燒結半干法脫硫灰中亞硫酸鈣氧化特性

錢大益; 王艷; 邢奕; 金明輝; 蘇偉; 張夢然; 鄭躍博; 劉媛夢; 段淑雅

doi:10.13374/j.issn2095-9389.2022.09.19.004

燒結半干法脫硫灰中亞硫酸鈣氧化特性

doi: 10.13374/j.issn2095-9389.2022.09.19.004

錢大益^{1, 2, ,},
王艷¹,
邢奕¹,
金明輝¹,
蘇偉¹,
張夢然¹,
鄭躍博²,
劉媛夢²,
段淑雅¹

1.
北京科技大學能源與環境工程學院，北京 100083
2.
伊犁師范大學化學與環境科學學院污染物化學與環境治理重點實驗室，伊寧 835000

基金項目: 新疆維吾爾自治區自然科學基金資助項目（2022D01C333）

詳細信息

通訊作者:
E-mail: qday@ustb.edu.cn

中圖分類號: X701.3
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出版歷程
- 收稿日期: 2022-09-19
- 網絡出版日期: 2022-11-28

Oxidation characteristics of calcium sulfite in sintering desulphurized ash

1.
School of Energy Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Key Laboratory of Pollutant Chemistry and Environmental Treatment, School of Chemistry and Environmental Science, Yili Normal University, Yining 835000, China

More Information

Corresponding author: E-mail: qday@ustb.edu.cn

摘要

摘要: 針對燒結半干法脫硫灰中CaSO₃在不同反應條件下干熱氧化的變化規律，研究了溫度、氣體中O₂含量與流速、鈣類化合物、鐵氧化物（Fe₂O₃）、水蒸汽含量與流速等對CaSO₃氧化的影響. 結果表明：反應遵循阿累尼烏斯方程，在空氣氛圍，升溫速度為10 ℃·min^–1的條件下，450 ℃、75 mL·min^–1的氣體流速為經濟性干熱氧化的最佳工藝條件，水汽對CaSO₃氧化反應具有兩面性；鈣的氧化物對CaSO₃氧化反應通過抑制$ {\text{O}}_{\text{2}}^{{-}} $、$ \text{S}{\text{O}}_{\text{3}}^{{-}} $自由基的生成而抑制反應進行，3種鈣類氧化物對CaSO₃氧化抑制作用從弱到強為：CaCO₃＜Ca(OH)₂＜CaCl₂；Fe₂O₃對CaSO₃的催化作用隨溫度、濃度變化而改變，溫度小于450 ℃，Fe₂O₃質量分數大于0.2%時，對氧化反應起到一定催化作用，溫度大于450 ℃及催化劑質量分數低于0.2%時，由溫度占主導地位. 微觀形貌表征顯示隨著CaSO₃被氧化為CaSO₄，形貌由團簇狀轉變為柱狀，CaCl₂即抑制氧化反應也抑制CaSO₄的晶型，Fe₂O₃促進CaSO₄結晶的形成. 實驗室升溫較快，溫度大于400 ℃時，脫硫灰5 min內部溫度大于500 ℃，此時，CaSO₃轉化率超過85%，中試升溫較慢，沒有這一特征；吉布斯自由能計算結果表明最有可能發生的是CaSO₃氧化反應，600 ℃以下鈣的氧化分解反應不可能發生；CaSO₃氧化過程中活性位點的數量與溫度有關，當溫度在623～723 K時，該反應為一級反應，當溫度大于723 K時，反應在5 min左右迅速完成，無法確定其反應級數.
- 半干法脫硫 /
- 脫硫灰 /
- 亞硫酸鈣 /
- 干熱法 /
- 氧化特性
Abstract: Considering the variation in dry heat oxidation of CaSO₃ in sintering semidry desulfurization ash under different reaction conditions, the effects of temperature, O₂ content and flow rate in gas, calcium compounds, iron oxide (Fe₂O₃), water vapor content, and flow rate on CaSO₃ oxidation were evaluated. It was determined that the reaction adheres to the Arrhenius equation. The oxidation rate of CaSO₃ increases from 380 ℃. Moreover, at 450 ℃, the oxidation rate of CaSO₃ exceeds 90%, and at 550 ℃, it is completely oxidized (98.2%). Under the condition of 10 ℃·min^?1 in the air atmosphere, the gas flow rate of 450 ℃ and 75 mL·min^?1 is the optimal process condition for economic dry heat oxidation. Water vapor is present on both sides of the CaSO₃ oxidation reaction. Moreover, the oxidation of CaSO₃ by calcium oxides was inhibited by inhibiting the generation of $ {\text{O}}_{\text{2}}^{-}\;\text{and }\;{\text{SO}}_{\text{3}}^{-} $ free radicals. The order of the inhibition of CaSO₃ oxidation by the three calcium oxides from weak to strong was CaCO₃ < Ca(OH)₂ < CaCl₂. The catalytic effect of Fe₂O₃ on the oxidation of CaSO₃ varies with temperature and concentration. When the temperature is less than 450 ℃ and the weight percentage of Fe₂O₃ is greater than 0.2%, it plays a certain catalytic role in the oxidation reaction. The doping of Fe₂O₃ accelerates the formation of $ {\text{O}}_{\text{2}}^{-} $ and $ \text{S}{\text{O}}_{\text{3}}^{-} $ free radicals. When the temperature exceeds 450 ℃ and the catalyst concentration is less than 0.2%, the catalyst concentration has no effect on the reaction process, and the temperature takes precedence. The microscopy analysis reveals that with the oxidation of CaSO₃ to CaSO₄, the morphology shifts from cluster to column. Furthermore, CaCl₂ inhibits not only the oxidation reaction but also the crystal form of CaSO₄. Fe₂O₃ aids the formation of CaSO₄ crystals. When the temperature exceeds 400 ℃, the internal temperature of desulfurized ash is higher than 500 ℃ for 5 min. Simultaneously, the conversion rate of CaSO₃ is greater than 85%, and the pilot test temperature is slower, which lacks this feature. The Gibbs free energy calculation results show that the most likely reaction is the oxidation of CaSO₃ and that oxidation and decomposition of calcium below 600 ℃ is not feasible. The number of active sites in the process of CaSO₃ oxidation is proportional to temperature. Thus, when the temperature is between 623 and 723 K, the reaction is a first-order reaction. When the temperature exceeds 723 K, the reaction will be completed quickly in about 5 min, and the reaction order cannot be determined.
- semi-dry desulfurization /
- desulfurization ash /
- calcium sulfite /
- dry method /
- oxidation characteristics

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圖 1 實驗系統裝置流程圖

Figure 1. Flowchart of experimental system installation

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圖 2 氣體流速對CaSO₃氧化的影響

Figure 2. Effect of gas flow rate on CaSO₃ oxidation

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圖 3 靜固態與氣體流速75 mL·min^–1時溫度對CaSO₃氧化性能的影響

Figure 3. Effect of temperature on the oxidation of CaSO₃ under the condition of static solid gas velocity and 75 mL·min^–1, respectively

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圖 4 氧氣含量對CaSO₃氧化的影響

Figure 4. Effect of oxygen content on CaSO₃ oxidation

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圖 5 鈣類化合物對CaSO₃氧化影響

Figure 5. Effect of calcium compounds on CaSO₃ oxidation

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圖 6 不同CaCl₂質量分數對CaSO₃氧化影響

Figure 6. Effect of CaCl₂ content on CaSO₃ oxidation

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圖 7 不同Fe₂O₃質量分數對CaSO₃氧化影響

Figure 7. Effect of Fe₂O₃ content on CaSO₃ oxidation

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圖 8 反應前后Fe 2p的XPS譜圖

Figure 8. XPS spectrum of Fe 2p

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圖 9 不同氣體流速下水汽對轉化率的影響

Figure 9. Effect of water vapor on the conversion rate under different gas flow rate at 75 mL·min^–1

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圖 10 75 mL·min^–1下不同水汽量對轉化率的影響

Figure 10. Effect of water vapor on the conversion rate

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圖 11 不同溫度條件下脫硫灰內部溫度變化

Figure 11. Internal temperature variation of desulfurized ash under different temperature

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圖 12 不同條件下氧化產物CaSO₄的SEM圖. (a) 400 ℃; (b) 450 ℃; (c) 450 ℃下添加4% CaCl₂; (d) 450 ℃下添加16% CaCl₂; (e) 400 ℃下添加0.2% Fe₂O₃; (f) 400 ℃下添加0.6% Fe₂O₃

Figure 12. SEM images of CaSO₄ under different conditions: (a) 400 ℃; (b) 450 ℃; (c) 450 ℃ and 4% CaCl₂; (d) 450 ℃ and 16% CaCl₂; (e) 400 ℃ and 0.2% Fe₂O₃; (f) 400 ℃ and 0.6% Fe₂O₃

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圖 13 反應（12）～（17）的Δ${G_T}^\ominus $

Figure 13. Δ${G_T}^\ominus $ of reaction (12) ～ (17)

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圖 14 干熱氧化反應過程機理分析圖. (a)初始氧化條圖; (b)增加氧濃度后反應圖; (c)提高反應溫度后反應示意圖

Figure 14. Analysis diagram of the mechanism of dry heat oxidation reaction process: (a) initial oxidation bar diagram; (b) reaction diagram after increasing oxygen concentration; (c) schematic diagram of the reaction after increasing the reaction temperature

Notes: Round shadows are desulfurized ash particles; round spheres represent oxygen molecules; blue spheres are activated oxygen molecules.

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圖 15 反應動力學曲線

Figure 15. Reaction kinetics curve

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表 1 脫硫灰化學成分（質量分數）

Table 1. Chemical composition of desulfurized ash %

Stage	CaO	SO₃	SiO₂	Fe₂O₃	Cl^–	Na₂O	MgO	K₂O	Al₂O₃
Pelletizing	50.5	30.1	0.537	0.224	10.50	0.103	0.648	0.0826	0.372
South of sintering	54.1	25.4	0.522	0.654	3.34	0.853	1.540	2.4400	0.347
North of sintering	50.0	32.7	0.723	0.310	2.83	0.524	0.930	0.7380	0.847

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表 2 CaSO₃最終氧化產物成分分析

Table 2. Composition analysis of the final oxidation products of CaSO₃

Stage	Mass fraction/%													Conversion rate/%
Stage	Loss	CaO		SO₃		SiO₂	Fe₂O₃	Cl^?	Na₂O	MgO	K₂O	Al₂O₂	Total sulfur	Conversion rate/%
Preoxidation	15.35	41.5	4.91		6.55		0.80	2.31	0.40	0.85	0.48	1.97	32.97	—
Post-xidation	14.17	39.9	30.36		6.30		0.77	2.42	0.39	0.82	0.46	1.89	31.70	94.82

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表 3 不同溫度與反應時間下CaSO₃氧化轉化率

Table 3. Oxidation conversion of CaSO₃ at different temperature and reaction times %

t/min	623 K	673 K	723 K	773 K	823 K	873 K
30	26.76	65.80	92.53	92.64	95.09	96.49
60	35.28	76.31	93.24	94.18	96.66	97.58
90	50.45	85.64	93.79	94.98	97.00	98.35
120	47.03	86.77	94.10	96.07	97.19	98.10
150	52.56	87.10	93.90	95.93	97.01	98.18

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