Progress and prospects of flue gas deNOx technology for the iron and steel industry
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摘要: 氮氧化物（NOx）已成为我国首要大气污染物，钢铁工业是工业源NOx排放的主要来源。烧结、球团、炼焦等工序是钢铁工业NOx超低排放改造的重点，但其烟气特性与火电厂烟气存在差异，烟气脱硝技术不能完全照搬现有燃煤锅炉脱硝工艺。目前，选择性催化还原（SCR）、活性炭（焦）（AC）吸附催化、臭氧（O3）氧化协同吸收等技术已在烧结、球团、炼焦等工序成功应用，并均取得了良好效果。本文针对钢铁工业超低排放的迫切需求，梳理了钢铁工业烧结、球团、炼焦等主要工序的现有烟气脱硝技术及其应用，重点总结并对比分析了SCR技术、AC吸附催化和O3氧化协同吸收技术的应用进展及优劣势。其中，SCR技术正逐步成为钢铁工业脱硝市场的主流技术，占比超过70%，因此脱硝催化剂及其再生具有长期巨大的市场需求。AC吸附催化和O3氧化协同吸收等新型技术因其适用温度低，无需烟气升温等，在钢铁工业越来越受到青睐，将逐步得到更多钢铁企业的支持。Abstract: Nitrogen oxides (NOx) are the primary air pollutant in China. The iron and steel industries have become the primary industrial sources of NOx emissions in China. The NOx emissions from iron and steel industries account for 27.3% of all industrial NOx emissions from sources nationwide, surpassing thermal power generation and cement manufacturing. Over the past ten years, China’s iron and steel industry has achieved tremendous results in flue gas desulfurization, but a huge gap in denitrogenate (deNOx) still remains. In 2019, the Ministry of Ecology and Environment and other departments jointly issued “Opinions on Promoting the Implementation of Ultra-low Emission in the Iron and Steel Industry”, which promoted the retrofitting of ultra-low emission in the iron and steel industry. Sintering, pelleting, coking, and other processes are the focus of retrofitting for NOx emissions. Because their low-temperature flue gas contains several contaminants that differ from the flue gas of thermal power plants, they cannot completely copy the existing deNOx technology for the coal-fired boiler flue gas of thermal power plants. At present, selective catalytic reduction (SCR), activated carbon (AC) adsorption catalysis, ozone (O3) oxidation and absorption, and other technologies are used in sintering, pelleting, and coking processes. These technologies have achieved good results. Herein, we investigated the existing flue gas deNOx technologies for sintering, pelleting, and coking processes in iron and steel industries and analyzed the advantages and disadvantages of SCR technology, AC adsorption catalysis, and O3 oxidation and absorption technologies. The SCR technology has high efficiency and reliable performance, but the operation process requires heating of the flue gas, which uses large amounts of blast furnace gas or coking oven gas, and the service life of the catalyst is typically approximately three years. The waste SCR catalysts are recognized as HW50 hazardous waste. AC adsorption catalytic technology can simultaneously desulfurize and deNOx; its operating temperature is low without flue gas reheating. The by-product of H2SO4 can be utilized, and the waste AC produced can be directly used for sintering or coking, while its deNOx efficiency is low. O3 oxidation and absorption technologies have a low initial investment cost and require little floor space. However, their operating cost is relatively high, and the coabsorption of NOx and SO2 makes the desulfurization ash mixed with nitrate, which increases the difficulty of comprehensive utilization. Finally, we analyzed the application possibilities of SCR and other technologies, providing a reference for the development and selection of deNOx technologies for flue gas from the iron and steel industry.
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表 1 我国钢铁工业NOx超低排放标准
Table 1. Ultra-low emissions of NOx for the iron and steel industry in China
Implemented region Limit of NOx emission for production processes (specific equipment)/(mg·m−3) Criterion number Sintering/pelletizing
(sintering head/pellet
firing machine)Blast furnace
ironmaking
(hot blast stove)Steel-smelting (lime
and dolomite kiln)Steel rolling (heat
treatment furnace)Coking (coke oven chimney) Nation 500,
300 (new project)300 350,
300 (new project)240,
200 (new project)GB 28662—2012,
GB 28663—2012,
GB 28664—2012,
GB 16717—2012Nation 50 200 200 150 (2019) No.35 Shanxi 50 200 200 200 DB14/2249—2020 Tianjin 50 200 150 200 150 DB12/1120—2022 Hebei 50 150 150 150 130 DB13/2169—2018,
DB13/2863—2018Shandong 50 150 150 100 (key area),
150 (general area)DB37/990—2019,
DB37/2376—2019Henan 50 150 150 100 DB41/1954—2020,
DB41/1955—2020
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表 2 山西五麟煤焦脱硝催化剂设计参数[22]
Table 2. Design parameters of catalysts for Shanxi Wulin Coal Coke Co., Ltd. [22]
Catalyst’s type Hole density Thermal expansion coefficient/℃−1 Compressive strength/MPa Size of catalyst/
(mm×mm×mm)Pitch/mm Density
/(kg·m−3)Cordierite honeycomb ceramic coating 100 holes per inch ≤1.6×10−6 Axial ≥ 15;
radial ≥ 2150×150 ×125 2.5 600–700 Components Operating temperature/℃ Amount of catalysts/m3 Arrangement Catalyst layers Gaseous hourly space velocity/h−1 Designed life/h V2O5-WO3/TiO2/ Cordierite 250–350 30.38 60×60 units per layer 3+1 6000-7000 24000
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Project Annual consumption Convert coefficient Convert to standard coal/GJ Activated carbon 701 t 29.3 MJ·kg−1 20529 Electric energy 1594×104 kW·h 3.6 MJ·kW·h−1 57399 NH3 1251 t 11.7 MJ·kg−1 14662 Coke oven gas 455×104 m3 16.7 MJ·m−3 76176 Compressed air 1226×104 m3 1.0 MJ·m−3 12249 N2 701×104 m3 11.7 MJ·m−3 82157 steam 26280 t 3.8 MJ·kg−1 99023 water 10512 t 4.2 MJ·kg−1 44044 Total 406250
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表 4 钢铁工业烟气脱硝技术优劣势对比
Table 4. Advantages and disadvantages of deNOx technology for the iron and steel industry
DeNOx Technologies Typical routes DeNOx temperature/℃ NOx removal/% Advantages Disadvantages SCR technology Wet/semidry desulfurization + SCR 200-300 ≥80 High NOx removal efficiency;
high stability.High facilities and catalyst replacement cost;
high cost for flue gas heating;
produce hazardous waste.AC adsorption and catalysis AC integrated technology 120-150 ≥50 Removal of SO2 and NOx simultaneously;
utilization of by-products;
easy to use of waste AC.Low NOx removal efficiency;
High cost of running and AC replacement;
potential risk of AC ignition.O3 oxidation with absorption O3 oxidation + wet/semidry desulfurization 90-150 ≥70 Low facilities cost;
low floor space;
high stability.Relative high running cost;
potential risk of O3 escape;
bad for utilization of desulfurization slag.
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