A graphene oxide / carbon nanotube-based coal combustion catalyst
By loading manganese oxide into a graphene oxide/carbon nanotube-based catalyst to form a three-dimensional structure, the problems of easy agglomeration and poor dispersibility of coal combustion catalysts are solved, thereby improving coal combustion efficiency and combustion performance.
Patent Information
- Application Number
- CN202610208760.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-13
- Publication Date
- 2026-05-26
AI Technical Summary
Existing coal-fired catalysts are prone to agglomeration and have poor dispersibility, which leads to a reduction in active components and affects the combustion-supporting effect.
A graphene oxide/carbon nanotube-based catalyst was used. By loading carbon nanotubes and manganese oxide during the synthesis of graphene oxide, a three-dimensional structure was formed. Manganese oxide was then loaded onto the graphene oxide via a redox reaction, which improved dispersibility and catalytic activity.
It improves coal combustion efficiency, reduces ignition temperature and reaction activation energy, and enhances combustion performance.
Smart Images
Figure FT_1 
Figure FT_2 
Figure FT_3
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic combustion technology for efficient coal utilization, specifically relating to a graphene oxide / carbon nanotube-based coal combustion catalyst, its preparation method, and its application. Background Technology
[0002] In modern social development, electricity, as a fundamental energy source, provides essential impetus for economic growth and people's lives. Thermal power generation has long played a crucial supporting role in ensuring the safety and stability of the power system. The latest data from the National Bureau of Statistics shows that from January to November 2025, the cumulative national thermal power generation reached 5.7125 trillion kilowatt-hours. As of the end of September 2025, the national installed capacity of thermal power was 1.503 billion kilowatts, accounting for 40.4% of the total installed capacity (3.72 billion kilowatts) during the same period. To promote green and low-carbon transformation, the state has clearly planned to carry out low-carbon transformation of coal-fired power plants, aiming to reduce carbon emissions per kilowatt-hour by about 50% by 2027 compared to 2023.
[0003] To improve coal resource utilization efficiency and enhance the economic benefits of coal-consuming industries, research on coal-fired catalysts has been conducted in fields such as thermal power generation and industrial boilers since the 19th century. Driven by both policy support and environmental protection requirements, research on coal combustion and catalytic combustion has continued to deepen. Initially, coal-fired catalyst technology was mainly applied to industrial boilers in thermal power generation and heating. In recent years, this technology has been gradually applied in cement production lines with a scale of 3000-5000 t / d. Practice has shown that the use of coal-fired catalysts results in significant coal savings, improved clinker production stability, increased strength of cement clinker at all ages, significantly improved f-CaO qualification rate, optimized raw material burnability, and a reduction in eutectic point of 50-100℃. Therefore, the application of coal-fired catalysts can bring significant economic and environmental benefits to related industries.
[0004] Currently, coal-fired catalysts studied both domestically and internationally can be mainly classified into three categories: the first category consists of mixed metal salts such as alkali metals, alkaline earth metals, and rare earth metals; the second category consists of metal oxides containing alkali metals, alkaline earth metals, and rare earth metals; and the third category consists of organic matter or biomass with low-molecular-weight alcohols as the main components. Among these, the first and second categories of catalysts have attracted much attention from researchers in recent years due to their stable physicochemical properties and excellent catalytic activity. Ji Li et al. used thermogravimetric analysis to study the effects of composite catalysts CuSO4 / Fe2(SO4)3, CuSO4 / ZnCl2, Fe2(SO4)3 / ZnCl2, and Fe2(SO4)3 / Zn(NO3)2 on the combustion characteristics of coal char. The results showed that the composite catalysts had good catalytic effects on the combustion of coal char in both anthracite and bituminous coal, with zinc chloride and sulfate showing the best catalytic effects. With the increase of coal metamorphism, the catalytic effect of CuSO4 / Fe2(SO4)3 was significantly enhanced, the decrease in coal char burnout temperature was greater, and the maximum combustion rate was increased. CuSO4 / ZnCl2 and Fe2(SO4)3 / ZnCl2 changed from inhibiting to promoting the ignition of coal char and promoted the burnout of coal char. The apparent activation energy of the coal samples loaded with each catalyst was lower than that of the raw coal char. Gong et al. used thermogravimetric analysis to study the effects of CeO2 and Fe2O3 on the combustion reaction characteristics of several fuels (including tertiary coal, graphite, and anthracite char). The results showed that the addition of CeO2 or Fe2O3 improved the combustion reaction characteristics of all samples except lignite. Although the above studies have confirmed the positive effects of coal-fired catalysts, they still suffer from problems such as easy agglomeration and poor dispersibility, which can lead to a significant reduction in active components and seriously affect combustion efficiency. Therefore, developing novel catalysts that can inhibit the agglomeration of rare earth metal oxides and improve dispersibility is of great significance for enhancing the overall performance of coal-saving agents. Summary of the Invention
[0005] The purpose of this invention is to provide a graphene oxide / carbon nanotube-based coal combustion catalyst, in which carbon nanotubes and manganese oxide are simultaneously loaded during the synthesis of graphene oxide, thereby effectively improving coal combustion efficiency and reducing the ignition temperature and activation energy of the coal reaction.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a graphene oxide / carbon nanotube-based coal combustion catalyst: using highly dispersed graphene oxide as a carrier and modified carbon nanotubes as the loading material, the two are combined through a condensation reaction, and then manganese oxide is loaded onto it using a redox reaction to obtain the graphene oxide / carbon nanotube-based coal combustion catalyst.
[0007] Includes the following steps: (1) In a water bath at room temperature, add 100 mL of concentrated sulfuric acid to 2 g of graphite and stir until fully dissolved. Then add 0.5 g of potassium permanganate every 10 min, for a total of 10 g of potassium permanganate. (2) Raise the water bath temperature to 55°C, stir the reaction for 3 hours, add hydroxylated modified carbon nanotubes, and react for 1 hour; (3) Add manganese chloride, react for 4 hours, then add 100 mL of deionized water; (4) Stir in a 90℃ water bath for 15 min, then add hydrogen peroxide dropwise until no bubbles are generated, then add 50 mL of hydrochloric acid, centrifuge and wash repeatedly until neutral, freeze dry to obtain the graphene oxide / carbon nanotube-based coal combustion catalyst.
[0008] Furthermore, the mass ratio of graphite to hydroxylated modified carbon nanotubes is 2:1.
[0009] Furthermore, the mass ratio of manganese chloride to potassium permanganate is 0.01:1.
[0010] The graphene oxide / carbon nanotube-based coal combustion catalyst was prepared by the method described above.
[0011] The graphene oxide / carbon nanotube-based coal combustion catalyst prepared by the method described above is applied to the catalytic combustion reaction of coal.
[0012] The beneficial effects of this invention are as follows: 1. A three-dimensional "point-line-surface" structure is constructed using graphene oxide, carbon nanotubes, and coal. From the perspective of physical combustion support, this widens the contact area between coal molecules and active oxygen, increases reactive sites, thereby improving the coal combustion rate, reducing activation energy, and improving overall combustion performance.
[0013] 2. By loading highly dispersed manganese oxide catalyst onto the surface of graphene oxide / carbon nanotube support via redox method, compared with physical mixing, it has a higher specific surface area and reaction stability, can fully release the catalytic ability of active components, effectively cut off coal side chains, accelerate volatile matter release, thereby reducing ignition point and improving combustion performance.
[0014] 3. The entire synthesis process is carried out under low temperature conditions. The reaction steps are simple, the operation is convenient, and the reaction rate is fast. There are no special requirements for the reaction vessel, and it has good process applicability and scalability. Attached Figure Description
[0015] Figure 1 This is a scanning electron microscope image of the graphene oxide / carbon nanotube-based coal combustion catalyst prepared in this invention. Figure 2 Thermogravimetric analysis (TGA) of coal powder with graphene oxide / carbon nanotube-based coal combustion catalyst added in Example 2; Figure 3 Thermogravimetric analysis (TGA) of coal powder without graphene oxide / carbon nanotube-based coal combustion catalyst is shown in Comparative Example 1. Detailed Implementation
[0016] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.
[0017] A method for preparing a graphene oxide / carbon nanotube-based coal combustion catalyst includes the following steps: (1) In a water bath at room temperature, add 100 mL of concentrated sulfuric acid to 2 g of graphite and stir until fully dissolved. Then add 0.5 g of potassium permanganate every 10 min, for a total of 10 g of potassium permanganate. (2) Raise the water bath temperature to 55°C, stir the reaction for 3 hours, add hydroxylated modified carbon nanotubes, and react for 1 hour; (3) Add manganese chloride, react for 4 hours, then add 100 mL of deionized water; (4) Stir in a 90℃ water bath for 15 min, then add hydrogen peroxide dropwise until no bubbles are generated, then add 50 mL of hydrochloric acid, centrifuge and wash repeatedly until neutral, freeze dry to obtain the graphene oxide / carbon nanotube-based coal combustion catalyst.
[0018] The mass ratio of graphite to hydroxylated modified carbon nanotubes is 2:1. The mass ratio of manganese chloride to potassium permanganate is 0.01:1.
[0019] The hydroxylated modified carbon nanotubes used in this invention were purchased from Shanghai Haohong Biomedical Technology Co., Ltd.; the coal powder was obtained by crushing coal and passing it through a 100-mesh sieve.
[0020] Thermogravimetric analysis (TGA) experiments were conducted using a TGA / DSC3+ simultaneous thermal analyzer from METTLER TOLEDO, Switzerland. The test conditions were set as follows: 20 mg of the sample was heated from 25°C to 950°C at a heating rate of 30°C / min under an oxygen atmosphere. The sample mass change as a function of temperature was monitored and recorded in real time during the experiment. Based on the obtained TGA data, key combustion characteristic parameters of the pulverized coal, such as ignition temperature, burnout temperature, ignition index, burnout index, and activation energy, were further analyzed and calculated.
[0021] In Example 1, 2 g of graphite was added to a 500 mL beaker and placed in a room temperature water bath. 100 mL of concentrated sulfuric acid was then added and stirred until fully dissolved. 0.5 g of potassium permanganate was added every 10 min, until a total of 10 g of potassium permanganate was added. After all the potassium permanganate was added, the water temperature was raised to 55°C, and the reaction was stirred for 3 h. Then, 1 g of hydroxylated modified carbon nanotubes was added, and the reaction continued for 1 h. Next, 0.1 g of manganese chloride was added, and the reaction continued for 4 h. Then, 100 mL of deionized water was added. The resulting reaction solution was placed in a 90°C water bath and stirred for 15 min. Hydrogen peroxide was then added dropwise until no more bubbles were generated. 50 mL of hydrochloric acid was added, and the product was repeatedly centrifuged and washed until neutral. It was then transferred to a freeze dryer and freeze-dried to obtain a modified graphene oxide / carbon nanotube-based combustion catalyst. Finally, 1 g of the modified graphene oxide / carbon nanotube-based combustion catalyst was mixed with 100 g of... Coal powder is mixed to obtain a catalyst-added coal powder sample to be tested.
[0022] In Example 2, 2 g of graphite was added to a 500 mL beaker and placed in a room temperature water bath. 100 mL of concentrated sulfuric acid was then added and stirred until fully dissolved. 0.5 g of potassium permanganate was added every 10 min, until a total of 10 g of potassium permanganate was added. After all the potassium permanganate was added, the water temperature was raised to 55°C, and the reaction was stirred for 3 h. Then, 1 g of hydroxylated modified carbon nanotubes was added, and the reaction continued for 1 h. Next, 0.1 g of manganese chloride was added, and the reaction continued for 4 h. Then, 100 mL of deionized water was added. The resulting reaction solution was placed in a 90°C water bath and stirred for 15 min. Hydrogen peroxide was then added dropwise until no more bubbles were generated. 50 mL of hydrochloric acid was added, and the product was repeatedly centrifuged and washed until neutral. It was then transferred to a freeze dryer and freeze-dried to obtain a modified graphene oxide / carbon nanotube-based combustion catalyst. Finally, 3 g of the modified graphene oxide / carbon nanotube-based combustion catalyst and 100 g of... Coal powder is mixed to obtain a catalyst-added coal powder sample to be tested.
[0023] In Example 3, 2 g of graphite was added to a 500 mL beaker and placed in a room temperature water bath. 100 mL of concentrated sulfuric acid was then added and stirred until fully dissolved. 0.5 g of potassium permanganate was added every 10 min, until a total of 10 g of potassium permanganate was added. After all the potassium permanganate was added, the water temperature was raised to 55°C, and the reaction was stirred for 3 h. Then, 1 g of hydroxylated modified carbon nanotubes was added, and the reaction continued for 1 h. Next, 0.1 g of manganese chloride was added, and the reaction continued for 4 h. Then, 100 mL of deionized water was added. The resulting reaction solution was placed in a 90°C water bath and stirred for 15 min. Hydrogen peroxide was then added dropwise until no more bubbles were generated. 50 mL of hydrochloric acid was added, and the product was repeatedly centrifuged and washed until neutral. It was then transferred to a freeze dryer and freeze-dried to obtain a modified graphene oxide / carbon nanotube-based combustion catalyst. Finally, 5 g of the modified graphene oxide / carbon nanotube-based combustion catalyst and 100 g of... Coal powder is mixed to obtain a catalyst-added coal powder sample to be tested.
[0024] Comparative Example 1: 100 g of coal powder was taken to obtain the coal powder sample to be tested.
[0025] As shown in Table 1, the combustion performance of coal is improved after adding a certain amount of catalyst. In Example 2, when the mass ratio of catalyst to coal is 3:100, the catalyst can minimize the ignition temperature and activation energy of coal. This is because the appropriate addition of catalyst opens up the combustion space of coal through the "point-line-surface" structure of the catalyst and coal, increases the proportion of reactive carbon atoms, and promotes coal combustion.
[0026] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.
Claims
1. A method for preparing a graphene oxide / carbon nanotube-based coal combustion catalyst, characterized in that: Using highly dispersed graphene oxide as a carrier and modified carbon nanotubes as the loading material, the two are combined through a condensation reaction, and then manganese oxide is loaded onto it using a redox reaction to obtain the graphene oxide / carbon nanotube-based coal combustion catalyst.
2. The method according to claim 1, characterized in that: Includes the following steps: (1) In a water bath at room temperature, add 100 mL of concentrated sulfuric acid to 2 g of graphite and stir until fully dissolved. Then add 0.5 g of potassium permanganate every 10 min, for a total of 10 g of potassium permanganate. (2) Raise the water bath temperature to 55°C, stir the reaction for 3 hours, add hydroxylated modified carbon nanotubes, and react for 1 hour; (3) Add manganese chloride, react for 4 hours, then add 100 mL of deionized water; (4) Stir in a 90℃ water bath for 15 min, then add hydrogen peroxide dropwise until no more bubbles are generated, then add 50 mL of hydrochloric acid, centrifuge and wash repeatedly until neutral, freeze dry to obtain the graphene oxide / carbon nanotube-based coal combustion catalyst.
3. The method according to claim 2, characterized in that: The mass ratio of graphite to hydroxylated modified carbon nanotubes is 2:
1.
4. The method according to claim 2, characterized in that: The mass ratio of manganese chloride to potassium permanganate is 0.01:
1.
5. A graphene oxide / carbon nanotube-based coal combustion catalyst prepared by the method according to any one of claims 1-4.
6. A graphene oxide / carbon nanotube-based coal combustion catalyst prepared by the method according to any one of claims 1-4, used in a coal catalytic combustion reaction, characterized in that: The mass ratio of the graphene oxide / carbon nanotube-based coal combustion catalyst to pulverized coal is 1-5:100.