Method for preparing carbon monoxide normal-temperature oxidation catalyst from electrolytic manganese residues and oil sludge

Abstract

The invention discloses a method for preparing a carbon monoxide normal-temperature oxidation catalyst by using electrolytic manganese residues and oil sludge, which comprises the following steps: uniformly mixing the oil sludge and the electrolytic manganese residues to obtain manganese oil sludge, uniformly stirring the manganese oil sludge and mixed halophilic desulfurizing bacteria, fermenting, and drying to constant weight to obtain fermented manganese oil sludge, the method comprises the following steps: carbonizing dry fermented manganese oil sludge to obtain a manganese carbide oil material, uniformly mixing the manganese carbide oil material with a blueberry extract to obtain a manganese carbide oil extract mixture, uniformly mixing and stirring the obtained manganese carbide oil extract mixture with a chloroplatinic acid solution, standing, filtering, washing, and drying to obtain the mixed halophilic desulfurizing bacteria. Drying to constant weight to obtain a platinum-doped carbonization extraction precursor, and finally roasting the platinum-doped carbonization extraction precursor to obtain the carbon monoxide oxidation catalyst. The composite catalyst with high specific surface area and multiple active sites is formed, and resource utilization of waste is achieved.

Description

Technical Field

[0001] This invention belongs to the field of industrial solid waste resource utilization, and particularly relates to a method for preparing a carbon monoxide oxidation catalyst at room temperature using electrolytic manganese slag and oil sludge. Background Technology

[0002] Traditional CO catalytic oxidants often use precious metals (Pt, Pd), which, while highly active, are expensive and prone to poisoning (e.g., by sulfides, chlorides). The main problems with non-precious metal catalysts are: manganese-based catalysts (MnO2, Mn3O4) exhibit excellent low-temperature activity but poor high-temperature stability, requiring doping with Ce, Co, or Fe, or constructing Mn-Ce solid solutions to improve performance; copper-based catalysts (CuO / CeO2) show outstanding low-temperature activity but are prone to sintering and deactivation, requiring nanostructure modulation or support modification to enhance stability; while monolithic catalysts can solve the problems of poor mass and heat transfer and large pressure drop associated with powdered catalysts.

[0003] There are significant limitations to the resource utilization pathways for electrolytic manganese slag: While building materials can be used to produce cementitious composites and non-fired bricks, the added value of these products is low, and improper control of sulfur content (≥20%) can easily lead to the release of ammonia gas from the cement. In the recovery of valuable components, although the efficiency of microbial manganese leaching reaches over 90%, the cultivation cycle of the strains is long and the conditions are harsh, and the acidic leaching method poses a risk of secondary pollution. Agricultural utilization is subject to the risk of enrichment of heavy metals such as lead and mercury, requiring the addition of additional solidifying agents, which makes the process complex and costly. Oil sludge, a typical hazardous waste from the petroleum industry, contains high concentrations of petroleum hydrocarbons (C10-C50), heavy metals, and toxic substances. Traditional treatment technologies all have significant drawbacks: physicochemical methods (such as centrifugation, hot washing, and solvent extraction) consume a lot of energy and reagents, and the residue still requires secondary treatment; biological treatment methods (land cultivation and composting) rely on natural microorganisms, have long degradation cycles, and low efficiency; bio-enhanced methods can increase the rate, but are limited by temperature, pH, and pollutant concentration, and pose a risk of secondary pollution; thermal conversion methods (pyrolysis and incineration) can recover energy, but are prone to producing toxic gases such as dioxins, and have large equipment investment and high operating costs. Summary of the Invention

[0004] To address the shortcomings of the existing technology, this invention provides a method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge, which solves the problems of pollution from electrolytic manganese slag stockpiling and high cost of oil sludge treatment, and synergistically utilizes electrolytic manganese slag and oil sludge to prepare a highly efficient room-temperature carbon monoxide oxidation catalyst.

[0005] The technical solution of this invention is as follows: A method for preparing a carbon monoxide oxidation catalyst at room temperature using electrolytic manganese slag and oil sludge, comprising the following steps: uniformly mixing oil sludge and electrolytic manganese slag to obtain manganese oil sludge; mixing the manganese oil sludge with mixed halophilic desulfurizing bacteria, fermenting and drying to constant weight to obtain fermented manganese oil sludge, wherein the mixed halophilic desulfurizing bacteria are composed of desulfurizing bacteria and halophilic bacteria; carbonizing the dried fermented manganese oil sludge to obtain manganese carbon oil, then uniformly mixing it with blueberry extract to obtain a manganese carbon oil extract mixture; mixing the obtained manganese carbon oil extract mixture with chloroplatinic acid solution, stirring evenly, allowing it to stand, and drying to constant weight to obtain platinum-doped carbonized extraction precursor; and finally calcining the platinum-doped carbonized extraction precursor to obtain a carbon monoxide oxidation catalyst.

[0006] Furthermore, the mass ratio of the oil sludge to the electrolytic manganese slag is 20-60:100.

[0007] Furthermore, when the manganese sludge is stirred evenly with the mixed halophilic desulfurizing bacteria, the mass ratio of the mixed halophilic desulfurizing bacteria to the manganese sludge is 0.5 to 2.5:100.

[0008] Furthermore, the fermentation temperature is 20–50°C, and the fermentation time is 5–25 days.

[0009] Furthermore, the carbonization temperature is 550–850°C, and the carbonization time is 2–6 hours.

[0010] Furthermore, when manganese carbide oil and blueberry extract are uniformly mixed, the mass ratio of blueberry extract to manganese carbide oil is 0.25–3.75:100.

[0011] Furthermore, the concentration of the chloroplatinic acid solution is 0.005–0.075 mol / L, and the liquid-to-solid ratio when the manganese carbide oil extract mixture and the chloroplatinic acid solution are mixed and stirred evenly is 0.4–0.8:1 mL / g.

[0012] Furthermore, the roasting temperature is 350–750°C, and the roasting time is 2–6 hours.

[0013] Furthermore, the desulfurizing bacteria are any one of the following: common desulfurizing Vibrio, Norwegian desulfurizing microbes, Escambia River desulfurizing microbes, Meista desulfurizing bacillus, desulfurizing subspecies of desulfurizing Vibrio, rod-shaped desulfurizing microbes, and desulfurizing Gordon's bacillus; and the halophilic bacteria are any one of the following: halophilic mycobacterium, halophilic bacillus, halophilic alkali bacillus, red halophilic alkali archaea, sedimentary halophilic red bacillus, halophilic fast-growing bacillus, red long-lived halophilic archaea, halophilic land bacillus, halophilic alkali bacteria, and halophilic alkali bacillus.

[0014] Furthermore, the mass ratio of desulfurizing bacteria to halophilic bacteria in the mixed halophilic desulfurizing bacteria is 1 to 3:5.

[0015] The reaction mechanism of this invention is as follows: Oil sludge is mixed with electrolytic manganese slag. The abundant organic matter, small amount of metal ions, and complex chemical components in the oil sludge come into contact with the manganese oxides and other inorganic components in the electrolytic manganese slag, undergoing a preliminary reaction to provide a diverse matrix for the subsequent fermentation process. The halophilic desulfurizing bacteria are a mixture of desulfurizing and halophilic bacteria. The desulfurizing bacteria can decompose sulfur-containing organic matter, converting sulfides into inorganic sulfides such as sulfates. This process involves a series of enzymatic reactions within the desulfurizing bacteria, oxidizing the sulfur element in the organic sulfides through the action of desulfurizing enzymes. The halophilic bacteria can grow in a high-salt environment, helping to regulate the osmotic pressure balance of the fermentation system. During fermentation, the desulfurizing and halophilic bacteria work synergistically, utilizing the organic matter in the manganese oil sludge as a carbon and energy source for metabolic activities. These metabolic activities alter the chemical environment of the fermentation system; oily organic matter is decomposed into small-molecule organic acids and alcohols, while metal ions are reduced and complexed by metabolic products, forming components with potential catalytic activity. Fermented manganese sludge was carbonized in a tubular furnace. The high-temperature environment caused the organic components in the fermented manganese sludge to undergo pyrolysis, generating small-molecule hydrocarbons and carbonaceous residues. Simultaneously, some metal components reacted with the carbonaceous residues to form metal carbides. Manganese oxides underwent a reduction reaction with carbon at high temperatures, generating manganese carbides. These carbides possess unique electronic structures and chemical activities, providing excellent carrier properties for subsequent loading of platinum and other active components. Blueberry extract contains abundant anthocyanins and other polyphenolic compounds. When mixed with manganese carbide oil, the active groups such as hydroxyl groups in anthocyanins can interact with the metal carbides and carbonaceous groups on the surface of the manganese carbide oil. Platinum ions in the chloroplatinic acid solution, upon contact with the manganese carbide oil extract mixture, undergo adsorption and ion exchange processes, binding with anthocyanins, carbonaceous groups, and active sites on the surface of metal carbides in the manganese carbide oil extract. During settling, platinum ions gradually accumulated on the surface and in the pores of the manganese carbide oil extract mixture. Platinum ions coordinate with the lone pairs of electrons on the oxygen and carbon atoms in anthocyanins. The reducing components in the manganese carbide oil extract undergo a reduction reaction with the platinum ions, reducing them to metallic platinum particles. During muffle furnace roasting, the organic components in the platinum-doped carbonized extraction precursor further decompose, and the volatilized platinum ions are further reduced to metallic platinum at high temperatures, exhibiting a deeper interaction with the manganese carbide oil extract carrier.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] This invention utilizes industrial wastes such as electrolytic manganese slag and oil sludge through mechanical activation, thermochemical treatment, and carrier loading. This process organically combines manganese and iron oxides from the electrolytic manganese slag with hydrocarbons and carbonaceous components from the oil sludge, forming a composite catalyst with high specific surface area and multiple active sites. This achieves resource utilization of waste, reduces environmental pollution, and lowers dependence on traditional precious metal catalyst raw materials. The prepared catalytic material exhibits high photocatalytic activity and can efficiently catalyze the oxidation of carbon monoxide at room temperature without requiring an additional heat source. Attached Figure Description

[0018] Figure 1 This is a schematic flowchart of the method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to the present invention. Detailed Implementation

[0019] The present invention will be further described below with reference to embodiments. It should be understood that these embodiments are only for illustrating the present invention and are not intended to limit the scope of the present invention. After reading this description, any modifications of this description in various equivalent forms by those skilled in the art will fall within the scope defined by the appended claims.

[0020] The process flow of the method for preparing carbon monoxide room temperature oxidation catalyst using electrolytic manganese slag and oil sludge in various embodiments of the present invention is as follows: Figure 1 As shown.

[0021] The raw materials involved in the various embodiments and comparative examples are described below:

[0022] Electrolytic manganese slag: The electrolytic manganese slag is sourced from Guizhou Energy and Minerals Manganese Industry Group Co., Ltd., and mainly includes 23.52% SO3, 13.17% SiO2, 15.21% CaO, 13.09% Fe2O3, 6.82% Al2O3, 10.21% MnO, 2.96% K2O, 1.55% MgO, 0.86% TiO2 and other components (unavoidable impurities and loss on ignition);

[0023] Oil sludge: The oil sludge was taken from Shaanxi Yanchang Petroleum Refining Plant and contains 34.51% extractable oil, 21.73% heavy oil, 27.44% residue and 16.32% water.

[0024] The microorganisms used were sourced from the China General Microbiological Culture Collection Center, and their preservation information is as follows:

[0025] Desulfurizing bacteria: Common desulfurizing Vibrio (CGMCC 1.5190), Norwegian desulfurizing microbes (CGMCC 1.3493), Escambia River desulfurizing microbes (CGMCC 1.3481), Maistella desulfurizing bacillus (CGMCC 1.3477), Desulfurizing Vibrio desulfurizing subsp. desulfurization (CGMCC 1.3469), rod-shaped desulfurizing microbes (CGMCC 1.3467), and Desulfurizing Gordon's bacillus (CGMCC 4.2492).

[0026] Halophilic bacteria: Halophilic Bacillus (CGMCC 1.15481), Halophilic Bacillus (CGMCC 1.15441), Halophilic Alkaloid Bacillus (CGMCC 1.15274), Red Halophilic Alkaloid Archaea (CGMCC 1.10388), Sedimentary Halophilic Red Alkaloid Bacillus (CGMCC 1.8981), Halophilic Fast-growing Bacillus (CGMCC 1.8891), Red Long-lived Halophilic Archaea (CGMCC 1.8743), Halophilic Soil Bacillus (CGMCC 1.7684), Halophilic Alkaloid Bacteria (CGMCC 1.5124), Halophilic Alkaloid Bacillus griseus (CGMCC 1.1967).

[0027] The information for the blueberry extract is as follows: The blueberry extract is provided by Shanxi Chengzhi Biotechnology Co., Ltd., brand: Chengzhi, appearance: purple powder, grade: premium.

[0028] Example 1: Effect of the mass ratio of oil sludge to electrolytic manganese slag on the performance of the prepared catalyst material.

[0029] Manganese sludge was mixed with electrolytic manganese slag at mass ratios of 12.5:100, 15:100, 17.5:100, 20:100, 40:100, 60:100, 65:100, 70:100, and 75:100, and stirred evenly to obtain manganese sludge. Halophilic desulfurizing bacteria and manganese sludge were then mixed at a mass ratio of 0.5:100, stirred evenly, and after fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 1:5. The desulfurizing bacteria were common desulfurizing Vibrio, and the halophilic bacteria were halophilic Mycobacterium sarcophagus. The fermentation time was 5 days, and the fermentation temperature was 20℃. The dried fermented manganese sludge was then placed in a tubular furnace for carbonization treatment to obtain carbonized manganese oil, with a carbonization time of 2 hours and a carbonization temperature of 550℃. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 0.25:100 and stirred until homogeneous to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and the manganese carbide oil extract mixture were mixed at a liquid-to-solid ratio of 0.4:1 mL / g and stirred until homogeneous. The mixture was allowed to stand for 4 hours and then dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the chloroplatinic acid concentration was 0.005 mol / L. The platinum-doped carbonized extraction precursor was calcined in a muffle furnace. After calcination, a carbon monoxide catalytic oxidant material was obtained, wherein the calcination temperature was 350℃ and the calcination time was 2 hours.

[0030] Carbon monoxide oxidation experiment: Under ambient temperature (25 ± 1°C), CO was oxidized to CO2 by exciting the catalyst material with 185nm vacuum ultraviolet light (VUV). The vacuum UV lamp was a low-pressure mercury lamp (L-shaped quartz window, 185nm output ≥5mW·cm²). -2 (A 254 nm cutoff filter is optional); the photoreactor is a cylindrical high-purity quartz tube with an effective optical path length L = 10.0 cm, an inner diameter d = 2.0 cm, and a volume V = 31.4 mL; the vacuum system is a turbomolecular pump with a cold trap (ultimate vacuum < 1 × 10⁻⁶). -3 Pa); After the reactor is evacuated, press the set total pressure P. total =101kPa injection of mixed gas (CO:O2:N2=1:1:8 (volume ratio), initial CO concentration C) CO,0 (≈100 ppm), close the inlet and outlet valves, let stand for 5 minutes, and record the initial concentration C. CO,0 , Turn on the VUV lamp and start timing. Continuously record the concentrations of CO and CO2 at a sampling frequency of 1 Hz; the reaction time is t = 0~30 min (preliminary experiments show that the reaction tends to reach equilibrium within 30 min). Keep the lamp power constant and measure the incident light intensity I0 using a UV radiometer (185 nm probe); record the temperature and pressure every 5 min, ensuring T = 25 ± 1°C and P change < 1%. Turn off the lamp and immediately extract the gas in the reactor to determine the final concentration C. CO,t , Potential water was captured using a cold trap, and the absence of other carbon-containing products was verified by gas chromatography-thermal conductivity detection (GC-TCD). The experiment was repeated three times, and the average value was taken. The ppm value (C) measured by the online analyzer was then used. CO,0 and C CO,t Convert y to mole fraction y CO,0 and y CO,t The number of moles of gas in the reactor is n = PV / (RT), where T = 298.15 K, and the carbon monoxide oxidation efficiency is η = (y CO,0 –y CO,t ) / y CO,0 ×100%.

[0031] The test results of this embodiment are shown in Table 1.

[0032] Table 1. Effect of the mass ratio of oil sludge to electrolytic manganese slag on the performance of the prepared catalyst material.

[0033]

[0034] As shown in Table 1, when the mass ratio of oil sludge to electrolytic manganese slag is less than 20:100 (e.g., in Table 1, the mass ratios of oil sludge to electrolytic manganese slag are 17.5:100, 15:100, 12.5:100, and even lower ratios not listed in Table 1), the amount of oil sludge added is small, and the reaction between the oil sludge and electrolytic manganese slag is insufficient, resulting in a significant decrease in carbon monoxide oxidation efficiency as the mass ratio of oil sludge to electrolytic manganese slag decreases. When the mass ratio of oil sludge to electrolytic manganese slag is equal to 20–60:100 (e.g., in Table 1, the mass ratios of oil sludge to electrolytic manganese slag are 20:100, 40:100, and 60:100), mixing the oil sludge and electrolytic manganese slag allows the large amount of organic matter, small amount of metal ions, and complex chemical components contained in the oil sludge to come into contact with the manganese oxides and other inorganic components contained in the electrolytic manganese slag, and a preliminary reaction occurs, providing a diversified substrate for the subsequent fermentation process. Ultimately, the carbon monoxide oxidation efficiency was consistently above 92%. When the mass ratio of oil sludge to electrolytic manganese slag was greater than 60:100 (as shown in Table 1, with mass ratios of 65:100, 70:100, 75:100, and higher ratios not listed in Table 1), the excessively high ratio resulted in excessive oil sludge addition and an imbalance in the reaction between the oil sludge and electrolytic manganese slag. Consequently, the carbon monoxide oxidation efficiency decreased significantly with further increases in the mass ratio of oil sludge to electrolytic manganese slag. Therefore, considering both efficiency and cost, a mass ratio of oil sludge to electrolytic manganese slag of 20–60:100 was most favorable for improving the CO oxidation performance of the prepared catalyst.

[0035] Example 2: Effect of the mass ratio of halophilic desulfurizing bacteria and manganese sludge on the performance of the prepared catalyst material.

[0036] Manganese sludge was obtained by mixing oil sludge and electrolytic manganese slag at a mass ratio of 60:100 and stirring evenly. Then, halophilic desulfurizing bacteria and manganese sludge were mixed at mass ratios of 0.25:100, 0.3:100, 0.4:100, 0.5:100, 1.5:100, 2.5:100, 2.75:100, 3:100, and 3.25:100, stirred evenly, and after fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 2:5. The desulfurizing bacteria were *Norwegian desulfurizing microorganisms*, and the halophilic bacteria were *Bacillus halophilus*. The fermentation time was 15 days, and the fermentation temperature was 35℃. The dried fermented manganese sludge was then placed in a tubular furnace for carbonization treatment to obtain carbonized manganese oil. The carbonization time was 4 hours, and the carbonization temperature was 700℃. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 2:100 and stirred until homogeneous to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and the manganese carbide oil extract mixture were mixed at a liquid-to-solid ratio of 0.6:1 mL / g, stirred until homogeneous, allowed to stand for 8 hours, and dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the chloroplatinic acid concentration was 0.04 mol / L. The platinum-doped carbonized extraction precursor was calcined in a muffle furnace. After calcination, a carbon monoxide catalytic oxidant material was obtained, wherein the calcination temperature was 550℃ and the calcination time was 4 hours.

[0037] The carbon monoxide oxidation test was the same as in Example 1. The test results of this example are shown in Table 2.

[0038] Table 2. Effect of mass ratio of halophilic desulfurizing bacteria and manganese sludge on the performance of the prepared catalyst materials.

[0039]

[0040] As shown in Table 2, when the mass ratio of halophilic desulfurizing bacteria to manganese sludge is less than 0.5:100 (as shown in Table 2, when the mass ratio of halophilic desulfurizing bacteria to manganese sludge is 0.4:100, 0.3:100, 0.25:100, and even lower ratios not listed in Table 2), less halophilic desulfurizing bacteria are added, and the reaction between halophilic desulfurizing bacteria and manganese sludge is insufficient, resulting in a significant decrease in carbon monoxide oxidation efficiency as the mass ratio of halophilic desulfurizing bacteria to manganese sludge decreases. When the mass ratio of halophilic desulfurizing bacteria to manganese sludge is 0.5–2.5:100 (as shown in Table 2, where the mass ratios are 0.5:100, 1.5:100, and 2.5:100), the halophilic desulfurizing bacteria are a mixture of desulfurizing and halophilic bacteria. The desulfurizing bacteria can decompose sulfur-containing organic matter, converting sulfides into inorganic sulfides such as sulfates. This process involves a series of enzymatic reactions within the desulfurizing bacteria, oxidizing the sulfur element in organic sulfides through the action of desulfurizing enzymes. The halophilic bacteria can grow in a high-salt environment, helping to regulate the osmotic pressure balance of the fermentation system. During fermentation, the desulfurizing and halophilic bacteria work synergistically, utilizing the organic matter in the manganese sludge as a carbon and energy source for metabolic activities. These metabolic activities alter the chemical environment of the fermentation system; oily organic matter is decomposed into small-molecule organic acids and alcohols, while metal ions are reduced and complexed by metabolic products, forming components with potential catalytic activity. Ultimately, the carbon monoxide oxidation efficiency is higher than 94%. When the mass ratio of halophilic desulfurizing bacteria to manganese sludge is greater than 2.5:100 (as shown in Table 2, where the mass ratios are 2.75:100, 3:100, 3.25:100, and higher values ​​not listed in Table 2), excessive addition of halophilic desulfurizing bacteria leads to an imbalance in the reaction between the bacteria and the manganese sludge. This results in a significant decrease in carbon monoxide oxidation efficiency as the mass ratio of halophilic desulfurizing bacteria to manganese sludge further increases. Therefore, considering both benefits and costs, a mass ratio of halophilic desulfurizing bacteria to manganese sludge of 0.5–2.5:100 is most favorable for improving the CO oxidation performance of the prepared catalyst.

[0041] Example 3: Effect of the mass ratio of blueberry extract to manganese carbide oil on the performance of the prepared catalyst material.

[0042] Manganese sludge was obtained by mixing oil sludge and electrolytic manganese slag at a mass ratio of 60:100 and stirring thoroughly. Then, halophilic desulfurizing bacteria and manganese sludge were mixed at a mass ratio of 2.5:100 and stirred thoroughly. After fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 3:5. The desulfurizing bacteria were *Escambia River* desulfurizing microorganisms, and the halophilic bacteria were *Bacillus halophilus*. The fermentation time was 25 days, and the fermentation temperature was 50℃. The dried fermented manganese sludge was then placed in a tubular furnace for carbonization treatment to obtain carbonized manganese oil. The carbonization time was 6 hours, and the carbonization temperature was 850℃. Blueberry extract and manganese carbide oil were mixed in mass ratios of 0.1:100, 0.15:100, 0.2:100, 0.25:100, 2:100, 3.75:100, 4:100, 4.25:100, and 4.5:100, and stirred evenly to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and the manganese carbide oil extract mixture were mixed in a liquid-to-solid ratio of 0.8:1 mL / g, stirred evenly, allowed to stand for 12 hours, and dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the chloroplatinic acid concentration was 0.075 mol / L. The platinum-doped carbonized extraction precursor was calcined in a muffle furnace. After calcination, a carbon monoxide catalytic oxidant material was obtained, wherein the calcination temperature was 750℃ and the calcination time was 6 hours.

[0043] The carbon monoxide oxidation test was the same as in Example 1. The test results of this example are shown in Table 3.

[0044] Table 3. Effect of the mass ratio of blueberry extract and manganese carbide oil on the performance of the prepared catalyst materials.

[0045]

[0046] As shown in Table 3, when the mass ratio of blueberry extract to manganese carbide oil is less than 0.25:100 (as shown in Table 3, when the mass ratio of blueberry extract to manganese carbide oil is 0.2:100, 0.15:100, 0.1:100, and even lower ratios not listed in Table 3), less blueberry extract is added, and the reaction between blueberry extract and manganese carbide oil is insufficient, resulting in a significant decrease in carbon monoxide oxidation efficiency as the mass ratio of blueberry extract to manganese carbide oil decreases. When the mass ratio of blueberry extract to manganese carbide oil is 0.25–3.75:100 (as shown in Table 3, where the mass ratios are 0.25:100, 2:100, and 3.75:100), the blueberry extract, rich in anthocyanins and other polyphenolic compounds, interacts with the metal carbides and carbonaceous groups on the surface of the manganese carbide oil when mixed with it. Platinum ions in the chloroplatinic acid solution undergo adsorption and ion exchange upon contact with the manganese carbide oil extract mixture, binding to the anthocyanins, carbonaceous groups, and active sites on the surface of the metal carbides. Ultimately, the carbon monoxide oxidation efficiency is higher than 96%. When the mass ratio of blueberry extract to manganese carbide oil is greater than 3.75:100 (as shown in Table 3, where the mass ratios are 4:100, 4.25:100, 4.5:100, and higher values ​​not listed in Table 3), excessive blueberry extract is added, leading to an imbalance in the reaction between the blueberry extract and manganese carbide oil. This results in a significant decrease in carbon monoxide oxidation efficiency as the mass ratio of blueberry extract to manganese carbide oil further increases. Therefore, considering both benefits and costs, a mass ratio of blueberry extract to manganese carbide oil between 0.25 and 3.75:100 is most favorable for improving the CO oxidation performance of the prepared catalyst.

[0047] Example 4: Effect of desulfurizing bacteria on the performance of the prepared catalyst material.

[0048] Manganese sludge was obtained by mixing oil sludge and electrolytic manganese slag at a mass ratio of 60:100 and stirring evenly. Then, halophilic desulfurizing bacteria and manganese sludge were mixed at a mass ratio of 1.5:100 and stirred evenly. After fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 2:5. The desulfurizing bacteria were any one of the following: common desulfurizing Vibrio, Norwegian desulfurizing microbes, Escambia River desulfurizing microbes, Mesta desulfuric bacillus, desulfurizing desulfurizing Vibrio desulfurization subspecies, rod-shaped desulfurizing microbes, and desulfurizing Gordon's bacterium. The halophilic bacteria were red halophilic archaea. The fermentation time was 25 days, and the fermentation temperature was 50℃. The dried fermented manganese sludge was then placed in a tubular furnace for carbonization treatment to obtain carbonized manganese oil. The carbonization time was 6 hours, and the carbonization temperature was 850℃. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 3.75:100 and stirred until homogeneous to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and the manganese carbide oil extract mixture were mixed at a liquid-to-solid ratio of 0.4:1 mL / g, stirred until homogeneous, allowed to stand for 12 hours, and dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the chloroplatinic acid concentration was 0.075 mol / L. The platinum-doped carbonized extraction precursor was calcined in a muffle furnace. After calcination, a carbon monoxide catalytic oxidant material was obtained, wherein the calcination temperature was 750℃ and the calcination time was 6 hours.

[0049] The carbon monoxide oxidation test was the same as in Example 1. The test results of this example are shown in Table 4.

[0050] Table 4. Effects of desulfurizing bacteria on the performance of the prepared catalyst materials.

[0051]

[0052] As shown in Table 4, when the desulfurizing bacteria are any one of the following: common desulfurizing Vibrio, Norwegian desulfurizing microorganism, Escambia River desulfurizing microorganism, Mesta desulfurizing bacillus, desulfurizing subspecies of desulfurizing Vibrio, rod-shaped desulfurizing microorganism, and desulfurizing Gordon's bacillus, the performance of the prepared catalyst materials is not significantly different.

[0053] Example 5: Effect of halophilic bacteria on the performance of the prepared catalyst material

[0054] Manganese sludge was obtained by mixing oil sludge and electrolytic manganese slag at a mass ratio of 60:100 and stirring evenly. Then, halophilic desulfurizing bacteria and manganese sludge were mixed at a mass ratio of 2.5:100 and stirred evenly. After fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing and halophilic bacteria at a mass ratio of 2:5. The desulfurizing bacteria were *Desulfuricius desulfurization subspecies*, and the halophilic bacteria were any one of the following: *Bacillus halophilus*, *Bacillus halophilus*, *Bacillus halophilus*, *Red halophilic archaea*, *Red halophilic red halophilic bacillus*, *Red long-lived halophilic archaea*, *Bacillus halophilus*, *Halophyte bacillus*, or *Halophyte halophilus*. The fermentation time was 25 days, and the fermentation temperature was 35℃. The dried fermented manganese sludge was then placed in a tubular furnace for carbonization treatment to obtain carbonized manganese oil. The carbonization time was 4 hours, and the carbonization temperature was 850℃. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 3.75:100 and stirred until homogeneous to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and the manganese carbide oil extract mixture were mixed at a liquid-to-solid ratio of 0.8:1 mL / g, stirred until homogeneous, allowed to stand for 12 hours, and dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the chloroplatinic acid concentration was 0.075 mol / L. The platinum-doped carbonized extraction precursor was calcined in a muffle furnace. After calcination, a carbon monoxide catalytic oxidant material was obtained, wherein the calcination temperature was 750℃ and the calcination time was 6 hours.

[0055] The carbon monoxide oxidation test was the same as in Example 1. The test results of this example are shown in Table 5.

[0056] Table 5. Effects of halophilic bacteria on the performance of the prepared catalyst materials.

[0057]

[0058] As shown in Table 5, when the halophilic bacteria are any one of the following: Halophilic Bacillus, Halophilic Bacillus, Halophilic Alkaloid Bacillus, Red Halophilic Alkaloid Archaea, Sedimentary Halophilic Red Bacillus, Halophilic Fast-growing Bacillus, Red Long-growing Halophilic Archaea, Halophilic Land Bacillus, Halophilic Alkaloid Bacteria, and Halophilic Alkaloid Bacillus griseus, the performance of the prepared catalyst materials is not significantly different.

[0059] Comparative experiment: The effect of different preparation processes on the performance of the prepared room temperature oxidation catalyst.

[0060] Example 6 of this invention: Oil sludge and electrolytic manganese slag were mixed at a mass ratio of 60:100 and stirred evenly to obtain manganese oil sludge. Halophilic desulfurizing bacteria and manganese oil sludge were mixed at a mass ratio of 2.5:100 and stirred evenly. After fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese oil sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 2:5. The desulfurizing bacteria were *Vibrio desulfurans* subsp. *desulfurans*, and the halophilic bacteria were *Halophilus gargiensis*. The fermentation time was 25 days, and the fermentation temperature was 35°C. The dried fermented manganese oil sludge was placed in a tube furnace for carbonization treatment to obtain manganese carbide oil. The carbonization time was 4 hours, and the carbonization temperature was 850°C. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 3.75:100 and stirred evenly to obtain a manganese carbide oil extract mixture. A mixture of chloroplatinic acid solution and manganese carbide oil extract was mixed at a liquid-to-solid ratio of 0.8:1 mL / g, stirred thoroughly, allowed to stand for 12 hours, and dried to constant weight to obtain a platinum-doped carbonized extraction precursor, wherein the concentration of chloroplatinic acid was 0.075 mol / L. The platinum-doped carbonized extraction precursor was then calcined in a muffle furnace to obtain a carbon monoxide catalytic oxidant material. The calcination temperature was 750℃, and the calcination time was 6 hours.

[0061] Comparative Example 1: Manganese sludge was obtained by mixing oil sludge and electrolytic manganese slag at a mass ratio of 60:100 and stirring evenly. Halophilic bacteria and manganese sludge were mixed at a mass ratio of 2.5:100 and stirred evenly. After fermentation, the fermented material was dried to constant weight to obtain fermented manganese sludge. The halophilic bacteria was *Halophilus gargiensis*, and the fermentation time was 25 days at 35℃. The dried fermented manganese sludge was carbonized in a tube furnace to obtain manganese carbide oil. The carbonization time was 4 hours at 850℃. Blueberry extract and manganese carbide oil were mixed at a mass ratio of 3.75:100 and stirred evenly to obtain a manganese carbide oil extract mixture. Chloroplatinic acid solution and manganese carbide oil extract mixture were mixed at a liquid-solid ratio of 0.8:1 mL / g, stirred evenly, allowed to stand for 12 hours, and dried to constant weight to obtain platinum-doped carbonization extraction precursor material, with a chloroplatinic acid concentration of 0.075 mol / L. Platinum-doped carbonized extraction precursors were placed in a muffle furnace for calcination. After calcination, carbon monoxide catalytic oxidant material was obtained. The calcination temperature was 750℃ and the calcination time was 6 hours.

[0062] Comparative Example 2: Oil sludge and electrolytic manganese slag were mixed at a mass ratio of 60:100 and stirred evenly to obtain manganese oil sludge. Halophilic desulfurizing bacteria and manganese oil sludge were mixed at a mass ratio of 2.5:100 and stirred evenly. After fermentation, the fermented material was removed and dried to constant weight to obtain fermented manganese oil sludge. The halophilic desulfurizing bacteria consisted of a mixture of desulfurizing bacteria and halophilic bacteria at a mass ratio of 2:5. The desulfurizing bacteria were *Vibrio desulfurans* subsp. *desulfurans*, and the halophilic bacteria were *Halophilus gargiensis*. The fermentation time was 25 days, and the fermentation temperature was 35℃. The dried fermented manganese oil sludge was placed in a tube furnace for carbonization treatment to obtain manganese carbonized oil. The carbonization time was 4 hours, and the carbonization temperature was 850℃. Chloroplatinic acid solution and manganese carbonized oil were mixed at a liquid-to-solid ratio of 0.8:1 mL / g, stirred evenly, allowed to stand for 12 hours, and dried to constant weight to obtain platinum-doped carbonized extraction precursor material. The concentration of chloroplatinic acid was 0.075 mol / L. Platinum-doped carbonized extraction precursors were placed in a muffle furnace for calcination. After calcination, carbon monoxide catalytic oxidant material was obtained. The calcination temperature was 750℃ and the calcination time was 6 hours.

[0063] The carbon monoxide oxidation test was the same as in Example 1. The results of this comparative test are shown in Table 6.

[0064] Table 6. Effects of different preparation processes on the performance of the prepared room-temperature oxidation catalysts.

[0065]

[0066] As shown in Table 6, the carbon monoxide oxidation efficiency achieved by the room temperature oxidation catalyst prepared in Example 6 of the present invention is much higher than that of Comparative Example 1 and Comparative Example 2.

Claims

1. A method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge, characterized in that, The process includes the following steps: uniformly mixing oil sludge and electrolytic manganese slag to obtain manganese oil sludge; mixing the manganese oil sludge with mixed halophilic desulfurizing bacteria, fermenting and drying to constant weight to obtain fermented manganese oil sludge, wherein the mixed halophilic desulfurizing bacteria are composed of desulfurizing bacteria and halophilic bacteria; carbonizing the dried fermented manganese oil sludge to obtain manganese carbonized oil, then uniformly mixing it with blueberry extract to obtain a manganese carbonized oil extract mixture; mixing the obtained manganese carbonized oil extract mixture with chloroplatinic acid solution, stirring evenly, allowing it to stand, and drying to constant weight to obtain platinum-doped carbonized extraction precursor; and finally calcining the platinum-doped carbonized extraction precursor to obtain a carbon monoxide oxidation catalyst.

2. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The mass ratio of the oil sludge to the electrolytic manganese slag is 20-60:

100.

3. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, When the manganese sludge is mixed with the mixed halophilic desulfurizing bacteria, the mass ratio of the mixed halophilic desulfurizing bacteria to the manganese sludge is 0.5 to 2.5:

100.

4. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The fermentation temperature is 20–50°C, and the fermentation time is 5–25 days.

5. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The carbonization temperature is 550–850°C, and the carbonization time is 2–6 hours.

6. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, When manganese carbide oil and blueberry extract are mixed evenly, the mass ratio of blueberry extract to manganese carbide oil is 0.25 to 3.75:

100.

7. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The concentration of the chloroplatinic acid solution is 0.005–0.075 mol / L, and the liquid-to-solid ratio when the manganese carbide oil extract mixture and the chloroplatinic acid solution are mixed and stirred evenly is 0.4–0.8:1 mL / g.

8. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The roasting temperature is 350–750°C, and the roasting time is 2–6 hours.

9. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1, characterized in that, The desulfurizing bacteria are any one of the following: common desulfurizing Vibrio, Norwegian desulfurizing microbes, Escambia River desulfurizing microbes, Mesta desulfurizing bacillus, desulfurizing subspecies of desulfurizing Vibrio, rod-shaped desulfurizing microbes, and desulfurizing Gordon's bacillus. The halophilic bacteria are any one of the following: halophilic mycobacterium, halophilic bacillus, halophilic alkali bacillus, red halophilic alkali archaea, sedimentary halophilic alkali red bacillus, halophilic fast-growing bacillus, red long-lived halophilic archaea, halophilic land bacillus, halophilic alkali bacteria, and halophilic alkali bacillus.

10. The method for preparing a room-temperature carbon monoxide oxidation catalyst using electrolytic manganese slag and oil sludge according to claim 1 or 9, characterized in that, The mass ratio of desulfurizing bacteria to halophilic bacteria in the mixed halophilic desulfurizing bacteria is 1 to 3:5.

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