A gopher-like manganese-based composite metal nanomaterial, a preparation method thereof and application thereof in pet deodorization

Abstract

The application belongs to the field of nanometer materials, and particularly relates to a rattan ball-shaped manganese-based composite metal nanometer material and a preparation method and application thereof. The method comprises the following steps: 1) placing montmorillonite in an organic amine compound solution, performing hydrothermal modification to obtain a carrier dispersion liquid; 2) dispersing lignin fine powder in the carrier dispersion liquid, performing ultrasonic treatment to obtain a composite carrier, and then performing filtration; 3) dispersing the composite carrier in a manganese salt solution, performing low-temperature hydrothermal treatment to obtain M@OMMT composite particles; 4) placing the M@OMMT composite particles in acetone, performing ultrasonic treatment to dissolve and separate a pre-product MeLN; and 5) performing pyrolysis calcination treatment on the pre-product MeLN to obtain the rattan ball-shaped manganese-based composite metal nanometer material. The application prepares a nanometer adsorption material with a special rattan ball-shaped configuration, the prepared nanometer adsorption material has a large specific surface area and strong adsorption activity, and has a great adsorption space.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of nanomaterials, and particularly relates to a dendritic manganese-based composite metal nanomaterial, a preparation method thereof, and application thereof in the field of pet deodorization. BACKGROUND

[0002] With the popularization of domestic pets, the types of pet products are increasingly diversified, and the demand for pet products is also increasingly high. However, the most prominent demand at present is pet deodorization.

[0003] Among them, the deodorization of excrement of domestic cats is particularly prominent. Since the nature of pet cats is different from that of pet dogs, their excretion process is mostly solved in the home environment, and the owner needs to use cat litter as a "pet toilet". However, most of the current cat litter only has adsorption performance, and the adsorption performance is very limited. Conventional pet cat litter such as bentonite cat litter has an ammonium adsorption capacity of almost only 0.1 mg / g, and the adsorption effect on hydrogen sulfide is even more limited. Therefore, more and more researchers have improved and improved the pet cat litter. The most important improvement form is to use a relatively simple way to build a nanomaterial with a large specific surface area and high adsorption capacity.

[0004] At present, nanomaterials have shown wide application prospects in various fields. Compared with conventional particulate materials, nanoparticles have many excellent properties such as high adsorption performance and active surface due to their large specific surface area and quantum size effect. In previous studies, our company developed a unique manganese dioxide material with nanoflower structure. Although it has a very small particle size and a very large specific surface area, it has excellent adsorption capacity and can quickly and efficiently absorb volatile gas pollutants and liquids, but the actual adsorption threshold is low, i.e. the adsorption capacity for volatile gas pollutants and liquids has a low upper limit.

[0005] Therefore, when used in cat litter manufacturing or in combination with cat litter, a large amount is required to ensure its long-term effectiveness. In some use scenarios, the amount needs to be reduced while maintaining long-term effectiveness, and the actual effect is relatively limited. Therefore, further improvement is needed to make it have long-acting adsorption capacity and greater adsorption capacity, which is an important research direction. SUMMARY

[0006] To solve the problem that the existing manganese dioxide nanomaterials can have good adsorption but have relatively low adsorption capacity and are difficult to maintain long-term effectiveness, the present application provides a dendritic manganese-based composite metal nanomaterial, a preparation method thereof, and application thereof.

[0007] The main purpose of the present application is:

[0008] I. Improve the adsorption capacity of the adsorption material;

[0009] II. Ensure that the adsorption material has long-term effectiveness;

[0010] III. Ensure that the adsorption material has good mechanical properties and agglomeration ability.

[0011] To achieve the above-mentioned purposes, the following technical solutions are adopted in the present application.

[0012] A preparation method of a gourd-shaped manganese-based composite metal nanomaterial,

[0013] The method comprises:

[0014] 1) Put the montmorillonite into an organic amine compound solution and perform hydrothermal modification to obtain a carrier dispersion liquid;

[0015] 2) Disperse the fine powder of lignin in the carrier dispersion liquid and perform ultrasonic treatment to obtain a composite carrier after filtration;

[0016] 3) Disperse the composite carrier in a manganese salt solution and perform low-temperature hydrothermal treatment to obtain M@OMMT composite particles;

[0017] 4) Put the M@OMMT composite particles into acetone and perform ultrasonic treatment to dissolve and separate a pre-product MeLN;

[0018] 5) Perform pyrolysis and calcination treatment on the pre-product MeLN to obtain the gourd-shaped manganese-based composite metal nanomaterial.

[0019] Preferably,

[0020] In step 1), the mesh number of the montmorillonite is 60-200 mesh;

[0021] In step 1), the organic amine compound solution is a DMFA solution of polyimide, and the polyimide is PMR type polyimide with a concentration of 12-15 wt%;

[0022] In step 1), the hydrothermal modification is performed at 60-80℃, and the modification process lasts for 45-75 min.

[0023] Preferably,

[0024] In step 2), the amount of lignin is 0.02-0.05 g / g of montmorillonite.

[0025] Preferably,

[0026] In step 3), the concentration of manganese ions in the manganese salt solution is 1.0-2.0 mol / L;

[0027] The manganese salt solution further contains 10-20 mmol / L titanium ions and 0.05-0.15 mol / L zinc ions.

[0028] As preferred,

[0029] The low-temperature hydrothermal treatment in step 3) is performed at 110-130 DEG C for 60-120 min.

[0030] As preferred,

[0031] The ultrasonic treatment in step 4) lasts for at least 30 min, and the pre-product MeLN is obtained after centrifugal separation of the montmorillonite.

[0032] As preferred,

[0033] The pyrolysis calcination treatment in step 5) includes steam preheating and calcination treatment.

[0034] The steam preheating process uses 120-150 DEG C hot steam to treat the pre-product MnO-N@OMMT-n for 25-35 min.

[0035] The calcination treatment is performed at 200-400 DEG C for 60-120 min.

[0036] A gourd-shaped manganese-based composite metal nanomaterial.

[0037] Application of the gourd-shaped manganese-based composite metal nanomaterial in the field of pet deodorization,

[0038] The gourd-shaped manganese-based composite metal nanomaterial is used for adsorbing volatile gas pollutants or adsorbing liquids containing volatile gas pollutants.

[0039] For the technical scheme of the present application, the core lies in constructing a primary structure by means of complexing method and chelation of organic amine, and further adjusting and controlling the microstructure based on the primary structure through chelation replacement.

[0040] Firstly, the montmorillonite belongs to a kind of layered silicate mineral, and its layered structure makes it have a good template form, and the complexing method can realize the simulation and formation of its nanosheet structure. Moreover, the crystal layer space of the montmorillonite has strong cation exchange capacity, so it has the ability to combine organic amine for self-modification and capture metal cations.

[0041] On this basis, the organic amine component embedded into the crystal layer space of the montmorillonite can effectively chelate metal ions, especially the manganese ions of the nanoadsorption material of the present application. The manganese-based nanoadsorption material with unique micro-nano structure can be effectively prepared by chelating manganese ions and then calcining.

[0042] But only so, only can build with sheet nanostructure aggregation of nanometer flower structure, and nanometer flower structure although has great specific surface area and extremely strong adsorption activity, but actual adsorption capacity is low, after adsorption also exists certain secondary release risk. Thus, the present application further adds lignin cooperation on this basis, and adds "impurity ions" in manganese salt solution. The addition of lignin enables it to realize secondary grafting with organic amine compounds. Organic amine compounds and lignin both have a large number of active sites, and especially the polar groups contained in organic amine compounds have strong grafting activity with lignin. Through this way, lignin can be effectively grafted on the original carrier constructed by montmorillonite and organic amine compounds, and then the metal cations are captured by montmorillonite and chelated and fixed by organic amine compounds and lignin.

[0043] In the process of chelation and fixation, the present application selects manganese salt solution containing other metal cations. This is because the addition of impurity metal cations can make the solution "heterogeneous". The heterogeneous manganese salt solution will hinder the chelation and fixation of manganese due to the energy level transition or valence state conversion and chelation displacement of metal cations, and change the morphology of manganese dioxide formed after hydrothermal and calcination heat treatment.

[0044] For this, the present application focuses on the important process of chelation displacement. Only organic amine compounds have similar chelation effect on metal cations, but lignin is different. The chelation of different metal cations and lignin has certain differences. Therefore, based on this factor, lignin and wood powder, wood chips, etc. are often used for selective capture of metal wastewater. As for lignin itself, it can form chelation with a variety of metal cations. The present application selectively adds titanium ions and zinc ions because the stability of metal chelates is higher for titanium ions than for zinc ions, and higher for zinc ions than for manganese ions. This leads to the fact that although manganese metal ions have high concentration and are easy to form chelation first, the presence of titanium ions and zinc ions will destroy the stability of manganese metal chelates and cause them to restructure.

[0045] On the other hand, the addition of titanium ions will enable the nano-adsorption material to have the ability of photocatalytic degradation of volatile gas pollutants such as ammonia, so that it can not only adsorb and remove, but also completely degrade. After the addition of zinc ions, zinc oxide is formed by calcination, which is an amphoteric oxide and has adsorption properties for both acids and bases. It can absorb ammonia and achieve desulfurization. Therefore, when used as cat litter, it can achieve the co-adsorption of ammonia and sulfur, greatly improving the use effect.

[0046] And the appropriate addition of titanium ions and zinc ions can greatly change the morphology of metal chelates under the cooperation of lignin, completely restructure the final micro-morphology of the obtained nanomaterials, and finally prepare materials such asFigure 1 The hollow rattan ball-shaped nanostructure has large specific surface area and strong adsorption activity, and has great internal structure space, so that the adsorption capacity of the nano-adsorption material is much larger than that of conventional adsorption materials, and the rattan ball-shaped nano-adsorption material can effectively avoid secondary escape of adsorbed volatile gas pollutants, and has higher adsorption stability.

[0047] The present application has the following advantages:

[0048] The nano-adsorption material prepared by the present application has special rattan ball-shaped configuration, large specific surface area, strong adsorption activity, and great adsorption space, so that the nano-adsorption material can effectively adsorb volatile gas pollutants, and has certain photocatalytic degradation effect, and can avoid secondary escape of volatile gas pollutants. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1 SEM characterization diagram of the sample prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0050] The present application will be further described and illustrated in detail in the following specific examples and accompanying drawings. Those skilled in the art will be able to implement the present application based on these descriptions. In addition, the examples of the present application involved in the following description are generally only a part of the examples of the present application, not all examples. Therefore, all other examples obtained by those skilled in the art based on the examples in the present application without creative labor should be within the scope of protection of the present application.

[0051] Unless otherwise specified, the raw materials used in the examples of the present application are commercially available or can be obtained by those skilled in the art. Unless otherwise specified, the methods used in the examples of the present application are methods mastered by those skilled in the art.

[0052] Unless otherwise specified, the nano-petal-shaped manganese dioxide described in the examples of the present application is prepared by the following method: montmorillonite is placed in a PMR type polyimide DMFA solution with a concentration of 12wt% at a dosage of 100g / L for 70℃ hydrothermal reaction for 60min to obtain a carrier, the carrier is immersed in a manganese sulfate aqueous solution with a concentration of 0.5mol / L at a ratio of 120g / L, and then 180℃ hydrothermal loading is carried out for 30min and acetone ultrasonic cleaning is carried out for 5min, respectively, and the hydrothermal loading and ultrasonic cleaning are repeated for three times each time, then a pre-product is obtained, the montmorillonite is removed by centrifugal separation, and then steam preheating treatment at 150℃ is carried out for 30min and calcination at 1050℃ is carried out for 90min, respectively, to obtain nano-petal-shaped manganese dioxide.

[0053] Example 1

[0054] A preparation method of a vine-ball-shaped manganese-based composite metal nanomaterial,

[0055] The method comprises the following steps:

[0056] 1) Put 120-mesh montmorillonite into a PMR-type polyimide DMFA (N,N-dimethylacetamide) solution with a concentration of 12 wt%, and the use ratio in this example is 100 g of montmorillonite: 1 L of PMR-type polyimide DMFA solution, and only need to ensure that the PMR-type polyimide DMFA solution can immerse the montmorillonite in actual production, and then perform a 70℃ hydrothermal reaction for 60 min for modification to obtain a carrier dispersion liquid;

[0057] 2) Disperse lignin powder into the carrier dispersion liquid according to a use ratio of 0.05 g / g of montmorillonite, and perform ultrasonic treatment for 30 min to obtain a composite carrier after filtration;

[0058] 3) Disperse the composite carrier in a 1.5 mol / L manganese nitrate aqueous solution according to a ratio of 120 g / 500 mL, and the manganese sulfate aqueous solution further contains 15 mmol / L of titanium nitrate and 0.10 mol / L of zinc nitrate, and perform a 120℃ low-temperature hydrothermal treatment for 90 min to obtain M@OMMT composite particles;

[0059] 4) Place the M@OMMT composite particles in excess acetone, and perform ultrasonic treatment for 30 min, and then centrifuge to remove the montmorillonite carrier, and filter and separate a pre-product MeLN;

[0060] 5) Perform steam preheating treatment on the pre-product MeLN using a 150℃ hot steam for 30 min and calcination at 350℃ for 90 min in sequence to obtain the vine-ball-shaped manganese-based composite metal nanomaterial.

[0061] The vine-ball-shaped manganese-based composite metal nanomaterial prepared in this example is subjected to SEM characterization, and the SEM characterization result is shown in Figure 1 From Figure 1 It can be clearly seen that the nanosorbent material prepared in the application has a very unique micro-morphology feature, which has a structure like a vine ball, an external uniform layering and interwoven strip structure, and an internal hollow, has a large specific surface area and good structural stability, and the internal hollow feature makes it have a very high adsorption capacity.

[0062] The vine-ball-shaped manganese-based composite metal nanomaterial prepared in this example is subjected to specific surface area characterization and particle size characterization, and the specific surface area characterization result shows that the specific surface area thereof can reach about 221 m 2 / g, and the average particle size is about 1.21 μm. It shows a large specific surface area and a small powder property.

[0063] In addition, performance characterization tests were performed. The rattan-shaped manganese-based composite metal nanomaterials referred to in this example and commercially available amphoteric bentonite cat litter were mixed at a mass ratio of 1:19 as experimental group composite cat litter samples, and commercially available amphoteric bentonite cat litter was used as a blank control group cat litter sample, which was placed in saturated ammonia water and saturated hydrogen sulfide aqueous solution at a ratio of 5 g / 100 mL of test solution, and then soaked for 20 min. After filtration, the saturated adsorption capacity of ammonium ions and the saturated adsorption capacity of hydrogen sulfide were calculated, and after the above tests, the clumped parts of the cat litter were scooped up, and whether the clumps were broken was recorded under the condition of no external force, "O" indicating that none of the clumps were broken, "N+" indicating that the clumps were broken after the ammonium ion saturated adsorption test, "S+" indicating that the clumps were broken after the hydrogen sulfide saturated adsorption test, and "X" indicating that all the clumps were broken. Thereafter, the clumps were observed to see whether they were scattered when they fell freely at a distance of 0.6 m from the ground, "O" indicating that none of the clumps were scattered, "N+" indicating that the clumps were scattered after the ammonium ion saturated adsorption test, "S+" indicating that the clumps were scattered after the hydrogen sulfide saturated adsorption test, and "X" indicating that all the clumps were scattered.

[0064] The test results are shown in the following table.

[0065] NH4 + adsorption capacity H2S adsorption capacity Crushed slag Spread out Experimental group sample 11.21 mg / g 2.13 mg / g ○ ○ Blank control group sample 0.811 mg / g 0.192 mg / g ○ S+

[0066] In the table, the adsorption capacity results of the experimental group samples are not direct detection values, but calculated results, which are used to represent the adsorption capacity of the rattan-shaped manganese-based composite metal nanomaterials without the interference of commercially available cat litter, and the specific calculation formula is as follows.

[0067]

[0068] In the formula, M represents NH4 + or H2S.

[0069] From the above characterization test results, the rattan-shaped manganese-based composite metal nanomaterials of the present application have extremely high ammonium ion adsorption capacity, which can be as high as 11.21 mg / g, which is much higher than that of commercially available amphoteric bentonite cat litter. In addition, the same adsorption capacity characterization was performed on the nanometer petal-shaped manganese dioxide jointly developed by our company, and the characterization results showed that the ammonium ion adsorption capacity of the nanometer petal-shaped manganese dioxide was about 3.617 mg / g, which also made great progress.

[0070] As can be seen, the rattan-shaped manganese-based composite metal nanomaterials of the present application have extremely high adsorption capacity, and also exhibit good use effect for hydrogen sulfide adsorption. In terms of scooping and dropping tests, the rattan-shaped manganese-based composite metal nanomaterials of the present application also have good mechanical properties and agglomeration ability.

[0071] Furthermore, after saturation adsorption, the sample was treated at 60℃ for 30 minutes to characterize its adsorption capacity, and the loss rates of ammonia and hydrogen sulfide were calculated to indicate the ability of volatile gaseous pollutants to escape if they were not treated promptly after adsorption. The characterization results showed that the ammonia loss rate was approximately 6.7%, and the hydrogen sulfide loss rate was approximately 21.2%. The same experiment was conducted on commercially available amphoteric bentonite cat litter and the nano-petal-shaped manganese dioxide jointly developed by our company. The ammonia loss rate of the commercially available amphoteric bentonite cat litter was approximately 39.6%, and the hydrogen sulfide loss rate was approximately 37.2%, both similar. However, the ammonia loss rate of the nano-petal-shaped manganese dioxide jointly developed by our company was approximately 27.3%, and the hydrogen sulfide loss rate was approximately 43.7%. Therefore, the spherical manganese-based composite metal nanomaterial prepared in this invention exhibits extremely high adsorption stability.

[0072] Example 2

[0073] A method for preparing a spherical manganese-based composite metal nanomaterial, the method comprising:

[0074] 1) Place 120 mesh montmorillonite in DMFA (N,N-dimethylacetamide) of PMR type polyimide with a concentration of 15 wt%. In this example, the ratio is 100 g montmorillonite: 1 L PMR type polyimide DMFA solution. Then, perform a hydrothermal reaction at 70 °C for 60 min to modify the carrier dispersion.

[0075] 2) Add lignin powder to the carrier dispersion at a ratio of 0.03 g / g montmorillonite, and then sonicate for 30 min to obtain a composite carrier by filtration.

[0076] 3) The composite carrier was dispersed in a 1.0 mol / L manganese nitrate aqueous solution at a ratio of 120 g / 500 mL. The manganese sulfate aqueous solution also contained 10 mmol / L titanium nitrate and 0.5 mol / L zinc nitrate. After hydrothermal treatment at 120℃ for 90 min, M@OMMT composite particles were obtained.

[0077] 4) The M@OMMT composite particles were placed in excess acetone and ultrasonically treated for 30 min, then centrifuged to remove the montmorillonite carrier, filtered and separated to obtain the preproduct MeLN.

[0078] 5) The pre-product MeLN was preheated with hot steam at 150℃ for 30 min and calcined at 350℃ for 90 min in sequence to obtain the spherical manganese-based composite metal nanomaterial.

[0079] The sample prepared in this example was characterized in the same way as in Example 1. The characterization results are shown in the table below.

[0080] Specific surface area Average particle size NH4 + adsorption capacity H2S adsorption capacity Crushed slag Spread out 215m 2 / g]]> 1.26 μm 11.07 mg / g 2.15 mg / g ○ ○

[0081] From the above characterization results, the rattan-shaped manganese-based composite metal nanomaterial prepared in this example also has extremely high adsorption capacity and exhibits good aggregation ability and acid-base amphoteric adsorption capacity.

[0082] Example 3

[0083] A method for preparing a rattan-shaped manganese-based composite metal nanomaterial,

[0084] The method comprises:

[0085] 1) Put 120-mesh montmorillonite into a PMR-type polyimide DMFA (N,N-dimethylacetamide) solution with a concentration of 15 wt%, the usage ratio in this example is 100 g of montmorillonite: 1 L of PMR-type polyimide DMFA solution, only need to ensure that the PMR-type polyimide DMFA solution can immerse the montmorillonite during actual preparation, then perform 70°C hydrothermal reaction for 60 min for modification to obtain a carrier dispersion liquid;

[0086] 2) Disperse the lignin fine powder into the carrier dispersion liquid according to a usage ratio of 0.02 g / g of montmorillonite, and perform ultrasonic treatment for 30 min to obtain a composite carrier after filtration;

[0087] 3) Disperse the composite carrier in a 2.0 mol / L manganese nitrate aqueous solution according to a ratio of 120 g / 500 mL, the manganese sulfate aqueous solution also contains 20 mmol / L titanium nitrate and 0.15 mol / L zinc nitrate, and perform 120°C low-temperature hydrothermal treatment for 90 min to obtain M@OMMT composite particles;

[0088] 4) Place the M@OMMT composite particles in excess acetone and perform ultrasonic treatment for 30 min, then centrifuge to remove the montmorillonite carrier, filter and separate the pre-product MeLN;

[0089] 5) Perform steam preheating treatment on the pre-product MeLN using 150°C hot steam for 30 min and calcination at 350°C for 90 min in sequence to obtain the rattan-shaped manganese-based composite metal nanomaterial.

[0090] The sample prepared in this example was subjected to the same characterization as in Example 1. The characterization results are shown in the following table.

[0091] Specific surface area Average particle size NH4 + adsorption capacity H2S adsorption capacity Crushed slag Spread out 220m 2 / g]]> 1.30 μm 10.97 mg / g 2.11 mg / g ○ ○

[0092] From the above characterization results, the rattan-shaped manganese-based composite metal nanomaterial prepared in this example also has extremely high adsorption capacity and exhibits good aggregation ability and acid-base amphoteric adsorption capacity.

[0093] Comparative Example 1

[0094] Preparation of rattan-shaped manganese-based composite metal nanomaterials based on Example 1:

[0095] 1) Put 120-mesh montmorillonite into a PMR-type polyimide DMFA (N,N-dimethylacetamide) solution with a concentration of 12 wt%, the use ratio in this example is 100 g of montmorillonite: 1 L of PMR-type polyimide DMFA solution, only need to ensure that the PMR-type polyimide DMFA solution can immerse the montmorillonite in actual preparation, then perform a 70℃ hydrothermal reaction for 60 min for modification, and filter to obtain a carrier;

[0096] 2) Disperse the carrier in a 1.5 mol / L manganese nitrate aqueous solution according to a ratio of 120 g / 500 mL, the manganese sulfate aqueous solution also contains 15 mmol / L titanium nitrate and 0.10 mol / L zinc nitrate, and perform a 120℃ low-temperature hydrothermal treatment for 90 min to obtain M@OMMT composite particles;

[0097] 3) Put the M@OMMT composite particles into excess acetone and ultrasonic treat for 30 min, then centrifuge to remove the montmorillonite carrier, filter and separate the pre-product MeLN;

[0098] 4) Steam preheat treat the pre-product MeLN with 150℃ hot steam for 30 min and calcine at 350℃ for 90 min in sequence, to obtain the rattan-shaped manganese-based composite metal nanomaterials.

[0099] The sample prepared in this example is characterized in the same way as Example 1. The characterization results are shown in the following table.

[0100] Specific surface area Average particle size NH4 + adsorption capacity H2S adsorption capacity Crushed slag Spread out 253m 2 / g]] 0.43 μm 2.87 mg / g 1.24 mg / g ○ ○

[0101] From the above characterization results, only without the cooperation of lignin in the chelation replacement process, the specific surface area of the sample prepared in this example has a large increase, the average particle size has a large decrease, but the actual adsorption capacity has a cliff-like drop. It can be seen that lignin has a significant microstructure regulating effect on the technical solution of the present application, and the microstructure formed after regulation can form a hollow rattan shape. Although the specific surface area decreases and the average particle size increases, the adsorption capacity is also significantly improved, which has a positive and beneficial effect.

[0102] Comparative Example 2

[0103] Preparation of rattan-shaped manganese-based composite metal nanomaterials based on Example 1:

[0104] 1) Put 120 mesh montmorillonite into a PMR type polyimide DMFA (N,N-dimethylacetamide) solution with a concentration of 12 wt%, the use ratio in this example is 100 g of montmorillonite: 1 L of PMR type polyimide DMFA solution, only need to ensure that the PMR type polyimide DMFA solution can immerse the montmorillonite in actual production, then modify by 70°C hydrothermal reaction for 60 min to obtain a carrier dispersion liquid;

[0105] 2) Disperse the lignin fine powder into the carrier dispersion liquid according to the use ratio of 0.05 g / g of montmorillonite, ultrasonic treatment for 30 min to obtain a composite carrier after filtration;

[0106] 3) Disperse the composite carrier in a 1.5 mol / L manganese nitrate aqueous solution according to the proportion of 120 g / 500 mL, and obtain M@OMMT composite particles after 120°C low-temperature hydrothermal treatment for 90 min;

[0107] 4) Put the M@OMMT composite particles into excess acetone and ultrasonic treatment for 30 min, then centrifuge to remove the montmorillonite carrier, filter and separate the pre-product MeLN;

[0108] 5) Steam preheating treatment of the pre-product MeLN with 150°C hot steam for 30 min and calcination at 350°C for 90 min in sequence, to obtain a gong-shaped manganese-based composite metal nanomaterial.

[0109] The sample prepared in this example was characterized in the same way as in Example 1. The characterization results are shown in the following table.

[0110] Specific surface area Average particle size NH4 + adsorption capacity H2S adsorption capacity Crushed slag Spread out 249m 2 / g]] 0.37 μm 3.06 mg / g 0.71 mg / g ○ ○

[0111] From the above characterization results, without the addition of zinc ions and titanium ions, the effective chelation replacement in the preparation process of this example cannot be achieved, so the specific surface area increases, the average particle size decreases, but the adsorption capacity also decreases significantly. It is particularly important to note that the adsorption capacity and capacity of hydrogen sulfide in this example decrease more significantly, which is much greater than that of Comparative Example 1. It can be seen from the combination of Comparative Example 1 and Comparative Example 2 that lignin and hetero-metal cations are the key to microstructure regulation, and zinc ions can indeed effectively improve the adsorption and capture effect of acidic components of the nano-adsorption material.

Claims

1. A method for preparing a spherical manganese-based composite metal nanomaterial, characterized in that, The method includes: 1) Montmorillonite was placed in an organic amine compound solution and subjected to hydrothermal modification to obtain a carrier dispersion; 2) Disperse fine lignin powder in a carrier dispersion, sonicate it, and then filter it to obtain a composite carrier; 3) The composite carrier is dispersed in a manganese salt solution and subjected to low-temperature hydrothermal treatment to obtain M@OMMT composite particles. The manganese salt solution contains 1.0–2.0 mol / L manganese ions and also contains 10–20 mmol / L titanium ions and 0.05–0.15 mol / L zinc ions. 4) The M@OMMT composite particles were placed in acetone, ultrasonically treated, and then centrifuged to separate the preproduct MeLN; 5) The pre-product MeLN was subjected to pyrolysis and calcination to obtain the spherical manganese-based composite metal nanomaterial.

2. The method for preparing a spherical manganese-based composite metal nanomaterial according to claim 1, characterized in that, Step 1) The montmorillonite used has a mesh size of 60-200. Step 1) The organic amine compound solution is a DMFA solution of polyimide, wherein the polyimide is a PMR type polyimide with a concentration of 12-15 wt%. Step 1) The hydrothermal modification is carried out at 60-80 °C for 45-75 min.

3. The method for preparing a spherical manganese-based composite metal nanomaterial according to claim 1, characterized in that, Step 2) The amount of lignin used is 0.02 to 0.05 g / g montmorillonite.

4. The method for preparing a spherical manganese-based composite metal nanomaterial according to claim 1, characterized in that, Step 3) The low-temperature hydrothermal treatment is carried out at 110-130 ℃ and maintained for 60-120 min.

5. The method for preparing a spherical manganese-based composite metal nanomaterial according to claim 1, characterized in that, Step 4) The ultrasonic treatment lasts for at least 30 minutes, followed by centrifugation to separate montmorillonite and obtain the preproduct MeLN.

6. The method for preparing a spherical manganese-based composite metal nanomaterial according to claim 1, characterized in that, Step 5) The pyrolysis calcination treatment includes steam preheating and calcination. The steam preheating process uses hot steam at 120–150 °C to treat the preproduct MeLN for 25–35 min; The calcination treatment was carried out at 200–400 °C for 60–120 min.

7. A spherical manganese-based composite metal nanomaterial prepared by any one of claims 1 to 6.

8. The application of the spherical manganese-based composite metal nanomaterial as described in claim 7 in the field of pet deodorization, characterized in that, The spherical manganese-based composite metal nanomaterial is used to adsorb volatile gaseous pollutants or liquids containing volatile gaseous pollutants.

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