鋼鐵工業煙氣脫硝技術應用進展及前景

張柏林; 洪華; 王天球; 張新遠; 鄔博宇; 劉波; 張深根

doi:10.13374/j.issn2095-9389.2022.11.26.001

鋼鐵工業煙氣脫硝技術應用進展及前景

doi: 10.13374/j.issn2095-9389.2022.11.26.001

張柏林^{1, 2, 3,},
洪華²,
王天球²,
張新遠¹,
鄔博宇¹,
劉波¹,
張深根^1, ,

1.
北京科技大學新材料技術研究院，北京 100083
2.
建龍鋼鐵控股有限公司，唐山 064200
3.
北京科技大學順德創新學院，佛山 528399

基金項目: 國家自然科學基金資助項目（52204414）; 佛山市人民政府科技創新專項資金資助項目（BK22BE001）; 北京科技大學順德創新學院博士后科研資助項目（2020BH012）; 中央高校基本科研業務費資助項目（FRF-TP-20-097A1Z）

詳細信息

通訊作者:
E-mail: zhangshengen@mater.ustb.edu.cn

中圖分類號: X511
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- 被引次數: 0
出版歷程
- 收稿日期: 2022-11-26
- 網絡出版日期: 2023-01-12
- 刊出日期: 2023-09-25

Progress and prospects of flue gas deNOx technology for the iron and steel industry

ZHANG Bolin^{1, 2, 3
,},
HONG Hua²,
WANG Tianqiu²,
ZHANG Xinyuan¹,
WU Boyu¹,
LIU Bo¹,
ZHANG Shengen^{1
, ,}

1.
Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
2.
Jianlong Steel Holdings Co. Ltd., Tangshan 064200, China
3.
Shunde Innovation School, University of Science and Technology Beijing, Foshan 528399, China

More Information

Corresponding author: E-mail: zhangshengen@mater.ustb.edu.cn

摘要

摘要: 氮氧化物（NO_x）已成為我國首要大氣污染物，鋼鐵工業是工業源NO_x排放的主要來源。燒結、球團、煉焦等工序是鋼鐵工業NO_x超低排放改造的重點，但其煙氣特性與火電廠煙氣存在差異，煙氣脫硝技術不能完全照搬現有燃煤鍋爐脫硝工藝。目前，選擇性催化還原（SCR）、活性炭（焦）（AC）吸附催化、臭氧（O₃）氧化協同吸收等技術已在燒結、球團、煉焦等工序成功應用，并均取得了良好效果。本文針對鋼鐵工業超低排放的迫切需求，梳理了鋼鐵工業燒結、球團、煉焦等主要工序的現有煙氣脫硝技術及其應用，重點總結并對比分析了SCR技術、AC吸附催化和O₃氧化協同吸收技術的應用進展及優劣勢。其中，SCR技術正逐步成為鋼鐵工業脫硝市場的主流技術，占比超過70%，因此脫硝催化劑及其再生具有長期巨大的市場需求。AC吸附催化和O₃氧化協同吸收等新型技術因其適用溫度低，無需煙氣升溫等，在鋼鐵工業越來越受到青睞，將逐步得到更多鋼鐵企業的支持。
- 氮氧化物 /
- 鋼鐵工業 /
- 超低排放 /
- 選擇性催化還原 /
- 活性炭 /
- 臭氧
Abstract: Nitrogen oxides (NO_x) are the primary air pollutant in China. The iron and steel industries have become the primary industrial sources of NO_x emissions in China. The NO_x emissions from iron and steel industries account for 27.3% of all industrial NO_x 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 NO_x 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 NO_x 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.
- nitrogen oxides /
- iron and steel industry /
- ultra-low emission /
- selective catalytic reduction /
- activated carbon /
- ozone

HTML全文

圖 1 燒結煙氣活性炭凈化工藝流程^[31]

Figure 1. Purification process of activated carbon from sintered flue gas^[31]

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圖 2 逆流式CSCR系統運行成本構成^[32]

Figure 2. Composition of running cost of reverse-flow carbon selective catalytic reduction system^[32]

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圖 3 O₃氧化協同吸收工藝的O₃消耗分布示意圖^[40]

Figure 3. O₃ consumption distribution schematic diagram for O₃ oxidation combined with absorption^[40]

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表 1 我國鋼鐵工業NO_x超低排放標準

Table 1. Ultra-low emissions of NO_x for the iron and steel industry in China

Implemented region	Limit of NO_x emission for production processes (specific equipment)/(mg·m^?3)					Criterion number
Implemented region	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)	Criterion number
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—2012
Nation	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—2018
Shandong	50	150		150	100 (key area), 150 (general area)	DB37/990—2019, DB37/2376—2019
Henan	50	150		150	100	DB41/1954—2020, DB41/1955—2020

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表 2 山西五麟煤焦脫硝催化劑設計參數^[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 ≥ 2	150×150 ×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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表 3 活性炭及介質消耗量^[33]

Table 3. Consumption of activated carbon and others^[33]

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 鋼鐵工業煙氣脫硝技術優劣勢對比

Table 4. Advantages and disadvantages of deNOx technology for the iron and steel industry

DeNOx Technologies	Typical routes	DeNOx temperature/℃	NO_x removal/%	Advantages	Disadvantages
SCR technology	Wet/semidry desulfurization + SCR	200–300	≥80	High NO_x 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 NO_x simultaneously; utilization of by-products; easy to use of waste AC.	Low NO_x 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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