A hydrogen peroxide stabilizer and a method for preparing the same

Abstract

The application relates to the chemical technology field, in particular to a hydrogen peroxide stabilizer and a preparation method thereof. The hydrogen peroxide enrichment and stabilizer is composed of an active component and a carrier, the active component is tin oxide, and the carrier is carbon-coated nickel; the active component is loaded on the pores and surface of the carrier; the mass of the active component accounts for 0.5-5% of the total mass of the hydrogen peroxide enrichment and stabilizer. The prepared hydrogen peroxide stabilizer can realize strong stabilizing effect by adding a small amount, and can be recycled multiple times; the solid form can be quickly separated through simple filtration, and the use cost is significantly reduced. The stabilizer can be added into other catalysts as an additive, can effectively enrich hydrogen peroxide under the condition of 1000 ppm low-concentration hydrogen peroxide, can form a high-concentration area locally, and can accelerate the reaction rate.

Description

Technical Field

[0001] This invention relates to the field of chemical technology, specifically to a hydrogen peroxide stabilizer and its preparation method. Background Technology

[0002] Hydrogen peroxide (H2O2) is a major industrial product widely used in chemical synthesis, water purification, biological treatment, and microelectronics manufacturing. In addition to these applications, H2O2 is increasingly recognized as a potential high-density energy carrier in sustainable energy systems, offering a safer and more convenient alternative to hydrogen in terms of storage and transportation. However, H2O2 is highly reactive and easily decomposes during transportation and use due to thermal heating or catalytic decomposition by other metal ions. Therefore, stabilizers are usually added to H2O2 solutions.

[0003] Common hydrogen peroxide stabilizers mainly include chelating agents such as phosphates, acetates, and organophosphonates. Their mechanism of action is to chelate metal ions in the solution, reducing the impact of metal ion-catalyzed decomposition of H2O2 during production and use. However, these hydrogen peroxide stabilizers are greatly affected by pH and temperature, and the stabilizers themselves have the potential to cause environmental pollution; removing pollution increases the cost of new applications. CN202111333065.4 uses the synergistic effect of sodium ethylenediaminetetraacetate and organophosphonates to inhibit the excessive decomposition of H2O2. Other existing technologies use sodium silicate, polyacrylic acid, etc. All of these stabilizers are in water-soluble salt form, making them difficult to separate and increasing the cost of subsequent wastewater treatment. Furthermore, when the H2O2 concentration is too low, the reaction efficiency is low, and the wastewater is often directly treated as wastewater, affecting the reuse of H2O2, resulting in resource waste and increased production costs. Summary of the Invention

[0004] To address the problems of weak stabilizing effect, high susceptibility to operating conditions, difficulty in separation, and lack of enrichment in existing hydrogen peroxide stabilizers, this invention provides a hydrogen peroxide stabilizer and its preparation method. By loading the active component tin oxide onto the surface of an activated carbon-coated nickel support, the electronic effect of the carbon-coated nickel support on the tin oxide causes electrons to transfer from the support to the tin oxide, thereby reducing the valence state of the Sn element in the tin oxide. This enhances the adsorption of H₂O₂ by the tin oxide, achieving enrichment and stabilization of hydrogen peroxide under a wide range of operating conditions. Experimental verification shows that this hydrogen peroxide stabilizer requires only a small amount to achieve strong stabilizing effect and can be recycled multiple times. Furthermore, the hydrogen peroxide stabilizer prepared by this invention is in solid form and can be separated by simple filtration, significantly reducing usage costs. This stabilizer can be added to other catalysts as an additive to effectively enrich hydrogen peroxide under low-concentration conditions, forming localized high-concentration zones and accelerating the reaction rate.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows.

[0006] The present invention provides a hydrogen peroxide stabilizer, wherein the hydrogen peroxide stabilizer is composed of an active component loaded on the pores and surface of a support; the active component is tin oxide, and the support is carbon-coated nickel; the active component is loaded on the pores and surface of the support; the mass of the active component accounts for 0.5% to 5% of the total mass of the hydrogen peroxide stabilizer.

[0007] This invention also provides a method for preparing a hydrogen peroxide stabilizer, comprising the following steps: Using carbon-coated nickel as a support, the carbon-coated nickel was calcined at 80℃~150℃ under an inert atmosphere to obtain an activated carbon-coated nickel support; the activated carbon-coated nickel support was impregnated in an aqueous solution of Sn salt precursor, and dried after impregnation to obtain a solid; the solid was heat-treated under an inert atmosphere to obtain a precursor; the precursor was reduced under a hydrogen-containing atmosphere to obtain a hydrogen peroxide stabilizer for enriching and stabilizing hydrogen peroxide.

[0008] Preferably, the Sn salt precursor is tin tetrachloride, stannous chloride, or tin acetate, and the concentration of the Sn salt precursor aqueous solution is 0.13M.

[0009] Preferably, the roasting time is 30 min to 120 min.

[0010] Preferably, the heat treatment temperature is 400℃~600℃, and the treatment time is 2h~4h.

[0011] Preferably, the temperature of the thermal reduction is 200℃~300℃, and the reduction time is 0.5h~4h.

[0012] Preferably, the inert atmosphere is nitrogen; the hydrogen-containing atmosphere is specifically 5% H2 and 95% N2.

[0013] The beneficial effects of this invention are: 1. This invention loads the active component tin oxide onto the surface of an activated carbon-coated nickel support. By utilizing the electronic effect of the carbon-coated nickel support on tin oxide, electrons from the support are transferred to the tin oxide, thereby reducing the valence state of Sn in the tin oxide. This enhances the adsorption of H2O2 by the tin oxide, achieving enrichment and stabilization of hydrogen peroxide under a wide range of operating conditions.

[0014] 0. Through experimental verification, the hydrogen peroxide stabilizer of the present invention only needs to be added in small amounts to achieve a strong stabilizing effect and can be recycled multiple times. Moreover, the hydrogen peroxide stabilizer prepared by the present invention is in solid form and can be separated by simple filtration, which significantly reduces the cost of use.

[0015] 1. The hydrogen peroxide stabilizer prepared by this invention can be added to other catalysts as an auxiliary agent to effectively enrich hydrogen peroxide under low concentration conditions of 1000ppm, forming a high concentration zone locally and accelerating the reaction rate. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0017] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] The technical solution of the present invention will be further described below through specific embodiments.

[0019] In the following embodiments, unless otherwise specified, the methods described are conventional methods; and unless otherwise specified, the reagents and materials described are commercially available.

[0020] Example 1 A method for preparing a hydrogen peroxide stabilizer includes the following steps: 0.2 mol of nickel hydroxide was dispersed in 300 mL of an aqueous solution containing 0.2 mol of citric acid monohydrate, and stirred at 70°C until the solvent was completely evaporated to obtain nickel citrate. The obtained nickel citrate was dried at 110°C for 10 hours and then placed in a tube furnace for pyrolysis under a nitrogen (N2) atmosphere. The temperature was increased to 700°C at a rate of 2°C / min and held for 2 hours. After cooling, the pyrolyzed solid was treated with 1M hydrochloric acid at 60°C for 2 hours to remove exposed nickel particles. The solid was then filtered, thoroughly washed with deionized water, and dried at 110°C for 10 hours to obtain carbon-coated nickel (Ni@C) support.

[0021] 5g of carbon-coated nickel (Ni@C) support was activated by calcination at 120℃ for 90min in a tube furnace under nitrogen atmosphere. 0.2470g of stannous chloride (SnCl2) was dissolved in 10mL of deionized water and stirred until dissolved. 5g of activated Ni@C was added to the SnCl2 solution, and the mixture was impregnated at room temperature for 12h, followed by drying at 80℃ for 12h. The dried solid was then calcined in a tube furnace at 500℃ for 3h under nitrogen atmosphere to obtain a precursor for hydrogen peroxide enrichment and stabilization. The hydrogen peroxide enrichment and stabilization precursor was reduced at 300℃ for 2h under a mixed atmosphere of 5% H2 and 95% N2 to obtain a hydrogen peroxide stabilizer, denoted as SnO2 / Ni@C-(SnCl2).

[0022] Example 2 A method for preparing a hydrogen peroxide stabilizer includes the following steps: 0.2 mol of nickel hydroxide was dispersed in 300 mL of an aqueous solution containing 0.2 mol of citric acid monohydrate, and stirred at 70°C until the solvent was completely evaporated to obtain nickel citrate. The obtained nickel citrate was dried at 110°C for 10 hours and then placed in a tube furnace for pyrolysis under a nitrogen (N2) atmosphere. The temperature was increased to 700°C at a rate of 2°C / min and held for 2 hours. After cooling, the pyrolyzed solid was treated with 1M hydrochloric acid at 60°C for 2 hours to remove exposed nickel particles. The solid was then filtered, thoroughly washed with deionized water, and dried at 110°C for 10 hours to obtain carbon-coated nickel (Ni@C) support.

[0023] 5g of Ni@C support was activated by calcining at 120℃ for 90min in a tube furnace under a nitrogen atmosphere. 0.3393g of tin tetrachloride (SnCl4) was dissolved in 10mL of deionized water with stirring. 5g of activated Ni@C was added to the SnCl4 solution, and the mixture was impregnated at room temperature for 12h, followed by drying at 80℃ for 12h. The dried solid was then calcined at 500℃ for 3h in a tube furnace under a nitrogen atmosphere to obtain a hydrogen peroxide enrichment and stabilizer precursor. The hydrogen peroxide enrichment and stabilizer precursor was reduced at 300℃ for 2h under a mixed atmosphere of 5% H2 and 95% N2 to obtain a hydrogen peroxide stabilizer, denoted as SnO2 / Ni@C-(SnCl4).

[0024] Example 3 A method for preparing a hydrogen peroxide stabilizer includes the following steps: 0.2 mol of nickel hydroxide was dispersed in 300 mL of an aqueous solution containing 0.2 mol of citric acid monohydrate, and stirred at 70°C until the solvent was completely evaporated to obtain nickel citrate. The obtained nickel citrate was dried at 110°C for 10 hours and then placed in a tube furnace for pyrolysis under a nitrogen (N2) atmosphere. The temperature was increased to 700°C at a rate of 2°C / min and held for 2 hours. After cooling, the pyrolyzed solid was treated with 1M hydrochloric acid at 60°C for 2 hours to remove exposed nickel particles. The solid was then filtered, thoroughly washed with deionized water, and dried at 110°C for 10 hours to obtain carbon-coated nickel (Ni@C) support.

[0025] 5g of Ni@C support was activated by calcining at 120℃ for 90min in a tube furnace under a nitrogen atmosphere. 0.3085g of tin acetate (Sn(CH3COO)2) was dissolved in 10mL of deionized water with stirring. 5g of activated Ni@C was added to the Sn(CH3COO)2 solution, and the mixture was impregnated at room temperature for 12h, followed by drying at 80℃ for 12h. The dried solid was then calcined at 500℃ for 3h in a tube furnace under a nitrogen atmosphere to obtain a hydrogen peroxide enrichment and stabilizer precursor. The hydrogen peroxide enrichment and stabilizer precursor was reduced at 300℃ for 2h under a mixed atmosphere of 5% H2 and 95% N2 to obtain a hydrogen peroxide stabilizer, denoted as SnO2 / Ni@C-(Sn(CH3COO)2).

[0026] Comparative Example 1 A method for preparing a hydrogen peroxide stabilizer includes the following steps: 5g of Na₂SiO₃ was calcined in a tube furnace at 120°C for 90 min under a nitrogen atmosphere. The calcined catalyst was then immersed in 10mL of deionized water for 12 h, followed by drying at 80°C for 12 h. The dried solid was then calcined in a tube furnace at 500°C for 3 h under a nitrogen atmosphere to obtain a stabilizer precursor. The stabilizer precursor was reduced at 300°C for 2 h under a mixed atmosphere of 5% H₂ and 95% N₂ to obtain a hydrogen peroxide stabilizer, denoted as Na₂SiO₃.

[0027] 0.5 g of the hydrogen peroxide stabilizer prepared in Examples 1-3 and Comparative Example 1 were weighed out, and 50 mL of 10000 ppm hydrogen peroxide was measured out. These were then loaded into a reaction vessel under high temperature and pressure. The reaction temperature was set at 50°C, and the reaction was carried out for 120 min. After the reaction, the hydrogen peroxide content was measured using a UV-Vis spectrophotometer, and the results are shown in Table 1.

[0028] Table 1. Stabilizing effect of different stabilizers on the thermal decomposition of hydrogen peroxide As shown in Table 1, the hydrogen peroxide stabilizer prepared in this invention can inhibit the thermal decomposition of hydrogen peroxide itself under different Sn metal sources.

[0029] 0.1 g of the hydrogen peroxide stabilizer prepared in Examples 1 to 3 and the hydrogen peroxide stabilizer prepared in Comparative Example 1 were weighed out, along with 0.1 g of ferric nitrate nonahydrate and 50 mL of 1000 ppm hydrogen peroxide. The mixture was added to the reaction vessel under high temperature and high pressure. The reaction temperature was set at 50°C and the reaction was carried out for 20 min. After the reaction was completed, the hydrogen peroxide content was measured using a UV-Vis spectrophotometer. The results are shown in Table 2.

[0030] Table 2. Stabilizing effect of different stabilizers on the catalytic decomposition of hydrogen peroxide As shown in Table 2, the hydrogen peroxide stabilizer prepared in this invention can inhibit the decomposition of hydrogen peroxide catalyzed by metal ions.

[0031] Weigh 0.5 g of the hydrogen peroxide stabilizers prepared in Examples 1 to 3 and Comparative Example 1, and load them into a reaction vessel under high temperature and pressure. Add 50 mL of 10000 ppm hydrogen peroxide. Adjust the pH to 2, 4, 7 and 10 with 1 mol / L sodium hydroxide solution and 1 mol / L hydrochloric acid solution, respectively. The reaction temperature is 30℃ and the reaction time is 60 min. After the reaction is completed, the hydrogen peroxide content is measured using a UV-Vis spectrophotometer. The results are shown in Table 3.

[0032] Table 3. Stabilizing effect of different stabilizers on the catalytic decomposition of hydrogen peroxide at different pH values. As shown in Table 3, the hydrogen peroxide stabilizer prepared in this invention can inhibit the decomposition of hydrogen peroxide over a wide pH range.

[0033] 0.0108 g of ferric nitrate nonahydrate was dissolved in 10 mL of deionized water, and the pH was adjusted to 4.5–5.5. 5 g of SnO2 / Ni@C-(Sn(CH3COO)2) prepared in Example 3 was weighed and added to the ferric nitrate solution. The mixture was impregnated at room temperature for 8 h, and then dried at 60 °C for 12 h. The dried solid was calcined at 300 °C for 4 h under an argon atmosphere to obtain Fe-SnO2 / Ni@C. 0.1 g of Fe-SnO2 / Ni@C and 50 mL of 1000 ppm hydrogen peroxide were added to a high-temperature, high-pressure reactor. The reaction temperature was 30 °C, and the reaction time was 20 min. After the reaction, the hydrogen peroxide content was determined using a UV-Vis spectrophotometer, and the results are shown in Table 4.

[0034] 5 g of the stabilizer SnO2 / Ni@C-(Sn(CH3COO)2) prepared in Example 3 was weighed and added to 15 mL of acetone. The pH was adjusted to 4.5–5.5. 0.0043 g of palladium diacetylacetonate was dissolved in 10 mL of acetone and sonicated. The two solutions were mixed under stirring and impregnated at room temperature for 8 h, then dried at 60 °C for 12 h. The dried solid was calcined at 300 °C for 4 h under an argon atmosphere to obtain Pd-SnO2 / Ni@C. 0.1 g of Pd-SnO2 / Ni@C and 50 mL of 1000 ppm hydrogen peroxide were added to a high-temperature, high-pressure reactor. The reaction temperature was 30 °C, and the reaction time was 20 min. After the reaction, the hydrogen peroxide content was determined using a UV-Vis spectrophotometer. The results are shown in Table 4.

[0035] 0.0043 g of palladium diacetylacetonate was dissolved in 10 mL of acetone and sonicated. 5 g of Ni@C was added to the palladium diacetylacetonate solution, and the mixture was impregnated at room temperature for 8 h, followed by drying at 60 °C for 12 h. The dried solid was calcined at 300 °C for 4 h under an argon atmosphere to obtain Pd-Ni@C. 0.1 g of Pd-Ni@C and 50 mL of 1000 ppm hydrogen peroxide were added to a high-temperature, high-pressure reactor, and the reaction was carried out at 30 °C for 20 min. After the reaction, the hydrogen peroxide content was determined using a UV-Vis spectrophotometer, and the results are shown in Table 4.

[0036] 0.0108 g of ferric nitrate nonahydrate was dissolved in 10 mL of deionized water. 5 g of Ni@C was added to the ferric nitrate solution, and the mixture was soaked at room temperature for 8 h, then dried at 60 °C for 12 h. The dried solid was calcined at 300 °C for 4 h under an argon atmosphere to obtain Fe-Ni@C. 0.1 g of Fe-Ni@C and 50 mL of 1000 ppm hydrogen peroxide were added to a high-temperature, high-pressure reactor. The reaction temperature was 30 °C, and the reaction was carried out for 20 min. After the reaction, the hydrogen peroxide content was determined using a UV-Vis spectrophotometer, and the results are shown in Table 4.

[0037] Table 4. Effect of catalysts on the decomposition of hydrogen peroxide As shown in Table 4, the hydrogen peroxide stabilizer prepared by this invention can be added to other catalysts as an auxiliary agent. Under the condition of low concentration of hydrogen peroxide of 1000 ppm, it can effectively enrich hydrogen peroxide and form a high concentration zone in a local area, which can effectively accelerate the reaction rate.

[0038] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A hydrogen peroxide stabilizer, characterized in that, The hydrogen peroxide stabilizer is composed of an active component loaded onto the pores and surface of a support; the active component is tin oxide, the support is carbon-coated nickel, and the mass of the active component accounts for 0.5% to 5% of the total mass of the hydrogen peroxide stabilizer.

2. A method for preparing the hydrogen peroxide stabilizer as described in claim 1, characterized in that, Includes the following steps: Using carbon-coated nickel as a support, the carbon-coated nickel was calcined at 80℃~150℃ under an inert atmosphere to obtain an activated carbon-coated nickel support; the activated carbon-coated nickel support was impregnated in an aqueous solution of Sn salt precursor, and dried after impregnation to obtain a solid; the solid was heat-treated under an inert atmosphere to obtain a precursor; the precursor was reduced under a hydrogen-containing atmosphere to load the active component onto the pores and surface of the support, thus obtaining a hydrogen peroxide stabilizer for enriching and stabilizing hydrogen peroxide.

3. The method for preparing the hydrogen peroxide stabilizer according to claim 2, characterized in that, The Sn salt precursor is tin tetrachloride, stannous chloride, or tin acetate, and the aqueous solution of the Sn salt precursor has a concentration of 0.13 M.

4. The method for preparing the hydrogen peroxide stabilizer according to claim 2, characterized in that, The roasting time is 30 min to 120 min.

5. The method for preparing the hydrogen peroxide stabilizer according to claim 2, characterized in that, The heat treatment temperature is 400℃~600℃, and the treatment time is 2h~4h.

6. The method for preparing the hydrogen peroxide stabilizer according to claim 2, characterized in that, The reduction treatment is performed at a temperature of 200℃ to 300℃ for a time of 0.5h to 4h.

7. The method for preparing the hydrogen peroxide stabilizer according to claim 2, characterized in that, The inert atmosphere is nitrogen; the hydrogen-containing atmosphere is specifically 5% H2 and 95% N2.

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