Preparation method of Zr (OH) 4-MnO2 composite metal oxide decontamination agent with efficient digestion performance on mustard gas

Abstract

The invention relates to the field of decontaminant preparation, in particular to a preparation method of a Zr (OH) 4-MnO2 composite metal oxide decontaminant with efficient digestion performance on mustard gas. Zirconium hydroxide is used as a carrier, manganese dioxide is deposited and loaded on zirconium hydroxide through a chemical reaction to prepare the Zr (OH) 4-MnO2 composite metal oxide decontamination agent, the defect that Zr (OH) 4 is low in mustard gas digestion performance can be overcome, and the Zr (OH) 4-MnO2 composite metal oxide decontamination agent has the capability of rapidly digesting mustard gas, so that the Zr (OH) 4-MnO2 composite metal oxide decontamination agent can be better applied to the decontamination field; according to the present invention, the Zr (OH) 4-MnO2 composite metal oxide is prepared by doping and loading MnO2 in the carrier zirconium hydroxide, the metal oxide has characteristics of lattice distortion, defect increase and active site increase due to component doping, and the decontamination agent has characteristics of Zr and Mn metal oxides so as to substantially improve the digestion performance of the decontamination agent on mustard gas;

Description

Technical Field

[0001] The present invention relates to the field of preparation of cleaning agents, and in particular to a Zr(OH) 4 -MnO 2 The invention discloses a preparation method of a composite metal oxide cleaning agent. Background Art

[0002] Mustard gas is a typical corrosive chemical warfare agent that can attack mucous membranes, causing irreversible alkylation reactions of human DNA, RNA, proteins, etc., thereby causing cell death. Especially, exposure to high doses of mustard gas in a short period of time can cause fatal damage to the human body. In addition, the synthesis process of mustard gas is simple and fast, and requires few synthetic raw materials. It is called the "king of poisons" and has the characteristics of being difficult to degrade and existing in the environment for a long time. Therefore, it is necessary to effectively treat and degrade it to reduce the harm it brings in the fields of war, production and storage. Decontamination is an important part of responding to chemical threats and an important measure to reduce casualties and prevent secondary pollution. Compared with traditional strong alkaline solutions, hydrogen peroxide oxidizing agents, porous activated carbon adsorbent detoxification agents and their substitutes, metal-based catalysts show excellent catalytic degradation effects and generate relatively weak toxic degradation products, reducing secondary pollution to the environment. In recent years, new adsorption-reaction disinfection materials made of single or composite metal oxides have excellent adsorption and reaction capabilities. They are currently a research hotspot in the field of military decontamination and have broad application prospects.

[0003] Disadvantages of the prior art: Zr(OH) 4 The surface is distributed with multiple active centers such as coordinated unsaturated metal cations, oxygen vacancies, bridging hydroxyl groups (b-OH) with Bronsted acidity and terminal hydroxyl groups (t-OH) with Bronsted basicity, and has both redox and acid-base properties, which has attracted widespread attention from researchers. In the current related reports, some researchers have used nuclear magnetic resonance technology (NMR) to monitor Zr(OH) 4 The half-life of VX and GD is 1 min and 8.7 min respectively, which can achieve rapid disinfecting in a short time; however, the half-life of HD is as high as 2.3 h, and the degradation rate does not continue to increase with time, which limits the application of Zr(OH) 4 Application in the field of decontamination. Therefore, for the rapid decomposition of a variety of typical toxic agents, a single Zr(OH) 4 There is a shortcoming in the ability to decompose mustard gas, and it is necessary to select suitable doped metals to prepare composite metal oxide disinfectant materials with high efficiency in decomposing mustard gas. Summary of the invention

[0004] The present invention is to solve the problem of Zr(OH)4 To solve the problem of insufficient mustard gas decomposition capacity, a Zr(OH) 4 -MnO 2 The preparation method of the composite metal oxide disinfectant is to enable it to have the ability to quickly decompose mustard gas through the doping loading of manganese dioxide, so that it can be better used in the field of disinfection.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: a Zr(OH) 4 -MnO 2 The preparation method of the composite metal oxide cleaning agent comprises the following steps: The first step is the preparation and synthesis of carrier zirconium hydroxide: adding NaOH solution to zirconium oxychloride solution, adjusting the pH to 8-11, stirring, washing, filtering and obtaining zirconium hydroxide, redispersing the zirconium hydroxide in deionized water to prepare a wet slurry, adding nitric acid aqueous solution to the wet slurry to adjust the pH of the slurry to 8, adding the solid product to a reactor for hydrothermal reaction after suction filtration, washing and filtering the product after the reaction, and drying it in an electric blast drying oven, and grinding to obtain a carrier zirconium hydroxide powder material; Step 2, Zr(OH) 4 -MnO 2 Preparation of composite metal oxides: The carrier zirconium hydroxide powder material prepared in the first step was sieved and dispersed in distilled water. MnSO 4 ·H 2 O aqueous solution was added to the zirconium hydroxide dispersion, and then KMnO 4 The aqueous solution was added to the zirconium hydroxide dispersion, and after continuous stirring for 1 h, the solution was gradually heated to boiling state, and continuous stirring was continued until boiling. After filtering and washing, it was dried in a drying oven at 80 °C to prepare Zr(OH) 4 -MnO 2 Composite metal oxides.

[0006] As a further limitation of the technical solution of the present invention, in the first step, the zirconium oxychloride solution is 20 g ZrOCl 2 8H 2 O was dissolved in 24.25 g of deionized water.

[0007] As a further limitation of the technical solution of the present invention, in the first step, the mass concentration of the NaOH solution is 10 wt%, and the NaOH solution is slowly added dropwise to the zirconium oxychloride solution at a rate of 0.5-3 mL / min, and the stirring time after the addition of the NaOH solution is 1-6 h.

[0008] As a further limitation of the technical solution of the present invention, the mass fraction of the nitric acid aqueous solution in the first step is 30%.

[0009] As a further limitation of the technical solution of the present invention, the conditions of the hydrothermal reaction are: 80-140° C., 3-8 h, and the drying conditions of the electric blast drying oven are: drying at 80° C. for 8 h.

[0010] As a further limitation of the technical solution of the present invention, in the second step, after the carrier zirconium hydroxide powder material is sieved with a 170-mesh sieve, 100 g is taken and dispersed in 2 L of distilled water.

[0011] As a further limitation of the technical solution of the present invention, in the second step, KMnO 4 The aqueous solution is 15.8 g KMnO 4 Dissolve in 300 mL distilled water; MnSO 4 ·H 2 O aqueous solution is 25.4 g MnSO 4 ·H 2 O was dissolved in 300 mL of distilled water.

[0012] As a further limitation of the technical solution of the present invention, the continuous stirring and boiling time in the second step is 4 hours.

[0013] Compared with the prior art, the present invention has the following beneficial effects: Doping MnO in the Supported Zirconium Hydroxide 2 Zr(OH) was prepared 4 -MnO 2 Composite metal oxides, due to component doping, cause lattice distortion of metal oxides, increase defects, and increase active sites. They also have the properties of both Zr and Mn metal oxides, thereby greatly improving the decomposition performance of disinfectants on mustard gas.

[0014] During the preparation process, the particle size of zirconium hydroxide powder and KMnO 4 、MnSO 4 ·H 2 O aqueous solution drop rate control to achieve MnO 2 In Zr(OH) 4 The uniform dispersion of Zr(OH) 4 -MnO 2 Improvement of mustard gas degradation performance by composite metal oxides. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Zr(OH) 4 and Zr(OH) 4 -MnO2 X-ray diffraction spectrum of composite metal oxides.

[0016] Figure 2 Zr(OH) 4 and Zr(OH) 4 -MnO 2 Test tube disinfection rate of composite metal oxides against mustard gas DETAILED DESCRIPTION

[0017] The present invention is further described below in conjunction with specific embodiments. Example

[0018] For laboratory scale Zr(OH) 4 -MnO 2 Preparation method of composite metal oxide disinfectant. The preparation method of this material is mainly divided into two parts: the first step is the preparation and synthesis of carrier zirconium hydroxide; the second step is Zr(OH) 4 -MnO 2 Preparation of composite metal oxides.

[0019] Step 1: Preparation and synthesis of carrier zirconium hydroxide. The specific method is as follows: 20 g of zirconium oxychloride octahydrate (ZrOCl 2 8H 2 O) was dissolved in 24.25 g of deionized water, and a certain amount of 10 wt% NaOH solution was slowly added to the zirconium oxychloride solution at a rate of (0.5~3) mL / min under stirring until the pH of the solution was controlled in the range of 8~11. After continuing to stir for (1~6) h, the zirconium hydroxide was redispersed in deionized water after washing and filtering to prepare a wet slurry, and the pH of the slurry was adjusted to 8 with a 30% nitric acid aqueous solution. After suction filtration, the solid product was added to the reactor, which was sealed and hydrothermally reacted at (80~140) °C for (3~8) h. After the reaction was completed, the product was washed with water, filtered, and dried in an electric blast drying oven at 80 °C for 8 h. After grinding, the carrier zirconium hydroxide powder material was obtained. The zirconium hydroxide prepared by this method has a large specific surface area (310~443 m² / g) and a pore volume (0.447~0.680 cm 3 / g), which can provide abundant mesopores for doping loading of other metal components.

[0020] Step 2: Zr(OH) 4 -MnO 2 Preparation of composite metal oxides. The specific method is as follows: the carrier zirconium hydroxide powder material prepared in the first step is sieved through a 170-mesh sieve, and 100 g is dispersed in 2 L of distilled water. Then 15.8 g KMnO 4and 25.4 g MnSO 4 ·H 2 O were dissolved in 300 mL of distilled water, and then MnSO 4 ·H 2 O aqueous solution was added to the zirconium hydroxide dispersion, and then KMnO 4 The aqueous solution was added thereto, stirred continuously for 1 h, and then the solution was gradually heated to boiling state, stirred and boiled continuously for 4 h, filtered, washed with water, and dried in a drying oven at 80 °C to obtain Zr(OH) 4 -MnO 2 Composite metal oxides. Figure 1 The support Zr(OH) is shown 4 and Zr(OH) 4 -MnO 2 X-ray diffraction spectrum of the composite. It can be seen from the figure that the prepared carrier Zr(OH) 4 It is amorphous, which indicates that the current hydrothermal reaction temperature (80~140)℃ is not enough to cause the transformation of zirconium hydroxide to monoclinic and tetragonal phases. 4 Medium load MnO 2 Later, MnO appeared at diffraction angles 2θ of 22°, 36.8°, 42.2°, and 55.8°. 2 The characteristic diffraction peaks of MnO 2 Successfully loaded on Zr(OH) 4 middle.

[0021] The determination of the disinfection rate of the mustard gas test tube by the disinfectant refers to GJB 3638A-2020 "Evaluation method of disinfection effect". The specific evaluation method is: use a pipette to draw 10 μL of mustard gas and add it to the bottom of a 10 mL test tube, and then slowly add Zr(OH) 4 or Zr(OH) 4 -MnO 2 1 g of composite metal oxide disinfectant was vortexed for 3 min (speed was 1800 r / min), and after the target time, 5 mL of petroleum ether was added and fully vortexed to extract the remaining mustard gas, and the solution was allowed to stand for 30 min to separate the layers. Finally, the upper layer of petroleum ether solution was taken and diluted to a certain multiple, and then analyzed by T-135 method. Zr(OH) 4 and Zr(OH) 4 -MnO 2 The change of the test tube disinfection rate of mustard gas by composite metal oxides over time is shown in Figure 2 As shown in the figure, the single Zr(OH) 4The test tube sterilization rate of mustard gas is low. In the range of (0.5~5)h, the test tube sterilization rate of mustard gas is only in the range of 17.2%~45.6%. 4 Medium load MnO 2 Later, Zr(OH) 4 -MnO 2 The sterilization rate of mustard gas in the test tube was significantly improved by the composite metal oxides, which gradually increased from 83.7% (0.5 h) to 91.2% (1 h), 96.3% (2 h) and 98.1% (5 h). 4 -MnO 2 Composite metal oxide cleaning agents can compensate for Zr(OH) 4 To overcome the shortcoming of insufficient mustard gas decomposition capability, the zirconium-based materials’ decomposition performance on mustard gas has been greatly improved.

[0022] The present invention dopes and loads MnO in the carrier zirconium hydroxide 2 Zr(OH) was prepared 4 -MnO 2 Composite metal oxides, due to component doping, cause lattice distortion of metal oxides, increase defects, and increase active sites. They also have the properties of both Zr and Mn metal oxides, thereby greatly improving the decomposition performance of disinfectants on mustard gas.

[0023] During the preparation process, the particle size of zirconium hydroxide powder and KMnO 4 、MnSO 4 ·H 2 O aqueous solution drop rate control to achieve MnO 2 In Zr(OH) 4 The uniform dispersion of Zr(OH) 4 -MnO 2 Improvement of mustard gas degradation performance by composite metal oxides.

Claims

1. A method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas, characterized in that: The following steps are involved: The first step is the preparation and synthesis of carrier zirconium hydroxide: adding NaOH solution to zirconium oxychloride solution, adjusting the pH to 8-11, stirring, washing, filtering and obtaining zirconium hydroxide, redispersing the zirconium hydroxide in deionized water to prepare a wet slurry, adding nitric acid aqueous solution to the wet slurry to adjust the pH of the slurry to 8, adding the solid product to a reactor for hydrothermal reaction after suction filtration, washing and filtering the product after the reaction, and drying it in an electric blast drying oven, and grinding to obtain a carrier zirconium hydroxide powder material; The second step is the preparation of Zr(OH)4-MnO2 composite metal oxide: the carrier zirconium hydroxide powder material prepared in the first step is sieved and dispersed in distilled water, and the MnSO4·H2O aqueous solution is first added to the zirconium hydroxide dispersion at a rate of 0.5~3mL / min, and then the KMnO4 aqueous solution is added to the zirconium hydroxide dispersion at a rate of 0.5~3mL / min. After continuous stirring for 1 hour, the solution is gradually heated to a boiling state, and continuous stirring is continued to boil. After filtering and washing, it is dried in a drying oven at 80°C to prepare the Zr(OH)4-MnO2 composite metal oxide.

2. A method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: In the first step, the zirconium oxychloride solution is obtained by dissolving 20 g of ZrOCl2·8H2O in 24.25 g of deionized water.

3. A method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: In the first step, the mass concentration of the NaOH solution is 10 wt%, and the NaOH solution is slowly added dropwise to the zirconium oxychloride solution at a rate of 0.5-3 mL / min. The stirring time after the addition of the NaOH solution is 1-6 h.

4. The method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: The mass fraction of the nitric acid aqueous solution in the first step is 30%.

5. The method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: The conditions of the hydrothermal reaction are: 80~140℃, 3~8 h, and the drying conditions of the electric blast drying oven are: drying at 80℃ for 8 h.

6. The method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: In the second step, the carrier zirconium hydroxide powder material was sieved with a 170-mesh sieve, and 100 g was dispersed in 2 L of distilled water.

7. The method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: In the second step, the aqueous solution of KMnO4 is 15.8 g KMnO4 dissolved in 300 mL distilled water; the aqueous solution of MnSO4·H2O is 25.4 g MnSO4·H2O dissolved in 300 mL distilled water.

8. The method for preparing a Zr(OH)4-MnO2 composite metal oxide cleaning agent having high efficiency in degrading mustard gas according to claim 1, characterized in that: In the second step, the boiling time was 4 h with continuous stirring.

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