Composition for preparing composite ozone catalyst as well as preparation method and application of composition

Abstract

The invention belongs to the field of catalysts, particularly relates to a composite ozone catalyst as well as a preparation method and application thereof, and more particularly relates to a composite ozone catalyst based on waste oil-absorbing resin as well as a preparation method and application thereof. The invention provides a composition for preparing a composite ozone catalyst. The composition is prepared from metal-doped oil-absorbing resin, sawdust, water-soluble starch, activated carbon powder, calcium oxide and glass powder. The composite ozone catalyst prepared from the composition has a good catalytic effect, and solves the problem of recovery of waste oil-absorbing resin.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to a composite ozone catalyst, its preparation method and application, and more specifically, to a composite ozone catalyst based on waste oil-absorbing resin, its preparation method and application. Background Technology

[0002] The advanced treatment of oily wastewater has always been a major challenge restricting the development of the petrochemical industry. In particular, the increase in marine oil spills and the discharge of various aromatic organic compounds has made oily wastewater treatment a research hotspot both domestically and internationally. Oil-absorbing resins, due to their oleophilic and hydrophobic properties, can effectively adsorb oils. Oil molecules penetrate into the resin and are absorbed into its mesh-like cavities. This material outperforms traditional oil-absorbing materials in terms of oil absorption rate, oil-water selectivity, and oil retention rate. It also has advantages such as absorbing a wide variety of oil types, having a density lower than water, absorbing oil but not water, small size, and convenient recovery, making it particularly suitable for the recovery of floating oil on water surfaces and the separation and purification of oily wastewater.

[0003] However, the widespread use of oil-absorbing resins has also led to the generation of a large amount of waste oil-absorbing resins every year. These waste resins are very stable in nature and contain non-degradable oil, aromatic hydrocarbons, and heterocyclic organic pollutants. Their impact on the environment has attracted widespread attention, and the recycling of waste resins plays an important role in resource utilization.

[0004] Therefore, there is a need in this field for a product that can recycle waste oil-absorbing resin, reduce the consumption of natural resources, and achieve resource recycling, thereby realizing sustainable development. Summary of the Invention

[0005] Heterogeneous ozone catalysis is a common technology for treating oily wastewater. The solid catalysts used in this technology can improve the mass transfer efficiency of ozone during the reaction process, and different functional applications can be achieved by adjusting the properties and structure of the catalyst in the early stages. Carbon materials are cheaper than metal oxides and also possess a large specific surface area, which is beneficial for the adhesion of metal oxides. Therefore, using waste oil-absorbing resin to prepare carbon materials with high specific surface area can not only solve the problem of waste oil-absorbing resin treatment and disposal, but also provide a new raw material for the preparation of carbon materials.

[0006] In view of the above, in a first aspect, the present invention provides a composition for preparing a composite ozone catalyst, comprising:

[0007] Metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder.

[0008] The composite ozone catalyst prepared using the above composition has good catalytic effect and solves the problem of recycling waste oil-absorbing resin.

[0009] Furthermore, the mass ratio of the metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder is (25-35):(5-10):(15-25):(5-10):(10-15):(15-20).

[0010] In some specific implementations, the mass ratio of the metal-doped oil-absorbing resin, wood chips, water-soluble starch, calcium oxide, and glass powder is 35:5:15:10:15:20.

[0011] In some specific embodiments, the metal salts incorporated into the metal-doped oil-absorbing resin include two or more of Fe, Mn, Cu, Ni, Co, Zn, or Ce.

[0012] In some specific embodiments, the mass ratio of the oil-absorbing resin to the metal salt in the metal-doped oil-absorbing resin is 1:(0.1 to 0.2).

[0013] In some specific embodiments, the particle size of the metal-doped oil-absorbing resin is 60–80 μm.

[0014] In some specific implementations, the water content of the metal-doped oil-absorbing resin is <5%.

[0015] In some specific embodiments, the metal-doped oil-absorbing resin is waste oil-absorbing resin, which contains 13% to 20% oil by weight of the total resin.

[0016] In one specific embodiment, the metal-doped oil-absorbing resin is Tulsimer ADS 850FG resin. Further, its particle size is 0.3–1.2 mm.

[0017] In some specific embodiments, the composition further includes boron powder and sodium hydroxide.

[0018] Secondly, the present invention provides a method for preparing a composite ozone catalyst, comprising the following steps:

[0019] Step S1: Pretreatment of oil-absorbing resin, wherein the oil-absorbing resin is crushed and dried;

[0020] Step S2: Pyrolysis and liquefaction of oil-absorbing resin, wherein the oil-absorbing resin pretreated in step S1 is mixed with sodium hydroxide, stirred and treated under the catalysis of boron powder, and then pyrolyzed and liquefied.

[0021] Step S3: Metal modification of oil-absorbing resin, wherein the oil-absorbing resin after pyrolysis and liquefaction in step S2 is mixed with a metal salt to obtain a metal-doped oil-absorbing resin.

[0022] Step S4: Processing the powder mixture, wherein the metal-doped oil-absorbing resin obtained in step S3 is mixed with sawdust, water-soluble starch, activated carbon powder, calcium oxide, and glass powder, extruded, and dried; and

[0023] Step S5: Calcination, wherein the mixture extruded and dried in step S4 is calcined at 550-750°C for 4-6 hours under nitrogen and argon protection to obtain a composite ozone catalyst.

[0024] Using the method of the present invention, the pretreatment process is simple, requiring no dilute sulfuric acid shaking and washing, no need for repeated washing steps, and also solves the problem of recycling waste oil-absorbing resin.

[0025] In some specific implementations, the particle size of the oil-absorbing resin after crushing in step S1 is 60-80 μm.

[0026] In some specific implementations, the drying parameters in step S1 are: a temperature of 60–75°C and / or a drying time of 4–6 hours.

[0027] In some specific implementations, the mass ratio of oil-absorbing resin, sodium hydroxide and boron powder in step S2 is (85-98):(2-5):(5-10).

[0028] In some specific implementations, the parameters for pyrolysis liquefaction in step S2 are: heating temperature of 120-150°C and / or heating time of 2-4 hours.

[0029] Sodium hydroxide can react chemically with functional groups in resins, such as undergoing a multi-step hydrolysis reaction with epoxy groups, thereby destroying the cross-linked structure of the resin and causing it to change from a solid to a liquid. Boron powder can react with sodium hydroxide under heating conditions to form borates, which can further react with the resin to promote resin liquefaction.

[0030] In some specific implementations, the metal salts incorporated into the metal-doped oil-absorbing resin in step S3 include two or more of Fe, Mn, Cu, Ni, Co, Zn, or Ce.

[0031] In some specific implementations, in step S3, the mass ratio of the oil-absorbing resin to the metal salt in the metal-doped oil-absorbing resin is 1:(0.1~0.2).

[0032] In some specific implementations, the mass ratio of the metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder in step S4 is (25-35):(5-10):(15-25):(5-10):(10-15):(15-20).

[0033] Water-soluble starch is used as a binder, activated carbon powder and wood chips are used as pore-forming agents, activated carbon powder and calcium oxide serve as the skeleton of the finished carbides, and waste glass powder has a low melting point and can melt during calcination to bind all materials and enhance the strength of the finished product.

[0034] In some specific implementations, the drying parameters in step S4 are: temperature of 60-75°C and / or time of 4-6 hours.

[0035] In some specific implementations, the heating rate and cooling rate in step S5 are both 5°C / min.

[0036] Thirdly, the present invention provides a composite ozone catalyst, which is prepared by the method described above.

[0037] Fourthly, the present invention provides an application of the above-mentioned composite ozone catalyst for treating industrial wastewater. Attached Figure Description

[0038] Figure 1 A schematic diagram of the catalyst prepared in Example 1;

[0039] Figure 2 A schematic diagram of the catalyst prepared in Comparative Example 3;

[0040] Figure 3 This is a schematic diagram of the catalyst prepared in Comparative Example 4. Detailed Implementation

[0041] The present invention will be described in detail below with reference to specific implementation schemes and embodiments, thereby making the advantages and various effects of the present invention more clearly apparent. Those skilled in the art should understand that these specific implementation schemes and embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0042] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0043] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined to form new technical solutions.

[0044] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0045] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0046] Unless otherwise specified, the terms used in this application have the common meanings as commonly understood by those skilled in the art.

[0047] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. When used herein, the singular forms “a,” “an,” and “the” are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the terms “comprise” and / or “comprising,” when used in this specification, identify the presence of the stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups. When used herein, the term “and / or” includes any and all combinations of the associated listed items.

[0048] In this invention, the term "oil-absorbing resin" refers to any resin that can be liquefied under conditions of sodium hydroxide, boron powder, and heating. Such resins can be used to prepare this type of catalyst. For example, Tulsimer ADS 850FG resin for water treatment is a spherical resin with a particle size of 0.3–1.2 mm. This type of resin experiences a significant performance degradation after 12–18 months of use, resulting in excessively high regeneration costs and eventual disposal. Different types of resins differ only in the proportion of auxiliary powders required for doping.

[0049] Example 1

[0050] Step 1: Pretreatment of waste super absorbent resin

[0051] The waste highly absorbent resin is dried in an oven, and then crushed using a jaw crusher to obtain waste highly absorbent resin powder for later use. The waste highly absorbent resin is non-renewable Tulsimer ADS 850FG resin used in oily wastewater treatment processes in the petrochemical industry for 12-18 months; it is in the form of brown granules. The particle size of the waste highly absorbent resin is approximately 0.3-1.2 mm, with an oil content of approximately 13%-20% of the total mass and a moisture content of approximately 15% of the total mass. After drying at 60-75℃ for 4-6 hours, the moisture content is <5%. The particle size of the crushed waste highly absorbent resin powder is 60-80 μm.

[0052] Step 2: Liquefaction of waste super absorbent resin

[0053] The dried micro-powder material obtained in the previous step was mixed with sodium hydroxide powder, and boron powder was used as a catalyst. The mixture was then stirred under heating conditions to ensure uniform mixing until the solid resin micro-powder liquefied through pyrolysis. The ratio of dried gel micro-powder material: sodium hydroxide: boron powder was 92 parts dried gel micro-powder material, 2 parts sodium hydroxide, and 6 parts boron powder. The heating conditions for resin liquefaction were 135℃ and 2.5 hours.

[0054] Step 3: Doping with active metal components

[0055] Metal salts with ozone catalytic properties are added to liquefied resin gels and stirred and mixed evenly under heating conditions. The amount of metal salts added is 15% of the mass of the resin gel, and the types of metal salts added are Fe and Mn.

[0056] Step 4: Mixing the powders

[0057] Wood chips, water-soluble starch, activated carbon powder, calcium oxide, and waste glass powder were added sequentially to a liquid resin gel containing various metal active components. The materials were mixed in a mass ratio of 30 (metal-doped oil-absorbing resin): 5 (wood chips): 20 (water-soluble starch): 10 (activated carbon powder): 15 (calcium oxide): 20 (glass powder). The uniformly mixed, moderately pliable lumps were extruded into cylindrical preforms with a diameter of 5 mm and a length of 4 mm. These preforms were then dried in an oven at 75°C for 4 hours and set aside for later use.

[0058] Step 5: Calcination

[0059] The dried columnar preform was calcined at high temperature under nitrogen and argon protection, and then naturally cooled to obtain a columnar porous composite ozone catalyst. The calcination temperature was 750℃, the calcination time was 4 hours, and the heating and cooling rates were both 5℃ / min. The resulting composite ozone catalyst is shown below. Figure 1 As shown.

[0060] Comparative Example 1

[0061] The preparation steps are the same as in Example 1, with the only difference being:

[0062] In step 4, the various materials are mixed in the following mass ratio: 25 (metal-doped oil-absorbing resin): 5 (wood chips): 15 (water-soluble starch): 10 (activated carbon powder): 15 (calcium oxide): 30 (glass powder).

[0063] Comparative Example 2

[0064] The preparation steps are the same as in Example 1, with the only difference being:

[0065] In step 4, the various materials are mixed in the following mass ratio: 35 (metal-doped oil-absorbing resin): 5 (wood chips): 25 (water-soluble starch): 10 (activated carbon powder): 15 (calcium oxide): 10 (glass powder).

[0066] Comparative Example 3

[0067] The preparation steps are the same as in Example 1, with the only difference being:

[0068] The calcination temperature in step 5 is 500℃, such as Figure 2As shown, the sample was clearly under-burned, with uneven foaming inside and out. The surface was foamed but the interior was either not foamed or had poor internal foaming. It had a hard texture, a small specific surface area, and poor catalytic effect.

[0069] Comparative Example 4

[0070] The preparation steps are the same as in Example 1, with the only difference being:

[0071] The calcination temperature in step 5 is 800℃, such as Figure 3 As shown. Overburned samples are grayish-black or pure black in color, with internal pores collapsing into flattened round shapes, or the sample melts, with internal gases escaping, and the surface exhibiting large pores while the interior has almost none. Excessive melting to a liquid state results in almost no pores inside or out, a dense structure, and excessive metal sintering, thus having almost no catalytic effect.

[0072] Catalytic performance experiment of the composite ozone catalyst prepared in this invention

[0073] The ozone catalysts prepared in the examples and comparative examples were used to conduct catalytic performance experiments, and the specific results are shown in Table 1. Table 1 shows that the catalyst of Example 1 has good molding properties, and its porosity and catalytic performance meet the requirements for a catalyst. In contrast, Comparative Examples 1-4 all have defects in molding, strength, porosity, and catalytic performance to varying degrees, and cannot be used for catalysis. Therefore, the method of the embodiments of the present invention can utilize waste oil-absorbing resin to modify it into a catalyst with good catalytic performance.

[0074] Table 1

[0075] Is it formed? strength Porosity Catalytic performance Example 1 yes 180N / particle 67％ 33.2％ Comparative Example 1 no 200N / particle 19％ 7.3％ Comparative Example 2 yes 120N / particle 37％ 21.7％ Comparative Example 3 yes 180N / particle 11％ 10.3％ Comparative Example 4 no 200N / particle 2.1％ 1.9％

[0076] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A composition for preparing a composite ozone catalyst, comprising: Metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder.

2. The composition according to claim 1, characterized in that, The mass ratio of the metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder is (25-35):(5-10):(15-25):(5-10):(10-15):(15-20).

3. The composition according to claim 1, characterized in that, The metal-doped oil-absorbing resin satisfies at least one of the following characteristics: The types of metal salts incorporated include two or more of Fe, Mn, Cu, Ni, Co, Zn, or Ce; or The mass ratio of oil-absorbing resin to metal salt is 1:(0.1~0.2).

4. The composition according to any one of claims 1 to 3, characterized in that, The metal-doped oil-absorbing resin has a particle size of 60–80 μm.

5. A method for preparing a composite ozone catalyst, comprising the following steps: Step S1: Pretreatment of oil-absorbing resin, wherein the oil-absorbing resin is crushed and dried; Step S2: Pyrolysis liquefaction of oil-absorbing resin, wherein the oil-absorbing resin pretreated in step S1 is mixed with sodium hydroxide, stirred under the catalysis of boron powder, and then pyrolyzed and liquefied. Step S3: Metal modification of oil-absorbing resin, wherein the oil-absorbing resin after pyrolysis and liquefaction in step S2 is mixed with a metal salt to obtain a metal-doped oil-absorbing resin. Step S4: Processing the powder mixture, wherein the metal-doped oil-absorbing resin obtained in step S3 is mixed with sawdust, water-soluble starch, activated carbon powder, calcium oxide, and glass powder, extruded, and dried; and Step S5: Calcination, wherein the mixture extruded and dried in step S4 is calcined at 550-750°C for 4-6 hours under nitrogen and argon protection to obtain a composite ozone catalyst.

6. The preparation method according to claim 5, characterized in that, In step S2, the mass ratio of oil-absorbing resin, sodium hydroxide and boron powder is (80-98):(2-5):(5-10).

7. The preparation method according to claim 5 or 6, characterized in that, The metal-doped oil-absorbing resin in step S3 satisfies at least one of the following characteristics: The types of metal salts incorporated include two or more of Fe, Mn, Cu, Ni, Co, Zn, or Ce; or The mass ratio of oil-absorbing resin to metal salt is 1:(0.1~0.2).

8. The preparation method according to claim 5, characterized in that, In step S4, the mass ratio of the metal-doped oil-absorbing resin, wood chips, water-soluble starch, activated carbon powder, calcium oxide, and glass powder is (25-35):(5-10):(15-25):(5-10):(10-15):(15-20).

9. A composite ozone catalyst, comprising the composite ozone catalyst prepared by any one of claims 5 to 8.

10. The application of the composite ozone catalyst according to claim 9 for the treatment of industrial wastewater.

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