ta d O xThe formula is as follows (where 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 required to make the catalyst electrically neutral): The pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.02 cm³. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 5m². 2 / g~60m 2 The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0067] In some embodiments, the catalyst is Mo a V b Bi c Ta d O x The formula is given by (where a is 1.0, b is 0.01 to 0.5, c is 0.005 to 0.2, and d is 0.005 to 0.1, where a, b, c, and d are determined by energy-dispersive X-ray spectroscopy, and x is the number of oxygen atoms required to make the catalyst electrically neutral), and the pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.02 cm³. 3 / g~0.25cm 3The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 5m². 2 / g~60m 2 The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0068] In some embodiments, the catalyst is Mo a V b Bi c Nb d O x The formula is as follows (where 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 required to make the catalyst electrically neutral): The pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.02 cm³. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 5m². 2 / g~60m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0069] In some embodiments, the catalyst is Mo a V b Bi c Nb d O x The formula is given by (where a is 1.0, b is 0.01 to 0.5, c is 0.005 to 0.2, and d is 0.005 to 0.1, where a, b, c, and d are determined by energy-dispersive X-ray spectroscopy, and x is the number of oxygen atoms required to make the catalyst electrically neutral), and the pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.02 cm³. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 5m². 2 / g~60m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0070] In some embodiments, the catalyst is Mo a V b Bi c Ta d O x The formula is given by (where a is 1.0, b is 0.3-0.4, c is 0.05-0.7, d is 0.03-0.05, and x is the number of oxygen atoms required to make the catalyst electrically neutral), and the pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.1 cm³. 3 / g~0.2cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 10m². 2 / g~25m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0071] In some embodiments, the catalyst is Mo a V b Bi c Nb d O x The formula is given by (where a is 1.0, b is 0.3-0.4, c is 0.05-0.7, d is 0.03-0.05, and x is the number of oxygen atoms required to make the catalyst electrically neutral), and the pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model is 0.1 cm³. 3 / g~0.2cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 10m². 2 / g~25m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0072] In some embodiments, the catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x , and Mo1V 0.33 Bi 0.06 Ta 0.04 O x The formula selected from (where x is the number of oxygen atoms required to make the catalyst electrically neutral) has a pore volume of 0.1 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.2cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 10m². 2 / g~25m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0073] In some embodiments, the catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Nb 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x , and Mo1V 0.33 Bi 0.06 Ta 0.04 O x The formula selected from (where x is the number of oxygen atoms required to make the catalyst electrically neutral) has a pore volume of 0.1 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.2cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 10m². 2 / g~25m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 35 It has at least 10 powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 0.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0074] In some embodiments, the catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Nb 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x , and Mo1V 0.33 Bi 0.06 Ta 0.04 O x The formula selected from (where x is the number of oxygen atoms required to make the catalyst electrically neutral) has a pore volume of 0.1 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.15cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 15m². 2 / g~18m 2The values ​​are / g, and the catalyst is 6.6°±0.2°, 7.8°±0.2°, 8.9°±0.2°, 10.7°±0.2°, 12.7°±0.2°, 13.9°±0.2°, 22.2°±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°, 29.1°±0.2°, 31.3°±0.2°, 3 It has at least five powder X-ray diffraction (PXRD) peaks (2θ degrees) selected from 5.2°±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°, where the PXRD pattern is obtained using CuKα radiation.

[0075] Furthermore, this specification also provides catalytic materials, which include a catalyst such as the catalyst of this disclosure and a catalyst support or carrier. As used herein, the term “catalytic material” refers to a material comprising an active catalyst capable of promoting the oxidative dehydrogenation of ethane to ethylene. The catalytic material may consist substantially of a catalyst. The catalytic material may be a plurality of particles or a formed catalytic material. Non-limiting examples of formed catalytic materials include extruded catalytic materials, 3D printed catalytic materials, spheroidized catalytic materials, compression-molded catalytic materials, and cast catalytic materials. Non-limiting examples of compression-molded and cast catalytic materials include pellets such as tablets, elliptical or spherical particles. A binder may be used to assist in the formation of the catalytic material. The formation of the catalytic material may include optional work-up steps such as de-bindering, calcination / sintering, and / or activation / pretreatment. Work-up steps may be introduced to prepare the catalytic material to be loaded into the reactor, to achieve the expected productivity, and to mitigate unexpected thermal runaway during startup.

[0076] Some supports or carriers are particularly suitable for catalytic materials, for example, because they are chemically compatible (e.g., they have virtually no effect on ethylene selectivity, or even improve it). Other supports may be less compatible and could lead to a significant decrease in catalytic performance (e.g., ethylene selectivity). Therefore, not any support can be selected, and careful selection is necessary based on both short-term and long-term catalytic performance testing. In some embodiments, long-term testing is emphasized to demonstrate no decrease in selectivity with uptime (e.g., TOS > 48 hours). As used herein, “uptime (TOS)” refers to the time the catalytic material is spent in the ODH process without interruption.

[0077] In some embodiments, the catalyst support or carrier is at least one of precipitated synthetic silica, fumed synthetic silica, silica-alumina, α-alumina, γ-alumina, titania, WO3-ZrO2, silicon carbide, MgAl spinel, calcium aluminate, zirconia, and boron nitride. In some embodiments, the catalyst support or carrier is selected from the group consisting of precipitated synthetic silica, fumed synthetic silica, silica-alumina, α-alumina, and anatase-type titania. In some embodiments, the catalyst support or carrier is α-alumina.

[0078] In some embodiments, the catalyst material comprises 1% to 80% by weight, 10% to 70% by weight, 20% to 60% by weight, 30% to 60% by weight, or 40% to 60% by weight of the catalyst support or carrier. In some embodiments, the catalyst material comprises 45% to 55% by weight, or 50% by weight of the catalyst support or carrier.

[0079] In some embodiments, the catalyst material includes a lubricant. Non-limiting examples of suitable lubricants include graphite, hexagonal boron nitride, calcium carbonate, fatty acids, fatty acid salts, methylcellulose, polyvinyl alcohol, calcium carbonate, stearates (e.g., magnesium stearate), polyethylene glycol (PEG), glycerol, propylene glycol, or any combination thereof. In some embodiments, the lubricant includes graphite, hexagonal boron nitride, calcium carbonate, fatty acids, fatty acid salts, or any combination thereof. In some embodiments, the lubricant includes graphite.

[0080] In some embodiments, the catalyst material includes a binder. Non-limiting examples of 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 polybutadiene emulsion. Examples of organic binders include, but are not limited to, starch, lignosulfonates, cellulose, cellulose-derived powders (e.g., PERIDUR®), microcrystalline cellulose powders (e.g., AVICEL®), polyethylene glycol, polyvinyl acetate, polyvinyl alcohol (e.g., MOWIOL® 8-88), polyacrylic acid, other synthetic polymers (e.g., ALCOTAC®), and modified starch brewing by-products (e.g., Brewex). In some embodiments, the starch is corn 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 substances.

[0081] In some embodiments, the binder comprises one or more liquid binders, organic binders, and inorganic binders. In some embodiments, the binder comprises water and at least one binder other than water. In some embodiments, the binder comprises polyethylene glycol, polyacrylic acid, and polyvinyl alcohol. In some embodiments, the catalyst material comprises one or more binders in amounts of 0.1% to 30% by weight, 0.5% to 20% by weight, or 1% to 10% by weight.

[0082] In some embodiments, the catalyst material has an axial compressive strength of 50N to 195N when measured using ASTM D4149-22. In some embodiments, the catalyst material has an axial compressive strength of 100N to 170N when measured using ASTM D4149-22. In some embodiments, the catalyst material has an axial compressive strength of 160N to 170N when measured using ASTM D4149-22.

[0083] In some embodiments, the catalyst material has a radial compressive strength of 80N to 120N when measured using ASTM D4149-22. In some embodiments, the catalyst material has a radial compressive strength of 90N to 110N when measured using ASTM D4149-22. In some embodiments, the catalyst material has a radial compressive strength of 95N to 105N when measured using ASTM D4149-22.

[0084] In some embodiments, the catalyst material has a bulk density of 1.2 g / cm³ as measured using ASTM D3766. 3 ~1.7g / cm 3 In some embodiments, the catalyst has a bulk density of 1.4 g / cm³ as measured using ASTM D3766. 3 ~1.6g / cm 3 In some embodiments, the catalyst material has a bulk density of 1,500 g / cm³ as measured using ASTM D3766. 3 ~1.570g / cm 3 That is the case.

[0085] In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area of ​​2 m² as determined by nitrogen physicoadsorption analysis. 2 / g~10m 2 / g, 3m 2 / g~10m 2 / g, 4m 2 / g~8m 2 / g, 5m 2 / g~8m 2 / g, or 5m 2 / g~6m 2 The value is / g. In some embodiments, the catalyst material has a Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis of 5 m². 2 It is / g.

[0086] In some embodiments, the catalyst material has a pore volume of 0.01 cm³, as determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda (BJH) model. 3 / g~0.25cm 3 The value is / g. In some embodiments, the catalyst material has a pore volume of 0.02 cm³, determined by nitrogen physicoadsorption analysis using the BJH model. 3 / g~0.2cm 3 The value is / g. In some embodiments, the catalyst material has a pore volume of 0.05 cm³, determined by nitrogen physicoadsorption analysis using the BJH model. 3 / g~0.2cm 3 / g, 0.05cm 3 / g~0.15cm 3 / g, or 0.05cm 3 / g~0.1cm 3 The value is / g. In some embodiments, the catalyst has a pore volume of 0.02 cm³, as determined by nitrogen physicoadsorption analysis using the BJH model. 3 / g, 0.03cm 3 / g, 0.04cm 3 / g, 0.05cm 3 / g, 0.06cm 3 / g, 0.07cm 3 / g, 0.08cm3 / g, 0.09cm 3 / g, or 0.10cm 3 It is / g.

[0087] In some embodiments, the catalyst material has a BET surface area of ​​5 m². 2 / g, pore volume of 0.02 cm³ 3 This indicates that the pellet is a non-porous pellet, as indicated by the weight per gram.

[0088] In some embodiments, the catalyst material has a drop strength such that at least 80% of the pellets remain intact, as measured using ASTM D8353-20. In some embodiments, the catalyst material has a drop strength such that at least 85% of the pellets remain intact, as measured using ASTM D8353-20. In some embodiments, the catalyst material has a drop strength such that at least 90% of the pellets remain intact, as measured using ASTM D8353-20. In some embodiments, the catalyst material has a drop strength such that at least 95% of the pellets remain intact, as measured using ASTM D8353-20.

[0089] In some embodiments, the catalyst material comprises a carrier or support and Mo a V b Bi c Ta d O x The catalyst comprises a catalyst having the formula (wherein 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 required to make the catalyst electrically neutral), wherein the catalyst material has an axial compressive strength of 50 N to 195 N as measured using ASTM D4149-22, a radial compressive strength of 80 N to 120 N as measured using ASTM D4149-22, and a drop strength of at least 80% of the pellets remaining intact as measured using ASTM D8353-20.

[0090] In some embodiments, the catalyst material comprises a carrier or support and Mo a Vb Bi c Ta d O x The catalyst comprises a catalyst having the formula (where 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 required to make the catalyst electrically neutral), and the catalyst material has a pore volume of 0.01 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 2m². 2 / g~10m 2 The value is / g, and the bulk density measured using ASTM D3766 is 1.2 g / cm³. 3 ~1.7g / cm 3 That is the case.

[0091] In some embodiments, the catalyst material comprises a carrier or support and Mo a V b Bi c Ta d O x The catalyst comprises a catalyst having the formula (where 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 required to make the catalyst electrically neutral), the catalyst material having an axial compressive strength of 50 N to 195 N when measured using ASTM D4149-22, a radial compressive strength of 80 N to 120 N when measured using ASTM D4149-22, and a pore volume of 0.01 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 2m². 2 / g~10m 2 The value is / g, and the bulk density measured using ASTM D3766 is 1.2 g / cm³. 3 ~1.7g / cm 3Therefore, it has a drop strength such that at least 80% of the pellets remain intact when measured using ASTM D8353-20.

[0092] In some embodiments, the catalyst material comprises a carrier or support and Mo a V b Bi c Nb d O x The catalyst comprises a catalyst having the formula (wherein 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 required to make the catalyst electrically neutral), wherein the catalyst material has an axial compressive strength of 50 N to 195 N as measured using ASTM D4149-22, a radial compressive strength of 80 N to 120 N as measured using ASTM D4149-22, and a drop strength of at least 80% of the pellets remaining intact as measured using ASTM D8353-20.

[0093] In some embodiments, the catalyst material comprises a carrier or support and Mo a V b Bi c Nb d O x The catalyst comprises a catalyst having the formula (where 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 required to make the catalyst electrically neutral), and the catalyst material has a pore volume of 0.01 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 2m². 2 / g~10m 2 The value is / g, and the bulk density measured using ASTM D3766 is 1.2 g / cm³. 3 ~1.7g / cm 3 That is the case.

[0094] In some embodiments, the catalyst material comprises a carrier or support and Mo a V b Bi c Nb d O x The catalyst comprises a catalyst having the formula (where 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 required to make the catalyst electrically neutral), the catalyst material having an axial compressive strength of 50 N to 195 N when measured using ASTM D4149-22, a radial compressive strength of 80 N to 120 N when measured using ASTM D4149-22, and a pore volume of 0.01 cm³ determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda model. 3 / g~0.25cm 3 The value is / g, and the Brunauer-Emmett-Teller surface area determined by nitrogen physicoadsorption analysis is 2m². 2 / g~10m 2 The value is / g, and the bulk density measured using ASTM D3766 is 1.2 g / cm³. 3 ~1.7g / cm 3 Therefore, it has a drop strength such that at least 80% of the pellets remain intact when measured using ASTM D8353-20.

[0095] Furthermore, this specification also provides a method for preparing a catalyst, comprising forming a slurry containing a metal oxide, a bismuth compound, a reducing agent, and water, and heating the slurry to form a catalyst. Examples of metal oxides include molybdenum oxide, vanadium oxide, and tantalum oxide or niobium oxide, or both. In some embodiments, examples of metal oxides include molybdenum oxide, vanadium oxide, and tantalum oxide. In some embodiments, examples of metal oxides include molybdenum oxide, vanadium oxide, and niobium oxide. In some embodiments, the molybdenum oxide is MoO3. In some embodiments, the vanadium oxide is V2O5. In some embodiments, if tantalum oxide is present, it is Ta2O5·xH2O, and if niobium oxide is present, it is Nb2O5·xH2O.

[0096] Bismuth compounds include bismuth oxide, bismuth hydroxide, or bismuth carbonate. As used herein, the term "bismuth carbonate" includes basic bismuth carbonates and bismuth oxide carbonates (bismuth carbonates). Examples of bismuth carbonate include basic bismuth carbonate or bismuth carbonate ((BiO)2CO3). In some embodiments, the bismuth compound is bismuth hydroxide.

[0097] A method for preparing a catalyst disclosed herein involves forming a slurry comprising a metal oxide, a bismuth compound, a reducing agent, and water. As used herein, the term “slurry” refers to a mixture of solids in a liquid and includes suspensions, pastes (i.e., mixtures that are viscous enough that they cannot move freely), or colloidal solutions.

[0098] In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is in the range of 0.1 ml to 10 ml of water per gram of catalyst. As used herein, the term “water in 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 used after the reaction. For example, “water in slurry” does not include water present in the hydrothermal synthesis vessel for heat transfer and / or maintenance of a humid atmosphere, or water used to wash the catalyst.

[0099] As used herein, “water” may refer to deionized water, distilled water, etc. In some embodiments, water is distilled water. In some embodiments, water is distilled deionized water. In some embodiments, the water may contain high levels of contaminants without harming the catalyst.

[0100] In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is in the range of 0.1 ml to 5 ml of water per gram of catalyst, for example, between 0.1 ml to 4 ml of water per gram of catalyst, between 0.1 ml to 3 ml of water per gram of catalyst, between 0.1 ml to 2 ml of water per gram of catalyst, between 0.1 ml to 1 ml of water per gram of catalyst, or between 0.1 ml to 0.5 ml of water per gram of catalyst. In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is in the range of 0.2 ml to 1 ml of water per gram of catalyst. In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is in the range of 0.3 ml to 0.5 ml of water per gram of catalyst.

[0101] In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is 0.1 ml of water per gram of catalyst, 0.2 ml of water per gram of catalyst, 0.3 ml of water per gram of catalyst, 0.4 ml of water per gram of catalyst, 0.5 ml of water per gram of catalyst, 0.6 ml of water per gram of catalyst, 0.7 ml of water per gram of catalyst, 0.8 ml of water per gram of catalyst, 0.9 ml of water per gram of catalyst, 1 ml of water per gram of catalyst, 2 ml of water per gram of catalyst, 3 ml of water per gram of catalyst, 4 ml of water per gram of catalyst, and 5 ml of water per gram of catalyst.

[0102] In some embodiments, the ratio of water in the slurry to the amount of catalyst formed is 0.25 ml of water per gram of catalyst, 0.26 ml of water per gram of catalyst, 0.27 ml of water per gram of catalyst, 0.28 ml of water per gram of catalyst, 0.29 ml of water per gram of catalyst, 0.30 ml of water per gram of catalyst, 0.31 ml of water per gram of catalyst, 0.32 ml of water per gram of catalyst, 0.33 ml of water per gram of catalyst, 0.34 ml of water per gram of catalyst, 0.35 ml of water per gram of catalyst, 0.36 ml of water per gram of catalyst, 0.37 ml of water per gram of catalyst, 0.38 ml of water per gram of catalyst, 0.39 ml of water per gram of catalyst, or 0.40 ml of water per gram of catalyst.

[0103] In some embodiments, the amount of water used in the slurry is minimized by optimizing the ratio of water in the slurry to the amount of catalyst formed, thereby minimizing the amount of wastewater generated while maintaining the saturated vapor pressure in the hydrothermal synthesis reaction.

[0104] In some embodiments, the slurry has a water-to-metal oxide ratio in the range of 0.1 mL of water per gram of metal oxide and 10 mL of water per gram of metal oxide, for example, between 0.1 mL of water per gram of metal oxide and 5 mL of water per gram of metal oxide, between 0.1 mL of water per gram of metal oxide and 4 mL of water per gram of metal oxide, between 0.1 mL of water per gram of metal oxide and 3 mL of water per gram of metal oxide, between 0.1 mL of water per gram of metal oxide and 2 mL of water per gram of metal oxide, or between 0.1 mL of water per gram of metal oxide and 1 mL of water per gram of metal oxide.

[0105] As used herein, the phrase “water-to-metal oxide ratio” refers to the ratio of water used in the slurry to the total mass of metal oxide used in the slurry, and the metal oxide includes one or both of molybdenum oxide, vanadium oxide, tantalum oxide, and niobium oxide. In embodiments where the reducing agent is a metal oxide, the total mass of metal oxide used in the slurry does not include the mass of the metal oxide used as the reducing agent. For example, a slurry containing 2.7 mL of water, 5.3673 g of MoO3, 1.0419 g of V2O5, and 0.4255 g of Ta2O5·xH2O contains a total of 6.8347 g of metal oxide, and the water-to-metal oxide ratio is 0.395.

[0106] In some embodiments, the slurry has a water-to-metal oxide ratio in the range of 0.2 mL of water per gram of metal oxide and 0.6 mL of water per gram of metal oxide, for example, between 0.3 mL of water per gram of metal oxide and 0.5 mL of water per gram of metal oxide, or between 0.3 mL of water per gram of metal oxide and 0.4 mL of water per gram of metal oxide. In some embodiments, the slurry has a water-to-metal oxide ratio in the range of 0.35 mL of water per gram of metal oxide and 0.45 mL of water per gram of metal oxide.

[0107] In some embodiments, the slurry has a water-to-metal oxide ratio of 0.1 mL per gram of metal oxide, 0.2 mL per gram of metal oxide, 0.3 mL per gram of metal oxide, 0.4 mL per gram of metal oxide, 0.5 mL per gram of metal oxide, 0.6 mL per gram of metal oxide, 0.7 mL per gram of metal oxide, 0.8 mL per gram of metal oxide, 0.9 mL per gram of metal oxide, 1 mL per gram of metal oxide, 2 mL per gram of metal oxide, 3 mL per gram of metal oxide, 4 mL per gram of metal oxide, or 5 mL per gram of metal oxide.

[0108] In some embodiments, the slurry has a water-to-metal oxide ratio of 0.25 mL per gram of metal oxide, 0.26 mL per gram of metal oxide, 0.27 mL per gram of metal oxide, 0.28 mL per gram of metal oxide, 0.29 mL per gram of metal oxide, 0.30 mL per gram of metal oxide, 0.31 mL per gram of metal oxide, 0.32 mL per gram of metal oxide, 0.33 mL per gram of metal oxide, 0.34 mL per gram of metal oxide, 0.35 mL per gram of metal oxide, 0.36 mL per gram of metal oxide, 0.37 mL per gram of metal oxide, 0.38 mL per gram of metal oxide, and 0.39 mL per gram of metal oxide. The ratio of water per gram of metal oxide is 0.40 mL, 0.41 mL, 0.42 mL, 0.43 mL, 0.44 mL, 0.45 mL, 0.46 mL, 0.47 mL, 0.48 mL, 0.49 mL, 0.50 mL, 0.51 mL, 0.52 mL, 0.53 mL, 0.54 mL, or 0.55 mL per gram of metal oxide.

[0109] The methods disclosed herein may further include processes for controlling the sizing of metal oxides and bismuth compounds. For example, the metal oxides and bismuth compounds may be ground, wet ground, dry ground, or crushed. The controlled sizing process can reduce the size of the metal oxides and bismuth compounds to improve reactivity, or allow aggregation of the metal oxides and / or bismuth compounds to enable the production of low-dusting powders or granules, and improve the loadability of the powder into the apparatus (e.g., improve the flowability or granulation of the powder).

[0110] In some embodiments, the metal oxide and the bismuth compound each have a particle size of less than 1 mm, for example, less than 60 mesh (250 μm). For example, the metal oxide and the bismuth compound may each have a particle size in the range of 0.5 μm to 250 μm, or 1 μm to 200 μm, or 1 μm to 150 μm, or 1 μm to 100 μm, or 1 μm to 50 μm, or 10 μm to 200 μm, or 10 μm to 150 μm, or 10 μm to 100 μm, or 10 μm to 50 μm, or 50 μm to 200 μm, or 50 μm to 150 μm, or 50 μm to 100 μm.

[0111] In some embodiments, the method further includes a process for controlling the size of the reducing agent. For example, the reducing agent is pulverized, wet-pulverized, dry-pulverized, or crushed.

[0112] Any suitable reducing agent may be included in the slurry. As used herein, the term “reducing agent” refers to a chemical substance that can reduce the oxidation state of one or more metals among metal oxides or bismuth compounds in the slurry. Suitable reducing agents for promoting the reaction include those that are easily decomposed or oxidized during the reaction process.

[0113] In some embodiments, the reducing agent is an alcohol, a carboxylic acid, an ester, or a metal oxide. Suitable examples of alcohol reducing agents include, but are not limited to, ethanol, methanol, reducing sugars, and polyols such as glycols 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. A suitable metal oxide is vanadium(IV) oxide. In some embodiments, the reducing agent is oxalic acid or ethanol. In some embodiments, the reducing agent is oxalic acid. In some embodiments, the reducing agent is ethanol.

[0114] The slurry may contain one reducing agent or two or more reducing agents. In some embodiments, the slurry contains one or more reducing agents. In some embodiments, the slurry contains one or fewer reducing agents. The methods disclosed herein offer the advantage of a simplified procedure using a single reducing agent compared to previously reported methods using two or more reducing agents.

[0115] The amount of reducing agent used in the slurry may be selected based in part on the properties of the reducing agent used. In some embodiments, the ratio of reducing agent used in the slurry to the amount of metal oxide used in the slurry is in the range between 0.05 g of reducing agent per gram of metal oxide and 1 g of reducing agent per gram of metal oxide. As used herein, the term "reducing agent" in the expression "ratio of reducing agent used in the slurry to the amount of metal oxide used in the slurry" refers to the total mass of reducing agent used in the slurry, which may be the mass of one type of reducing agent, the mass of one or fewer types of reducing agents, or the combined mass of two or more types of reducing agents. As used herein, the term "metal oxide in the slurry" in the expression "ratio of reducing agent used in the slurry to the amount of metal oxide used in the slurry" refers to the total mass of metal oxide used in the slurry, which may include molybdenum oxide, vanadium oxide, and one or both of tantalum oxide or niobium oxide. In embodiments where the reducing agent is a metal oxide, the total mass of metal oxide used in the slurry does not include the mass of the metal oxide used as the reducing agent.

[0116] For example, a slurry containing 1.5025 g of oxalic acid, 5.359 g of MoO3, 1.0674 g of V2O5, and 0.4075 g of Ta2O5·xH2O as reducing agents contains a total of 6.8339 g of metal oxides, and the ratio of the total reducing agent in the slurry to the total metal oxides used in the slurry is 0.22.

[0117] In some embodiments, the ratio of reducing agent used in the slurry to the metal oxide used in the slurry is in the range of 0.1 g of reducing agent per gram of metal oxide and 0.5 g of reducing agent per gram of metal oxide. In some embodiments, the ratio of reducing agent used in the slurry to the metal oxide used in the slurry is in the range of 0.15 g of reducing agent per gram of metal oxide and 0.25 g of reducing agent per gram of metal oxide. In a non-limiting example, the reducing agent is oxalic acid, the amount of oxalic acid used in the slurry is in the range of 1 g to 2 g, and the amount of metal oxide used in the slurry is in the range of 6 g to 8 g. In another non-limiting example, the amount of oxalic acid used in the slurry is in the range of 12 g to 14 g, and the amount of metal oxide used in the slurry is in the range of 68 g to 72 g.

[0118] In some embodiments of the methods disclosed herein, the metal oxides include molybdenum oxide, vanadium oxide, and tantalum oxide. In some embodiments, the slurry contains MoO3, V2O5, Ta2O5·xH2O, and Bi(OH)3. In some embodiments, the slurry contains MoO3, V2O5, Ta2O5·xH2O, and Bi(OH)3 in a mass ratio of MoO3:V2O5:Ta2O5·xH2O:Bi(OH)3, where the mass ratio is 1 g MoO3 : 0.1 to 0.3 g V2O5 : 0.01 g to 0.10 g Ta2O5·xH2O : 0.01 g to 0.20 g Bi(OH)3. This mass ratio can be used on any suitable reaction scale. For example, the slurry may contain 4-6 g of MoO3, 0.5-1.5 g of V2O5, 0.2-0.6 g of Ta2O5·xH2O, and 0.05-0.2 g of Bi(OH)3. In another non-limiting example, the slurry may contain 20-25 g of MoO3, 3-6 g of V2O5, 1-3 g of Ta2O5·xH2O, and 1-3 g of Bi(OH)3.

[0119] In some embodiments, the metal oxides include molybdenum oxide, vanadium oxide, and niobium oxide. In some embodiments, the slurry contains MoO3, V2O5, Nb2O5·xH2O, and Bi(OH)3. In some embodiments, the slurry contains MoO3, V2O5, Nb2O5·xH2O, and Bi(OH)3 in a mass ratio of MoO3:V2O5:Nb2O5·xH2O:Bi(OH)3, where the mass ratio is 1g MoO3:0.1-0.3g V2O5:0.01g-0.10g Nb2O5·xH2O:0.01g-0.20g Bi(OH)3. This mass ratio can be used on any suitable reaction scale. For example, the slurry may contain 4-6 g of MoO3, 0.5-1.5 g of V2O5, 0.2-0.6 g of Nb2O5·xH2O, and 0.05-0.2 g of Bi(OH)3.

[0120] In some embodiments, the slurry is substantially free of tellurium compounds. As used herein, the term “substantially free” means less than 10 ppm, less than 5 ppm, less than 2 ppm, or less than 1 ppm.

[0121] In some embodiments, the slurry is substantially free of strong acids. Those skilled in the art will understand that strong acids are acids that are completely or nearly completely ionized in solution. For example, in some embodiments, the slurry is substantially free of nitric acid.

[0122] In the methods disclosed herein, the catalyst is produced in a hydrothermal synthesis reaction by heating a slurry. Any suitable reaction vessel can be used for the hydrothermal synthesis reaction. In some embodiments, the slurry is heated in a hydrothermal synthesis vessel. In some embodiments, the slurry is formed in a hydrothermal synthesis vessel and then heated in the hydrothermal synthesis vessel. In some embodiments, the slurry is transferred to a hydrothermal synthesis vessel after slurry formation and then heated in the hydrothermal synthesis vessel.

[0123] As used herein, the term “hydrothermal synthesis vessel” refers to a reaction vessel suitable for carrying out a reaction under high temperature and pressure, and includes, but is not limited to, autoclaves, decomposition tanks, pressure vessels, hydrothermal synthesis reactors, or polytetrafluoroethylene (PTFE) high-pressure tanks. In some embodiments, the hydrothermal synthesis vessel is an autoclave.

[0124] A slurry can be heated by increasing its temperature and then maintaining that temperature. Temperature increases can be used to avoid surface boiling of the slurry. As used herein, the expression "temperature increase" refers to changing the temperature from an initial temperature to a final temperature over a period of time. For example, the temperature of a slurry can be increased from an initial temperature of room temperature to a final temperature higher than room temperature over a specified period of time. The final temperature may be the holding temperature. As used herein, the term "room temperature" refers to a temperature between 15°C and 28°C. As used herein, the term "holding temperature" refers to the temperature at which the reaction vessel is held, which can be measured by the ambient temperature of the oven in which the reaction vessel is placed.

[0125] In some embodiments, the slurry is heated by raising its temperature from ambient temperature to a temperature between 100°C and 200°C over a heating time of 2 hours and 48 hours, and then holding it at a holding temperature between 100°C and 200°C for a holding time of 12 hours and 160 hours. In some embodiments, the slurry is heated by raising its temperature from ambient temperature to a temperature between 100°C and 200°C over a heating time of 2 hours and 48 hours, and then holding it at a holding temperature between 100°C and 200°C for a holding time of 12 hours and 120 hours. In some embodiments, the slurry is heated by raising its temperature from ambient temperature to a temperature between 150°C and 200°C over a heating time of 2 hours and 24 hours, and then holding it at a holding temperature between 150°C and 200°C for a holding time of 24 hours and 60 hours.

[0126] In a non-limiting example, the slurry is heated by raising its temperature from ambient temperature to 180°C over 12 hours, and then holding it at 180°C for 48 hours. In another non-limiting example, the slurry is heated by raising its temperature from ambient temperature to 180°C over 24 hours, and then holding it at 180°C for 60 hours. In yet another non-limiting example, the slurry is heated by raising its temperature from ambient temperature to 180°C over 2 hours, and then holding it at 180°C for 48 hours. In yet another non-limiting example, the slurry is heated by raising its temperature from ambient temperature to 180°C over 24 hours, and then holding it at 180°C for 156 hours.

[0127] In some embodiments, the method further includes a step of washing the catalyst with water. For example, the catalyst may be washed with water until the filtrate is colorless. In some embodiments, the method further includes a step of drying the catalyst at a temperature below 100°C, for example. Drying can be carried out by any suitable method, such as drying at ambient temperature for a suitable amount of time, or drying overnight in an oven at a temperature of 90°C, for example.

[0128] The method may further include the step of calcining the catalyst to form a calcined catalyst. Those skilled in the art will be familiar with appropriate methods for calcining catalysts. In some embodiments, the catalyst is calcined by placing it in a furnace in an oxygen-free environment, raising the furnace temperature from ambient temperature to 500°C to 620°C over a heating time of 2 to 10 hours, and holding the furnace temperature at a holding temperature of 500°C to 620°C for a holding time of 1 to 10 hours. For example, the catalyst is calcined by placing it in a furnace, raising the furnace temperature from ambient temperature to 600°C over a heating time of 6 hours, and holding the furnace temperature at a holding temperature of 600°C for a holding time of 2 hours.

[0129] As used herein, “oxygen-free environment” refers to an environment with a molecular oxygen content of less than 10 ppm. For example, the furnace may be placed in an inert atmosphere such as a purified nitrogen atmosphere or a purified argon atmosphere, or in a CO2 atmosphere and / or a vapor atmosphere.

[0130] In some embodiments, the ratio of water in the slurry to the amount of calcination catalyst is in the range between 0.1 mL of water per gram of calcination catalyst and 10 mL of water per gram of calcination catalyst, for example, between 0.1 mL of water per gram of calcination catalyst and 5 mL of water per gram of calcination catalyst, between 0.1 mL of water per gram of calcination catalyst and 4 mL of water per gram of calcination catalyst, between 0.1 mL of water per gram of calcination catalyst and 3 mL of water per gram of calcination catalyst, between 0.1 mL of water per gram of calcination catalyst and 2 mL of water per gram of calcination catalyst, or between 0.1 mL of water per gram of calcination catalyst and 1 mL of water per gram of calcination catalyst.

[0131] As used herein, the term "amount of calcined catalyst" refers to the mass of catalyst after all catalysts obtained from catalyst synthesis have undergone calcination, such as calcination, as described herein. In non-limiting examples, the ratio of water in the slurry to the amount of calcined catalyst formed may be in the range of 0.3 mL of water per gram of calcined catalyst, 0.8 mL of water per gram of calcined catalyst, 0.4 mL of water per gram of calcined catalyst, 0.6 mL of water per gram of calcined catalyst, or 0.5 mL of water per gram of calcined catalyst.

[0132] In some embodiments, the ratio of water in the slurry to the amount of calcined catalyst is 0.1 mL of water per gram of calcined catalyst, 0.2 mL of water per gram of calcined catalyst, 0.3 mL of water per gram of calcined catalyst, 0.4 mL of water per gram of calcined catalyst, 0.5 mL of water per gram of calcined catalyst, 0.6 mL of water per gram of calcined catalyst, 0.7 mL of water per gram of calcined catalyst, 0.8 mL of water per gram of calcined catalyst, 0.9 mL of water per gram of calcined catalyst, 1 mL of water per gram of calcined catalyst, 2 mL of water per gram of calcined catalyst, 3 mL of water per gram of calcined catalyst, 4 mL of water per gram of calcined catalyst, or 5 mL of water per gram of calcined catalyst.

[0133] In some embodiments, the ratio of water in the slurry to the amount of calcined catalyst formed is 0.40 mL of water per gram of calcined catalyst, 0.41 mL of water per gram of calcined catalyst, 0.42 mL of water per gram of calcined catalyst, 0.43 mL of water per gram of calcined catalyst, 0.44 mL of water per gram of calcined catalyst, or 0.45 mL of water per gram of calcined catalyst, 0.46 mL of water per gram of calcined catalyst, 0.47 mL of water per gram of calcined catalyst, 0.48 mL of water per gram of calcined catalyst, 0.49 mL of water per gram of calcined catalyst, 0.50 mL of water per gram of calcined catalyst, 0.51 mL of water per gram of calcined catalyst, calcined catalyst The amounts of water per gram of catalyst are 0.52 mL, 0.53 mL, 0.54 mL, 0.55 mL, 0.56 mL, 0.57 mL, 0.58 mL, 0.59 mL, 0.60 mL, 0.61 mL, 0.62 mL, 0.63 mL, 0.64 mL, or 0.65 mL.

[0134] In some embodiments, the ratio of the total amount of water used to prepare the catalyst is between 0.1 mL of water per gram of catalyst and 60 mL of water per gram of catalyst. In some embodiments, the ratio of the total amount of water used to prepare the catalyst is between 0.1 mL of water per gram of catalyst and 25 mL of water per gram of catalyst. As used herein, “total amount of water used to prepare the catalyst” includes not only water in the slurry but also water used in other steps, such as any step of washing the catalyst with water, and / or water used to transfer materials between reaction vessels. In some embodiments, the ratio of the total amount of water used to prepare the catalyst is in the range of 0.1 mL of water per gram of catalyst and 20 mL of water per gram of catalyst, 0.5 mL of water per gram of catalyst and 15 mL of water per gram of catalyst, 1 mL of water per gram of catalyst and 10 mL of water per gram of catalyst, 5 mL of water per gram of catalyst and 10 mL of water per gram of catalyst, 0.1 mL of water per gram of catalyst and 5 mL of water per gram of catalyst, or 0.1 mL of water per gram of catalyst and 1 mL of water per gram of catalyst. In some embodiments, the ratio of the total amount of water used to prepare the catalyst is in the range of 0.2 mL of water per gram of catalyst and 10 mL of water per gram of catalyst.

[0135] The catalysts prepared by the methods disclosed herein include molybdenum (Mo), vanadium (V), bismuth (Bi), tantalum (Ta), or niobium (Nb), or both, and oxygen (O). In some embodiments, the catalyst is Mo a V b Bi c Ta d O x , and Mo a V b Bi c Nb d O x It has an expression that is selected from.

[0136] In some embodiments, the methods for preparing the catalysts disclosed herein may further include providing a catalyst material by combining a calcined catalyst with one or more solid supports, carriers, binders, and lubricants (such as solid supports, carriers, binders, and lubricants disclosed elsewhere herein). In some embodiments, the catalyst material is prepared by a method comprising preparing an aqueous mixture comprising (i) a catalyst disclosed herein, (ii) a solid support or carrier, and (iii) a lubricant and / or binder. In some embodiments, the method may further include removing a substantial amount of water (e.g., 50% to 99% by weight) from the aqueous mixture by heating the mixture at a temperature of 50°C to 100°C, for example. In some embodiments, the method includes forming the catalyst material into a formed catalyst material, such as a pelletized catalyst material.

[0137] The catalysts disclosed herein may be suitable as catalysts in oxidative dehydrogenation reactions. This disclosure further provides a process for oxidative dehydrogenation from ethane to ethylene in an oxidative dehydrogenation reactor using any of the oxidative dehydrogenation catalysts described herein. The catalyst may be contained in any of the catalyst materials disclosed herein.

[0138] As used herein, the terms “oxidative dehydrogenation” or “ODH” mean, as further described herein, alkane (C) n H 2n+2 This refers to a process that combines the endothermic dehydrogenation of ) with the strong exothermic oxidation of hydrogen, thereby producing alpha-olefins, among other things. 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 and propane. In some embodiments, the alkane is ethane. When testing catalysts, the ODH reaction as used herein is assumed to refer to the ODH of ethane.

[0139] In some embodiments, the catalyst has a 45% ethane conversion temperature of 300°C to 420°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 300°C to 400°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 325°C to 390°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 340°C to 390°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 350°C to 400°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 350°C to 380°C. In some embodiments, the catalyst has a 45% ethane conversion temperature of 360°C to 375°C. As used herein, the term "45% ethane conversion temperature" refers to the temperature at which 45% of the ethane in the gas stream is converted to non-ethane products at a given fixed feed composition, space velocity per w / h (weight), and reactor inlet pressure. The 45% ethane conversion temperature of an oxidative dehydrogenation catalyst can be determined using a microreactor unit (MRU).

[0140] In a microreactor unit, the 45% ethane conversion temperature of the catalyst can be determined by passing the feed gas through the catalyst bed in the reactor tube. The MRU reactor tube has an outer diameter of 0.5 inches, an inner diameter of 0.4 inches, and a length of 15 inches. For example, the reactor tube can be a stainless steel SWAGELOK® tube with a wall thickness of 0.049 inches. The feed gas can contain ethane and oxygen in a molar ratio of 70:30 to 90:10. For example, the feed gas can contain ethane and oxygen in a molar ratio of 82:18. Alternatively, the feed gas can contain ethane, oxygen, and nitrogen. The molar ratio of ethane:oxygen:nitrogen can be 18:8:74 to 54:18:28. For example, the molar ratio of ethane:oxygen:nitrogen can be 20:10:70. The flow rate of the feed gas can be 70 standard cubic centimeters per minute (sccm) to 80 sccm. For example, the flow rate of the supply gas can be 75 sccm (e.g., 74.6 sccm). The catalyst bed consists of an oxidative dehydrogenation catalyst and a packing material such as quartz sand, with a volume ratio of 1:0.5 to 1:3, and the total weight of the oxidative dehydrogenation catalyst is 1.96 to 2.00 g. The remaining space in the reactor tube (e.g., below or above the catalyst bed) is filled with additional packing material such as quartz sand. The 45% ethane conversion temperature is when the space velocity per hour (WHSV) is 3.57 h. -1 (WHSV is based on the catalyst weight in the sample), gas space velocity per hour (GHSV) is 2,000-5,000 h -1 This is determined by the following. As used herein, the expression “space velocity per second” refers to the value obtained by dividing the total feed gas weight flow rate by the weight of the catalyst. Typically, the inlet pressure is in the range of 1 pound / 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 discharged from the catalyst bed is analyzed by gas chromatography to determine the proportions of various hydrocarbons (e.g., ethane and ethylene), as well as the proportions of other gases such as O2, CO2, and CO, as needed.

[0141] The conversion rate of ethane feed gas to the product in the ODH process is calculated as the change in the volume flow rate of ethane in the product compared to the volume flow rate of the feed ethane, using the following formula:

number

[0142] In Equation 1, C is the percentage (mol %) of the ethane feed gas converted from ethane to another product (i.e., the ethane conversion rate), and X is the molar concentration of the corresponding compound in the gaseous effluent discharged from the reactor at the corresponding temperature.

[0143] Furthermore, by analyzing the gas emitted from the reactor using gas chromatography, the selectivity of the catalyst or catalytic material to ethylene (i.e., the molar proportion of ethane that produces ethylene) can be determined. The selectivity to ethylene can be determined using the following formula:

number

[0144] In formula 2, S エチレン X is the selectivity to ethylene, and X is the molar concentration of the corresponding compound in the gaseous effluent discharged from the reactor at the corresponding temperature. As used herein, the term "selectivity to ethylene" refers to the molar proportion of the conversion or reacted ethane that produces ethylene.

[0145] In some embodiments, the catalyst has a selectivity for ethylene of 65% to 99%. In some embodiments, the catalyst material has a selectivity for ethylene of 75% to 95%. In some embodiments, the catalyst has a selectivity for ethylene of 83% to 93%. In some embodiments, the catalyst has an ethylene selectivity of at least 90% with an ethane conversion rate of at least 45%.

[0146] In some embodiments, the catalyst has a selectivity to acetic acid of less than 38 mol% in the oxidative dehydrogenation process from ethane to ethylene. In some embodiments, the catalyst has a selectivity to acetic acid of less than 25 mol%. For example, the catalyst material may have a selectivity to acetic acid of 1 mol% to 15 mol%, 3 mol% to 12 mol%, or 7 mol% to 12 mol% in the oxidative dehydrogenation process from ethane to ethylene. In some embodiments, the catalyst material has a selectivity to acetic acid of 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, or 13 mol% in the oxidative dehydrogenation process from ethane to ethylene. As used herein, the term “selectivity to acetic acid” refers to the molar proportion of the conversion that produces acetic acid, or the ethane that reacted.

[0147] The gas-per-spatiotemporal velocity (GHSV) is defined as the volumetric flow rate 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, any diluent particles, and voids within the catalyst bed. For GHSV values ​​of catalyst materials, the catalyst bed is treated as catalyst only (without support), and it is assumed that the volume of the catalyst is the total volume of the measured catalyst material multiplied by the weight percentage of the catalyst. GHSV can be calculated based on the measured volume of compressed particles (before mixing with quartz sand) and varies depending on the bulk density of each catalyst or catalyst material. For the catalyst materials discussed herein, the reported GHSV is for catalyst only, and it is assumed that the volume of the catalyst is the total volume of the measured catalyst material multiplied by the weight percentage of the catalyst.

[0148] Ethylene obtained by ODH of ethane using the catalysts, catalytic materials, and processes described herein can then be converted into a variety of products. For example, ethylene can be converted into very low-density polyethylene (VLDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), ethylene chloride, ethylene oxide, ethylbenzene, linear alcohols, vinyl acetate, alkanes, alpha-olefins (e.g., 1-hexene and 1-octene), various hydrocarbon fuels, ethanol, and the like. These products can then be further processed using methods well known to those skilled in the art to obtain other useful chemicals and consumer products.

[0149] In some embodiments, the ethylene provided by the ODH process described herein is converted to polyethylene. In some embodiments, the 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).

[0150] Although the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values ​​shown in specific examples are reported as accurately as possible. However, each numerical value inherently contains a certain degree of error that inevitably arises from the standard deviation found in each test measurement.

[0151] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges contained therein. For example, the range "1 to 10" or "between 1 and 10" is intended to include all subranges between the stated minimum value of 1 and the stated maximum value of 10, i.e., the minimum value is 1 or greater and the maximum value is 10 or less. Since the disclosed numerical ranges are continuous, they include all values ​​between the minimum and maximum values. Unless otherwise specified, the various numerical ranges specified in this application are approximations.

[0152] In this document, the terms "a," "an," or "the" are used to include one or more unless the context clearly indicates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise specified. The phrase "at least one of A and B" is synonymous with "A, B, or A and B." Please understand that expressions and terms used herein are for illustrative purposes only and not for limitation unless otherwise defined. [Examples]

[0153] <Reagents> Molybdenum(VI) oxide (MoO3), vanadium(V) oxide (V2O5), tellurium dioxide (TeO2), and oxalic acid dihydrate were purchased from Sigma Aldrich. Bismuth(III) hydroxide (Bi(OH)3) was purchased from Alfa Aesar / Fisher Scientific Canada. Tantalum pentoxide hydrate (Ta2O5·xH2O) was purchased from BassTech International. The value of x in Ta2O5·xH2O was measured as 2.57 by thermogravimetric analysis. Niobium pentoxide hydrate (Nb2O5·xH2O) was purchased from Companhia Brasileira de Metalugia e Mineracao. The value of x in Nb2O5·xH2O was measured as 4.57 by thermogravimetric analysis. Alpha alumina was purchased from Fisher Scientific Canada. All reagents were used without further purification. All the water used was distilled and deionized water.

[0154] <Preparation of comparative sample 1C> Comparative sample 1C was prepared using the solid samples listed in Table 1.

[0155] [Table 1]

[0156] The solid reagents were mixed and lightly ground using a mortar and pestle. Next, the solid mixture was transferred to an 8 mL glass vial and 2 mL of distilled water solvent was added. The sample was lightly stirred with a glass stirring rod to form a thick orange slurry, and the sample adhering to the stirring rod was washed off with 1 mL of water and returned to the vial. Next, the vial was placed in a glass-lined steel autoclave, and water was filled around the vial to the height of the solid to promote heat transfer and maintain a humid atmosphere inside the container. The autoclave was then sealed and heated in an oven from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then the power was turned off and it was cooled to room temperature over 3-4 hours.

[0157] After the reaction, the sample became a hard, dark purple solid, and its volume increased by approximately 1.5 times. The sample was scraped from the vial onto filter paper in a vacuum filtration apparatus and washed with approximately 50 mL of distilled water. The filtrate was a clear, dark blue color. The sample was washed until the filtrate was colorless, and dried on the filter paper to obtain a glossy, dark purple powder solid. Next, the solid was calcined at 60°C for 12 hours under an N2 gas flow in a tubular autoclave (linear velocity of 3.9 cm / min at standard temperature and pressure (STP), residual oxygen of 0.25 ppm (volume)). After that, it was heated to 600°C over 6 hours, held at 600°C for 2 hours, then the furnace power was turned off, and the sample was cooled to ambient temperature over approximately 12 hours. After calcination, the sample was a dark purple powder. The mass of the solid sample was 8.0214 g before calcination and 5.9457 g after calcination.

[0158] <Preparation of Examples 2E to 5E>

[0159] <Preparation of catalyst> Four separate Examples 2E to 5E were prepared using the solid reagents listed in Table 2. In each example, the solid reagents were mixed and lightly ground using a mortar and pestle. Next, the solid mixtures were transferred to individual glass vials, and a portion of the distilled water solvent was added. The samples were lightly stirred with a glass stirring rod to form a thick orange slurry, and the sample adhering to the stirring rod was washed off with another portion (1 mL) of water before being returned to the vials (the total amount of water used for slurry formation and rinsing the samples is shown in Table 2).

[0160] [Table 2]

[0161] Each vial of sample 2E to 5E was placed in a glass-lined steel autoclave along with a blank reference vial filled with water. The autoclave was filled to a solid height around the vials to promote heat transfer and maintain a humid atmosphere inside the vessel. The autoclave was a 300 mL PARR reactor manufactured by Parr Instrument Company in Maureen, Illinois, USA (assembly head serial number: 453HC T316 091902 24820B, assembly body serial number: 452HC T316 091902 24820A).

[0162] The autoclave was sealed and heated in an oven from room temperature to 180°C over 12 hours, then maintained at 180°C for 48 hours. After that, the power was turned off and it was cooled to ambient temperature over 3-4 hours. After the reaction, the sample became a hard, dark purple solid, and its volume had increased by approximately 1.5 times. The sample was scraped from the vial onto separate filter papers in a vacuum filtration apparatus and washed with approximately 50 mL of distilled water. The filtrate was clear and pale blue for sample 2E, and dark blue for samples 3E and 4E. Each sample was washed until the filtrate was colorless and dried on the filter paper to obtain a glossy, dark purple powder solid.

[0163] Next, each solid from Examples 2E to 5E was calcined at 60°C for 12 hours under an N2 gas flow in a tubular autoclave. Afterward, it was heated to 600°C over 6 hours, held at 600°C for 2 hours, then the furnace power was turned off, and the samples were cooled to room temperature over approximately 12 hours. The masses of each catalyst from Examples 2E to 5E after calcination are shown in Table 2. The PXRD patterns of Examples 2E to 5E are shown in Figures 2 to 5.

[0164] <Preparation of Example 5E (pelletized form)> In this procedure, 50% by weight of the catalyst phase and 50% by weight of alumina were used as targets after sintering (as described herein). An additional 2% by weight of polyethylene glycol 1000 and 3% by weight of polyvinyl alcohol (MOWIOL® 8-88) were added together with 1000 ppm of polyacrylic acid to act as binders. All components shown in Table 3 were mixed in a beaker at 90°C using an overhead stirrer until most of the water evaporated and a thick purple paste remained.

[0165] [Table 3]

[0166] Next, the beaker was transferred to an oven and dried overnight at 90°C. After drying, the hard solid was crushed using a mortar and pestle, and the particles were sieved to obtain particles with a size of 180–500 μm. To the sieved particles, 1% by weight of natural graphite flakes (>325 mesh) was added, and the mixture was shaken in a sealed container to coat the granules. The graphite-coated particles were then fed into a Dott Bonapace CPR-6 pellet press equipped with a 3 mm cylindrical die, and the die settings were adjusted to form cylindrical pellets with an axial compressive strength exceeding 50 N. The dimensions of the pellets were approximately 3 mm in diameter and 5 mm in length.

[0167] The pellets were fired in a two-step procedure. First, under an airflow (linear velocity of 1.9 cm / min using STP), the pellets were heated to 400°C at a rate of 1.0°C / min, held at 400°C for 1 hour, and then cooled to room temperature over approximately 8 hours. Next, the furnace was purged for 8 hours using a nitrogen airflow (linear velocity of 3.9 cm / min using STP), then heated to 600°C at a rate of 1.6°C / min, after which heating was stopped, and the furnace was cooled to room temperature over approximately 12 hours. The axial compressive strength of the catalyst pellets remained largely constant before and after the sintering process.

[0168] <Preparation of Examples 6E and 7E> Examples 6E and 7E were prepared by increasing the amount of Bi(OH)3 used and either washing (6E) or not washing (7E), and synthesized using the same procedure as described in Samples 2E-5E. The amounts of reagents used are shown in Table 4. All solid components were added to a blender and mixed by repeating 1-minute pulses four times, then the solids were crushed and blended. The sides of the container were shaken or tapped between pulses. Next, the solid mixture was transferred to a 60 mL disposable glass hypovial. Water was added and the mixture was stirred to form an orange slurry. Next, the vial was placed in a 300 mL steel autoclave, and the outside of the vial was filled with water to improve heat transfer and maintain a relative humidity of 100% inside the container. The autoclave was sealed and placed in an oven, heated from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then the heating was stopped, and the container was passively cooled to room temperature over approximately 6 hours.

[0169] [Table 4]

[0170] After cooling, the autoclave was evacuated and the vial was removed. As the reaction progressed, the orange slurry turned into a dark purple solid. This solid was crushed and separated into two nearly equal parts. One part was used as is without any additional washing (Example 6E), and the other part was washed with water using a vacuum filter until the filtrate was colorless and clear (Example 7E). Both samples were dried overnight in an oven at 90°C to obtain 31.8692 g of Example 6E and 38.1755 g of Example 7E.

[0171] The solid samples were calcined in a tubular quartz furnace under an N2 gas flow (linear velocity of 3.9 cm / min in STP). The solids were heated 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 samples were passively cooled to room temperature under an N2 gas flow for approximately 12 hours. After calcination, mass losses of 3.25% and 2.48% were observed in Examples 6E and 7E, respectively. The PXRD patterns of Examples 6E and 7E after calcination are shown in Figures 6 and 7, respectively.

[0172] <Preparation of Example 8E> Example 8E was synthesized using the reagent amounts listed in Table 5, following the same procedure as Example 6E. After drying, 65.8639 g was obtained.

[0173] [Table 5]

[0174] The solid sample was calcined in a tubular quartz furnace under an N2 gas flow (linear velocity of 3.9 cm / min in STP). The solid was heated to 600°C at a rate of 1.6°C / min, held at 600°C for 2 hours, then the heating was stopped, and it was passively cooled to room temperature under an N2 gas flow for approximately 12 hours. A mass loss of 2.7% was observed after calcination. The PXRD patterns of Example 8E before and after calcination are shown in Figure 8.

[0175] <Preparation of Example 9E> Example 9E was prepared using a large-scale reaction that omitted the solid grinding step. All the solids and water 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. Next, the beaker was placed in a 2 L steel autoclave, and 50 mL of water was added to the outside of the PTFE beaker to maintain a relative humidity of 100% inside the container. The container was then sealed and placed in an oven, heated from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then the heating was stopped, and the container was cooled to room temperature over approximately 6 hours. The container was evacuated in a fume hood, and the dark purple solid was transferred to a 3 L beaker. Water (1 L) was added to the beaker, and the mixture was stirred overnight using an overhead stirrer. The purple slurry was then vacuum filtered, washed in 1 L increments with 3 L of water, and dried in an oven at 90°C for 24 hours to obtain 813.27 g of dried catalyst.

[0176] [Table 6]

[0177] Dry catalyst 9E was calcined in a tubular quartz furnace under a nitrogen gas flow (linear velocity of 3.9 cm / min in STP). After purging the furnace with nitrogen for a sufficient amount of time (approximately 8 hours), 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 sample was cooled to room temperature over approximately 12 hours. The PXRD patterns of catalyst 9E before and after calcination are shown in Figure 9.

[0178] Nitrogen physicoadsorption analysis was performed using a TriStar gas adsorption analyzer from Micromeritics Instruments. Powder samples were loaded into a physicoadsorption cell and degassed overnight (12 hours or more) at 120°C before adsorption measurement. Nitrogen gas adsorption analysis was performed using a liquid nitrogen bath at -196°C to collect data. The surface area of ​​the sample was determined using the Brunauer-Emmett-Teller (BET) model. Figure 15 shows the BJH plot of pore volume for sample 9E. Total pore volume was calculated using a relative pressure P / P0 = 0.99. The BET surface area was 17 m².2 / g, pore volume is 0.14 cm³ 3 It was measured as / g.

[0179] <Preparation of Example 10E> Example 10E was synthesized using a procedure largely similar to Example 9E, except that the holding time at 180°C was extended to 156 hours (from 48 hours). The amounts of reagents used are shown in Table 7.

[0180] [Table 7]

[0181] <Preparation of Example 11E> The metal oxides and hydroxides listed in Table 8 were added to a blender and mixed three times with 30-second pulses. The blended solids, oxalic acid, and water 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 mL of water was added to the outside of the PTFE beaker to maintain a relative humidity of 100% inside the container. The container was then sealed and placed in an oven, heated from room temperature to 180°C over 12 hours, held at 180°C for 48 hours, then the heating was stopped, and the container was cooled to room temperature over approximately 6 hours. The container was evacuated in a fume hood, and the dark purple solid was transferred to a 3 L beaker. Water (1 L) was added to the beaker, and the mixture was stirred overnight using an overhead stirrer. The purple slurry was then vacuum filtered, washed in 1 L portions with 3 L of water, and then transferred to an oven to dry for 24 hours. Figure 10 shows the PXRD of Example 11E before firing.

[0182] [Table 8]

[0183] Next, the dry catalyst was calcined in a tubular quartz furnace under a nitrogen gas flow (linear velocity of 3.9 cm / min in STP). After purging the furnace with nitrogen (for about 8 hours), 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 sample was cooled to room temperature over approximately 12 hours. The PXRD pattern of Example 11E is shown in Figure 10.

[0184] <Equipment and Measurement>

[0185] <Elemental analysis> The catalyst metal composition of calcined samples 4E, 5E, 9E, and 11E was measured by energy-dispersive X-ray spectroscopy (EDX). EDX was performed using a JEOL JED-2300 DRY SDD EDX detector. EDX scans were performed on the largest rectangular area covered by the sample (approximately 2.8 mm × 2.1 mm, typically at a magnification of approximately 50x, but this may vary depending on the sample size and coverage). Data analysis software used was AnalysisStation from JEOL. Scans were performed at an accelerating voltage of 25 kV. The results of the EDX analysis of catalysts 4E, 5E, 9E, and 11E are shown in Table 9.

[0186] [Table 9]

[0187] Scanning electron microscope (SEM) Scanning electron microscope (SEM) images were acquired using a JEOL-JSM300LV SEM. Samples were prepared on aluminum studs using double-sided carbon tape. Figures 11 to 14 show SEM images of samples 2E, 4E, 5E, and 11E, respectively.

[0188] <Powder X-ray Diffraction (PXRD)> Powder X-ray diffraction (PXRD) experiments were performed using a PANalytical Empyrean powder X-ray diffractometer equipped with a monochromator and CuKα-ray X-ray source. Data were acquired at a scan rate of 1° / min in the range of 3–80°²θ. The data were analyzed using PANalytical HighScore software version 4.8.

[0189] Powder X-ray diffraction (PXRD) analysis was performed on sample 1C (Figure 1) and examples 2E to 4E after calcination (Figures 2 to 4, respectively). PXRD characterized all three samples as a doped molybdenum vanadium oxide phase known in academic literature as M1. This analysis demonstrates that the catalytically active M1 phase can be produced with high crystalline purity by the method provided herein.

[0190] Figure 5 shows superpositions of the PXRD patterns of unfired, fired, and compounded / sintered catalyst 5E. These indicate that no significant degradation of the M1 catalyst phase is observed even after multiple heating cycles.

[0191] The PXRD patterns of catalyst 6E and catalyst 7E are shown in Figures 6 and 7, respectively. These also show the M1 phase, which exhibits catalytic activity.

[0192] Figures 8 and 9 show superimposed PXRD patterns of Example 8E and Example 9E before and after firing, respectively. In Figure 9, a small peak originating from unreacted MoO3 was observed in the unfired sample. Table 10 shows a list of PXRD peak positions (°2θ), calculated areas, and relative intensities for Example 9E.

[0193] [Table 10-1] [Table 10-2]

[0194] <Nitrogen gas adsorption analysis> Nitrogen gas adsorption analysis was performed using a MICROMERITICS® TriStar instrument after degassing the sample under reduced pressure at 120°C for 12 hours prior to analysis. Nitrogen adsorption was performed at 77K using a liquid nitrogen bath. The nitrogen physicoadsorption plot for Example 9E is shown in Figure 16.

[0195] Brunnauer-Emmett-Teller (BET) surface area analysis measures the specific surface area (m²) of a solid sample. 2 The BET (Body-Efficiency Test) was applied to quantify nitrogen by multilayer adsorption and measured as a function of relative pressure. By applying BET analysis, the surface area of ​​solids can be quantitatively compared by determining the monolayer capacity from nitrogen multilayer adsorption experiments. Monolayer capacity represents the total specific surface area and includes both the external area and pore area of ​​porous solids. BET analysis was performed using Micromeritics MicroActive software. The surface areas of Example 9E and Example 11E are shown in Table 11.

[0196] [Table 11]

[0197] The Barrett-Joyner-Halenda (BJH) method uses a Kelvin model from experimentally collected adsorption isotherms to determine the pore volume (cm³) of the more packed pores. 3 This was used to calculate ( / g). BJH analysis was performed using Micromeritics MicroActive software. The BJH plot for Example 9E is shown in Figure 15. The pore volumes for Example 9E and Example 11E are shown in Table 12.

[0198] [Table 12]

[0199] <Thermogravimetric analysis (TGA)> The water of hydration for niobium oxide and tantalum oxide starting materials was determined using thermogravimetric analysis (TGA). TGA was performed using a TA Instruments SDT650 thermogravimetric analyzer. Heating was carried out under an N2 gas stream at a rate of 2°C / min from 25 to 550°C.

[0200] <Compression strength test> The compressive strength of pelletized catalysts was tested using a Torbal FB Thor force gauge. The axial and radial compressive strengths of cylindrical pellets were determined according to ASTM D4179-22. The axial compressive strength of compounded catalyst materials (e.g., pelletized with a support or carrier) was observed to be in the range of 90–120 N.

[0201] <Density (envelope density and bulk density)> Density was measured according to ASTM D3766. Envelope density was measured at once by individually measuring the dimensions of 5-10 pellets with a digital caliper, followed by measuring the weight of the pellets. Bulk density was measured by filling a graduated cylinder with pellets and measuring the volume and mass before and after tapping to settle the pellets.

[0202] <Catalyst Testing> The catalysts described herein were tested for their ability to catalyze the oxidative dehydrogenation (ODH) of ethane using a microreactor unit (MRU). The MRU consisted of reactor tubes made of stainless steel SWAGELOK® tubing, with an outer diameter of 0.5 inches (1.27 cm), an inner diameter of 0.4 inches (1.02 cm), and a length of 13.4–15 inches (34.0–38.1 cm). The experimental temperature of the MRU was measured by inserting a 6-point WIKA Instruments Ltd. K-type thermocouple with an outer diameter of 0.125 inches (0.318 cm) into the reactor. This 6-point thermocouple was used to measure and control the temperature within the catalyst bed. A stainless steel condenser at room temperature was placed after the reactor to collect the water / acetic acid condensate. If product gas analysis was required, the gas product flow was either evacuated or directed to an Agilent 8890 "hot gas" gas chromatograph (HGGC).

[0203] The sample was compressed into pellets using a steel die and a hydraulic press, then the pellets were crushed, and particles with a size of 425-710 μm were sieved and loaded into the MRU. Approximately 2 g of the sample was placed in the reactor. In the case of pellets containing catalyst and alumina in a 50:50 ratio, approximately 4 g of the sample was placed in the reactor. After loading the catalyst bed into the reactor and connecting it to the MRU apparatus, the test was carried out as described herein.

[0204] The catalyst bed was loaded into the intermediate zone of the reactor, and quartz sand was loaded into the remaining volume of the reactor to bring the catalyst bed volume to 6 mL, ensuring a sufficient catalyst volume to cover the thermocouple area between points 2 and 5. The materials loaded into the reactor were then secured with glass wool from both the top and bottom of the reactor. Additional quartz sand was added to bring the catalyst bed volume to 6 mL, ensuring a sufficient catalyst volume to cover the thermocouple area.

[0205] The gas supply flow rate is set to the target value of 150 sccm (space velocity per hour (WHSV) = 3.57 h). -1The target gas supply composition was adjusted to 20 mol% ethane, 10 mol% oxygen, and 70 mol% nitrogen in all tests. The target pressure was 20 psig. The gas composition was determined by gas chromatography (GC) using an Agilent 6890N gas chromatograph, and data evaluation was performed using Chrom Perfect-Analysis version 6.1.10. The samples were left in the flow at a temperature of 380-420°C for approximately 5 days until the data reached equilibrium.

[0206] The ethane conversion temperature in mol% is 3.57h for WHSV. -1 , gas space velocity per hour (GHSV) is 2000-5000 h -1 The range was determined. Gaseous products discharged from the catalyst bed were exhausted during operation. When analyzing the gaseous products, they were temporarily redirected to a gas chromatograph to determine the proportions of ethane, ethylene, O2, CO2, CO, and optionally acetic acid. The gas discharged from the reactor was analyzed by gas chromatography. The conversion rate I of the ethane feed gas was calculated as the change in volume flow rate of ethane in the product compared to the feed ethane mass flow rate, using the following formula:

number

[0207] In Equation 1, X is the molar concentration of the corresponding compound in the gaseous effluent discharged from the reactor at the corresponding temperature.

[0208] The gas emitted from the reactor was analyzed by GC to measure the selectivity of the catalyst or catalytic material to ethylene (i.e., the molar ratio of ethane that produces ethylene). Selectivity to ethylene (S エチレン ) was determined using the following formula:

number

[0209] In equation 2 above, S エチレンX is the selectivity for ethylene, and X is the molar concentration of the corresponding compound in the gaseous effluent discharged from the reactor at the corresponding temperature.

[0210] To investigate the mass balance of ODH experiments based on GC analysis of non-condensable products, it was assumed that all non-condensable gas products behaved as ideal gases. The ideal gas law is accurate in predicting the behavior of gas mixtures at operating pressures close to 1 atmosphere (absolute pressure). In the ODH experiments, product gas samples were collected at operating pressures close to 1 atmosphere (absolute pressure) and injected into a gas chromatograph (GC). Therefore, it is expected that the behavior of the gas mixture can be accurately predicted by assuming the behavior of ideal gases. To calculate the amount of condensable products, the bulk chemical reactions shown in Table 13 were assumed. The reactions in Table 13 were used for the purpose of calculating a stoichiometrically balanced mass balance and do not represent the chemical reactions that actually occur in the ODH reaction.

[0211] [Table 13]

[0212] Based on the reactions shown in Table 13, the following method was programmed and used in MS Excel. The objective was to set the absolute deviation between the estimated oxygen from the reactor and the measured value to zero by using the GRG nonlinear solution method and changing the acetic acid output value of the solver.

[0213] In Step 1, the total molar flow rate of C2 (ethane) to the reactor is calculated using Equation 3:

number

[0214] In Step 2, the molar flow rate of all reactive compounds in the product effluent discharged from the reactor is calculated, excluding the inert diluent.

[0215] Total molar flow rate of acetic acid in the product [mmol / min] (F AAout ) is estimated by Equation 4:

number

[0216] The total molar flow rate of C2 in the non-condensable compounds in the reactor product is calculated using Equation 5:

number

[0217] The total molar flow rate of O2 from the reactor is calculated using the following algorithm:

[0218] F 2OUTC-2 -(100000*F Total *(0.5*C CO2 If ) / 22.4))>0, use equation 6:

number

[0219] F 2OUTCO2 -(100000*F Total *(0.5*C CO2 If ) / 22.4))<0, use formula 7:

number

[0220] The total molar flow rate of H2O from the reactor is calculated using Equation 8:

number

[0221] In step 3, the mole fraction of all reactive compounds in the product effluent discharged from the reactor is calculated from step X04. AAout The calculation is performed using the dry (anhydrous) standard.

[0222] The mole fraction of acetic acid in the product is calculated using Equation 9:

number

[0223] The mole fractions of ethane, ethylene, CO2, and C2 in CO in the product are calculated using Equation 10:

number

[0224] The mole fraction of oxygen in the product is calculated using Equation 11:

number

[0225] In step 4, the absolute deviation between the estimated and measured values ​​of O2 in the non-condensable product from the reactor is calculated using Equation 12:

number

[0226] Step 5 is the judgment point, D O2 10 -4 If less than D, proceed to step 6. O2 10 -4If it is not less than, return to step 2 and repeat. In the repeated steps, FAAout=y (where y = new estimate [mmol / min]) is changed, and in step 410 D O2 The steps are repeated to determine whether the value is approaching the target value.

[0227] In step 6, the ethane conversion rate is calculated using equation 13:

number

number

[0228] <Overview of catalyst performance> The results for comparative sample 1C and samples 4E, 5E, 6E, 7E, 8E, 9E, and 10E are summarized in Table 14.

[0229] [Table 14]

[0230] Figure 17 is a plot of the ethane conversion rates of comparative catalyst 1C and sample 4E. Figure 18 is a plot of the selectivity for ethylene production of comparative catalyst 1C and sample 4E.

[0231] As shown in Table 14 and Figure 17, sample 4E, containing bismuth dopant, exhibits activity equivalent to sample 1C, containing telluride dopant. As shown in Table 14 and Figure 18, sample 4E shows improved selectivity to ethylene compared to sample 1C. The data in Table 14 also indicates that increasing the amount of bismuth hydroxide during synthesis may negatively affect catalyst selectivity. Furthermore, this data suggests that failure to wash the catalyst sample after synthesis may reduce catalyst activity, but the impact on selectivity is small. In addition, reducing the amount of tantalum may have beneficial effects on both activity and selectivity. Moreover, a simplified synthesis omitting the solid grinding step yielded a catalyst with good activity and good selectivity.

[0232] Long-term tests were conducted using the 5E catalyst pellet at 405°C for a total of 1032 hours. As shown in Figure 19 and Table 15, the performance degradation during this period was within acceptable limits. Since catalyst activity is strongly positively correlated with pressure, data points where the pressure deviated significantly from 23.5 ± 1.0 psig were excluded.

[0233] [Table 15]

[0234] Non-limiting embodiments of this disclosure include:

[0235] Embodiment A. Formula: Mo a V b Bi c M d O x A catalyst composed of the following (wherein M is Ta or 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, x is the number of oxygen atoms required to make the catalyst electrically neutral, and a, b, c, and d are determined based on the amount of each starting material used to form the catalyst).

[0236] Embodiment B. The catalyst according to Embodiment A, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

[0237] Embodiment C. The catalyst according to Embodiment A or B, wherein b is 0.2 to 0.4, c is 0.01 to 0.07, and d is 0.01 to 0.07.

[0238] Embodiment D. The catalyst according to Embodiment A, B, or C, wherein b is 0.30 to 0.35, c is 0.04 to 0.05, and d is 0.03 to 0.05.

[0239] Embodiment E. The catalyst according to Embodiment A, B, or C, wherein b is 0.2 to 0.3, c is 0.05 to 0.07, and d is 0.02 to 0.04.

[0240] Embodiment F. The catalyst according to Embodiment A, B, or C, wherein b is 0.3 to 0.4, c is 0.05 to 0.07, and d is 0.03 to 0.05.

[0241] Embodiment G. The catalyst is Mo1V 0.31 Bi 0.04 M 0.05 O x Mo1V 0.31 Bi 0.05 M 0.05 O x Mo1V 0.31 Bi 0.06 M 0.05 O x Mo1V 0.32 Bi 0.05 M 0.05 O x Mo1V 0.32 Bi 0.04 M 0.03 O x Mo1V 0.33 Bi 0.05 M 0.04 O x Mo1V 0.26 Bi 0.06 M 0.03 O x Mo1V 0.33 Bi 0.06 M 0.04 Ox , and Mo1V 0.26 Bi 0.05 M 0.05 O x A catalyst according to Embodiment A, B, or C, having a formula selected from the following.

[0242] Embodiment H. The catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x Mo1V 0.33 Bi 0.06 Ta 0.04 O x , and Mo1V 0.26 Bi 0.05 Ta 0.05 O x A catalyst according to Embodiment A, B, or C, having a formula selected from the following.

[0243] Embodiment I. The catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.05 Ta 0.05 O x , and Mo1V 0.26 Bi 0.06 Ta 0.03 O x A catalyst according to Embodiments A, B, C, or H, having a formula selected from, the formula determined by energy-dispersive X-ray spectroscopy (EDX).

[0244] The pore volume determined by nitrogen physicoadsorption analysis using the J. Barrett-Joyner-Halenda (BJH) model in this embodiment was 0.02 cm³. 3 / g~0.25cm 3 A catalyst according to Embodiment A, B, C, D, E, F, G, H, or I, which is in the range of / g.

[0245] Embodiment K. The pore volume determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda (BJH) model was 0.1 cm³. 3 / g~0.2cm 3 A catalyst according to Embodiments A, B, C, D, E, F, G, H, I, or J, in the range of / g.

[0246] Embodiment L. The Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis is 5 m². 2 / g~60m 2 A catalyst according to Embodiments A, B, C, D, E, F, G, H, I, J, or K, in the range of / g.

[0247] Embodiment M. The Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis is 10 m². 2 / g~25m 2 A catalyst according to Embodiments A, B, C, D, E, F, G, H, I, J, K, or L, in the range of / g.

[0248] Embodiment N. A catalyst material comprising the catalyst described in Embodiments A, B, C, D, E, F, G, H, I, J, K, L, or M, and a catalyst support or carrier.

[0249] Embodiment O. The catalyst according to Embodiment N, wherein the catalyst support or carrier is selected from the group consisting of precipitated synthetic silica, fumed synthetic silica, silica-alumina, α-alumina, γ-alumina, titania, WO3-ZrO2, silicon carbide, MgAl spinel, calcium aluminate, zirconia, and boron nitride.

[0250] Embodiment P. The catalyst according to Embodiment N or O, wherein the catalyst support or carrier is α-alumina.

[0251] Embodiment Q. The catalyst according to Embodiments A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the catalyst has an ethane conversion rate of at least 45% and an ethylene selectivity of at least 90% in the oxidative dehydrogenation reaction of ethane.

[0252] Embodiment R. The catalyst according to Embodiments A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the catalyst has a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane.

[0253] Embodiment S. The catalyst according to Embodiments A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the catalyst has a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

[0254] Embodiment T. A catalyst material according to Embodiment N or O, having at least 45% ethane conversion rate and at least 90% ethylene selectivity in an oxidative dehydrogenation reaction of ethane.

[0255] Embodiment U. A catalyst material according to Embodiment N or O, having a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane.

[0256] Embodiment V. A catalyst material according to Embodiment N or O, having a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

[0257] Embodiment W. A method for preparing a catalyst, comprising the steps of forming a slurry containing a metal oxide, a bismuth compound, a reducing agent, and water, and heating the slurry to form a catalyst, wherein the metal oxide includes molybdenum oxide, vanadium oxide, and tantalum oxide or niobium oxide or both, and the bismuth compound includes bismuth oxide, bismuth hydroxide, or bismuth carbonate.

[0258] Embodiment X. The method according to Embodiment W, wherein the ratio of water in the slurry to the amount of catalyst formed is in the range between 0.1 mL of water per gram of catalyst and 10 mL of water per gram of catalyst.

[0259] Embodiment Y. The method according to Embodiment W or X, wherein the ratio of water in the slurry to the amount of catalyst formed is in the range between 0.2 mL of water per gram of catalyst and 1 mL of water per gram of catalyst.

[0260] Embodiment Z. The method according to Embodiment W, X, or Y, wherein the slurry has a water-to-metal oxide ratio in the range of 0.2 mL of water per gram of metal oxide and 0.6 mL of water per gram of metal oxide.

[0261] Embodiment AA. The method according to Embodiment W, X, Y, or Z, wherein the slurry has a water-to-metal oxide ratio in the range of 0.3 mL of water per gram of metal oxide and 0.5 mL of water per gram of metal oxide.

[0262] Embodiment AB. The method according to Embodiments W, X, Y, Z, or AA, wherein the molybdenum oxide is MoO3.

[0263] Embodiment AC. The method according to Embodiments W, X, Y, Z, AA, or AB, wherein the vanadium oxide is V2O5.

[0264] Embodiment AD. The method according to Embodiments W, X, Y, Z, AA, AB, or AC, wherein if tantalum oxide is present, it is Ta2O5·xH2O, and if niobium oxide is present, it is Nb2O5·xH2O.

[0265] Embodiment AE. The method according to Embodiments W, X, Y, Z, AA, AB, AC, or AD, wherein the bismuth compound is bismuth hydroxide.

[0266] Embodiment AF. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, or AE, further comprising the steps of grinding, wet grinding, dry grinding, or crushing a metal oxide and a bismuth compound.

[0267] Embodiment AG. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, or AF, further comprising the step of grinding, wet grinding, dry grinding, or crushing the reducing agent.

[0268] Embodiment AH. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, or AG, wherein the reducing agent comprises an alcohol, a carboxylic acid, or an ester.

[0269] Embodiment AI. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, or AH, wherein the reducing agent is oxalic acid.

[0270] Embodiment AJ. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, or AI, wherein the slurry contains one or fewer reducing agents.

[0271] Embodiment AK. A method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, or AJ, comprising the step of heating a slurry by raising the temperature from ambient temperature to a temperature of 100°C to 200°C over a heating time of 2 hours to 48 hours, and holding the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 hours to 160 hours.

[0272] Embodiment AL. A method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, or AJ, comprising the step of heating a slurry by raising the temperature from ambient temperature to a temperature of 100°C to 200°C over a heating time of 2 hours to 48 hours, and holding the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 hours to 120 hours.

[0273] Embodiment AM. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, or AL, further comprising the step of washing the catalyst with water.

[0274] Embodiment AN. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, AL, or AM, further comprising the step of calcining a catalyst to form a calcined catalyst.

[0275] Embodiment AO. A method according to Embodiment AN, comprising the steps of calcining a catalyst by placing the catalyst in a furnace in an oxygen-free environment, raising the furnace temperature from ambient temperature to a temperature of 500°C to 620°C over a heating time of 2 to 10 hours, and maintaining the furnace temperature at a holding temperature of 500°C to 620°C for a holding time of 1 to 10 hours.

[0276] Embodiment AP. A method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, AL, AM, AN, or AO, wherein the catalyst is of the formula:Mo a V b Bi c M d O x A method comprising the formula, where M is Ta or 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, x is the number of oxygen atoms required to make the catalyst electrically neutral, and a, b, c, and d are determined based on the amount of each starting material used to form the catalyst.

[0277] Embodiment AQ. The method according to Embodiment AP, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

[0278] Embodiment AR. The catalyst is Mo1V 0.31 Bi 0.04 M 0.05 O xMo1V 0.31 Bi 0.05 M 0.05 O x Mo1V 0.31 Bi 0.06 M 0.05 O x Mo1V 0.32 Bi 0.05 M 0.05 O x Mo1V 0.32 Bi 0.04 M 0.03 O x Mo1V 0.33 Bi 0.05 M 0.04 O x Mo1V 0.26 Bi 0.06 M 0.03 O x Mo1V 0.33 Bi 0.06 M 0.04 O x , and Mo1V 0.26 Bi 0.05 M 0.05 O x The method according to embodiment AP or AQ, having an expression selected from the following.

[0279] Embodiment AS. The catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.03 O x Mo1V 0.33 Bi 0.06 Ta 0.04 O x , and Mo1V 0.26 Bi 0.05 Ta 0.05 O x The method according to embodiment AP or AQ, having an expression selected from the following.

[0280] Embodiment AT. The method according to Embodiments W, X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, AL, AM, AN, AO, AP, AQ, AR, or AS, wherein the metal oxide and bismuth compound each have a particle size distribution in the range of 0.5 μm to 250 μm.

[0281] Embodiment AU. The method according to Embodiments X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, AL, AM, AN, AO, AP, AQ, AR, AS, or AT, wherein the ratio of the total amount of water used to prepare the catalyst is in the range between 0.2 mL of water per gram of catalyst and 25 mL of water per gram of catalyst.

[0282] Embodiment AV. The method according to Embodiments X, Y, Z, AA, AB, AC, AD, AE, AF, AG, AH, AI, AJ, AK, AL, AM, AN, AO, AP, AQ, AR, AS, AT, or AU, wherein the catalyst has at least 45% ethane conversion and at least 90% ethylene selectivity in the oxidative dehydrogenation reaction of ethane.

[0283] Embodiment AW. A process for the oxidative dehydrogenation of ethane, the process comprising contacting a gaseous feed containing ethane and oxygen with a catalyst in a reactor to produce an effluent containing ethylene, wherein the catalyst is of the formula: Mo a V b Bi c M d O x A process having the following characteristics, where M is Ta or 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, x is the number of oxygen atoms required to make the catalyst electrically neutral, and a, b, c, and d are determined based on the amount of each starting material used to form the catalyst.

[0284] Embodiment AX: The process according to Embodiment AW, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

[0285] Embodiment AY: The process according to Embodiment AW or AX, wherein b is 0.2 to 0.4, c is 0.01 to 0.07, and d is 0.01 to 0.07.

[0286] Embodiment AZ. The process according to Embodiment AW, AX, or AY, wherein b is 0.30 to 0.35, c is 0.04 to 0.05, and d is 0.03 to 0.05.

[0287] Embodiment AAA: The process according to Embodiment AW or AX, wherein b is 0.2 to 0.3, c is 0.05 to 0.07, and d is 0.02 to 0.04.

[0288] Embodiment AAB. The process according to Embodiment AW or AX, wherein b is 0.3 to 0.4, c is 0.05 to 0.07, and d is 0.03 to 0.05.

[0289] Embodiment AAC. The catalyst is Mo1V 0.31 Bi 0.04 M 0.05 O x Mo1V 0.31 Bi 0.05 M 0.05 O x Mo1V 0.31 Bi 0.06 M 0.05 O x Mo1V 0.32 Bi 0.05 M 0.05 O x Mo1V 0.32 Bi 0.04 M 0.03 O x Mo1V 0.33 Bi 0.05 M 0.04 O x Mo1V 0.26 Bi 0.06 M 0.03 O x Mo1V 0.33 Bi 0.06 M 0.04 O x , and Mo1V 0.26 Bi0.05 M 0.05 O x A process according to embodiment AW, AX, or AY, having an expression selected from the following.

[0290] Embodiment AAD. The catalyst is Mo1V 0.32 Bi 0.04 Ta 0.03 O x Mo1V 0.33 Bi 0.05 Ta 0.04 O x Mo1V 0.26 Bi 0.06 Ta 0.03 O x Mo1V 0.31 Bi 0.06 Nb 0.01 O x Mo1V 0.33 Bi 0.06 Ta 0.04 O x , and Mo1V 0.26 Bi 0.05 Ta 0.05 O x A process according to embodiment AW, AX, or AY, having an expression selected from the following.

[0291] Embodiment AAE. The process according to Embodiments AW, AX, AY, AZ, AAA, AAB, AAC, or AAD, wherein the catalyst is contained in a catalyst material, and the catalyst material includes a catalyst support or carrier.

[0292] Embodiment AAF. The process according to Embodiment AAE, wherein the catalyst support or carrier is α-alumina.

[0293] Embodiment AAG: The process according to Embodiments AW, AX, AY, AZ, AAA, AAB, AAC, AAD, AAE, or AAF, having a 45% ethane conversion temperature of 300°C to 420°C.

[0294] Embodiment AAH: The process according to Embodiments AW, AX, AY, AZ, AAA, AAB, AAC, or AAD, AAE, or AAF, having a 45% ethane conversion temperature of 350°C to 400°C.

[0295] Embodiment AAI. The process according to Embodiment AW, AX, AY, AZ, AAA, AAB, AAC, or AAD, AAE, AAF, AAG, or AAH, further comprising converting ethylene into a product.

[0296] Embodiment AAJ. The process according to Embodiment AAI, wherein the product is polyethylene 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).

[0297] Other embodiments are also included in the claims.

Claims

1. Formula: Mo ａ V ｂ Bi ｃ M ｄ O ｘ A catalyst composed of, During the ceremony, M is Ta or Nb or a mixture thereof. a is 1.0, b is between 0.01 and 0.

5. c is between 0.005 and 0.

2. d is between 0.005 and 0.

1. x is the number of oxygen atoms required to make the catalyst electrically neutral. a, b, c, and d are catalysts, determined based on the amount of each starting material used to form the catalyst.

2. The catalyst according to claim 1, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

3. b is between 0.2 and 0.4, c is between 0.01 and 0.07, d is between 0.01 and 0.

07. The catalyst according to claim 1.

4. b is between 0.30 and 0.

35. c is between 0.04 and 0.

05. d is between 0.03 and 0.

05. The catalyst according to claim 1.

5. b is between 0.2 and 0.3, c is between 0.05 and 0.07, d is between 0.02 and 0.

04. The catalyst according to claim 1.

6. b is between 0.3 and 0.4, c is between 0.05 and 0.07, d is between 0.03 and 0.

05. The catalyst according to claim 1.

7. The catalyst is Mo １ V ０．３１ Bi ０．０４ M ０．０５ O ｘ 、Mo １ V ０．３１ Bi ０．０５ M ０．０５ O ｘ 、Mo １ V ０．３１ Bi ０．０６ M ０．０５ O ｘ 、Mo １ V ０．３２ Bi ０．０５ M ０．０５ O ｘ 、Mo １ V ０．３２ Bi ０．０４ M ０．０３ O ｘ 、Mo １ V ０．３３ Bi ０．０５ M ０．０４ O ｘ 、Mo １ V ０．２６ Bi ０．０６ M ０．０３ O ｘ 、Mo １ V ０．３３ Bi ０．０６ M ０．０４ O ｘ 、and Mo １ V ０．２６ Bi ０．０５ M ０．０５ O ｘ The catalyst according to claim 1, having a formula selected from

8. The catalyst is Mo １ V ０．３２ Bi ０．０４ Ta ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０５ Ta ０．０４ O ｘ Mo １ V ０．２６ Bi ０．０６ Ta ０．０３ O ｘ Mo １ V ０．３１ Bi ０．０６ Nb ０．０１ O ｘ Mo １ V ０．３３ Bi ０．０６ Ta ０．０４ O ｘ , and Mo １ V ０．２６ Bi ０．０５ Ta ０．０５ O ｘ The catalyst according to claim 1, having a formula selected from the following.

9. The catalyst is Mo １ V ０．３２ Bi ０．０４ Ta ０．０３ O8]]O ｘ 、 Mo １ V ０．３３ Bi ０．０５ Ta ０．０４ O ｘ 、 Mo １ V ０．２６ Bi ０．０５ Ta ０．０５ O ｘ 、 and Mo １ V ０．２６ Bi ０．０６ Ta ０．０３ O ｘ having a formula selected from, the formula being determined by energy dispersive X-ray spectroscopy (EDX), the catalyst according to claim 1.

10. The pore volume, determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda (BJH) model, was 0.02 cm³. ３ / g ~ 0.25cm ３ The catalyst according to claim 1, wherein the range is within / g.

11. The pore volume, determined by nitrogen physicoadsorption analysis using the Barrett-Joyner-Halenda (BJH) model, was 0.1 cm³. ３ / g ~ 0.2cm ３ The catalyst according to claim 1, wherein the range is within / g.

12. The Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis was 5 m². ２ / g ~ 60m ２ The catalyst according to claim 1, wherein the range is within / g.

13. The Brunauer-Emmett-Teller (BET) surface area determined by nitrogen physicoadsorption analysis was 10 m². ２ / g to 25m ２ The catalyst according to claim 1, wherein the range is within / g.

14. A catalyst material comprising the catalyst described in claim 1 and a catalyst support or carrier.

15. The catalyst support or carrier is precipitated synthetic silica, fumed synthetic silica, silica-alumina, α-alumina, γ-alumina, titania, WO ３ -ZrO ２ The catalyst material according to claim 14, selected from the group consisting of silicon carbide, MgAl spinel, calcium aluminate, zirconia, and boron nitride.

16. The catalyst material according to claim 15, wherein the catalyst support or carrier is α-alumina.

17. The catalyst according to claim 1, wherein the catalyst has an ethane conversion rate of at least 45% and an ethylene selectivity of at least 90% in the oxidative dehydrogenation reaction of ethane.

18. The catalyst according to claim 1, wherein the catalyst has a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane.

19. The catalyst according to claim 1, wherein the catalyst has a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

20. The catalyst material according to claim 14, having at least 45% ethane conversion rate and at least 90% ethylene selectivity in the oxidative dehydrogenation reaction of ethane.

21. The catalyst material according to claim 14, having a 45% ethane conversion temperature of 300°C to 420°C in the oxidative dehydrogenation reaction of ethane.

22. The catalyst material according to claim 14, having a 45% ethane conversion temperature of 350°C to 400°C in the oxidative dehydrogenation reaction of ethane.

23. A method for preparing a catalyst, A step of forming a slurry containing a metal oxide, a bismuth compound, a reducing agent, and water, A step of heating the slurry to form a catalyst, and Includes, Metal oxides are, Molybdenum oxide, Vanadium oxide, and Tantalum oxide or niobium oxide, or both. Includes, A method comprising bismuth compounds, including bismuth oxide, bismuth hydroxide, or bismuth carbonate.

24. The method according to claim 23, wherein the ratio of water in the slurry to the amount of catalyst formed is in the range between 0.1 mL of water per gram of catalyst and 10 mL of water per gram of catalyst.

25. The method according to claim 23, wherein the ratio of water in the slurry to the amount of catalyst formed is in the range between 0.2 mL of water per gram of catalyst and 1 mL of water per gram of catalyst.

26. The method according to claim 23, wherein the slurry has a water-to-metal oxide ratio in the range between 0.2 mL of water per gram of metal oxide and 0.6 mL of water per gram of metal oxide.

27. The method according to claim 23, wherein the slurry has a water-to-metal oxide ratio in the range between 0.3 mL of water per gram of metal oxide and 0.5 mL of water per gram of metal oxide.

28. Molybdenum oxide is MoO ３ The method according to claim 23.

29. Vanadium oxide is V ２ O ５ The method according to claim 23.

30. If tantalum oxide is present, Ta ２ O ５ ・xH ２ It is O, and if niobium oxide is present, then Nb ２ O ５ ・xH ２ The method according to claim 23, wherein the result is O.

31. The method according to claim 23, wherein the bismuth compound is bismuth hydroxide.

32. The method according to claim 23, further comprising the steps of grinding, wet grinding, dry grinding, or crushing a metal oxide and a bismuth compound.

33. The method according to claim 23, further comprising the step of crushing, wet crushing, dry crushing, or crushing a reducing agent.

34. The method according to claim 23, wherein the reducing agent comprises an alcohol, a carboxylic acid, or an ester.

35. The method according to claim 34, wherein the reducing agent is oxalic acid.

36. The method according to claim 23, wherein the slurry contains one or less reducing agents.

37. The method according to claim 23, The temperature is raised from the ambient temperature to a temperature of 100°C to 200°C over a heating time of 2 hours to 48 hours, and Maintain the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 hours to 160 hours. A method comprising the step of heating a slurry.

38. The method according to claim 23, The temperature is raised from the ambient temperature to a temperature of 100°C to 200°C over a heating time of 2 hours to 48 hours, and Maintain the temperature at a holding temperature of 100°C to 200°C for a holding time of 12 to 120 hours. A method comprising the step of heating a slurry.

39. The method according to claim 23, further comprising the step of washing the catalyst with water.

40. The method according to claim 23, further comprising the step of calcining a catalyst to form a calcined catalyst.

41. The method according to claim 40, The catalyst is placed inside a furnace in an oxygen-free environment. The furnace temperature is raised from the ambient temperature to a temperature of 500°C to 620°C over a heating time of 2 to 10 hours, and The furnace temperature is maintained at a holding temperature of 500°C to 620°C for a holding time of 1 to 10 hours. A method comprising the step of calcining a catalyst.

42. The method according to claim 23, wherein the catalyst is of formula: Mo ａ V ｂ Bi ｃ M ｄ O ｘ It consists of, During the ceremony, M is Ta or Nb or a mixture thereof. a is 1.0, b is between 0.01 and 0.

5. c is between 0.005 and 0.

2. d is between 0.005 and 0.

1. x is the number of oxygen atoms required to make the catalyst electrically neutral. a, b, c, and d are determined based on the amounts of each starting material used to form the catalyst, in a method.

43. The method according to claim 42, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

44. The catalyst is Mo １ V ０．３１ Bi ０．０４ M ０．０５ O ｘ Mo １ V ０．３１ Bi ０．０５ M ０．０５ O ｘ Mo １ V ０．３１ Bi ０．０６ M ０．０５ O ｘ Mo １ V ０．３２ Bi ０．０５ M ０．０５ O ｘ Mo １ V ０．３２ Bi ０．０４ M ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０５ M ０．０４ O ｘ Mo １ V ０．２６ Bi ０．０６ M ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０６ M ０．０４ O ｘ , and Mo １ V ０．２６ Bi ０．０５ M ０．０５ O ｘ The method according to claim 42, having an expression selected from.

45. The catalyst is Mo １ V ０．３２ Bi ０．０４ Ta ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０５ Ta ０．０４ O ｘ Mo １ V ０．２６ Bi ０．０６ Ta ０．０３ O ｘ Mo １ V ０．３１ Bi ０．０６ Nb ０．０１ O ｘ Mo １ V ０．３３ Bi ０．０６ Ta ０．０４ O ｘ , and Mo １ V ０．２６ Bi ０．０５ Ta ０．０５ O ｘ The method according to claim 42, having an expression selected from.

46. The method according to claim 23, wherein the metal oxide and the bismuth compound each have a particle size distribution in the range of 0.5 μm to 250 μm.

47. The method according to claim 23, wherein the ratio of the total amount of water used to prepare the catalyst is in the range between 0.2 mL of water per gram of catalyst and 25 mL of water per gram of catalyst.

48. The method according to claim 23, wherein the catalyst has at least 45% ethane conversion rate and at least 90% ethylene selectivity in the oxidative dehydrogenation reaction of ethane.

49. A process for the oxidative dehydrogenation of ethane, The process includes contacting a gaseous feed containing ethane and oxygen with a catalyst in a reactor to produce an ethylene-containing effluent, wherein the catalyst is of formula: Mo ａ V ｂ Bi ｃ M ｄ O ｘ It has, During the ceremony, M is Ta or Nb or a mixture thereof. a is 1.0, b is between 0.01 and 0.

5. c is between 0.005 and 0.

2. d is between 0.005 and 0.

1. x is the number of oxygen atoms required to make the catalyst electrically neutral. a, b, c, and d are processes determined based on the amount of each starting material used to form the catalyst.

50. The process according to claim 49, wherein the values ​​of a, b, c, and d are also determined by elemental analysis.

51. b is between 0.2 and 0.4, c is between 0.01 and 0.07, d is between 0.01 and 0.

07. The process according to claim 49.

52. b is between 0.30 and 0.

35. c is between 0.04 and 0.

05. d is between 0.03 and 0.

05. The process according to claim 49.

53. b is between 0.2 and 0.3, c is between 0.05 and 0.07, d is between 0.02 and 0.

04. The process according to claim 49.

54. b is between 0.3 and 0.4, c is between 0.05 and 0.07, d is between 0.03 and 0.

05. The process according to claim 49.

55. The catalyst is Mo １ V ０．３１ Bi ０．０４ M ０．０５ O ｘ Mo １ V ０．３１ Bi ０．０５ M ０．０５ O ｘ Mo １ V ０．３１ Bi ０．０６ M ０．０５ O ｘ Mo １ V ０．３２ Bi ０．０５ M ０．０５ O ｘ Mo １ V ０．３２ Bi ０．０４ M ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０５ M ０．０４ O ｘ Mo １ V ０．２６ Bi ０．０６ M ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０６ M ０．０４ O ｘ , and Mo １ V ０．２６ Bi ０．０５ M ０．０５ O ｘ The process according to claim 49, having an expression selected from.

56. The catalyst is Mo １ V ０．３２ Bi ０．０４ Ta ０．０３ O ｘ Mo １ V ０．３３ Bi ０．０５ Ta ０．０４ O ｘ Mo １ V ０．２６ Bi ０．０６ Ta ０．０３ O ｘ Mo １ V ０．３１ Bi ０．０６ Nb ０．０１ O ｘ Mo １ V ０．３３ Bi ０．０６ Ta ０．０４ O ｘ , and Mo １ V ０．２６ Bi ０．０５ Ta ０．０５ O ｘ The process according to claim 49, having a formula selected from, the formula being determined by energy-dispersive X-ray spectroscopy (EDX).

57. The process according to claim 49, wherein the catalyst is contained in a catalytic material, and the catalytic material includes a catalytic support or carrier.

58. The process according to claim 57, wherein the catalyst support or carrier is α-alumina.

59. The process according to claim 49, having a 45% ethane conversion temperature of 300°C to 420°C.

60. The process according to claim 49, having a 45% ethane conversion temperature of 350°C to 400°C.

61. The process according to claim 49, further comprising converting ethylene into a product.

62. The process according to claim 61, wherein the product is polyethylene 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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