Catalyst with amorphous metal oxide as well as preparation method and application of catalyst

Abstract

The invention relates to the technical field of catalysts for sewage treatment, in particular to a catalyst with an amorphous metal oxide as well as a preparation method and application of the catalyst. The preparation method comprises the following steps: carrying out first roasting on a precursor of a metal oxide to obtain an amorphous metal oxide; the amorphous rho-aluminum oxide and the amorphous metal oxide are mixed and granulated to obtain catalyst green pellets; carrying out hydration reaction on the catalyst green pellets to obtain a catalyst roasting raw material; carrying out second roasting on the catalyst roasting raw material to obtain a catalyst product with an amorphous metal oxide; wherein the temperature difference of the first roasting is more than or equal to 300 DEG C, and the time of the first roasting is less than or equal to 600s. According to the present invention, the metal oxide with the complete amorphous state or the partial amorphous state can be obtained by carrying out the short-time rapid first roasting on the precursor of the metal oxide so as to finally obtain the gamma-alumina ball carrier type ozone oxidation catalyst with the high catalytic effect;

Description

Technical Field

[0001] The present application relates to the technical field of catalysts for sewage treatment, and in particular to a catalyst having an amorphous metal oxide, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of highly polluting industries such as petroleum, chemical, pharmaceutical, and printing and dyeing, more and more industrial wastewater with high chemical oxygen demand needs to be treated. At present, in the secondary treatment of conventional sewage treatment plants, biochemical treatment has removed most of the biodegradable COD pollutants, and the remaining ones are mainly organic matter that is difficult to be biodegraded. Therefore, it is necessary to add advanced oxidation treatment processes to further degrade organic matter that is difficult to be biodegraded. At present, the advanced oxidation treatment processes mainly include ozone catalytic oxidation, Fenton reaction, wet catalytic oxidation and other oxidation methods; among these oxidation methods, ozone catalytic oxidation has the advantages of simple operation, no chemical addition, no secondary pollution, no sludge generation, and low operation and use costs compared to other advanced oxidation processes. This has made ozone catalytic oxidation a hot spot in the research and development of water treatment technology today.

[0003] At present, there are three main aspects of research and improvement on ozone oxidation catalysts: the first is the optimization and compatibility of different metal or metal oxide components; the second is the selection and improvement of different carriers; and the third is the improvement of the loading methods of different carriers and active components. At present, for catalytic effect and cost considerations, ozone oxidation catalysts generally use active γ-alumina balls as carriers and use a large amount of crystalline metals or metal oxides. However, the loading capacity of γ-alumina ball carriers is limited, and the catalytic effect of crystalline metals or metal oxides is limited, which leads to poor catalytic effect of ozone oxidation catalysts. Summary of the invention

[0004] The present application provides a catalyst having an amorphous metal oxide, a preparation method and an application thereof, in order to solve the following technical problem: how to improve the catalytic effect of a γ-alumina ball carrier type ozone oxidation catalyst.

[0005] In a first aspect, the present application provides a method for preparing a catalyst having an amorphous metal oxide, the preparation method comprising:

[0006] The metal oxide precursor is first calcined to quickly lose crystal water and gasifiable components to obtain an amorphous metal oxide;

[0007] Mixing and granulating amorphous ρ-alumina and the amorphous metal oxide to obtain catalyst green pellets;

[0008] The catalyst green pellets are subjected to a hydration reaction to obtain a catalyst roasting raw material;

[0009] The catalyst calcined raw material is subjected to a second calcination to obtain a catalyst product having an amorphous metal oxide;

[0010] Wherein, the temperature difference of the first calcination is ≥300° C., and the time of the first calcination is ≤600 s.

[0011] Optionally, the temperature difference of the first calcination is 300° C. to 1000° C., and the time of the first calcination is 0.5 s to 600 s;

[0012] The first roasting method includes at least one of the following:

[0013] Air flow suspension flash roasting, boiling furnace roasting, indirect rapid heat contact roasting and microwave heating roasting.

[0014] Optionally, the weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=(0.01-0.5):1.

[0015] Optionally, the metal oxide precursor includes at least one of the following:

[0016] Metal oxide hydrates, inorganic metal salt compounds, organic metal salt compounds and metal component precursors;

[0017] The metal oxide in the metal oxide precursor includes at least one of the following:

[0018] Iron oxides, copper oxides, manganese oxides, titanium oxides, rhenium oxides, cerium oxides, cobalt oxides and nickel oxides.

[0019] Optionally, the temperature of the hydration reaction is 35° C. to 90° C., and the time of the hydration reaction is ≥ 24 h.

[0020] Optionally, the temperature of the second calcination is 200° C. to 800° C., and the time of the second calcination is 1 h to 6 h.

[0021] Optionally, the mixing and granulation further comprises mixing and granulating by adding an aqueous auxiliary agent, wherein the aqueous auxiliary agent comprises at least one of the following:

[0022] Forming additives, pore structure adjustment additives and catalytic performance additives.

[0023] Optionally, the weight m3 of the aqueous auxiliary agent and the weight m1 of the amorphous ρ-alumina satisfy the relationship: m3:m1=(0.1-1):1.

[0024] In the second aspect, the present application provides a catalyst having an amorphous metal oxide, which is prepared by the preparation method described in the first aspect, and the weight m2 of the amorphous metal oxide and the total weight m5 of the catalyst satisfy the relationship: m2:m5=(0.01~0.5):1.

[0025] In a third aspect, the present application provides an ozone oxidation catalyst, the ozone oxidation catalyst comprising the catalyst described in the second aspect; the pore volume of the ozone oxidation catalyst is 0.1 mL / g to 0.8 mL / g, and the specific surface area of ​​the ozone oxidation catalyst is 100 m 2 / g~400m 2 / g.

[0026] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0027] An embodiment of the present application provides a method for preparing a catalyst having an amorphous metal oxide, the preparation method comprising: subjecting a metal oxide precursor to a first calcination to quickly lose crystallization water and gasifiable components to obtain an amorphous metal oxide; mixing and granulating amorphous ρ-alumina and the amorphous metal oxide to obtain catalyst raw balls; subjecting the catalyst calcined raw material to a second calcination to obtain a catalyst product having an amorphous metal oxide; wherein the temperature difference of the first calcination is ≥300°C, and the time of the first calcination is ≤600s. The temperature difference of the first calcination can be ≥300°C, and the time of the first calcination can be ≤600s. Sufficient heat can be provided by the first calcination in a very short time to cause the metal oxide precursor to lose crystal water and gasifiable components and undergo thorough or partial decomposition, thereby avoiding the metal oxide precursor from being calcined for a long time to generate a metal oxide with a complete lattice, so as to obtain a metal oxide with a completely amorphous state or a partially amorphous state. The metal oxide with a completely amorphous state or a partially amorphous state has a large number of spatial cracks in a macroscopic state and a large number of lattice defects in a microscopic state. On the one hand, amorphous metal oxides with sufficient spatial cracks and lattice defects can effectively combine with alumina molecules to increase the number of amorphous metal oxides carried by the γ-alumina ball carrier. Sufficient amorphous metal oxides can effectively improve the ability of the catalyst to catalyze ozone to produce hydroxyl radicals. On the other hand, amorphous metal oxides with sufficient spatial cracks and lattice defects can effectively combine with ozone molecules to improve the ability of the catalyst to catalyze ozone to produce hydroxyl radicals, thereby obtaining a γ-alumina ball carrier type ozone oxidation catalyst with a higher catalytic effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0029] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0030] Figure 1 A schematic flow chart of a method for preparing a catalyst having an amorphous metal oxide provided in an embodiment of the present application;

[0031] Figure 2 A schematic diagram of the actual process of preparing a catalyst having an amorphous metal oxide provided in an embodiment of the present application. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0033] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a rigid limitation on the scope of the present application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within the range; for example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range; in addition, whenever a numerical range is indicated in this document, it is meant to include any cited numbers (fractions or integers) within the indicated range.

[0034] In this document, the terms including "including" and "including" mean "including but not limited to". Relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. "And / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone; where A and B can be singular or plural. "At least one" means one or more, and "plurality" means two or more; "at least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items; for example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0035] Figure 1 The schematic diagram of the process for preparing a catalyst having an amorphous metal oxide provided in an embodiment of the present application is exemplarily shown;

[0036] Figure 2 The actual process diagram of a method for preparing a catalyst having an amorphous metal oxide provided in an embodiment of the present application is exemplarily shown.

[0037] like Figure 1 and Figure 2 As shown, the present application embodiment provides a method for preparing a catalyst having an amorphous metal oxide, the preparation method comprising:

[0038] S1. The metal oxide precursor is first calcined to quickly lose crystal water and gasifiable components to obtain an amorphous metal oxide;

[0039] S2. The amorphous ρ-alumina and the amorphous metal oxide are mixed and granulated to obtain catalyst raw balls;

[0040] S3. The catalyst raw balls are subjected to a hydration reaction to obtain a catalyst roasting raw material;

[0041] S4. The catalyst raw material is calcined for a second time to obtain a catalyst product having an amorphous metal oxide;

[0042] Wherein, the temperature difference of the first calcination is ≥300° C., and the time of the first calcination is ≤600 s.

[0043] The temperature difference of the first calcination may be 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C or 1000°C.

[0044] The first calcination time can be 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 1.0s, 1.5s, 2.0s, 2.5s, 3.0s, 3.5s, 4.0s, 4.5s, 5.0s, 10s, 20s, 30s, 40s, 50s, 60s, 120s, 180s, 240s, 300s or 600s.

[0045] It should be noted that the amorphous ρ-alumina can be obtained by rapid dehydration of alumina. The specific rapid dehydration temperature can be 700°C to 1000°C, and the rapid dehydration time can be 1s to 10s. The specific rapid dehydration treatment can refer to the process of preparing amorphous ρ-alumina by the aluminum hydroxide rapid dehydration method, that is, grinding the aluminum hydroxide to a specified particle size, for example, D50 = 10μm to 15μm, and sending it into hot air at 700°C to 1000°C to stay for 1s to 10s, thereby quickly removing 60% to 85% of the crystallization water in the moisture to generate amorphous ρ-alumina.

[0046] It should be noted that the first calcination and the second calcination are merely differences in calcination processes, and do not refer to different calcination process sequences.

[0047] It should be noted that the mixing and granulating method may be rolling, extrusion, squeezing, spraying, jetting, or stirring extrusion.

[0048] It should be noted that the waste heat from the second roasting can be recycled as heat for the hydration reaction.

[0049] In some optional embodiments, the temperature difference of the first calcination is 300°C to 1000°C, and the time of the first calcination is 0.5s to 600s;

[0050] The first roasting method includes at least one of the following:

[0051] Air suspension flash roasting, fluidized bed roasting, indirect rapid thermal contact roasting and microwave heating roasting;

[0052] In these embodiments, the temperature difference of the first calcination can be 300°C to 1000°C, and the time of the first calcination can be 0.5s to 10s. Sufficient heat can be provided by the first calcination in a very short time to cause the metal oxide precursor to lose crystal water and gasifiable components and undergo thorough or partial decomposition, thereby avoiding the metal oxide precursor from being calcined for a long time to generate a metal oxide with a complete lattice, so as to obtain a metal oxide with a completely amorphous state or a partially amorphous state. The metal oxide with a completely amorphous state or a partially amorphous state has a large number of spatial cracks in a macroscopic state and a large number of lattice defects in a microscopic state, thereby obtaining a γ-alumina ball carrier-based ozone oxidation catalyst with a higher catalytic effect; in addition, the first calcination method can include: at least one of airflow suspension flash calcination, boiling furnace calcination, indirect rapid thermal contact calcination and microwave heating calcination, which can cover most of the rapid calcination processes, thereby obtaining a metal oxide with a completely amorphous state or a partially amorphous state.

[0053] The temperature difference of the first calcination may be 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C or 1000°C.

[0054] The first calcination time may be 0.5 s, 1.0 s, 1.5 s, 2.0 s, 2.5 s, 3.0 s, 3.5 s, 4.0 s, 4.5 s, 5.0 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 120 s, 180 s, 240 s, 300 s or 600 s.

[0055] In some optional embodiments, the weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=(0.01-0.5):1;

[0056] In these embodiments, the weight m2 of the amorphous metal oxide and the weight m1 of aluminum hydroxide can satisfy the relationship: m1:m2=(0.01-0.5):1, which can promote sufficient mixing between the amorphous metal oxide and aluminum hydroxide to facilitate subsequent dehydration treatment and obtain a sufficient amount of amorphous ρ-alumina.

[0057] The weight m2 of the amorphous metal oxide and the weight m1 of aluminum hydroxide can satisfy the relationship: m1:m2=0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1 or 0.50:1.

[0058] In some optional embodiments, the metal oxide precursor includes at least one of the following:

[0059] Metal oxide hydrates, inorganic metal salt compounds, organic metal salt compounds and metal component precursors;

[0060] The metal oxide in the metal oxide precursor includes at least one of the following:

[0061] iron oxides, copper oxides, manganese oxides, titanium oxides, ruthenium oxides, cerium oxides, cobalt oxides, and nickel oxides;

[0062] In these embodiments, the metal oxide precursor may include: at least one of a metal oxide hydrate, an inorganic metal salt compound, an organic metal salt compound and a metal component precursor, and the metal oxide in the metal oxide precursor includes: at least one of iron oxide, copper oxide, manganese oxide, titanium oxide, ruthenium oxide, cerium oxide, cobalt oxide and nickel oxide, which can cover most of the metal oxide precursors with catalytic ozone oxidation and the metal oxide with catalytic ozone oxidation, thereby facilitating the subsequent first calcination to obtain a sufficient amount of amorphous metal oxide.

[0063] It should be noted that the metal component precursor may be other metal component precursors that can generate oxides through heating, pressure change, radiation, photoelectrochemical effect, etc.

[0064] In some optional embodiments, the temperature of the hydration reaction is 35° C. to 90° C., and the time of the hydration reaction is ≥ 24 h.

[0065] In these embodiments, the temperature of the hydration reaction can be 35°C to 90°C, and the time of the hydration reaction can be 6h to 48h, which can promote the reaction between the ρ-alumina component in the catalyst green balls and water to ultimately obtain a catalyst roasted raw material with sufficient strength, thereby facilitating the subsequent second roasting to obtain a catalyst product with amorphous metal oxide.

[0066] The temperature of the hydration reaction can be 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C.

[0067] The hydration reaction time can be 6h, 12h, 18h, 24h or 48h.

[0068] In some optional embodiments, the temperature of the second calcination is 200° C. to 800° C., and the time of the second calcination is 1 h to 6 h.

[0069] In these embodiments, the temperature of the second calcination can be 200°C to 800°C, and the time of the second calcination can be 1h to 6h. The structural water of the calcined raw material can be effectively removed by the second calcination to obtain a catalyst product having a variety of pore structures and a large specific surface area, thereby further improving the catalytic effect of the catalyst product.

[0070] The temperature of the second calcination may be 200°C, 300°C, 400°C, 500°C, 600°C, 700°C or 800°C.

[0071] The second calcination time can be 1 h, 2 h, 3 h, 4 h, 5 h or 6 h.

[0072] In some optional embodiments, the mixing and granulation further comprises mixing and granulating by adding an aqueous auxiliary agent, wherein the aqueous auxiliary agent comprises at least one of the following:

[0073] Forming additives, pore structure adjustment additives and catalytic performance additives.

[0074] In these embodiments, the mixed granulation may also include mixing and granulating by adding an aqueous additive, and the aqueous additive may include: at least one of a molding additive, a pore structure adjustment additive and a catalytic performance additive. The aqueous additive can further increase the number of pore structures and the specific surface area of ​​the catalyst product, thereby improving the effect of the catalyst product in catalyzing ozone oxidation.

[0075] In some optional embodiments, the weight m3 of the aqueous additive and the weight m1 of the amorphous ρ-alumina satisfy the relationship: m3:m1=(0.1-1):1.

[0076] In these embodiments, the weight m3 of the aqueous additive and the weight m1 of the amorphous ρ-alumina can satisfy the relationship: m3:m1=(0.1~1):1, which can promote the addition of a sufficient amount of aqueous additive to the amorphous ρ-alumina. The sufficient amount of aqueous additive can increase the number of pore structures and specific surface area of ​​the catalyst product, thereby improving the catalytic ozone oxidation effect of the catalyst product.

[0077] The weight m3 of the aqueous auxiliary agent and the weight m1 of the amorphous ρ-alumina may satisfy the relationship: m3:m1=0.1:1, 0.2:1, 0.3:1, 0.5:1 or 1:1.

[0078] It should be noted that the aqueous auxiliary agent may be kaolin, starch, polyethylene glycol, pseudo-boehmite, hydrated alumina, or a rare earth oxide auxiliary agent.

[0079] Based on a general inventive concept, the present application example provides a catalyst having an amorphous metal oxide, wherein the catalyst is prepared by the preparation method described in the first aspect, and the weight m2 of the amorphous metal oxide and the total weight m5 of the catalyst satisfy the relationship: m2:m5=(0.01~0.5):1.

[0080] The catalyst is realized by the above-mentioned preparation method. The specific steps of the preparation method can refer to the above-mentioned embodiments. Since the catalyst adopts part or all of the technical solutions of the above-mentioned embodiments, it at least has all the beneficial effects brought by the technical solutions of the above-mentioned embodiments, which will not be repeated here one by one.

[0081] In these embodiments, the weight m2 of the amorphous metal oxide and the total weight m5 of the catalyst can satisfy the relationship: m2:m5=(0.01-0.5):1, which can promote the presence of sufficient amorphous metal oxide in the catalyst, and sufficient amorphous metal oxide can effectively increase the catalytic effect of the catalyst on ozone oxidation.

[0082] The weight m2 of the amorphous metal oxide and the total weight m5 of the catalyst can satisfy the relationship: m2:m5=0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1 or 0.50:1.

[0083] Based on a general inventive concept, the present application provides an ozone oxidation catalyst, the ozone oxidation catalyst comprising the catalyst; the pore volume of the ozone oxidation catalyst is 0.1 mL / g to 0.8 mL / g, the specific surface area of ​​the ozone oxidation catalyst is 100 m 2 / g~400m 2 / g.

[0084] The ozone oxidation catalyst is realized based on the above-mentioned catalyst. The specific composition of the catalyst can refer to the above-mentioned embodiment. Since the ozone oxidation catalyst adopts part or all of the technical solutions of the above-mentioned embodiments, it has at least all the beneficial effects brought by the technical solutions of the above-mentioned embodiments, which will not be described one by one here.

[0085] In these embodiments, the pore volume of the ozone oxidation catalyst may be 0.1 mL / g to 0.8 mL / g, and the specific surface area of ​​the ozone oxidation catalyst may be 100 m 2 / g~400m 2 / g, which can indicate that the ozone oxidation catalyst has sufficient pore structure and sufficient specific surface area to improve the catalytic ozone oxidation effect of the catalyst product.

[0086] The pore capacity of the ozone oxidation catalyst may be 0.1 mL / g, 0.2 mL / g, 0.3 mL / g, 0.4 mL / g, 0.5 mL / g, 0.6 mL / g, 0.7 mL / g, or 0.8 mL / g.

[0087] The specific surface area of ​​the ozone oxidation catalyst can be 100m 2 / g, 150m 2 / g, 200m 2 / g, 250m 2 / g、300m 2 / g, 350m 2 / g or 400m 2 / .

[0088] The present application is further described below in conjunction with specific examples. The experimental methods in the following examples that do not specify specific conditions are usually measured according to industry standards; if there are no corresponding industry standards, they are carried out according to common international standards, conventional conditions, or conditions recommended by the manufacturer.

[0089] Example 1

[0090] like Figure 1 and Figure 2 As shown, a method for preparing a catalyst having an amorphous metal oxide comprises:

[0091] S1. The metal oxide precursor is first calcined to quickly lose crystal water and gasifiable components to obtain an amorphous metal oxide;

[0092] S2. The amorphous ρ-alumina and the amorphous metal oxide are mixed and granulated to obtain catalyst raw balls;

[0093] S3. The catalyst raw balls are subjected to hydration reaction to obtain catalyst roasting raw materials;

[0094] S4. The catalyst raw material is calcined for a second calcination to obtain a catalyst product having an amorphous metal oxide;

[0095] The initial temperature of the first calcination is 900°C, the final temperature of the first calcination is 300°C, and the time of the first calcination is 1s.

[0096] The first roasting method is air flow suspension flash roasting.

[0097] The weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=0.1:1.

[0098] The precursor of the metal oxide is iron oxide trihydrate.

[0099] The metal oxide in the metal oxide precursor is ferric oxide (ferric hydroxide).

[0100] The temperature of the hydration reaction is 60°C, and the time of the hydration reaction is 24h.

[0101] The temperature of the second calcination is 500° C., and the time of the second calcination is 2 h.

[0102] Example 2

[0103] Based on the contents disclosed in Example 1, the following modifications are further made:

[0104] The initial temperature of the first calcination was 1000° C., the end temperature of the first calcination was 500° C., and the time of the first calcination was 0.5 s.

[0105] The weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=0.05:1.

[0106] The precursor of the metal oxide is copper carbonate.

[0107] The metal oxide in the metal oxide precursor is copper oxide.

[0108] The temperature of the hydration reaction is 80°C, and the time of the hydration reaction is 24h.

[0109] The temperature of the second calcination is 500° C., and the time of the second calcination is 2 h.

[0110] Example 3

[0111] Based on the contents disclosed in Example 1, the following modifications are further made:

[0112] The initial temperature of the first calcination is 600° C., the final temperature of the first calcination is 300° C., and the time of the first calcination is 300 s.

[0113] The weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=8:82.

[0114] The precursor of the metal oxide is a mixture of trihydrated iron oxide and copper oxalate, and the weight m4 of the trihydrated iron oxide and the weight m5 of the copper oxalate satisfy the relationship: m4:m5=3:1.

[0115] The metal oxides in the metal oxide precursor are iron oxide and multivalent manganese dioxide.

[0116] The temperature of the hydration reaction is 80°C, and the time of the hydration reaction is 24h.

[0117] The temperature of the second calcination is 500° C., and the time of the second calcination is 2 h.

[0118] The mixing and granulating also includes mixing and granulating by adding a water-containing auxiliary agent, wherein the water-containing auxiliary agent is macroporous pseudo-boehmite.

[0119] The weight m3 of the aqueous additive and the weight m1 of the amorphous ρ-alumina satisfy the relationship: m3:m1=10:82.

[0120] Comparative Example 1

[0121] Based on the contents disclosed in Example 1, the following modifications are further made:

[0122] Conventional crystalline iron oxide is used instead of amorphous iron oxide.

[0123] Comparative Example 2

[0124] Based on the contents disclosed in Example 2, the following modifications are further made:

[0125] Conventional crystalline copper oxide is used instead of amorphous copper oxide.

[0126] Comparative Example 3

[0127] Based on the contents disclosed in Example 3, the following modifications are further made:

[0128] Conventional crystalline iron oxide and manganese dioxide are used instead of amorphous iron oxide and amorphous manganese dioxide, respectively.

[0129] Related experiments and effect data:

[0130] The catalyst products obtained in each embodiment and comparative example were collected, and catalytic experiments were carried out under the conditions that the COD value of the initial raw water was 350 mg / L and ozone was introduced at a certain rate. In the catalyst product experiments of embodiment 1 and comparative example 1, the ozone introduction rate was 10 mg / L·h -1 The catalytic reaction time was 60 min, and the ozone introduction rate in the catalyst product experiments of the other embodiments and comparative examples was 20 mg / L·h -1 The catalytic reaction time is 120 min. The catalytic effect is reflected by the removal rate of COD in the raw water. The specific results are shown in Table 1.

[0131] Table 1 Catalytic efficiency results of the catalyst products of various embodiments and comparative examples

[0132]

[0133] Detailed analysis of Table 1:

[0134] The degree of improvement in catalytic effect refers to the improvement ratio of the CDO removal rate V1 of the catalyst product obtained in the example compared with the CDO removal rate V2 of the catalyst product obtained in the comparative example, and the specific calculation method is: degree of improvement in catalytic effect = (V1-V2) / V2.

[0135] As can be seen from Table 1, the method for preparing a catalyst having an amorphous metal oxide provided in an embodiment of the present application can obtain a metal oxide in a completely amorphous state or a partially amorphous state by subjecting a metal oxide precursor to a short and rapid first calcination, thereby ultimately obtaining a γ-alumina ball-supported ozone oxidation catalyst with a higher catalytic effect.

[0136] In addition, the embodiment of the present application provides a method for preparing a catalyst having an amorphous metal oxide. Starting from the influence of the microstructure such as the crystal form and morphology of the metal component on the COD removal performance of the catalyst, the optimal crystal type of the metal component in the catalyst required for ozone oxidation catalytic treatment is established and determined. In addition, the detailed preparation process of these catalysts is also determined. Not only can a catalyst product with superior catalytic performance be obtained, so as to greatly improve the catalytic effect of the ozone oxidation catalyst through the catalyst, but also the preparation cost of the catalyst can be reduced; in addition, the overall process of the preparation method is mature, which is conducive to further promotion.

[0137] The above is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. It will be apparent to those skilled in the art that various modifications to these embodiments are possible, and the general principles defined in the present application can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown in the present application, but will conform to the widest scope consistent with the principles and novel features applied for by the present application.

Claims

1. A method for preparing a catalyst having an amorphous metal oxide, characterized in that: The preparation method comprises: The metal oxide precursor is first calcined to quickly lose crystal water and gasifiable components to obtain an amorphous metal oxide; Mixing and granulating amorphous ρ-alumina and the amorphous metal oxide to obtain catalyst green pellets; The catalyst green pellets are subjected to a hydration reaction to obtain a catalyst roasting raw material; The catalyst calcined raw material is subjected to a second calcination to obtain a catalyst product having an amorphous metal oxide; Wherein, the temperature difference of the first calcination is ≥300° C., and the time of the first calcination is ≤600 s.

2. The preparation method according to claim 1, characterized in that: The temperature difference of the first calcination is 300°C to 1000°C, and the time of the first calcination is 0.5s to 600s; The first roasting method includes at least one of the following: Air flow suspension flash roasting, boiling furnace roasting, indirect rapid heat contact roasting and microwave heating roasting.

3. The preparation method according to claim 1, characterized in that: The weight m2 of the amorphous metal oxide and the weight m1 of the amorphous ρ-aluminum oxide satisfy the relationship: m2:m1=(0.01-0.5):

1.

4. The preparation method according to claim 1, characterized in that: The metal oxide precursor includes at least one of the following: Metal oxide hydrates, inorganic metal salt compounds, organic metal salt compounds and metal component precursors; The metal oxide in the metal oxide precursor includes at least one of the following: Iron oxides, copper oxides, manganese oxides, titanium oxides, rhenium oxides, cerium oxides, cobalt oxides and nickel oxides.

5. The preparation method according to claim 1, characterized in that: The temperature of the hydration reaction is 35° C. to 90° C., and the time of the hydration reaction is ≥ 24 h.

6. The preparation method according to claim 1, characterized in that: The temperature of the second calcination is 200° C. to 800° C., and the time of the second calcination is 1 hour to 6 hours.

7. The preparation method according to claim 1, characterized in that: The mixing and granulation further comprises mixing and granulating by adding an aqueous auxiliary agent, wherein the aqueous auxiliary agent comprises at least one of the following: Forming additives, pore structure adjustment additives and catalytic performance additives.

8. The preparation method according to claim 7, characterized in that: The weight m3 of the aqueous auxiliary agent and the weight m1 of the amorphous ρ-alumina satisfy the relationship: m3:m1=(0.1-1):

1.

9. A catalyst having an amorphous metal oxide, characterized in that The catalyst is prepared by the preparation method described in any one of claims 1 to 8, and the weight m2 of the amorphous metal oxide and the total weight m5 of the catalyst satisfy the relationship: m2:m5=(0.01-0.5):

1.

10. An ozone oxidation catalyst, characterized in that: The ozone oxidation catalyst comprises the catalyst according to claim 9; the pore volume of the ozone oxidation catalyst is 0.1 mL / g to 0.8 mL / g, and the specific surface area of ​​the ozone oxidation catalyst is 100 m 2 / g~400m 2 / g.

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