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The application of calcium hydroxide desulfurizers with high specific surface area: In recent years, dry flue gas desulfurization technology has been increasingly used in small and medium-sized flue gas desulfurization systems; it is a mature technology with stable operation. Among them, the SDS desulfurization process using sodium bicarbonate as the base source has seen its market share expand rapidly due to advantages such as high desulfurization efficiency, wide availability of the desulfurizing agent, and low difficulty in implementation. As the number of installations increases, the disadvantages of this technical approach have begun to become apparent, and how to deal with desulfurization ash has turned into a new environmental challenge. Sodium-based desulfurization ash is a mixture of sodium sulfate, sodium sulfite, and sodium carbonate; it has good water solubility and belongs to the category of general solid waste that is difficult to dispose of in compliance with regulations. According to official statistics, the coking industry alone generates as much as 300,000 tons of sodium-based desulfurization ash per year; when accounting for the power boilers, hot blast stoves, and heating furnaces in steel plants, as well as glass and cement kilns, the amount of sodium-based desulfurization ash increases even further. Some companies rent premises to build warehouses for storage, while others sell the waste to qualified agencies for disposal; the cost per ton ranges from 100 to 500 yuan, adding to the financial burden on these companies. On September 1, 2020, the revised Law of the People’s Republic of China on the Prevention and Control of Environmental Pollution by Solid Wastes came into full effect. It introduced new obligations for enterprises that generate solid waste, stipulating severe penalties for any illegal activities. Business pressures are soaring! Highly active calcium hydroxide with a high specific surface area features porosity, high activity, good dispersibility, and high utilization efficiency. Its specific surface area (BET) is over 40 m2/g, which is 3–4 times that of ordinary calcium hydroxide, while its desulfurization efficiency is above 95% ; The pore volume of calcium hydroxide with a high specific surface area exceeds 0.2 cm3/g, enabling rapid adsorption and absorption of HCl and SO2 in flue gas, with an utilization rate of over 85% ; Calcium hydroxide with a high specific surface area has good fluidity and is less likely to clog pipes during use. In the 1980s, Europe, the United States, and Japan began using calcium hydroxide with a high specific surface area extensively for desulfurization in waste-to-energy plants and thermal power plants, successfully replacing soda ash; it is currently recognized worldwide as an excellent dry desulfurization agent. In 2010, Lhoist introduced a highly reactive calcium hydroxide desulfurizer in the domestic market for use in flue gas treatment in waste incineration plants, glass furnaces, and ceramic kilns. This marked the beginning of the application of calcium-based desulfurizers with high specific surface area in China. The main components of the desulfurization by-products—such as calcium sulfate, calcium carbonate, and calcium hydroxide—are general solid wastes that can be recycled. However, due to the high cost of the desulfurizer, it has not been widely adopted. After months of intensive research and the efforts of technical personnel, highly active calcium hydroxide with a high specific surface area was successfully developed; its specific surface area (BET) exceeded 45 m2/g. Industrial production was established, and it was launched on the market in June 2021. The HNPS desulfurization system developed by the company has undergone pilot tests and industrial use over several months with different users; it exhibits good operational performance, low costs, and satisfies the users. At present, it has been successfully applied at the coke pusher ground station of coke ovens for dust removal in the dry quenching process of coke, as well as for the desulfurization of flue gases from coke ovens. Advantages of HNPS desulfurization technology: 1. It uses highly active calcium-based desulfurizing agents with a high specific surface area, which are directly injected into the flue gas and thoroughly mixed with it, thereby enabling the adsorption and absorption of acidic substances in the flue gas; this results in high desulfurization efficiency ; 2. The HNPS dry desulfurization process is employed; there is no temperature drop during the reaction. The existing bag filters or additional bag filters are used to remove solid waste. Calcium-based solid waste does not absorb moisture, is not corrosive, and does not compact. 3. Compared with SDS, desulfurization has almost no temperature restrictions; there is no need for a grinding system on site, and it results in low investment and operating costs. It can directly replace soda ash in existing SDS processes ; 4. The main components of desulfurization by-products, such as calcium sulfate, calcium carbonate, and calcium hydroxide, are all considered ordinary solid wastes that can be recycled ; 5. Fewer devices and equipment are required, offering flexible layout and low investment costs ; Feed is delivered using tank trucks; the system is fully sealed, resulting in no dust generation at the site ; Roots blower or compressed air delivery, with low power consumption.
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How should desulfurization ash containing some coke powder be treated or recycled?
I. Direct use as cement admixture: The coke powder in desulfurization ash can be used as an admixture in cement. When desulfurization ash is added to cement, the setting time of the mixed cement is longer and its hydration heat is lower, which can increase the output of mills and the grinding efficiency, while reducing the amount of clinker required for cement production. However, attention must be paid to the incorporation ratio to ensure the quality of the cement. Concrete admixtures: The desulfurization ash produced by dry desulfurization has a high calcium content, and it can be used to replace part of the cement as a concrete admixture. The replacement amount should be determined based on the specific application, by measuring compressive strength, flexural strength, and setting time. Subgrade materials: Desulfurized ash can also be used as a base material for roads, dam construction, and embankment building. When desulfurization ash is used as a base material for roads, it can replace ordinary fly ash; it is recommended to add a small amount of activator to improve its performance. II. Recycling: Magnetic separation: If the content of coke powder in the desulfurization ash is high and this coke powder has significant value for recovery, it can be separated from the desulfurization ash using physical methods such as magnetic separation, thereby enabling the recycling of the coke powder. Chemical treatment: Specific components in desulfurization ash, such as sulfur, iron, calcium, and other elements, can be treated and recovered through chemical methods. For example, through fluidized reaction in a high-temperature furnace, the sulfur in desulfurization ash can be converted into sulfuric acid, while the residue can be used to produce products such as calcium oxide and magnetite. III. Other utilization methods: Coal cinder blocks: When produced from dry desulfurization ash in small proportions, the mechanical properties and shrinkage characteristics of such coal cinder blocks meet the required standards for quality. This type of block does not shrink, and its curing time is short, making it a very promising approach for utilization. Stable plastic clays: Due to the high content of lime in dry desulfurization ash, it can be used to stabilize plastic clays, and it does not slow down the development of the strength of the stabilized soil like ordinary fly ash does.
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