SO2-tolerant catalyst and method for preparing the same

Abstract

Various aspects of the present disclosure are directed to apparatuses, systems, and methods for preparing catalysts. In some embodiments, the catalyst includes a catalytically active component and a support material including a crystalline structure containing anatase phase TiO 2 and a secondary material. In some embodiments, the support material includes secondary materials such as SiO 2 , MoO 3 , WO 3 and Al 2 O 3 .

Description

Technical Field

[0001] Cross - reference to related applications This application claims the benefit of Provisional Application No. 63 / 342,342, filed May 16, 2022, the entire disclosure of which is hereby incorporated by reference herein for all purposes.

[0002] Field The present disclosure generally relates to SO 2 supported catalysts and methods for preparing supported catalysts. More specifically, the present disclosure relates to supported catalysts and methods for preparing supported catalysts by dry - mixing and heat - treating.

Background Art

[0003] Background Conventional methods used to manufacture supported catalysts generally include the preparation of pellets or supports, the liquid impregnation of the catalyst support into a solution containing a catalyst precursor, a subsequent drying process to remove the liquid, and a subsequent calcination process. The liquid impregnation and drying steps typically take more than 5 hours, and the calcination step performed after the liquid impregnation and drying may also take more than 5 hours.

[0004] Furthermore, among commercially available denitration (DeNOx) catalysts (e.g., catalysts used to remove NO and NO 2 ), some are not ideal for direct use in filter bags. For example, monolith denitration (DeNOx) catalysts and pellet denitration (DeNOx) catalysts need to be milled into smaller particles, and among commercially available powder denitration (DeNOx) catalysts, some do not have sufficient catalytic activity, particle size distribution, shape, or morphology to maximize catalytic performance in the form of filter bags.

[0005] Furthermore, air pollution has drawn great attention worldwide. In the past few years, many countries have been focusing on NO xStrict emission requirements are announced to minimize emissions. Generally, a DeNOx catalyst filter system is known, but under certain operating conditions common in specific industries (for example, industries where the process is carried out at low temperatures or industries with high concentrations of SO 2 such as cement manufacturing), rapid deactivation of the DeNOx catalyst may occur.

[0006] Therefore, there is a need for low-temperature selective catalytic reduction ("SCR") DeNOx catalysts with high SO 2 resistance, and methods for manufacturing these catalysts more efficiently. There is also a need to improve methods for removing NO x compounds, dioxins and dioxin-like compounds, halogenated compounds, and particulate matter from industrial flue gases such as those from cement manufacturing plants. SUMMARY OF THE INVENTION

[0007] Abstract The present disclosure generally relates to an SO 2 resistant catalyst, and a method for preparing an SO 2 resistant supported catalyst, which includes mixing a dry catalyst precursor containing a metal and a ligand with a dry carrier material to form a mixture, and firing the mixture.

[0008] According to a first embodiment ("Embodiment 1"), a catalyst is provided that includes a catalytic active component and a carrier material including TiO 2 having a crystal structure including anatase phase. In some embodiments, the carrier material includes a secondary material.

[0009] Embodiment 2 is the catalyst of Embodiment 1, and the secondary material is selected from the group consisting of at least one of SiO 2 , MoO 3 , WO 3 and Al 2 O 3 .

[0010] Embodiment 3 is the catalyst of Embodiments 1 to 2, and the secondary material has a mass percentage of 2% to 35% based on the total mass of the catalyst.

[0011] Embodiment 4 is the catalyst of Embodiments 1 to 3, and the secondary material is SiO 2 and is.

[0012] Embodiment 5 is the catalyst of Embodiments 1 to 4, and the ratio [(Ia / Ib)×100] of the intensity [Ia] of the peak indicating the anatase crystal present in the range of 2θ = 24.7° to 2θ = 25.7° in the powder X-ray diffraction of TiO 2 to the intensity [Ib] of the peak indicating the anatase crystal present in the range of 2θ = 24.7° to 2θ = 25.7° in the powder X-ray diffraction of the standard sample composed of anatase-type titanium oxide is 30% to 360%.

[0013] Embodiment 6 is the catalyst of Embodiments 1 to 5, and the catalyst has an NO x removal efficiency of 30% to 90% in the temperature range of 150°C to 280°C.

[0014] Embodiment 7 is the catalyst of Embodiment 6, and the catalyst has an apparent reaction rate constant of 40 to 400 cm 3 for the selective catalytic reduction of NO x by NH 3 / g in the temperature range of 150°C to 280°C.

[0015] Embodiment 8 is the catalyst of Embodiments 1 to 7, and the catalyst has an NO x removal efficiency of 60% to 80% in the temperature range of 170°C to 220°C.

[0016] Embodiment 9 is the catalyst of Embodiments 1 to 8, and when the catalyst is tested in the selective catalytic reduction of NO 2 by NH 3 in the presence of SO x , the initial inactivation rate is reduced as compared with the catalyst containing the carrier material having TiO 2 .

[0017] Embodiment 10 is the catalyst of Embodiments 1 to 9, and the carrier material has a specific surface area of 50 to 500 m 2 / g.

[0018] Embodiment 11 is the catalyst of Embodiments 1 to 10, and the catalyst active component is vanadium monoxide (VO), vanadium trioxide (V 2 O 3 ), vanadium dioxide (VO 2 ), vanadium pentoxide (V 2 O 5 ), molybdenum trioxide (MoO 3 ), manganese oxide (MnO 2 ), iron(III) oxide (Fe 2 O 3 ), iron(II) oxide (FeO), copper oxide (CuO), or at least one of any combination thereof.

[0019] Embodiment 12 is the catalyst of Embodiments 1 to 11, and the catalyst active component has a loading rate of 4% by mass to 50% by mass based on the total mass of the catalyst.

[0020] Embodiment 13 is the catalyst of Embodiments 1 to 12, and the catalyst active component has a loading rate of 10% by mass to 30% by mass based on the total mass of the catalyst.

[0021] Embodiment 14 is the catalyst of Embodiments 1 to 13, and the carrier material includes particles having an average diameter of 0.5 μm to 1000 μm.

[0022] Embodiment 15 is the catalyst of Embodiments 1 to 14, the catalyst active component is V 2 O 5 , the carrier material is TiO 2 , and the secondary material is SiO 2 .

[0023] Embodiment 16 is a catalyst product including the catalyst of Embodiments 1 to 15.

[0024] Embodiment 17 is a method for catalyzing a reaction, including contacting a reactant stream with the catalyst of Embodiments 1 to 15.

[0025] Embodiment 18 is the catalyst of claims 1 to 15 or the catalyst article of claim 16, and the catalyst or the catalyst article has a NO removal efficiency of 10% to 99% in the temperature range of 150°C to 280°C. x It has a removal efficiency.

[0026] Embodiment 19 is a method for reducing the amount of a certain compound from a gas stream, including providing a first gas stream containing the compound at a first concentration, and contacting the gas stream with the catalyst article of Embodiment 16 to form a second gas stream containing the compound at a second concentration. In some embodiments, the first concentration is higher than the second concentration.

[0027] Embodiment 20 is the method of Embodiment 19, and the first gas stream contains SO at a concentration of 1 to 200 ppm. 2 It contains.

[0028] Embodiment 21 is the method of Embodiments 19 to 20, and the compound contains NO. x It contains.

[0029] Embodiment 22 is the method of Embodiments 19 to 21, and the compound contains at least one of nitrogen (N), dioxin or dioxin-like compounds, halogen or halogenated compounds. 2 ).

[0030] Embodiment 23 is the method of Embodiments 19 to 22, and the first gas stream further contains at least one of oxygen (O), water (H₂O), carbon monoxide (CO), carbon dioxide (CO₂), sulfur dioxide (SO₂), sulfur trioxide (SO₃), hydrocarbons or one or more organic or inorganic materials. 2 ), water (H 2 O), carbon monoxide (CO), carbon dioxide (CO 2 ₂), sulfur dioxide (SO 2 ₂), sulfur trioxide (SO 3 ₃), hydrocarbons or one or more organic or inorganic materials, etc.

[0031] Embodiment 24 is the method of Embodiments 19 to 23, and the gas stream is a flue gas stream having a temperature of 140 to 280°C.

[0032] Embodiment 25 is the method of Embodiment 24, and further includes increasing the compound removal efficiency of the catalyst article, and ammonia (NH 3 ) is added at a concentration in the range of 0.0001% to 0.5% of the concentration of the flue gas stream, and the temperature of the flue gas stream is increased to 240°C to 280°C. In some embodiments, the compound can be NO x .

[0033] Embodiment 26 is the method of Embodiment 24, and further includes increasing the compound removal efficiency of the catalyst article, and introducing additional NO 2 into the flue gas stream to increase the NO 2 concentration to a range of 2% to 99% of the total concentration of NO x in the first gas stream.

[0034] Embodiment 27 is a method for manufacturing a catalyst, including mixing a catalyst precursor having a metal and a ligand with a carrier material containing TiO 2 to form a mixture, firing the mixture, and adding a secondary material to the carrier material so that the crystal structure of TiO 2 remains substantially the same.

[0035] Embodiment 28 is the method of Embodiment 27, and the metal is selected from one or more of transition metals, alkali metals, alkaline earth metals, or salts thereof.

[0036] Embodiment 29 is the method of Embodiments 27 to 28, and the metal is selected from the group consisting of vanadium, molybdenum, copper, iron, or mixtures thereof.

[0037] Embodiment 30 is the method of Embodiments 27 to 29, and the ligand is carbonyl, oxalate, ammonium, cyclopentadienyl, diketonate, or a ligand of Formula I.

[0038] [Chemical formula]

[0039] In the above formula, R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl, and substituted acyl.

[0040] Embodiment 31 is the method of Embodiments 27 to 30, and the catalyst precursor is selected from the group consisting of vanadyl acetylacetonate, vanadium(III) acetylacetonate, bis(acetylacetonato) dioxomolybdenum(VI), iron(III) acetylacetonate, and copper(II) acetylacetonate.

[0041] Embodiment 32 is the method of Embodiments 27 to 31, and the catalyst has a metal content of 4 wt% to 50 wt% based on the total mass of the catalyst.

[0042] Embodiment 33 is a method for producing a catalyst, including mixing a catalyst precursor containing a metal and a ligand with a carrier material to form a mixture, and firing the mixture. In some embodiments, the carrier material has a crystal structure containing anatase phase TiO 2 and includes a secondary material.

[0043] Embodiment 34 is a method for producing a catalyst, including mixing TiO 2 with a secondary material to form a carrier material having a crystal structure containing anatase phase TiO 2 including mixing a catalyst precursor containing a metal and a ligand with the carrier material to form a mixture, and firing the mixture.

[0044] Embodiment 35 is the method of Embodiments 27 to 34, and the secondary material is selected from the group consisting of SiO 2 , MoO 3 , WO 3 and Al 2 O 3 .

[0045] The foregoing examples are merely examples and should not be construed as limiting or narrowing the scope of any of the inventive concepts separately provided by the present disclosure. Although multiple examples are disclosed, other embodiments will become apparent to those skilled in the art from the following detailed description which illustrates exemplary examples. Therefore, the drawings and the detailed description are not essentially limiting and should be considered as exemplary.

Brief Description of the Drawings

[0046] Brief Description of the Drawings The accompanying drawings are included to provide a further understanding of the present disclosure, are incorporated herein, form a part thereof, illustrate embodiments, and together with the description serve to explain the principles of the present disclosure.

[0047]

Figure 1

[0048]

Figure 2

[0049]

Figure 3

[0050]

Figure 4

[0051]

Figure 5

[0052]

Figure 6

[0053]

Figure 7

[0054] Detailed Description Definitions and Terms The present disclosure should not be construed in a limiting sense. For example, the terms used in this application should be construed broadly in the context of the meaning given to such terms by those skilled in the art.

[0055] Regarding inaccurate terms, the terms "about" and "approximately" can be used interchangeably to refer to measurements that include the stated measurement value and measurements that are reasonably close to the stated measurement value. Measurements that are reasonably close to the stated measurement value deviate from the stated measurement value by a reasonably small amount that is understood and easily confirmed by those skilled in the relevant art. Such deviations can be due to, for example, measurement errors, differences in calibration of measurement and / or manufacturing equipment, human errors in reading and / or setting measurement values, small adjustments made to optimize performance and / or structural parameters considering differences in measurement values related to other components, specific implementation scenarios, inaccurate adjustment and / or operation of an object by a person or machine, and / or the like. If those skilled in the relevant art determine that such reasonably small difference values cannot be easily confirmed, the terms "about" and "approximately" are understood to mean plus or minus 10% of the stated value.

[0056] As used herein, the term "dioxin-like compound" means a compound including polychlorinated dibenzo-p-dioxin ("PCDD" or "dioxin"), polychlorinated dibenzofuran ("PCDF" or "furan"), polychlorinated biphenyl ("PCB"), or polybrominated analogs of dioxin, furan, and PCB.

[0057] The term "NO x " means nitrogen oxides such as NO or NO 2 .

[0058] The term "denitration (DeNOx) catalyst" means a catalyst used for the removal of NO x , and is sometimes used for emission control.

[0059] The term "apparent reaction rate constant (k m )" can be calculated as follows.

Equation

[0060] In the above formula, k m is the first-order apparent reaction rate based on the catalyst mass (cm 3 / g s), V is the gas flow rate (cm 3 / s) under the reaction conditions, and W is the catalyst mass (g). The denitration (DeNO x ) efficiency is defined as follows.

[0061]

Equation

[0062] The apparent reaction rate constant is an index of the amount of gas processed per unit time in meters and the mass of the catalyst.

[0063] The term "selective catalytic reduction ("SCR")" means a means of converting NO x into diatomic nitrogen and water with the aid of a catalyst. A reducing agent (e.g., anhydrous ammonia (NH3 ), aqueous ammonia (NH 4 OH) or urea (CO(NH 2 ) 2 ) solution) is added to the flue or exhaust gas stream and reacted on a catalyst. For example, NO x During the SCR, NH 3 is introduced as a reducing agent, and NO is removed from the surface of the DeNOx catalyst. x and reacts.

[0064] The term "relative DeNOx efficiency" means the ratio of the DeNOx efficiency at a given time in the deactivation cycle to the initial DeNOx efficiency of a fresh catalyst.

[0065] The term "initial deactivation rate" refers to the relative decrease in deNOx efficiency over time.

[0066] Description of Various Embodiments Those skilled in the art will readily appreciate that the various aspects of the present disclosure may be implemented by any number of methods and devices configured to perform the intended functions. It should also be noted that the accompanying drawings referenced herein are not necessarily drawn to scale and may be exaggerated to illustrate various aspects of the present disclosure, and in that regard, the drawings should not be construed as limiting.

[0067] This disclosure generally relates to SO 2 The method includes mixing a dry catalyst precursor, including a metal and a ligand, with a dry support material to form a mixture, and calcining the mixture. 2 The present invention relates to a method for preparing a resistant supported catalyst.

[0068] In some embodiments, the catalyst comprises a catalytically active component and a TiO having a crystal structure with an anatase phase. 2 The carrier material may include

[0069] In some embodiments, the catalyst comprises at least one catalytically active component. In some embodiments, the at least one catalytically active component is vanadium monoxide (VO), vanadium trioxide (V 2 O 3 ), vanadium dioxide (VO 2 ), vanadium pentoxide (V 2 O 5 ), tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), manganese oxide (MnO 2 ), iron(III) oxide, iron(II) oxide, or at least one of any combination thereof. In one embodiment, the at least one catalytically active component is vanadium monoxide (VO), vanadium trioxide (V 2 O 3 ), vanadium dioxide (VO 2 ), vanadium pentoxide (V 2 O 5 ), or at least one of any combination thereof. In an exemplary embodiment, the at least one catalytically active component comprises only V 2 O 5 .

[0070] In some examples, the carrier material comprises a secondary material. In some embodiments, the secondary material can be SiO 2 , Fe 2 O 3 , CrO 3 , Re 2 O 7 , Nb 2 O 5 , K 2 O, MoO 3 , WO 3 , Al 2 O 3 , or zeolite. In an exemplary embodiment, the secondary material is SiO 2 .

[0071] In some embodiments, the carrier material is TiO 2The ratio [(Ia / Ib)×100] of the intensity [Ia] of the peak indicating the anatase crystal present in the range of 2θ = 24.7° to 2θ = 25.7° of the powder X-ray diffraction to the intensity [Ib] of the peak indicating the anatase crystal present in the range of 2θ = 24.7° to 2θ = 25.7° of the powder X-ray diffraction of the standard sample composed of anatase-type titanium oxide is 30% to 360%, and it has a crystal structure showing this. For example, TiO 2 can be M311 Hombikat TiO from Venator. 2

[0072] In some embodiments, the secondary material has a mass percentage of about 2 wt% to about 35 wt%, or about 3 wt% to 30 wt%, or about 4 wt% to 25 wt%, or about 5 wt% to about 20 wt%, or about 10 wt% to about 15 wt% based on the total mass of the catalyst.

[0073] Figure 1 is a bar graph showing comparative data of the NO x removal efficiency (i.e., catalyst activity) of various catalysts at different temperatures according to an embodiment. The data in Figure 1 is calculated based on the data collected according to the catalyst evaluation procedure 1, which will be described in more detail below.

[0074] As shown in the figure, the catalyst can have a catalyst activity of about 30% to about 90%, or about 40% to about 90%, or about 50% to about 90%, or about 60% to about 80%, or about 60% to about 80% in the temperature range of 150°C to 250°C. More specifically, the catalyst can have a catalyst activity of about 60% to about 80%, or about 65% to about 80%, or about 70% to about 80% in the temperature range of 170°C to 220°C.

[0075] In some embodiments, the catalyst can exhibit catalyst activity within the temperature range of 150°C to 280°C, or about 152°C to 260°C, or 155°C to 240°C, or 160°C to 230°C, or 165°C to 225°C, or 170°C to 220°C, or 175°C to 220°C, or 175°C to 200°C.

[0076] ​For example, the catalyst may have about 30% to about 90% catalytic activity in the temperature range of 150°C to 250°C, and the catalyst may have 60% to 80% catalytic activity in the temperature range of 170°C to 220°C.

[0077] 2 is a line graph showing comparative apparent reaction rate constants for various catalysts at different temperatures, according to an embodiment. The data in FIG. 2 is calculated based on data collected according to Catalyst Evaluation Procedure 1, which is described in more detail below.

[0078] As shown, the catalyst is NH 3 By NO x For selective catalytic reduction of 3 / gs, or about 50 to about 350 cm 3 / gs, or about 60 to about 300 cm 3 / gs, or about 70 to about 250 cm 3 / gs, or about 80 to about 220 cm 3 / gs, or about 90 to about 200 cm 3 / gs, or about 100 to about 180 cm 3 / gs, or about 110 to about 160 cm 3 / gs apparent reaction rate constant.

[0079] FIG. 3 illustrates a SO over a period of time, according to an embodiment. 2 The relative NO of two different catalysts when exposed to x 3 is a line graph showing removal efficiency. The data in FIG. 3 is calculated based on data collected according to Catalyst Evaluation Procedure 2, which is described in more detail below. As shown, the catalytically active component is low and the TiO 2 Relative NO of catalysts using x The removal efficiency is high when the catalytic activity is high and TiO 2 and secondary materials (SiO 2 ) as the support material, the catalytic activity decreases at a faster rate over time.

[0080] FIG. 4 illustrates a SO over a period of time, according to an embodiment.2 It is a bar graph showing the initial inactivation rates of two different catalysts when exposed. As shown, the catalyst with fewer catalytic active components and using TiO 2 as the carrier material has a greater initial inactivation than the catalyst with more catalytic active components and using TiO 2 and secondary material (SiO 2 ) as the carrier material. In some embodiments, when tested by selective catalytic reduction of NO 2 by NH 3 in the presence of SO x , the catalyst with more catalytic active components and using TiO 2 -SiO 2 as the carrier material has a lower initial inactivation rate compared to the catalyst with fewer catalytic active components and using TiO 2 as the carrier material.

[0081] Figure 5 is a graph showing the X-ray diffraction patterns of catalysts according to embodiments, including various carrier materials and TiO 2 . The method of X-ray diffraction measurement will be described in more detail in the section of the following test methods.

[0082] The peaks indicating anatase crystals typically exist in the range of 2θ = 24.7° to 2θ = 25.7°. As shown in Figure 5, TiO 2 (standard sample, M311 Hombikat TiO 2 from Venator) has a high crystallinity of anatase-type titanium dioxide according to peak 502. Furthermore, TiO 2 -SiO 2 and 20%V 2 O 5 -TiO 2 -SiO 2(Catalyst Sample 4) According to peaks 504 and 506, the crystallinity of anatase titanium dioxide in the sample is high. The intensity (a.u.) of peak 502 indicating anatase crystalline titanium dioxide in the standard sample is 2177. The intensity (a.u.) of peak 506 indicating anatase crystalline titanium dioxide in catalyst sample 4 is 1988. The ratio of the intensity [Ia] of peak 506 indicating anatase crystals in the catalyst sample to the intensity [Ib] of peak 502 indicating anatase crystals in the standard sample is 91.3%.

[0083] In some embodiments, the carrier material is about 10 m 2 / g to about 3000 m 2 / g, about 15 m 2 / g to about 2500 m 2 / g, about 20 m 2 / g to about 2000 m 2 / g, about 25 m 2 / g to about 1500 m 2 / g, about 30 m 2 / g to about 1000 m 2 / g, about 35 m 2 / g to about 800 m 2 / g, about 40 m 2 / g to about 600 m 2 / g, about 45 m 2 / g to about 500 m 2 / g, about 50 m 2 / g to about 400 m 2 / g, about 55 m 2 / g to about 350 m 2 / g, or can have a specific surface area within these ranges. In some embodiments, the carrier material is about 60 m 2 / g to about 340 m 2 / g, about 65 m 2 / g to about 330 m 2 / g, about 70 m 2 / g to about 320 m 2 / g, or about 75 m 2 / g to about 310 m 2 / g. In an exemplary embodiment, the carrier material is about 50 m 2 / g to about 500 m 2It can have a specific surface area of / g.

[0084] In some embodiments, the carrier material can include particles having an average diameter of about 0.5 μm to about 1000 μm, about 0.6 μm to about 900 μm, about 0.7 μm to about 800 μm, about 0.8 μm to about 700 μm, about 0.9 μm to about 600 μm, about 1.0 μm to about 500 μm, about 1.1 μm to about 400 μm, about 1.2 μm to about 300 μm, about 1.3 μm to about 200 μm, about 1.4 μm to about 100 μm, or can include particles having an average diameter within these ranges. In some embodiments, the carrier material 106 can include particles having an average diameter of about 1.5 μm to about 90 μm, about 1.6 μm to about 80 μm, about 1.7 μm to about 70 μm, about 1.8 μm to about 60 μm, about 1.9 μm to about 55 μm, or about 1.95 μm to about 54 μm. In an exemplary embodiment, the carrier material can include particles having an average diameter of about 2.0 μm to about 52 μm. In another exemplary embodiment, the carrier material can include particles having an average diameter of 0.5 μm to 1000 μm.

[0085] In some embodiments, the catalytic active component can have a mass loading ratio of about 4 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 6 wt% to about 40 wt%, about 7 wt% to about 35 wt%, about 8 wt% to about 32.5 wt%, about 9 wt% to about 30 wt%, about 10 wt% to about 27.5 wt%, about 11 wt% to about 25 wt%, about 12 wt% to about 22.5 wt%, about 15 wt% to about 20 wt% based on the total mass of the catalyst. In yet another embodiment, the catalytic active component has a mass loading ratio of 10% to 30% based on the total mass of the catalyst.

[0086] As discussed above and shown in FIGS. 1-4, the denitration (DeNOx) catalyst according to the present disclosure has a low loading wt% of the catalytic active component and, compared to a catalyst using only TiO as the carrier material, has a low initial deactivation rate while maintaining catalytic activity, and thus exhibits higher SO 2 resistance. In an exemplary embodiment, the denitration (DeNOx) catalyst uses V as the catalytic active component. 2 2 2O 5 containing TiO as a carrier material 2 and SiO 2 As shown in FIG. 5, the anatase peak 506 of the catalyst sample 4 has substantially the same intensity (e.g., 91.3%) compared to the anatase peak 502 of the standard sample. Further, the peak 506 also maintains the full width at half maximum (FWHM), indicating that the crystal structure of TiO in the catalyst sample 4 2 has not changed. Without intending to be bound by theory, the reason why the crystal structure of TiO in the catalyst sample 4 2 has not changed is presumably that the position of SiO 2 is mainly in the pores or on the outer surface of TiO 2 and is not mixed with TiO at the atomic level. 2

[0087] The catalyst article can include the catalyst described above and can further include at least one additional material. The additional material is not limited to a specific type of material and can be, for example, a membrane, a felt mat, a ceramic substrate (including but not limited to a ceramic candle), a honeycomb substrate, a monolith substrate, or any combination thereof. The catalyst composite article can be, in some non-limiting examples, a porous catalyst film. For example, the catalyst article can include a catalyst having a NO x removal efficiency of about 20% to about 99%. In some embodiments, the method of catalyzing a reaction includes contacting a reactant stream with the catalyst described above. The NO x removal efficiency can be about 10% to about 99% for the catalyst described above or a catalyst article including the catalyst.

[0088] The methods shown in FIGS. 6-7 are examples of various features of methods of preparing and / or using a catalyst, and combinations of these illustrated features are clearly within the scope of the invention, but the examples and illustrations thereof are not intended to suggest that the inventive concepts provided herein are limited to fewer features, additional features, or alternative features with respect to one or more of the features shown in FIGS. 6-7.

[0089] ​Furthermore, one or more steps of the following methods can be optional steps and / or can be modified by one or more steps of other embodiments described herein. Additionally, one or more steps of other embodiments described herein can be added to the method.

[0090] Figure 6 is a flowchart showing a method 600 for reducing the amount of a compound from a gas stream according to an embodiment.

[0091] In step 602, method 600 can optionally include adding a secondary material to a carrier material. In some embodiments, adding the secondary material to the carrier material substantially maintains the crystal structure of TiO within the carrier material. 2 in the carrier material.

[0092] In step 604, method 600 can include mixing a dried catalyst precursor with a dried carrier material to form a mixture. In some embodiments, the dried catalyst precursor can include a metal and a ligand. In some embodiments, the catalyst precursor can contain no aqueous liquid or organic liquid at all. In some embodiments, the carrier material can contain no aqueous liquid or organic liquid at all.

[0093] In some embodiments, the dried carrier material can include TiO having an anatase phase and a secondary material. In some embodiments, the dried carrier material is produced by mixing TiO with a secondary material to form a carrier material containing TiO having the crystal structure of the anatase phase, and the secondary material is SiO, FeO, CrO, ReO, NbO, KO, MoO, WO, and AlO. 2 2 2 2 2 3 3 2 7 2 5 2 3 3 2 3 ​​​​​​​​​​​​​​​It is selected from a group containing at least one of them.

[0094] In some embodiments, the dry catalyst precursor can include a metal and a ligand. In some embodiments, the metal can be selected from one or more of transition metals, lanthanides, alkali metals, alkaline earth metals, or salts thereof. In some embodiments, the metal can be selected from Group 3 to Group 14 of the periodic table, such as, for example, V, Cr, Mn, Ce, Fe, Cu, Zn, Sn, Ta, Ni, Co, Nb, Sb, La, Eu, Gd, etc.

[0095] In an exemplary embodiment, the metal is selected from the group consisting of vanadium, copper, iron, molybdenum, or mixtures thereof.

[0096] In some embodiments, the ligand is carbonyl, oxalate, ammonium, dimethylamino, bromide, chloride, cyclopentadienyl, diketonate, or a ligand of formula (I) [Chemical formula]

[0097] (wherein R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl, and substituted acyl).

[0098] In an exemplary embodiment, the catalyst precursor can include a metal and an acetylacetonate group or a ketone group. For example, the precursor can be zinc(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), dioxomolybdenum(VI) bis(acetylacetonate), chromium(III) acetylacetonate, chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), cobalt(II) hexafluoroacetylacetonate hydrate, copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), copper bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), copper(II) acetylacetonate, copper(II) ethylacetoacetate, copper(II) hexafluoroacetylacetonate hydrate, copper(II) trifluoroacetylacetonate, europium(III) acetylacetonate hydrate, gadolinium(III) acetylacetonate hydrate, iron(III) acetylacetonate, lithium acetylacetonate, manganese(II) acetylacetonate, nickel(II) acetylacetonate, nickel(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), nickel(II) hexafluoroacetylacetonate hydrate, vanadyl acetylacetonate, vanadium(III) acetylacetonate, or zinc acetylacetonate hydrate.

[0099] In an exemplary embodiment, the catalyst precursor is selected from the group consisting of vanadyl acetylacetonate, vanadium(III) acetylacetonate, dioxomolybdenum(VI) bis(acetylacetonate), iron(III) acetylacetonate, and copper(II) acetylacetonate.

[0100] In some embodiments, step 604 can be performed using a vortex mixer, a shaking mixer, a double cone mixer, or a combination thereof. In some embodiments, step 604 can be performed using manual shaking within a scintillation vial. It will be readily apparent that other mixing devices are suitable. In some embodiments, step 604 is performed under inert, dry, or ambient conditions, i.e., for example, in the absence of O 2 and in the presence of dry N 2 and can be performed under conditions where it is present.

[0101] In some embodiments, step 604 can be performed over a time period of from about 30 seconds to about 10 hours, from about 35 seconds to about 9.5 hours, from about 40 seconds to about 9 hours, from about 45 seconds to about 8.5 hours, from about 50 seconds to about 8 hours, from about 55 seconds to about 7.5 hours, from about 1 minute to about 7 hours, from about 1.5 minutes to about 6.5 hours, from about 2 minutes to about 6 hours, from about 2.5 minutes to about 5.5 hours, from about 3 minutes to about 5 hours, or can be performed over a time period within these ranges. In some embodiments, step 604 can be performed over a time period of from about 30 seconds to about 4.5 hours, from about 40 seconds to about 4 hours, or from about 50 seconds to about 3.5 hours. In an exemplary embodiment, step 604 can be performed for about 1 minute.

[0102] In step 606, method 600 can include firing the mixture to form a supported catalyst. The firing step 606 can include heat-treating the dry mixture formed in step 604. The firing step 606 can be performed using a standard firing apparatus such as, for example, a rotary kiln. In an embodiment, the mixing step 604 and the firing step 606 can be performed simultaneously (i.e., integrated into one step). In some embodiments, the mixing step 604 and the firing step 606 can be performed consecutively.

[0103] In some embodiments, the firing step 606 can be performed using a rapid heating method (e.g., heating the dry mixture in an aluminum pan placed on a preheated hot plate). In some embodiments, the firing step 606 can be performed using a slow heating method (e.g., slowly heating the dry mixture in a crucible placed in a muffle furnace from room temperature). In some embodiments, the mixture can be heated by placing it in a preheated oven.

[0104] In some embodiments, the dry mixture can be fired at a temperature of about 100 °C to about 500 °C, about 105 °C to about 480 °C, about 110 °C to about 460 °C, about 115 °C to about 440 °C, about 120 °C to about 430 °C, about 125 °C to about 420 °C, about 130 °C to about 410 °C, about 135 °C to about 400 °C, about 140 °C to about 390 °C, about 145 °C to about 380 °C, or a temperature within these ranges. In some embodiments, the dry mixture can be fired at a temperature of about 146 °C to about 375 °C, about 147 °C to about 370 °C, or about 148 °C to about 365 °C. In an exemplary embodiment, the dry mixture can be fired at a temperature of about 360 °C.

[0105] In some embodiments, the dry mixture can be fired at a rate of about 1 °C / min to about 50 °C / min, about 1.25 °C / min to about 45 °C / min, about 1.5 °C / min to about 40 °C / min, about 1.75 °C / min to about 35 °C / min, about 2 °C / min to about 30 °C / min, about 2.25 °C / min to about 25 °C / min, about 2.5 °C / min to about 20 °C / min, about 2.75 °C / min to about 15 °C / min, about 3 °C / min to about 10 °C / min, or a rate within these ranges. In some embodiments, the dry mixture can be fired at a rate of about 3.2 °C / min to about 9 °C / min, about 3.4 °C / min to about 8 °C / min, about 3.6 °C / min to about 7 °C / min, or about 3.8 °C / min to about 6 °C / min. In an exemplary embodiment, the dry mixture can be fired at a rate of about 4 °C / min to about 5 °C / min.

[0106] In some embodiments, the dried mixture can be calcined in an atmosphere containing from about 1 to about 25 volume % oxygen, from about 2 to about 20 volume % oxygen, from about 3 to about 15 volume % oxygen, from about 3.5 to about 10 volume % oxygen, from about 4 to about 9 volume % oxygen, from about 4.5 to about 8 volume % oxygen, from about 5 to about 7 volume % oxygen, from about 5.5 to about 6.5 volume % oxygen, or a volume % oxygen within these ranges. In an exemplary embodiment, the dried mixture can be calcined in an atmosphere containing about 21 volume % oxygen.

[0107] In an exemplary embodiment, the dried catalyst precursor can be vanadyl acetylacetonate or vanadium(III) acetylacetonate, and the support material can be TiO 2 -SiO 2 and the calcination can be carried out at a temperature of about 360 °C.

[0108] The catalyst can be prepared by steps 604, 606 and optionally 602 of method 600. In some embodiments, the catalyst has a metal content (wt%) based on the total mass of the catalyst. In some embodiments, the catalyst has a metal content of from about 0.1 wt% to about 50 wt%, from about 0.25 wt% to about 45 wt%, from about 0.5 wt% to about 40 wt%, from about 1 wt% to about 35 wt%, from about 1.5 wt% to about 32.5 wt%, from about 2.0 wt% to about 30 wt%, from about 2.25 wt% to about 27.5 wt%, from about 2.5 wt% to about 25 wt%, from about 2.75 wt% to about 22.5 wt%, from about 3.0 wt% to about 20 wt%, or a metal content (wt%) within these ranges. In some embodiments, the catalyst has a metal content of about 3.2 wt% to about 19 wt%, about 3.4 wt% to about 18 wt%, about 3.6 wt% to about 17 wt%, or about 3.8 wt% to about 16 wt%. In one embodiment, the catalyst has a metal content of about 4 wt% to about 50 wt%. In an exemplary embodiment, the catalyst has a metal content of about 20 wt%.

[0109] In some embodiments, the catalyst has a NOx removal efficiency of about 1% to about 99%, about 5% to about 90%, about 10% to about 80%, about 15% to about 70%, about 20% to about 60%, or has a NOx removal efficiency included within these ranges.

[0110] In step 608, method 600 can include providing a first gas stream containing a compound at a certain concentration. In step 610, method 600 can include contacting the gas stream with the catalyst formed in step 606 to form a second gas stream containing the compound at a second concentration. In some embodiments, method 600 can include contacting the gas stream with a catalyst article including the catalyst formed in step 606 to form a second gas stream containing the compound at a second concentration. In an exemplary embodiment, the compound can include, for example, nitrogen monoxide (NO) and / or nitrogen dioxide (NO 2 ) and can include NO containing x . The compound can also include at least one of nitrogen (N 2 ), dioxin or dioxin-like compounds, halogen or halogenated compounds. In some examples, the first gas stream can further include at least one of oxygen (O 2 ), water (H 2 O), carbon monoxide (CO), carbon dioxide (CO 2 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), hydrocarbons, or one or more organic or inorganic materials. In an exemplary embodiment, the gas stream is a flue gas stream having a temperature of 140 to 250 °C.

[0111] In some embodiments, the first gas stream having the compound at the first concentration is upstream, and the second gas stream having the compound at the second concentration is downstream. In some embodiments, the first concentration is higher than the second concentration.

[0112] The first gas stream contains SO at a concentration of about 1 to 200 ppm, or about 10 to 180 ppm, or about 20 to 160 ppm, or about 30 to 140 ppm, or about 40 to 120 ppm, or about 50 to 100 ppm. 2 including.

[0113] In some embodiments, in step 612a, the above compound contains NO x and method 600 optionally includes adding ammonia (NH 3 ) at a concentration in the range of 0.0001% to 0.5% of the concentration of the flue gas stream.

[0114] In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.0001% to 0.5% of the concentration of the flue gas stream. In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.001% to 0.5% of the concentration of the flue gas stream. In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.01% to 0.5% of the concentration of the flue gas stream. In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.1% to 0.5% of the concentration of the flue gas stream.

[0115] In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.0001% to 0.1% of the concentration of the flue gas stream. In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.0001% to 0.05% of the concentration of the flue gas stream. In some embodiments, improving the NO x removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.0001% to 0.005% of the concentration of the flue gas stream.

[0116] In some embodiments, improving the NO removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.005% to 0.1% of the concentration of the flue gas stream. In some embodiments, improving the NO removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.005% to 0.05% of the concentration of the flue gas stream. x In some embodiments, improving the NO removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.005% to 0.1% of the concentration of the flue gas stream. In some embodiments, improving the NO removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.005% to 0.05% of the concentration of the flue gas stream. x In some embodiments, improving the NO removal efficiency of the catalyst article includes adding ammonia at a concentration in the range of 0.005% to 0.05% of the concentration of the flue gas stream.

[0117] In subsequent step 614a, method 600 can optionally include raising the temperature of the flue gas stream to between 240°C and 280°C.

[0118] Alternatively, in step 612b, method 600 can optionally include introducing additional NO into the flue gas stream to raise the NO concentration to a range of 2% to 99% of the total concentration of NO in the first gas stream. 2 By introducing additional NO into the flue gas stream, the NO concentration can be raised to a range of 2% to 99% of the total concentration of NO in the first gas stream. 2 The NO concentration can be raised to a range of 2% to 99% of the total concentration of NO in the first gas stream. x By introducing additional NO into the flue gas stream, the NO concentration can be raised to a range of 2% to 99% of the total concentration of NO in the first gas stream.

[0119] Performing optional steps 612a, 614a, and 612b can improve the compound removal efficiency of the catalyst article and regenerate the catalyst.

[0120] FIG. 7 is a flowchart showing a method for reducing the amount of a compound from a gas stream according to an embodiment.

[0121] In step 702, method 700 can include mixing a dried catalyst precursor with a dried support material to form a mixture. In some embodiments, the dried catalyst precursor can include a metal and a ligand. In some embodiments, the catalyst precursor can contain no aqueous or organic liquids. In some embodiments, the support material can contain no aqueous or organic liquids.

[0122] In some embodiments, the dry catalyst precursor can include a metal and a ligand. In some embodiments, the metal can be selected from Groups 3 to 14 of the periodic table, such as V, Cr, Mn, Ce, Fe, Cu, Zn, Sn, Ta, Ni, Co, Nb, Sb, La, Eu, Gd, etc. In an exemplary embodiment, the metal is selected from the group consisting of vanadium, copper, iron, molybdenum, or mixtures thereof.

[0123] In some embodiments, the dry carrier material can include TiO having an anatase phase. 2 The dry carrier material can further include a secondary material. In some embodiments, the dry carrier material is prepared by mixing TiO 2 with a secondary material to form a carrier material containing TiO having a crystal structure of the anatase phase. The secondary material is selected from the group consisting of at least one of SiO 2 2 2 3 3 2 7 2 5 2 3 3 2 3 2 In some embodiments, the dry carrier material can be a commercially available mixture of TiO and the secondary material.

[0124] In step 704, method 700 can include firing the mixture to form a supported catalyst. The firing step 704 can include heat-treating the dry mixture formed in step 702. The firing step 704 can be performed using a standard firing apparatus, such as a rotary kiln. In some embodiments, the mixing step 702 and the firing step 704 can be performed simultaneously (i.e., integrated into one step). In some embodiments, the mixing step 702 and the firing step 704 can be performed sequentially.

[0125] ​​​​​​​​​​​​​​ In some embodiments, the firing step 704 can be carried out using a rapid heating method (e.g., heating the dry mixture in an aluminum pan placed on a preheated hot plate). In some embodiments, the firing step 704 can be carried out using a slow heating method (e.g., slowly heating the dry mixture in a crucible placed in a muffle furnace from room temperature). In some embodiments, heating can also be effected by placing the mixture in a preheated oven.

[0126] In some embodiments, method 700 can optionally include step 706. In optional step 706, method 700 can include adding a secondary material to a carrier material, where the carrier material can include TiO having an anatase phase. 2 In some embodiments, optional step 706 includes adding a secondary material to the carrier material such that the crystal structure of TiO remains substantially the same. In some examples, the secondary material is selected from the group consisting of at least one of SiO, FeO, CrO, ReO, NbO, KO, MoO, WO, AlO, and zeolite. 2 In some embodiments, optional step 706 includes adding a secondary material to the carrier material such that the crystal structure of TiO remains substantially the same. In some examples, the secondary material is selected from the group consisting of at least one of SiO, FeO, CrO, ReO, NbO, KO, MoO, WO, AlO, and zeolite. 2 、Fe 2 O 3 、CrO 3 、Re 2 O 7 、Nb 2 O 5 、K 2 O、MoO 3 、WO 3 、Al 2 O 3 and zeolite.

[0127] In step 708, method 700 can include providing a first gas stream containing a compound at a certain concentration. In step 710, method 700 can include contacting the gas stream with a catalyst to form a second gas stream containing the compound at a second concentration. In some embodiments, method 700 can include contacting the gas stream with a catalyst article containing a catalyst to form a second gas stream containing the compound at a second concentration. In an exemplary embodiment, the compound is, for example, nitrogen monoxide (NO) and / or nitrogen dioxide (NO2 ) including NO x can include. The compound can also be nitrogen (N 2 ), dioxin or dioxin-like compounds, halogen or halogenated compounds. In some examples, the first gas stream can further include at least one of oxygen (O 2 ), water (H 2 O), carbon monoxide (CO), carbon dioxide (CO 2 ), sulfur dioxide (SO 2 ), sulfur trioxide (SO 3 ), hydrocarbons or one or more organic or inorganic materials. In an exemplary embodiment, the gas stream is a flue gas stream having a temperature of 140 - 250 °C.

[0128] In some embodiments, the first gas stream having the compound at the first concentration is upstream and the second gas stream having the compound at the second concentration is downstream. In some embodiments, the first concentration is higher than the second concentration.

Example

[0129] Test method Although specific methods and apparatuses are described below, it should be understood that other methods or apparatuses determined to be suitable by those skilled in the art may be used instead.

[0130] Catalyst evaluation procedure 1 - NO x Catalyst powder performance test for removal NO x To test the performance of the catalyst for NO x removal, the following procedure was used. The NO 2 removal reaction of the as-prepared catalyst powder was carried out at different temperatures in a fixed-bed quartz flow reactor. 0.1 gram of catalyst powder was used during the test. The feed gas mixture included 100 ppm of NO, 20 ppm of NO 3 , 105 ppm of NH 2 , 6 vol% of O 2 and the balance N x The NOx To determine the removal efficiency, the upstream (i.e., the NO concentration entering the chamber before being exposed to the catalyst powder) and the downstream NO concentration were monitored with an MKS MULTI-GAS™ 2030D FTIR analyzer (MKS Instruments, Andover, Massachusetts). x concentration) x The NO removal efficiency (i.e., “DeNOx efficiency (%)”) was calculated based on the following formula.

[0131] NO x In the above formula, NO

Equation

[0132] In the above formula, NO x = the total concentration of NO and NO 2 in the stream, NO x in = the upstream concentration of NO x and NO x out = the downstream concentration of NO x .

[0133] The apparent reaction rate constant (k m ) was calculated based on the following formula.

Equation

[0134] In the above formula, k m = the first-order apparent reaction rate based on the catalyst mass (cm 3 / g s), v = the gas flow rate under the reaction conditions (cm 3 / s), and W = the catalyst mass (g).

[0135] Catalyst Evaluation Procedure 2 - SO 2 Catalyst Powder Performance Test Using The following procedure was used to test the performance of the catalyst powder when exposed to SO 2 while NO x ​The performance of the removed catalyst was tested. The SO of the catalyst powder as prepared 2 under the NO exposure conditions x removal reaction was carried out at 220 °C in a fixed-bed quartz flow reactor. During the test, 0.1 g of the catalyst powder was mixed with 0.5 g of silicon carbide (Sigma Aldrich) and used. The feed gas mixture contained 200 ppm of NO, 9 ppm of SO 2 , 200 ppm of NH 3 , 6% by volume of O 2 , 5% by volume of moisture and the balance N 2 . The NO x removal reaction was measured at a total flow rate of 0.8 L / min. To determine the NO x removal efficiency, the upstream (i.e., the concentration of NO entering the chamber before being exposed to the catalyst powder) and downstream NO x concentrations were monitored with an MKS MULTI-GAS™ 2030D FTIR analyzer (MKS Instruments, Andover, Massachusetts). The NO x removal efficiency was calculated according to the following formula. x

Equation

[0136] In the above formula, NO x = the total concentration of NO and NO 2 in the stream, NO x in = the upstream concentration of NO x , NO x out = the downstream concentration of NO x .

[0137] The relative denitrification (DeNO x ) efficiency was calculated based on the following formula.

Equation

[0138] The initial inactivation rate in the first 21 hours was calculated based on the following formula.

Number

[0139] X-ray diffraction measurement X-ray diffraction measurement was carried out using a Rigaku SmartLab high-resolution X-ray diffractometer equipped with a CuKα (40 kV / 45 mA) source. The incident optical system used was a parallel beam cross beam optical system (5° solar slit, 1.0 mm divergence slit, 10 mm length limiting slit). The receiving optical system was a nickel filter for CuKβ (5° solar slit, 2.0 mm and 2.1 mm light receiving slits, HyPix 3000 detector operating in zero D continuous mode). The scan settings were a 2θ range of 10 - 60°, an increment of 0.02°, and 2.0° / min. The powder was placed in a 20 x 20 x 0.5 mm well of a glass plate. Sufficient powder was used to fill the entire volume of the well and pressed flat with a glass spacer. The excess powder was scraped off with a razor.

[0140] Examples Example 1 - Preparation of Catalyst Sample 1 10 wt% V 2 O 5 -TiO 2 The catalyst powder was prepared by adding 0.116 grams of vanadyl acetylacetonate (Sigma - Aldrich) to 0.36 grams of TiO 2 (Hombikat M311, specific surface area is approximately 304 m 2 / g) in a scintillation vial. The two dry powders were mixed by shaking with a vortex mixer (Cole - Parmer) for 1 minute. Then, the powder mixture was transferred to an aluminum weighing dish and heat - treated at 300 °C for 3 hours at a heating rate of 5 °C / min.

[0141] Example 2 - Preparation of Catalyst Sample 2 10 wt% V 2 O 5 -TiO 2 -SiO 2 The catalyst powder was 0.36 grams of TiO 2 -SiO2 (Hombikat M411 - 10% SiO 2 、 with a specific surface area of approximately 291 m 2 / g), 0.116 grams of vanadyl acetylacetonate (Sigma - Aldrich) was added and prepared. The two dry powders were shaken and mixed for 1 minute using a vortex mixer (Cole - Parmer). Then, the powder mixture was transferred to an aluminum weighing dish and heat - treated at 360 °C for 3 hours at a heating rate of 5 °C / min.

[0142] Example 3 - Preparation of Catalyst Sample 3 15 wt% of V 2 O 5 -TiO 2 -SiO 2 The catalyst powder was prepared by adding 0.167 grams of vanadyl acetylacetonate (Sigma - Aldrich) to 0.344 grams of TiO 2 -SiO 2 (Hombikat M411 - 10% SiO 2 、 with a specific surface area of approximately 291 m 2 / g). The two dry powders were shaken and mixed for 1 minute using a vortex mixer (Cole - Parmer). Then, the powder mixture was transferred to an aluminum weighing dish and heat - treated at 360 °C for 3 hours at a heating rate of 5 °C / min.

[0143] Example 4 - Preparation of Catalyst Sample 4 20 wt% of V 2 O 5 -TiO 2 -SiO 2 The catalyst powder was 0.32 grams of TiO 2 -SiO 2 (Hombikat M411 - 10% SiO 2 、 with a specific surface area of approximately 291 m 2It was prepared by adding 0.233 grams of vanadyl acetylacetonate (Sigma-Aldrich) to (g). The two dry powders were mixed by shaking with a vortex mixer (Cole-Parmer) for 1 minute. Then, the powder mixture was transferred to an aluminum weighing dish and heat-treated at 360 °C for 3 hours at a heating rate of 5 °C / min.

[0144] The invention of the present application has been described above, generally and with respect to specific embodiments. It is apparent that those skilled in the art can make various changes and modifications to the embodiments without departing from the scope of the disclosure. Therefore, the embodiments are intended to cover the changes and modifications of the present invention as long as they are within the scope of the appended claims and their equivalents.

Claims

1. A catalyst comprising a catalytically active component and TiO having a crystal structure containing anatase phase ２ a carrier material containing comprising a carrier material that includes a secondary material.

2. The secondary material is SiO ２ , MoO ３ , WO ３ and Al ２ O ３ The catalyst according to claim 1, selected from the group comprising at least one of them.

3. The catalyst according to claim 1 or 2, wherein the secondary material has a mass percentage of 2% to 35% based on the total mass of the catalyst.

4. The secondary material is SiO ２ The catalyst according to any one of claims 1 to 3, wherein the secondary material is SiO ２ .

5. The TiO ２ The ratio [(Ia / Ib)×100] of the intensity [Ia] of the peak indicating the anatase crystal existing in the range of 2θ = 24.7° to 2θ = 25.7° in the powder X-ray diffraction of the powder to the intensity [Ib] of the peak indicating the anatase crystal existing in the range of 2θ = 24.7° to 2θ = 25.7° in the powder X-ray diffraction of the standard sample composed of anatase-type titanium oxide is 30% to 360%. The catalyst according to any one of claims 1 to 4.

6. The catalyst has a NO removal efficiency of 30% to 90% in the temperature range of 150°C to 280°C, and is the catalyst according to any one of claims 1 to 5. ｘ ​

7. The catalyst is NH ３ for the selective catalytic reduction of NO ｘ having an apparent reaction rate constant of 40 to 400 cm ３ / gs in the temperature range of 150°C to 280°C, the catalyst according to claim 6.

8. The catalyst has a NO removal efficiency of 60% to 80% in the temperature range of 170°C to 220°C, and is the catalyst according to any one of claims 1 to 7. ｘ ​

9. The catalyst is SO ２ in the presence of NH ３ by NO ｘ When tested by selective catalytic reduction, compared with a catalyst containing a carrier material composed of TiO ２ The catalyst according to any one of claims 1 to 8, wherein the initial inactivation rate is reduced.

10. The carrier material has a specific surface area of 50 to 500 m ２ / g, and the catalyst according to any one of claims 1 to 9.

11. The catalyst active component is vanadium monoxide (VO), vanadium trioxide (V ２ O ３ ), vanadium dioxide (VO ２ ), vanadium pentoxide (V ２ O ５ ), molybdenum trioxide (MoO ３ ), manganese oxide (MnO ２ ), iron(III) oxide (Fe ２ O ３ ), iron(II) oxide (FeO), copper oxide (CuO), or at least one of any combination thereof, and the catalyst according to any one of claims 1 to 10.

12. The catalyst according to any one of claims 1 to 11, wherein the catalytically active component has a loading rate by mass of 4% to 50% based on the total mass of the catalyst.

13. The catalyst according to any one of claims 1 to 12, wherein the catalytically active component has a loading rate by mass of 10% to 30% based on the total mass of the catalyst.

14. The catalyst according to any one of claims 1 to 13, wherein the carrier material includes particles having an average diameter of 0.5 μm to 1000 μm.

15. The catalyst active component is V ２ O ５ and the carrier material is TiO ２ and the secondary material is SiO ２ The catalyst according to any one of claims 1 to 14

16. A catalyst article comprising the catalyst according to any one of claims 1 to 15.

17. A method for catalyzing a reaction, comprising contacting a reactant stream with the catalyst according to any one of claims 1 to 15.

18. The catalyst or catalyst article has a NO removal efficiency of 10% to 99% in a temperature range of 150°C to 280°C, and is the catalyst according to any one of claims 1 to 15 or the catalyst article according to claim 16. ｘ ​

19. A method for reducing the amount of a compound from a gas stream, comprising providing a first gas stream containing the compound at a first concentration, and contacting the gas stream with the catalyst article according to claim 16 to form a second gas stream containing the compound at a second concentration, comprising wherein the first concentration is higher than the second concentration.

20. The first gas stream contains SO at a concentration of 1 to 200 ppm ２ The method according to claim 19, comprising:

21. The method according to any one of claims 19 to 20, wherein the compound includes NOx.

22. The compound contains at least one of nitrogen (N ２ ), dioxin or dioxin-like compounds, halogen or halogenated compounds, and the method according to any one of claims 19 to 21.

23. The first gas stream further includes at least one of oxygen (O ２ ), water (H ２ O), carbon monoxide (CO), carbon dioxide (CO ２ ), sulfur dioxide (SO ２ ), sulfur trioxide (SO ３ ), hydrocarbons, or one or more organic or inorganic materials, etc., and the method according to any one of claims 19 to 22.

24. The method according to any one of claims 19 to 23, wherein the gas stream is a flue gas stream having a temperature of 140 to 280 °C.

25. Further comprising increasing the compound removal efficiency of the catalyst article, Add ammonia (NH ３ ) at a concentration in the range of 0.0001% to 0.5% of the concentration of the flue gas stream, and raising the temperature of the flue gas stream to 240 °C to 280 °C, comprising, said compound being NO ｘ The method according to claim 24, wherein the method is as such.

26. Further comprising increasing the compound removal efficiency of the catalyst article, Introducing additional NO into the flue gas stream, ２ so that the NO ２ concentration is increased to within the range of 2% to 99% of the total concentration of NO in the first gas stream, ｘ The method according to claim 24, comprising.

27. Mix a catalyst precursor containing a metal and a ligand with a carrier material containing TiO ２ to form a mixture. firing the mixture, and TiO ２ adding a secondary material to the carrier material such that the crystal structure of ２ remains substantially the same, comprising a method for preparing a catalyst.

28.

29. The method according to claim 27, wherein the metal is selected from one or more of transition metals, alkali metals or alkaline earth metals or salts thereof.

30. The ligand is carbonyl, oxalate, ammonium, cyclopentadienyl, diketonate, or Formula I 【Chemical 1】 wherein R1 and R2 are independently alkyl, substituted alkyl, aryl, substituted aryl, acyl, and substituted acyl, and the method according to any one of claims 27 to 29. **Claim 31** The catalyst precursor is selected from the group consisting of vanadyl acetylacetonate, vanadium(III) acetylacetonate, bis(acetylacetonato) dioxomolybdenum(VI), iron(III) acetylacetonate, and copper(II) acetylacetonate, and the method according to any one of claims 27 to 30. **Claim 32** The catalyst has a metal content of 4 wt% to 50 wt% based on the total mass of the catalyst, and the method according to any one of claims 27 to 31. **Claim 33** A method for preparing a catalyst, comprising mixing a catalyst precursor containing a metal and a ligand with a carrier material to form a mixture, and calcining the mixture. The carrier material is TiO having a crystal structure containing anatase phase ２ and a secondary material, a method for preparing a catalyst. **Claim 34** TiO ２ is mixed with a secondary material to form a carrier material containing TiO ２ having a crystal structure containing anatase phase. Mixing a catalyst precursor containing a metal and a ligand with the carrier material to form a mixture, and calcining the mixture, which comprises a method for preparing a catalyst. **Claim 35** The secondary material is SiO ２ , MoO ３ , WO ３ and Al ２ O ３ The method according to any one of claims 27 to 34, selected from the group consisting of.

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