Catalyst and method for decomposing hydrogen peroxide

Abstract

The invention provides a catalyst for decomposing hydrogen peroxide and a method for decomposing hydrogen peroxide. The catalyst for decomposing hydrogen peroxide includes a metal oxide represented by AaBbCcOx. Wherein A is Mn; b is Ce; c is Y, La, Nd or Dy; a + b + c = 1; and x varies with valence balance.

Description

Technical Field

[0001] The present invention relates to a catalyst and method for decomposing hydrogen peroxide, and more particularly to a catalyst and method for decomposing hydrogen peroxide including rare earth metal oxides. Background Art

[0002] One of the common techniques for treating peroxides such as hydrogen peroxide (H 2 O 2 ) is the "catalytic oxidation method", but the currently used catalytic oxidation method is still subject to various limitations.

[0003] Current transition metal catalysts have relatively high requirements for the pH of the solution. For example, when a transition metal catalyst is used in a liquid phase including water and an organic solvent, it needs to be operated under alkaline conditions of pH = 10 to pH = 11 to have better peroxide removal efficiency. However, under neutral conditions such as about pH = 7, there is a problem of insufficient peroxide removal efficiency. Or, current transition metal catalysts also have relatively high requirements for the concentration of peroxides. For example, when a transition metal catalyst is used in a solution including a high concentration of peroxides, a large amount of heat generated during the peroxide decomposition process will cause the transition metal catalyst to quickly deactivate.

[0004] Therefore, although the existing catalysts for decomposing hydrogen peroxide and the methods for decomposing hydrogen peroxide have gradually met their intended uses, they still do not fully meet the requirements in all aspects. Therefore, there are still some problems to be overcome regarding the catalysts for decomposing hydrogen peroxide and the methods for decomposing hydrogen peroxide. Summary of the Invention

[0005] The catalyst including metal oxides of the present invention can effectively remove hydrogen peroxide with a wide concentration range (0.1 wt% to 5 wt%) in an aqueous phase and / or an organic phase and a liquid phase with a pH value of 4 to 11. Furthermore, since the metal oxides of the present invention include two different rare earth metal elements, the stability of the catalyst including metal oxides of the present invention can be improved, thereby reducing the problem of cerium (Ce) precipitation.

[0006] In some embodiments, a catalyst for decomposing hydrogen peroxide is provided. The catalyst for decomposing hydrogen peroxide includes a metal oxide represented by A a B b C c O x . Wherein, A is Mn; B is Ce; C is Y, La, Nd or Dy; a + b + c = 1; and x changes according to the valence balance.

[0007] In some embodiments, a method for decomposing hydrogen peroxide is provided. The method for decomposing hydrogen peroxide includes adding a catalyst to a solution containing hydrogen peroxide to decompose hydrogen peroxide into water and oxygen, wherein the catalyst includes a metal oxide represented by A a B b C c O x wherein A is Mn; B is Ce; C is Y, La, Nd or Dy; a + b + c = 1; and x changes according to the valence balance.

[0008] The catalyst for decomposing hydrogen peroxide of the present invention can be applied to various types of decomposition devices. To make the components and advantages of the present invention more obvious and understandable, various embodiments are specifically given below and described in detail with the accompanying drawings as follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] When read in conjunction with the attached Figure 1 drawings, the present invention can be more fully understood from the following detailed description. It should be noted that, in accordance with the standard practice in the industry, the components are not drawn to scale. In fact, for clarity, the dimensions of the components can be arbitrarily enlarged or reduced.

[0010] Figure 1 FIG. is a preparation flow chart of a catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention;

[0011] Figure 2 FIG. is an X-ray diffraction analysis diagram of a catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention;

[0012] Figures 3 to 10 FIGS. are respectively removal efficiency analysis diagrams of a catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention;

[0013] Figure 11 Removal efficiency analysis diagram of a catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention and a comparative example.

[0014]

SYMBOL DESCRIPTION

[0015] S1, S2: Steps. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to specific embodiments and the accompanying drawings.

[0017] The catalyst for decomposing hydrogen peroxide and the method for decomposing hydrogen peroxide in each embodiment of the present invention will be described in detail below. It should be understood that the following description provides many different embodiments for implementing different forms of some embodiments of the present invention. The specific components and arrangements described below are only for simply and clearly describing some embodiments of the present invention. Of course, these are only for illustration and not for limiting the present invention. In addition, similar and / or corresponding component symbols may be used in different embodiments to indicate similar and / or corresponding components to clearly describe the present invention. However, the use of these similar and / or corresponding component symbols is only for simply and clearly describing some embodiments of the present invention, and does not represent any relevance between the different embodiments and / or structures discussed.

[0018] It should be understood that the ordinal numbers such as "first", "second", etc. used in the specification and the claims are used to modify components, and they do not themselves intend to imply or represent that the component (or these components) has any previous ordinal number, nor does it represent the order between one component and another component or the order in the manufacturing method. The use of these ordinal numbers is only to clearly distinguish a component with a certain name from another component with the same name. The claims and the specification may not use the same terms. For example, the first component in the specification may be the second component in the claims.

[0019] In the text, the terms "approximate" and "about" generally mean within 10%, within 5%, within 3%, within 2%, within 1%, or within 0.5% of a given value or range. The given quantity is an approximate quantity, that is, even if the terms "approximate" and "about" are not specifically stated, the meaning of "approximate" and "about" can still be implied. In the text, the term "ranging from the first value to the second value" or "the first value ~ the second value" means that the range includes the first value, the second value, and other values between them.

[0020] Furthermore, there may be a certain error between any two values used for comparison. If the first value is equal to the second value, it implies that there may be an error within 10%, within 5%, within 3%, within 2%, within 1%, or within 0.5% between the first value and the second value. In the text, the term "the ratio of the first value to the second value" means the ratio with the first value as the numerator and the second value as the denominator (the first value / the second value). In the text, the term "the proportion of the first value to the second value" means the proportion of the first value: the second value.

[0021] In the following specification and claims, words such as "comprising", "containing", "having", etc. are open-ended terms and should therefore be construed to mean "including but not limited to...". Thus, when the terms "comprising", "containing", and / or "having" are used in the description of the present invention, they specify the presence of the corresponding components, regions, steps, operations, and / or assemblies, but do not exclude the presence of one or more corresponding components, regions, steps, operations, and / or assemblies.

[0022] It should be understood that, without departing from the spirit of the present invention, components in multiple different embodiments can be replaced, recombined, and combined to complete other embodiments in the following examples. As long as the components between the embodiments do not violate the spirit of the present invention or conflict with each other, they can be arbitrarily combined and used.

[0023] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It can be understood that these terms, such as those defined in a commonly used dictionary, should be interpreted to have a meaning consistent with the relevant technology and the background or context of the present invention, and should not be interpreted in an idealized or overly formal manner, unless specifically defined in the embodiments of the present invention.

[0024] Figure 1 A preparation flowchart for a catalyst for decomposing hydrogen peroxide is provided according to some embodiments of the present invention.

[0025] In step S1, transition metal salts, first rare earth metal salts, and second rare earth metal salts are mixed to obtain a mixture. For example, the transition metal salts may include manganese (Mn) salts. For example, the first rare earth metal salts may include cerium (Ce) salts. For example, the second rare earth metal salts may include yttrium (Y) salts, lanthanum (La) salts, neodymium (Nd) salts, or dysprosium (Dy) salts. In some embodiments, after mixing and stirring the transition metal salts, first rare earth metal salts, and second rare earth metal salts with a solvent (e.g., water) evenly, a liquid mixture is obtained.

[0026] In step S2, the liquid mixture is heated to obtain a catalyst of the present invention including metal oxides. For example, the heating process may be a calcining process. In some embodiments, the heating temperature of the heating process may be 200°C to 400°C. For example, the heating temperature may be 200°C, 250°C, 300°C, 350°C, 400°C, or any value or range of values between the above values, but the present invention is not limited thereto. In some embodiments, the heating time of the heating process may be 4 hours to 8 hours. For example, the heating time may be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or any value or range of values between the above values, but the present invention is not limited thereto.

[0027] In some embodiments, after the heating process, a grinding process may be further performed. For example, the grinding process may be performed by a grinder. In some embodiments, after the grinding process, a filtering process may be further performed. For example, powders with too large particle sizes may be sieved out through a sieve with 100-400 mesh. For example, a sieve with 200 mesh may be used.

[0028] In some embodiments, the metal oxide may be represented by Formula (1):

[0029] A a B b C c O x Formula (1)

[0030] wherein A is Mn; B is Ce; C is Y, La, Nd, or Dy; a + b + c = 1; and x changes with the valence balance. Herein, A, B, C, and O respectively represent elements, and a, b, c, and x respectively represent the proportions of the elements. In some embodiments, the oxidation state of Mn may be +1, +2, +3, +4, +5, +6, or +7. In some embodiments, the oxidation state of Ce may be +2, +3, or +4. In some embodiments, the oxidation state of Y may be +1, +2, or +3. In some embodiments, the oxidation state of La may be +1, +2, or +3. In some embodiments, the oxidation state of Nd may be +2, +3, or +4. In some embodiments, the oxidation state of Dy may be +2, +3, or +4. In some embodiments, the oxidation state of O may be -1 or -2. Therefore, in the case where the oxidation states of A, B, and C are positive and the oxidation state of O is negative, the oxidation state of the catalyst may be made 0 by adjusting the value of x, thereby achieving valence balance (e.g., electrical neutrality). In some embodiments, the valence balance may be to balance the valences of the elements in the metal oxide.

[0031] In some embodiments, a = b + c. For example, a = 0.5 and b + c = 0.5. In some embodiments, c = 0.01 to 0.1. For example, c can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or any value between the above values or any numerical range composed of any values, but the present invention is not limited thereto. In some embodiments, b = 0.4 to 0.49. For example, b can be 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or any value between the above values or any numerical range composed of any values, but the present invention is not limited thereto. In some embodiments, a = 0.3 to 0.7, b = 0.3 to 0.7, and c = 0.05.

[0032] Catalyst Synthesis Example

[0033] Example 1, Mn 0.1 Ce 0.9 O x

[0034] Take 1.32 grams (g) of Mn(NO 3 ) 2 ·4H 2 O (molecular weight (MW): 251.01) and 19.53 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and dissolve them in 50 milliliters (mL) of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the Mn 0.1 Ce 0.9 O x catalyst. Among them, x changes with the valence balance.

[0035] Example 2, Mn 0.3 Ce 0.7 O x

[0036] Take 3.84 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01) and 15.19 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the Mn0.3 Ce 0.7 O x Catalyst. Among them, x changes with the valence balance.

[0037] Example 3, Mn 0.4 Ce 0.6 O x

[0038] Take 5.12 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01) and 13.0 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.4 Ce 0.6 O x Catalyst. Among them, x changes with the valence balance.

[0039] Example 4, Mn 0.5 Ce 0.5 O x

[0040] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01) and 10.85 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.5 Ce 0.5 O x Catalyst. Among them, x changes with the valence balance.

[0041] Example 5, Mn 0.6 Ce 0.4 O x

[0042] Take 7.68 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01) and 8.68 g of Ce(NO 3 ) 3 ·6H 2O (MW: 434.22) is dissolved in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.6 Ce 0.4 O x catalyst. Among them, x changes with the valence balance.

[0043] Example 6, Mn 0.7 Ce 0.3 O x

[0044] Take 8.96 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01) and 6.51 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) is dissolved in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.7 Ce 0.3 O x catalyst. Among them, x changes with the valence balance.

[0045] Example 7, Mn 0.5 Ce 0.45 Y 0.05 O x

[0046] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 9.76 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 0.96 g of Y(NO 3 ) 3 ·6H 2 O (MW: 383.01) is dissolved in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.5 Ce 0.45 Y 0.05 O x catalyst. Among them, x changes with the valence balance. Among them, Mn(NO 3 ) 2 ·4H 2 O can be used as a transition metal salt, Ce(NO 3 )3 ·6H 2 O can be used as the first rare earth metal salt, and Y(NO 3 ) 3 ·6H 2 O can be used as the second rare earth metal salt.

[0047] Example 8, Mn 0.5 Ce 0.49 Y 0.01 O x

[0048] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 10.6 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 0.19 g of Y(NO 3 ) 3 ·6H 2 O (MW: 383.01) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.5 Ce 0.49 Y 0.01 O x catalyst. Among them, x changes with the valence balance.

[0049] Example 9, Mn 0.5 Ce 0.4 Y 0.1 O x

[0050] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 8.68 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 1.91 g of Y(NO 3 ) 3 ·6H 2 O (MW: 383.01) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain Mn 0.5 Ce 0.4 Y 0.1 O x catalyst. Among them, x changes with the valence balance.

[0051] Example 10, Mn 0.5 Ce 0.45 La 0.05 O x

[0052] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 9.76 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 1.08 g of La(NO 3 ) 3 ·6H 2 O (MW: 433.01) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the Mn 0.5 Ce 0.45 La 0.05 O x catalyst. Among them, x changes with the valence balance.

[0053] Example 11, Mn 0.5 Ce 0.45 Nd 0.05 O x

[0054] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 9.76 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 1.09 g of Nd(NO 3 ) 3 ·6H 2 O (MW: 438.35) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the Mn 0.5 Ce 0.45 Nd 0.05 O x catalyst. Among them, x changes with the valence balance. In some embodiments, the Ce precipitation amount in the aging experiment of the Mn 0.5 Ce 0.45 Nd 0.05 O x catalyst is 399.5 ppb.

[0055] Example 12, Mn 0.5 Ce 0.45 Dy 0.05 O x

[0056] Take 6.40 g of Mn(NO 3 ) 2 ·4H 2 O (MW: 251.01), 9.76 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and 1.14 g of Dy(NO 3 ) 3 ·6H 2 O (MW: 456.60) and dissolve them in 50 mL of water to form an aqueous solution of manganese salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the Mn 0.5 Ce 0.45 Dy 0.05 O x catalyst. Among them, x changes with the valence balance. In some embodiments, the Ce precipitation amount in the Mn 0.5 Ce 0.45 Dy 0.05 O x catalyst aging experiment is 441.8 ppb.

[0057] Examples 13 to 33, D 0.05 Ce 0.95 O x

[0058] Take "d" grams (g) of D(NO 3 ) 2 hydrate and 20.63 g of Ce(NO 3 ) 3 ·6H 2 O (MW: 434.22) and dissolve them in 50 mL of water to form an aqueous solution of D-containing salt and cerium salt. Stir until completely dissolved. Then heat the above solution to 300 °C and react for 6 hours to obtain the D 0.05 Ce 0.95 O x catalyst. Among them, x changes with the valence balance. The preparation ratios of Examples 13 to 33 are shown in Table 1.

[0059] Table 1

[0060]

[0061]

[0062] X-ray Diffraction Analysis of Catalyst

[0063] Figure 2 This is the X-ray diffraction analysis (power X-Ray diffraction analysis, PXRD) diagram for decomposing the hydrogen peroxide catalyst powder according to some embodiments of the present invention. Using a powder X-ray diffractometer (model: PW3040), analysis was carried out with a scan range of 20 to 100 degrees and a scan step size of 0.04 degrees. For ease of explanation, Example 4 (Mn 0.5 Ce 0.5 O x ) was used for PXRD analysis. Additionally, Figure 2 The reference numbers of the Powder Diffraction Standards (The Joint Committee on Powder Diffraction Standards, JCPDS) are also shown.

[0064] As Figure 2 shown, after comparing Example 4 with the Powder Diffraction Standards (JCPDS) analysis, it was confirmed that the catalyst of Example 4 may include CeO 2 、Mn 2 O 3 and Mn 3 O 4 . Similarly, other examples were analyzed in the same manner.

[0065] Inductively Coupled Plasma Mass Spectrometry Analysis

[0066] Analysis was carried out using an Inductively coupled plasma mass spectrometry (ICP-MS) analyzer (model: NexION 350X, brand: Perkin Elmer). For ease of explanation, Example 7 (Mn 0.5 Ce 0.45 Y 0.05 O x ) was used for ICP-MS analysis. The results are shown in Table 2.

[0067] Table 2

[0068]

[0069] As shown in Table 2, it was confirmed that the metal ratio in the catalyst of Example 7 met the expectations. Similarly, other examples were analyzed in the same manner.

[0070] Analysis Process of Sample Solution

[0071] In some embodiments, a sample solution containing hydrogen peroxide with a first concentration (or input concentration) is prepared. In some embodiments, the concentration of hydrogen peroxide in the sample solution is 0.1 wt% to 5 wt%. For example, the concentration of hydrogen peroxide in the sample solution can be 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between the above values or any range of values composed of these values, but the present invention is not limited thereto.

[0072] In some embodiments, the sample solution is an aqueous phase, an organic phase, or a combination thereof. In some embodiments, the sample solution may include water, C 1 ~C 10 alcohols, C 1 ~C 10 ketones, or a combination thereof. For example, C 1 ~C 10 alcohols may include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, nonanol, decanol, or the like. For example, C 1 ~C 10 ketones may include acetone, butanone, pentanone, hexanone, nonanone, decanone, or the like. In some embodiments, the pH value of the sample solution is 4 to 11. For example, the pH value of the sample solution can be 4, 5, 6, 7, 8, 9, 10, 11, or any value between the above values or any range of values composed of these values, but the present invention is not limited thereto.

[0073] Hydrogen peroxide concentration sample with a concentration of 2 wt%

[0074] In some embodiments, 3.33 g of H 2 O 2 (with a concentration of 30 wt%) is mixed with 2.66 g of deionized water and 44 g of isopropanol (IPA), and stirred until completely homogeneous to obtain 50 g of H 2 O 2 sample solution with a hydrogen peroxide concentration of 2 wt% and an IPA concentration of 88 wt%. Among them, 44 g of isopropanol (IPA) can be replaced with acetone, ethanol, or deionized water.

[0075] Hydrogen peroxide concentration sample with a concentration of 5 wt%

[0076] In some embodiments, 8.33 g of H 2 O 2 (with a concentration of 30 vol%) is mixed with 41.67 g of isopropanol (IPA), and stirred until completely homogeneous to obtain 50 g of H 2 O 2A sample solution with a concentration of 2 wt% and an IPA concentration of 83.3 wt%. Among them, 41.67 g of isopropanol (IPA) can be replaced with acetone, ethanol, or deionized water.

[0077] In some embodiments, the concentration of hydrogen peroxide in the sample solution can be measured first using a hydrogen peroxide analyzer (model: SemiChem 4102, manufacturer: Entergis). Then, a powder catalyst is added to the sample solution and mixed, and continuous stirring is carried out during a reaction time to allow the catalyst to react with hydrogen peroxide to decompose hydrogen peroxide into water and hydrogen. In some embodiments, the reaction time can be 1 minute to 120 minutes. For example, the reaction time can be 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 60 minutes, 120 minutes, or any value between the above values or any value range composed of any values, but the present invention is not limited thereto. In some embodiments, the reaction temperature can be room temperature. For example, the reaction temperature can be 15°C, 20°C, 25°C, 30°C, or any value between the above values or any value range composed of any values, but the present invention is not limited thereto. In some embodiments, the reaction pressure can be atmospheric pressure. For example, the reaction pressure can be 0.9 atm, 0.95 atm, 1 atm, 1.1 atm, or any value between the above values or any value range composed of any values, but the present invention is not limited thereto. Hereinafter, the reaction temperature can be 25°C, and the reaction pressure can be 1 atm.

[0078] In some embodiments, the amount of catalyst added is based on the total weight of the sample solution. That is, the catalyst amount (wt%) is the weight of the catalyst / the weight of the sample solution * 100%. In some embodiments, the weight of the catalyst can be 0.04 wt% to 5 wt% of the weight of the sample solution, that is, the catalyst amount can be 0.04 wt% to 5 wt%. For example, the weight of the catalyst can be 0.04 wt%, 0.05 wt%, 0.075 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between the above values or any value range composed of any values, but the present invention is not limited thereto. In some embodiments, when 0.05 g of the catalyst is added to 50 g of the sample solution, the catalyst amount is 0.1 wt%. When 0.5 g of the catalyst is added to 50 g of the sample solution, the catalyst amount is 1 wt%. When 2.5 g of the catalyst is added to 50 g of the sample solution, the catalyst amount is 5 wt%.

[0079] In some embodiments, the liquid hourly space velocity (LHSV (unit: h-1 )) can represent the processing capacity of the catalyst when the reactant is in the liquid phase, and is calculated as (volume of sample solution / volume of catalyst) / reaction time (hours). The volume of the catalyst is calculated by catalyst weight (g) / catalyst density (g / cm 3 ). In some embodiments, the catalyst density can be 0.4 - 0.5 g / cm 3 . For example, the catalyst density can be 0.4 g / cm 3 , 0.42 g / cm 3 , 0.44 g / cm 3 , 0.46 g / cm 3 , 0.48 g / cm 3 , 0.5 g / cm 3 or any value between the above values or any numerical range composed of any values, but the present invention is not limited thereto. For the sake of illustration, hereinafter, the catalyst density can be 0.44 g / cm 3 . Hereinafter, the equivalent LHSV of each reaction condition is shown.

[0080] Continuing from the above, after the reaction time, a filter paper (model: Advantec No. 5C) is used to remove the catalyst powder and the filtrate is retained, and then the concentration of hydrogen peroxide in the filtrate is analyzed by a hydrogen peroxide analyzer, and this concentration can be called the second concentration (or, the output concentration). In some embodiments, the hydrogen peroxide removal efficiency (%) is the percentage of the second concentration in the first concentration, that is, calculated as second concentration / first concentration * 100%. Among them, the hydrogen peroxide removal efficiency can show the efficiency of the catalyst in decomposing hydrogen peroxide.

[0081] In some embodiments, the elements in the filtrate can be further analyzed by inductively coupled plasma mass spectrometry (ICP-MS) to confirm whether the catalyst is damaged by the heat generated during the reaction of the catalyst with hydrogen peroxide. For example, to confirm whether the catalyst structure is damaged, resulting in the detection of the elements in the catalyst by ICP-MS (as described in subsequent Figure 7 and Table 3).

[0082] Figure 3 is an analysis diagram of the hydrogen peroxide decomposition catalyst removal efficiency according to some embodiments of the present invention. Figure 3 is an analysis diagram of catalysts (CeO x and Examples 13 - 25) with different catalyst compositions and (v.s.) peroxide removal efficiency. Among them, Figure 3 the x-axis of represents the metal composition ratio (in moles) in the metal oxide, and the number of moles of oxygen atoms changes with the valence balance, so the ratio of oxygen atoms is omitted from display. Figure 3The y-axis represents the peroxide removal efficiency (%). The reaction conditions are as follows: the concentration of H 2 O 2 in the sample solution is 2 wt%, the concentration of IPA is 88 wt%, the catalyst dosage is 5 wt%, the reaction time is 20 minutes, and the equivalent LHSV is 33.2 h -1 .

[0083] As Figure 3 shown, in the case where the catalyst does not include transition metal elements, the peroxide removal efficiency of CeO x including Ce but not other rare earth metals can be greater than that of the catalyst including two rare earth metals. That is, in the case where the catalyst does not include Mn, the peroxide removal efficiency of the catalyst including only one rare earth metal (Ce) can be greater than that of the catalyst including two rare earth metals. For example, the removal efficiency of CeO x is greater than that of Y 0.05 Ce 0.95 O x , La 0.05 Ce 0.95 O x , Nd 0.05 Ce 0.95 O x and Dy 0.05 Ce 0.95 O x . In addition, among the catalysts including two rare earth metals, the peroxide removal efficiency of Y 0.05 Ce 0.95 O x , La 0.05Ce0.95 O x , Nd 0.05 Ce 0.95 O x is less than that of Dy 0.05 Ce 0.95 O x .

[0084] Catalyst composition - types of the first rare earth metal element and transition metal element

[0085] Figure 4 is an analysis chart of the removal efficiency of the hydrogen peroxide decomposition catalyst according to some embodiments of the present invention. Figure 4 is an analysis chart of the catalysts (CeO x and Examples 26 to 33) with different catalyst compositions and the peroxide removal efficiency. Among them, Figure 4 the x-axis represents the metal composition ratio (in moles) in the metal oxide, and the ratio of oxygen atoms is omitted from display. Figure 4The y-axis represents the peroxide removal efficiency (%). The reaction conditions are as follows: the concentration of H 2 O 2 in the sample solution is 2 wt%, the concentration of IPA is 88 wt%, the catalyst dosage is 5 wt%, and the reaction time is 10 minutes, with an equivalent LHSV of 66.4 h -1 .

[0086] As Figure 4 shown, the removal efficiency of Mn 0.05 Ce 0.95 O x and Co 0.05 Ce 0.95 O x reaches 99.0%. Therefore, the hydrogen peroxide removal efficiency of the catalyst including the first rare earth metal element (Ce) and the transition metal (Mn or Co) can be greater than that of CeO x including Ce without other rare earth metals. In contrast, the hydrogen peroxide removal efficiency of the catalyst including the first rare earth metal element (Ce) and other transition metals (V, Cr, Fe, Ni, Cu, Zn) can be lower than that of CeO x including Ce without other rare earth metals.

[0087] Figure 5 is an analysis chart of the decomposition hydrogen peroxide catalyst removal efficiency according to some embodiments of the present invention. Figure 5 is an analysis chart of the catalysts with different catalyst compositions (Example 28 and Example 30) and the peroxide removal efficiency. Among them, Figure 5 the x-axis represents the metal composition ratio (in moles) in the metal oxide, and the ratio of oxygen atoms is omitted from display. Figure 5 the y-axis represents the peroxide removal efficiency (%). The reaction conditions are as follows: the concentration of H 2 O 2 in the sample solution is 2 wt%, the concentration of IPA is 88 wt%, the catalyst dosage is 1 wt%, and the reaction time is 10 minutes, with an equivalent LHSV of 332 h -1 .

[0088] As Figure 5 shown, compared with Figure 4 using a catalyst dosage of 5 wt%, in the case of using a lower catalyst dosage of 1 wt%, the hydrogen peroxide removal efficiency of Mn 0.05 Ce 0.95 O x is better than that of Co 0.05 Ce 0.95 O xRemoval efficiency. Therefore, the catalyst of the present invention may include Mn as a transition metal element and include Ce as a first rare earth metal element.

[0089] Catalyst composition - Ratio of the first rare earth metal element (Ce) and the transition metal element (Mn)

[0090] Figure 6 It is an analysis diagram of the removal efficiency of the catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention. Figure 6 It is an analysis diagram of the catalysts with different catalyst compositions (Examples 1 to 6, Example 28, and MnO x ) and peroxide removal efficiency. Among them, the catalyst can be represented by A a B b O x where A is Mn, B is Ce, and x changes according to the valence balance. Among them, Figure 6 the x-axis of represents the proportion of Mn in the total metal in the metal oxide (Mn / (Mn + Ce), that is, a / (a + b)), and the proportion of oxygen atoms is omitted. Among them, b can be 0, representing MnO x . Figure 6 the y-axis of represents the peroxide removal efficiency (%). The reaction conditions are as follows: the concentration of H 2 O 2 in the sample solution is 2 wt%, the IPA concentration is 88 wt%, the reaction time is 10 minutes, and the catalyst dosage is 0.1 wt% (equivalent LHSV is 3320 h -1 ) or 5 wt% (equivalent LHSV is 66.4 h -1 ).

[0091] As Figure 6 shown, when a / (a + b) is 0.5 to 0.7, the peroxide removal efficiency is greater than 95%. In other words, when a / b is 1 to 2.3, the peroxide removal efficiency is greater than 95%. When a / (a + b) is 0.5 and 0.6, the peroxide removal efficiency is as high as 97.6% or 98.6%. In other words, when a / b is 1 to 1.5, the peroxide removal efficiency is as high as 97.6% or 98.6%. Therefore, the catalyst of the present invention may include Mn and Ce, and a / b is about 1 to 2.3. For example, a / b can be 1, 1.2, 1.3, 1.5, 1.7, 2, 2.1, 2.2, 2.3, or any value between the above values or any value range composed of any values, but the present invention is not limited thereto.

[0092] Catalyst composition - Types of the first rare earth metal element (Ce), the second rare earth metal element, and the transition metal element (Mn)

[0093] Figure 7Analysis chart of the removal efficiency of the catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention. Figure 7 Analysis chart of the catalyst with different catalyst compositions (Example 4, Example 7, Examples 10-12) and peroxide removal efficiency. Among them, the catalyst can be A a B b C c O x It means that A is Mn, B is Ce, C is Y, La, Nd or Dy, and x changes with the valence balance. Among them, c can be 0, representing Mn 0.5 Ce 0.5 O x . The reaction conditions are as follows: the concentration of H 2 O 2 in the sample solution is 5 wt%, the IPA concentration is 83.3 wt%, the catalyst dosage is 0.04 wt%, and the reaction time is 15 minutes, and the equivalent LHSV is 5532 h -1 .

[0094] As Figure 7 shown, the peroxide removal efficiency of Mn 0.5 Ce 0.45 Y 0.05 O x can be greater than that of Mn 0.5 Ce 0.5 O x , Mn 0.5 Ce 0.45 La 0.05 O x , Mn 0.5 Ce 0.45 Nd 0.05 O x , Mn 0.5 Ce 0.45 Dy 0.05 O x . Furthermore, when the concentration of H 2 O 2 in the sample solution is 5 wt% and the equivalent LHSV is as high as 5532 h -1 , the peroxide removal efficiency of Mn 0.5 Ce 0.45 La 0.05 O x can be greater than 60%, and the peroxide removal efficiency of Mn 0.5 Ce 0.45 Nd 0.05 O x and Mn 0.5 Ce 0.45 Dy 0.05 O x can be greater than 70%, and Mn0.5 Ce 0.45 Y 0.05 O x has a peroxide removal efficiency of up to 99.6%.

[0095] Next, Figure 7 is compared with Figure 3 . At an equivalent LHSV of Figure 3 of only 33.2 h -1 , for Y 0.05 Ce 0.95 O x , La 0.05 Ce 0.95 O x , Nd 0.05 Ce 0.95 O x and Dy 0.05 Ce 0.95 O x the peroxide removal efficiencies are only 69%, 56%, 68% and 71.8% respectively. However, when the LHSV is significantly increased by more than 166 times (5532 / 33.2 = 166.63) as in Figure 7 , for Mn 0.5 Ce 0.45 Y 0.05 O x , Mn 0.5 Ce 0.45 La 0.05 O x , Mn 0.5 Ce 0.45 Nd 0.05 O x , Mn 0.5 Ce 0.45 Dy 0.05 O x the peroxide removal efficiencies are 99.6%, 60.8%, 71.6% and 72.8% respectively. This means that in a significantly more severe LHSV situation, adding Mn to the catalysts of two rare earth metals can significantly improve the hydrogen peroxide removal effect. Moreover, the hydrogen peroxide removal efficiency of the catalysts including Mn and two rare earth metals can even exceed that of the catalysts including Mn and one rare earth metal. For example, the removal efficiency of Mn 0.5 Ce 0.45 Y 0.05 O x is greater than that of Mn 0.5 Ce 0.5 O x . That is, referring to Figure 3 and Figure 7It can be found that the catalyst "not including Mn and including two rare earth metals" is inferior to the catalyst "not including Mn and including one rare earth metal", but the catalyst "including Mn and including two rare earth metals" can be superior to the catalyst "including Mn and including one rare earth metal". Accordingly, when the catalyst of the present invention includes specific components of Mn and two rare earth metals, it can achieve excellent and unexpected hydrogen peroxide removal effect.

[0096] Continuing from the above, a catalyst aging experiment was carried out on the sample solution that had reacted for 15 minutes to confirm whether the structure of the catalyst was damaged by the heat generated during the reaction of the catalyst with hydrogen peroxide, so that the elements in the catalyst could be detected in the filtrate.

[0097] Catalyst aging experiment

[0098] Continuing Figure 7 The experimental parameters of and referring to Table 3, Table 3 is catalyst A with different catalyst compositions a B b C c O x The metal precipitation results. Among them, the elements in the filtrate (unit: parts per billion concentration (ppb)) can be further analyzed by inductively coupled plasma mass spectrometry (ICP-MS) to confirm whether the catalyst is damaged, so that the catalyst ages or deactivates.

[0099] Table 3

[0100]

[0101] Among them, N / A means not applicable. As shown in Table 3, compared with Mn 0.5 Ce 0.5 O x The Ce precipitation amount of is 132.5 ppb, Mn 0.5 Ce 0.45 La 0.05 O x The Ce precipitation amount of is 51.6 ppb, and Mn 0.5 Ce 0.45 Y 0.05 O x The Ce precipitation amount of is 47.7 ppb. Therefore, adding metal oxides of La or Y can effectively reduce the Ce precipitation amount. In other words, by adding a second rare earth metal element to the catalyst, it is possible to avoid the problem that a large amount of heat generated during the peroxide decomposition process causes the catalyst to quickly deactivate while maintaining the peroxide removal efficiency.

[0102] Accordingly, the metal oxide of the present invention can be synthesized by a simple process and in H 2 O2 In a sample solution with a high hydrogen peroxide concentration of 5%, it has high catalytic activity, high removal efficiency, high decomposition stability, and / or low aging property.

[0103] Catalyst composition - ratio of the first rare earth metal element (Ce) and the second rare earth metal element (Y)

[0104] Figure 8 It is an analysis chart of the removal efficiency of a catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention. Figure 8 It is an analysis chart of catalysts with different catalyst compositions (Examples 7 - 9) and peroxide removal efficiency. Among them, the catalysts are represented by A a B b C c O x where A is Mn, B is Ce, C takes Y as an example, but the present invention is not limited thereto, and x changes with the valence balance. The reaction conditions are as follows: the H 2 O 2 concentration of the sample solution is 5 wt% and the IPA concentration is 83.3 wt%, the catalyst dosage is 0.04 wt%, the reaction time is 10 minutes, and the equivalent LHSV is 8298 h -1 .

[0105] As Figure 8 shown, when a part of Ce in Mn 0.5 Ce 0.5 O x is replaced by Y, the catalyst activity can be improved due to the reduction of Ce precipitation. However, when an excessive amount of Y replaces Ce, the catalyst activity will instead decrease. For example, when the metal element in the catalyst includes 10% of Y (c / (a + b + c) = 0.1), the removal efficiency exceeds 84%. When the metal element in the catalyst includes 5% of Y (c / (a + b + c) = 0.05), the removal efficiency exceeds 90%. When the metal element in the catalyst includes 1% of Y (c / (a + b + c) = 0.01), the removal efficiency is slightly lower than 80%. In some embodiments, c / (a + b + c) can be 0.01 - 0.1. For example, c / (a + b + c) can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or any value or range of values between the above values, but the present invention is not limited thereto.

[0106] Furthermore, in the case where the H 2 O 2 concentration of the sample solution is 5 wt% and the equivalent LHSV is as high as 8298 h -1 of Mn 0.5 Ce 0.45 Y0.01 O x with Mn 0.5 Ce 0.45 Y 0.1 O x The peroxide removal efficiency of can be approximately 80%, and for Mn 0.5 Ce 0.45 Y 0.05 O x the peroxide removal efficiency of can be as high as 91.5%.

[0107] Different liquid-phase environments - types of sample solutions

[0108] Figure 9 is an analysis chart of the removal efficiency of the catalyst for decomposing hydrogen peroxide according to some embodiments of the present invention. Figure 9 is for catalyst A a B b C c O x and the analysis chart of the peroxide removal efficiency for different sample solutions. Among them, taking A as Mn, B as Ce, C as Y, a as 0.5, b as 0.45, c as 0.05 (Example 7) as an example, but the present invention is not limited thereto, and x changes with the valence balance. The reaction conditions are as follows: the catalyst dosage is 0.04 wt%, the reaction time is 30 minutes, and the equivalent LHSV is 2766 h -1 .

[0109] The parameters of the sample solution are shown in Table 4.

[0110] Table 4

[0111]

[0112] Among them, solution 1 represents the aqueous phase, and solutions 2 - 4 represent the mixed phase of the aqueous phase and the organic phase, and can be substantially regarded as the organic phase.

[0113] As Figure 9 shown, when using the same catalyst, the solvent type of the sample solution can be adjusted to analyze whether different liquid-phase environments have an impact on the catalyst. The metal oxides representing the present invention have excellent peroxide removal efficiency (greater than 99%) in the sample solutions of different solvents.

[0114] Different liquid-phase environments - pH value

[0115] In some embodiments, the pH value of the sample solution can be adjusted by adding NaOH (30%) and H 2 SO 4 (30%), and the pH value is measured with a pH tester (model: pH 700, brand: Eutech Instruments).

[0116] Figure 10 Analysis chart of the decomposition hydrogen peroxide catalyst removal efficiency according to some embodiments of the present invention. Figure 10 For catalyst A a B b C c O x And the analysis chart of the peroxide removal efficiency for different sample solutions. Wherein, taking A as Mn, B as Ce, C as Y, a as 0.5, b as 0.45, c as 0.05 (Example 7) as an example, but the present invention is not limited thereto, and x changes with the valence balance. The reaction conditions are as follows: The H 2 O 2 concentration of the sample solution is 5 wt% and the rest is water (95 wt%), the catalyst dosage is 0.04 wt%, and the reaction time is 5 minutes, and the equivalent LHSV is 16596 h -1 .

[0117] As Figure 10 shown, when using the same catalyst, the pH value of the sample solution can be adjusted to analyze whether different liquid phase environments have an impact on the catalyst. The metal oxide representing the present invention has a removal efficiency of approximately 80% when pH = 4 to pH = 11. In other words, the metal oxide of the present invention can have excellent removal efficiency whether in an alkaline environment, an acidic environment or a neutral environment. Furthermore, the removal efficiency of the metal oxide of the present invention is as high as 99.6% when pH = 7 to pH = 9.

[0118] Compare with the catalyst comparative example

[0119] Figure 11 Analysis chart of the removal efficiency of the decomposition hydrogen peroxide catalyst and the comparative example according to some embodiments of the present invention. The present invention takes Mn 0.5 Ce 0.45 Y 0.05 O x (Example 7) as an example. Comparative example 1 is Mn 0.43 Co 0.43 Ce 0.14 O x , and comparative example 2 is Mn 0.67 Co 0.13 Ce 0.2 O x . The reaction conditions are as follows: Use solution 1 and solution 2 in Table 4, the catalyst dosage is 0.04 wt%, and the reaction time is 15 minutes, and the equivalent LHSV is 5532 h -1 .

[0120] As Figure 11 shown, whether in an aqueous or organic phase sample solution, the Mn of the present invention0.5 Ce 0.45 Y 0.05 O x has a better removal efficiency than Comparative Examples 1 and 2. For example, even if the removal efficiency of Comparative Example 1 (Mn 0.43 Co 0.43 Ce 0.14 O x ) and Example 7 of the present invention (Mn 0.5 Ce 0.45 Y 0.05 O x ) is the same in the environment of Solution 1 (aqueous phase), but the removal efficiency of Comparative Example 1 in the environment of Solution 2 (organic phase) is lower than that of Example 7 of the present invention. It means that Comparative Example 1 is not applicable to the organic phase environment, while the examples of the present invention are applicable to the organic phase environment. Similarly, the removal efficiency of Comparative Example 2 is lower than that of the examples of the present invention in both the aqueous phase environment and the organic phase environment. Accordingly, the catalyst for decomposing hydrogen peroxide of the present invention has less requirements and restrictions on whether the liquid phase is an aqueous phase or an organic phase.

[0121] The catalyst for decomposing hydrogen peroxide of the present invention can be synthesized by a simple process, and has high catalytic activity, high removal efficiency, high decomposition stability and / or low aging property in hydrogen peroxide solutions with high concentrations and a wide pH range. Therefore, the catalyst for decomposing hydrogen peroxide of the present invention has less requirements and restrictions on the pH and composition (aqueous phase or organic phase) of the liquid phase, and on the concentration of peroxide, and can be widely used in different applications. Furthermore, the catalyst for decomposing hydrogen peroxide of the present invention includes two different rare earth metal elements, which can improve the stability of the catalyst of the present invention and enhance the removal efficiency of hydrogen peroxide. For example, adding the second rare earth metal element (Y or La) can reduce the problem of precipitation of the first rare earth metal element (Ce).

[0122] The protection scope of the present invention is not limited to the processes, machines, manufactures, compositions of matter, devices, methods and steps in the specific embodiments described in the specification. Any person skilled in the art in the relevant technical field can understand the processes, machines, manufactures, compositions of matter, devices, methods and steps developed currently or in the future from the disclosure of the present invention. As long as the same functions can be implemented or the same results can be obtained in the embodiments described herein, they can be used according to the present invention. Therefore, the protection scope of the present invention includes the above-mentioned processes, machines, manufactures, compositions of matter, devices, methods and steps. Any embodiment or claim of the present invention does not have to achieve all the purposes, advantages and / or features disclosed by the present invention.

[0123] The above outlines multiple embodiments so that those skilled in the art in the technical field to which the present invention pertains can better understand the viewpoints of the embodiments of the present invention. Those skilled in the art in the technical field to which the present invention pertains should understand that they can, based on the embodiments of the present invention, design or modify other processes and structures to achieve the same purposes and / or advantages as the embodiments introduced herein. Those skilled in the art in the technical field to which the present invention pertains should also understand that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and they can make various changes, substitutions, and replacements without departing from the spirit and scope of the present invention.

[0124] The specific embodiments described above further elaborate on the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A catalyst for decomposing hydrogen peroxide, comprising: A metal oxide, represented by formula (1): A a B b C c O x Formula (1) Wherein, A is Mn; B is Ce; C is Y, La, Nd or Dy; a+b+c=1; and x changes with the valence balance.

2. The catalyst for decomposing hydrogen peroxide according to claim 1, wherein a=b+c.

3. The catalyst for decomposing hydrogen peroxide according to claim 1, wherein c = 0.01 to 0.

1.

4. The catalyst for decomposing hydrogen peroxide according to claim 1, wherein a=0.3-0.7, b=0.3-0.7, and c=0.

05.

5. A method for decomposing hydrogen peroxide, comprising: A catalyst is added to a solution containing hydrogen peroxide to decompose the hydrogen peroxide into water and oxygen, wherein the catalyst comprises a metal oxide represented by formula (1), A a B b C c O x Formula (1) Wherein, A is Mn; B is Ce; C is Y, La, Nd or Dy; a+b+c=1; and x changes with the valence balance.

6. The method for decomposing hydrogen peroxide according to claim 5, wherein the concentration of the hydrogen peroxide in the solution is 0.1 wt% to 5 wt%.

7. The method for decomposing hydrogen peroxide according to claim 5, wherein the weight of the catalyst is 0.04 wt% to 5 wt% of the weight of the solution.

8. The method for decomposing hydrogen peroxide according to claim 5, wherein the solution is an aqueous phase, an organic phase or a combination thereof.

9. The method for decomposing hydrogen peroxide according to claim 5, wherein the solution comprises water, C1-C 10 Alcohols, C1~C 10 Ketones or combinations thereof.

10. The method for decomposing hydrogen peroxide according to claim 5, wherein the pH value of the solution is 4-11.

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