A method for preparing hydrogen peroxide based on barium cycle

Abstract

The present application relates to a novel hydrogen peroxide preparation method, at least comprising the following steps: mixing barium-based oxygen carrier with aqueous solution containing carbon dioxide gas, reacting to obtain aqueous solution containing hydrogen peroxide and carbonate precipitate; calcining the carbonate precipitate to obtain the barium-based oxygen carrier. The method simultaneously realizes enrichment and conversion of low-concentration carbon dioxide gas. The present technology has low raw material cost, environmentally friendly reaction process, low metal impurity content and high hydrogen peroxide component content of the obtained hydrogen peroxide, can simultaneously realize enrichment and separation of low-concentration carbon dioxide gas, and can effectively couple heating devices based on electric heating, photothermal and the like, realize low-carbon and efficient hydrogen peroxide preparation, and has very broad application prospect. The device investment is small, the barium-based oxygen carrier can be recycled, and there is no emission of polluting gas or solid waste in the production process, and the process is green and environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of hydrogen peroxide preparation, and more specifically to a method for preparing hydrogen peroxide based on the barium cycle. Background Technology

[0002] Hydrogen peroxide (H₂O₂) is an aqueous solution of hydrogen peroxide. Because the H₂O₂ molecule contains unstable peroxide bonds, these bonds easily break and are reduced to oxygen or water during reactions, thus exhibiting strong oxidizing properties. Furthermore, this compound contains only H and O elements, and the products in various reactions are generally in the form of water or oxygen. Currently, due to its strong oxidizing properties, hydrogen peroxide is widely used in many fields such as papermaking, metallurgy, environmental remediation, textiles, food processing, pharmaceuticals, electronics, and chemicals.

[0003] The main methods for preparing hydrogen peroxide include electrolysis, isopropanol oxidation, and anthraquinone method. Electrolysis was the earliest industrialized method, yielding high-quality products with low impurity content, facilitating further concentration. However, its overall production scale is limited, and increasing output relies on increasing the number of electrolytic cells, resulting in high production costs. The isopropanol oxidation method was first used by Shell in the United States. Its advantages include the absence of a catalyst, using air or oxygen to directly oxidize isopropanol, simultaneously producing hydrogen peroxide and acetone. The process is relatively simple, but its disadvantages are equally significant; its cost heavily depends on the market prices and demand for isopropanol and acetone. Currently, the anthraquinone method is the most widely used method for hydrogen peroxide preparation, accounting for over 95% of the market share. The anthraquinone method mainly consists of four reaction processes: anthraquinone hydrogenation, hydrogenated anthraquinone oxidation, hydrogen peroxide extraction, working solution purification, and recycling. This method offers advantages such as mild reaction conditions, high single-pass yield, no direct contact between hydrogen and oxygen, and high reaction safety. However, due to the limitations of the process, the alkyl anthraquinones and organic working fluids require complex purification before recycling, resulting in large equipment investments and high energy consumption. Furthermore, the hydrogen peroxide produced contains a large amount of organic matter, requiring further purification, which further increases production costs. Therefore, this method only has a certain economic advantage when used on a large scale. In addition, the raw materials hydrogen and anthraquinone used in this industrial process are both flammable and explosive materials, posing significant safety hazards. Simultaneously, the process generates flammable and toxic substances such as heavy aromatics and trioctyl phosphate, as well as carcinogens such as dioxins and chloroform. With increasingly stringent environmental and safety requirements, the economic benefits of the anthraquinone method are gradually decreasing. Therefore, there is an urgent need to develop new, efficient, and energy-saving hydrogen peroxide preparation processes.

[0004] As early as the beginning of the 20th century, scholars proposed methods for preparing hydrogen peroxide based on metal peroxides (Na2O2, BaO2, etc.) (J. Am. Chem. Soc., 1926, 48, 3019-3021). The principle involves the reaction of metal peroxides with strong acids (sulfuric acid and nitric acid) to produce hydrogen peroxide, while simultaneously generating metal nitrates or sulfates. Although the reaction is simple, the process suffers from high raw material costs, stringent requirements for equipment corrosion resistance, difficulties in subsequent separation, and the challenge of recycling byproducts (metal nitrates and sulfates), hindering its industrial application. Currently, extensive research has been conducted on the efficient synthesis of hydrogen peroxide, and scholars have proposed various green synthesis processes, including photocatalysis, direct hydrogen-oxygen synthesis, oxygen cathode reduction, and plasma methods. However, these technologies are still in the basic research stage, and many key scientific problems, such as low production efficiency and low hydrogen peroxide concentration in the products, remain to be solved. Summary of the Invention

[0005] In order to overcome the problems in the prior art, the purpose of this invention is to provide a novel hydrogen peroxide preparation method based on the barium cycle, which is simple, easy to implement, and suitable for large-scale production.

[0006] According to one aspect of this application, a method for preparing hydrogen peroxide based on the barium cycle is provided, comprising at least the following steps:

[0007] (1) The barium-based oxygen carrier is mixed with an aqueous solution containing carbon dioxide gas and reacted to obtain an aqueous solution containing hydrogen peroxide and a carbonate precipitate.

[0008] (2) The carbonate precipitate obtained in (1) is calcined to obtain the barium-based oxygen carrier.

[0009] The barium-based oxygen support is selected from barium peroxide;

[0010] Optionally, the barium-based oxygen support further includes at least one of barium peroxide, calcium peroxide, calcium oxide, or magnesium oxide.

[0011] In the aqueous solution containing carbon dioxide gas, the mass concentration of carbon dioxide is 0.1% to 7%.

[0012] The amount of carbon dioxide in the aqueous solution containing carbon dioxide gas is 50% to 100% of the amount of the barium-based oxygen carrier.

[0013] This means that the total amount of CO2 in the aqueous solution is not higher than the amount of barium-based oxygen carrier, ensuring that all carbonate precipitates are formed and no soluble salts are produced, thus avoiding contamination of the hydrogen peroxide.

[0014] The carbon dioxide is selected from at least one of pure carbon dioxide, industrial waste gas containing carbon dioxide, biogas containing carbon dioxide, or landfill gas containing carbon dioxide.

[0015] The reaction temperature is 10–50°C;

[0016] The reaction time is 5–240 min;

[0017] The roasting process includes high-temperature roasting and regeneration roasting.

[0018] The high-temperature roasting temperature is 800–1300℃;

[0019] The high-temperature roasting time is 1 to 12 hours;

[0020] The high-temperature calcination is divided into vacuum calcination and assisted calcination;

[0021] The auxiliary roasting includes auxiliary components;

[0022] The auxiliary component is selected from coke or methane;

[0023] The ambient pressure for vacuum calcination is 0.001–0.1 mbar;

[0024] The ambient pressure for the auxiliary roasting is 0.1 mbar to 1 bar.

[0025] The temperature of the regeneration roasting is 500–700°C;

[0026] The regeneration roasting time is 1 to 15 hours;

[0027] The atmosphere for the regeneration roasting is an oxidizing atmosphere;

[0028] The oxidizing atmosphere contains oxygen at a volume concentration of 20% to 100%.

[0029] The pressure of the regeneration roasting is 0.1–10 MPa;

[0030] Optionally, the pressure of the regeneration roasting is 2 to 4 MPa.

[0031] The barium-based oxygen support obtained after calcination can be used to prepare hydrogen peroxide.

[0032] Specifically, it includes the following processes:

[0033] The reaction mainly consists of the following three steps: 1) Reaction of barium-based oxygen carrier with aqueous solution containing carbon dioxide gas to generate hydrogen peroxide solution and carbonate precipitate; 2) Filtering the carbonate precipitate to obtain hydrogen peroxide solution, and decomposing the carbonate by high-temperature calcination to obtain the corresponding metal oxide; 3) Further reaction of the above metal oxide with oxygen to prepare metal peroxide, i.e. barium-based oxygen carrier, to realize the recycling of barium-based oxygen carrier.

[0034] Compared with existing technologies, the essential features of this invention are:

[0035] 1. The raw materials for H2O2 in the hydrogen peroxide of this application are derived from water (H2O) and oxygen (oxygen comes directly from the air and does not need to be separated), which is inexpensive and avoids the use of flammable and explosive gases (mainly hydrogen), making the production process safe.

[0036] 2. This application does not involve the use of strong acids (such as sulfuric acid, nitric acid, etc.), requires little equipment investment, and the barium-based oxygen carrier can be recycled. The production process does not emit polluting gases or solid waste, making the process green and environmentally friendly.

[0037] 3. This application can achieve the enrichment and utilization of low-concentration carbon dioxide gas. When coupled with methane reforming technology, carbon reduction technology or photothermal heating technology, it can realize the high-value utilization of carbon dioxide and co-produce high-value-added products such as syngas or carbon monoxide, while improving the energy-saving effect of the process. Detailed Implementation

[0038] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0039] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0040] Examples 1-10:

[0041] Different concentrations of carbon dioxide aqueous solutions were reacted with an oxygen carrier. Specifically, barium-based oxygen carriers were added to aqueous solutions containing different concentrations of carbon dioxide at different reaction temperatures. After thorough stirring and filtration, hydrogen peroxide aqueous solutions were obtained. The concentration of hydrogen peroxide in the product was measured by chemical titration.

[0042] The conditions and results are shown in Table 1.

[0043] Table 1. Effects of different concentrations of carbon dioxide aqueous solution on hydrogen peroxide preparation.

[0044]

[0045]

[0046] As shown in Table 1, carbon dioxide in aqueous solution can react with barium peroxide, an oxygen carrier, to produce hydrogen peroxide. The yield of hydrogen peroxide reaches 90% or more of the theoretical yield (the theoretical molar yield is the amount of barium peroxide in the oxygen carrier), demonstrating the high efficiency of this method. Specifically, by continuously introducing carbon dioxide gas into the reaction solution and adjusting the amount of oxygen carrier added, the final concentration of hydrogen peroxide can reach over 15%.

[0047] The reaction temperature has a slight effect on the reaction. When the reaction temperature is increased from 10℃ to 25℃, the hydrogen peroxide production rate increases by about 36%. Further increasing the temperature does not change the reaction rate significantly.

[0048] Examples 11-16:

[0049] By fixing the concentration of the carbon dioxide aqueous solution, adding different barium-based oxygen carriers, and then stirring and filtering, the synthesis rate of hydrogen peroxide on different oxygen carriers was tested.

[0050] The conditions and results are shown in Table 2.

[0051] Table 2. Effects of different oxygen carriers on hydrogen peroxide generation rate

[0052]

[0053] Note: a t50 represents the time required for hydrogen peroxide production to reach 50% of the theoretical output.

[0054] As shown in Table 2, with the addition of BaO, CaO, CaO2 and MgO to the oxygen carrier, the reaction rate between the oxygen carrier and the carbon dioxide solution is significantly increased, which is beneficial to improving production efficiency.

[0055] Examples 17-39:

[0056] The samples after the reaction were calcined at high temperatures, either under vacuum (vacuum degree ≤ 0.1 mbar), CH4 atmosphere, or with added coke, at temperatures of 800–1300 °C.

[0057] The conditions and results are shown in Table 3.

[0058] Example 23 uses an air atmosphere and is a comparative example.

[0059] Table 3. Study on carbonate decomposition under different vacuum calcination conditions.

[0060]

[0061]

[0062] As shown in Table 3, compared to air roasting, vacuuming, carbon reduction, or methane reduction all promote carbonate decomposition, with the order of promotion effect being vacuuming < methane reduction < carbon reduction. For carbon-reduced samples, calcination at 1000°C for 4 hours decomposed 95% of the carbonates. Furthermore, the addition of CaO and MgO can also promote carbonate decomposition in the product to some extent.

[0063] Examples 40-53:

[0064] The oxygen carrier powder obtained after the above calcination is oxidized and calcined in an atmosphere with a certain oxygen content to regenerate the peroxides therein. The reaction temperature is 500-700℃, the volume concentration of oxygen is 20%-100%, and the total gas pressure is 0.1-10 MPa.

[0065] The conditions and results are shown in Table 4.

[0066] Table 4. Studies on the regeneration of barium-based oxygen carriers under different oxidation conditions.

[0067]

[0068]

[0069] Note: a Regeneration performance refers to the ratio of the total amount of hydrogen peroxide produced after oxidation regeneration and reaction with an excess of carbon dioxide aqueous solution to the amount of hydrogen peroxide produced under the same reaction conditions as fresh oxygen carrier.

[0070] As shown in Table 4, both oxygen partial pressure and reaction temperature have a significant impact on the regeneration of the oxygen carrier. Higher oxygen concentrations and greater total oxygen partial pressures are beneficial for the oxidative regeneration of barium peroxide. Adding CaO or MgO to the oxygen carrier also improves regeneration efficiency. Importantly, even when using air as the regeneration gas, the regeneration efficiency of the oxygen carrier can reach over 80% at relatively low pressures (2–4 MPa). This means that this process can directly regenerate the oxygen carrier using air, thus avoiding the use of pure oxygen and reducing process costs.

[0071] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing hydrogen peroxide based on barium cycle, comprising the following steps: (1) mixing a barium-based oxygen carrier with an aqueous solution containing carbon dioxide gas, and reacting to obtain an aqueous solution containing hydrogen peroxide and a carbonate precipitate; the barium-based oxygen carrier is barium peroxide, or a combination of barium peroxide and at least one of calcium peroxide, calcium oxide, and magnesium oxide; (2) subjecting the carbonate precipitate obtained in (1) to high-temperature calcination and regeneration calcination in sequence to obtain the barium-based oxygen carrier; the high-temperature calcination is auxiliary calcination; the auxiliary calcination comprises an auxiliary component; the auxiliary component is selected from coke or methane; the regeneration calcination is carried out in an oxidizing atmosphere; and the pressure of the regeneration calcination is 0.1-10 MPa. 2.The method according to claim 1, wherein the mass concentration of carbon dioxide in the aqueous solution containing carbon dioxide gas is 0.1-7%; and the amount of substance of carbon dioxide in the aqueous solution containing carbon dioxide gas is 50%-100% of the amount of substance of the barium-based oxygen carrier. 4.The method according to claim 1, wherein the carbon dioxide gas is selected from at least one of pure carbon dioxide, industrial waste gas containing carbon dioxide, biogas containing carbon dioxide, or landfill gas containing carbon dioxide. 5.The method according to claim 1, wherein the reaction time is 5-240 min. 6.The method according to claim 1, wherein the temperature of the high-temperature calcination is 800-1300 ℃; and the time of the high-temperature calcination is 1-12 h. 7.The method according to claim 1, wherein the environmental pressure of the auxiliary calcination is 0.1 mbar-1 bar. 8.The method according to claim 1, wherein the temperature of the regeneration calcination is 500-700 ℃; the time of the regeneration calcination is 1-15 h; the oxidizing atmosphere contains oxygen with a volume concentration of 20%-100%; and the pressure of the regeneration calcination is 2-4 MPa.

3. The preparation method according to claim 1, characterized in that, 10.The method according to claim 1, wherein the barium-based oxygen carrier obtained after calcination is continuously used for preparing hydrogen peroxide. ​ ​ ​ The temperature of the reaction is 10-50 o C; ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 9. The method of claim 1, wherein, ​ ​ ​

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