TiO2光催化強化[HO2MMim][HSO4]?H2O2脫除煤中有機硫的研究

王蘭云; 溫興琳; 劉澤健; 張亞娟; 盧曉冉; 劉真; 周華健; 徐永亮

doi:10.13374/j.issn2095-9389.2021.06.24.003

TiO₂光催化強化[HO₂MMim][HSO₄]?H₂O₂脫除煤中有機硫的研究

doi: 10.13374/j.issn2095-9389.2021.06.24.003

王蘭云^{1, 2, 3},
溫興琳^{1, 4},
劉澤健¹,
張亞娟¹,
盧曉冉¹,
劉真¹,
周華健¹,
徐永亮^{1, 2, 3, ,}

1.
河南理工大學安全科學與工程學院，焦作 454003
2.
煤炭安全生產與清潔高效利用省部共建協同創新中心，焦作 454003
3.
河南省瓦斯地質與瓦斯治理重點實驗室—省部共建國家重點實驗室培育基地，焦作 454003
4.
南京工業大學安全科學與工程學院，南京 211806

基金項目: 國家自然科學基金資助項目（51874124，52074108）; 河南科技攻關資助項目（212102310007）; 河南理工大學杰出青年基金資助項目（J2019-5）

詳細信息

通訊作者:
E-mail: xylcumt@hpu.edu.cn

中圖分類號: TF704.3
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- 文章訪問數: 488
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- 被引次數: 0
出版歷程
- 收稿日期: 2021-06-24
- 網絡出版日期: 2021-09-09
- 刊出日期: 2023-01-01

Photocatalytic enhanced [HO₂MMim][HSO₄]?H₂O₂ removal of organic sulfur from coal

WANG Lan-yun^{1, 2, 3},
WEN Xing-lin^{1, 4},
LIU Ze-jian¹,
ZHANG Ya-juan¹,
LU Xiao-ran¹,
LIU Zhen¹,
ZHOU Hua-jian¹,
XU Yong-liang^{1, 2, 3
, ,}

1.
College of Safety Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China
2.
Collaborative Innovation Center of Coal Work Safety and Clean High Efficiency Utilization, Jiaozuo 454003, China
3.
State Key Laboratory Cultivation Base for Gas Geology and Gas Control, Henan Polytechnic University, Jiaozuo 454003, China
4.
College of Safety Science and Engineering, Nanjing Tech University, Nanjing 211806, China

More Information

Corresponding author: E-mail: xylcumt@hpu.edu.cn

摘要

摘要: 燃煤中的硫嚴重影響了煤炭的高效利用，將光催化氧化引入到萃取脫硫體系，可以顯著地提高離子液體萃取脫硫效率。為了進一步研究脫硫機理，采用實驗結合計算機仿真模擬對其進行了分析。實驗結果表明將光催化反應過程與離子液體萃取過程耦合，可有效脫除煤中的有機硫，[HO₂MMim][HSO₄]?H₂O?H₂O₂?TiO₂（質量比5∶5∶10∶4）光催化處理后的煤的有機硫脫硫率最高可達12.40%。Materials Studio分析得出由光催化產生的羥基自由基(·OH)具有較強的氧化性，·OH的氧原子附近所在區域呈負電性，容易與噻吩中S原子的正電勢點產生靜電力并形成S=O雙鍵；另外，離子液體的加入使得原本噻吩環上的最低空軌道消失，還降低了最高占據分子軌道（HOMO）和最低未占分子軌道（LUMO）的能級差，使反應更容易進行。使用COSMO軟件分析發現離子液萃取作用體現在[HO₂MMim][HSO₄]中咪唑的五元雜環結構通過范德華力與噻吩、砜分子之間成鍵，使硫化物不斷被萃取到離子液體相中；外加氧化劑使反應中化學勢較高的砜比噻吩更容易進入到化學勢低的離子液[HO₂MMim][HSO₄]中。
- 光催化氧化脫硫 /
- 噻吩 /
- 砜 /
- 羥基自由基 /
- Materials Studio /
- COSMO
Abstract: Coal is considered one of the largest energy sources globally, but the sulfur in coal combustion seriously affects the efficient utilization of coal. Moreover, the sulfide produced by burning high sulfur coal is one of the leading causes of several diseases and environmental pollution. Incorporating photocatalytic oxidation into the extraction desulfurization system can significantly improve the efficiency of ionic liquid reactive extraction desulfurization. To further study the mechanism of desulfurization, experiment and computer simulation were used to analyze it. The experimental results show that coupling the photocatalytic reaction process and the ionic liquid extraction process can effectively remove organic sulfur in coal. The desulfurization rate of organic sulfur in the coal treated by [HO₂MMim][HSO₄]–H₂O–H₂O₂–TiO₂（mass ratio 5∶5∶10∶4）can reach 12.40%. In addition, an appropriate amount of water can improve the desulfurization rate of coal, but an excessive amount of aqueous solution can reduce the concentration of hydrogen peroxide and the organic sulfur desulfurization rate in coal. Materials Studio analysis shows that the hydroxyl radical (·OH) generated by photocatalytic activity has strong oxidability, and the area near the oxygen atom of ·OH is electronegative, which is easy to form S=O double bond with the positively charged S atom in thiophene via electrostatic attraction. In addition, the addition of ionic liquid makes the original lowest vacant orbital on the thiophene ring disappear. Moreover, it lowers the energy level difference between the HOMO and the LUMO, making the reaction easier to proceed with. Using COSMO analysis, it is found that the five-member heterocyclic structure of imidazole in [HO₂MMim][HSO₄] formed bonds with thiophene and sulfone molecules through van der Waals forces; thus, sulfide was constantly extracted into the ionic liquid phase and that adding the oxidizer can make it easier for sulfone with higher chemical potential to enter the lower chemical potential ionic solution [HO₂MMim][HSO₄] than thiophene.
- photocatalytic oxidative desulfurization /
- thiophene /
- sulfone /
- hydroxyl radical /
- Materials Studio /
- COSMO

HTML全文

圖 1 常溫常壓下不同劑量的溶劑對煤有機硫脫硫率和無機硫脫硫率的影響

Figure 1. Effect of different dosages of solvents on coal organic sulfur desulfurization rate and inorganic sulfur desulfurization rate under normal temperature and pressure

下載: 全尺寸圖片幻燈片

圖 2 脫硫機理圖

Figure 2. Desulfurization mechanism diagram

下載: 全尺寸圖片幻燈片

圖 3 光照時間對脫硫率的影響

Figure 3. Effect of ultraviolet (UV) irradiation time on the desulfurization rate

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圖 4 常溫常壓下處理前后煤的XPS光譜圖

Figure 4. X-ray photoelectron spectroscopy (XPS) spectra of coal before and after treatment at normal temperature and pressure

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圖 5 常溫常壓下原煤與光催化處理后煤中各種形態硫的相對含量

Figure 5. Relative content of various forms of sulfur in raw coal and coal after photocatalytic treatment at normal temperature and pressure

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圖 6 噻吩、[HO₂MMim][HSO₄]和H₂O₂前線軌道等值面及其能量

Figure 6. Frontal orbital isosurface and energy of thiophene, [HO₂MMim][HSO₄] and H₂O₂

下載: 全尺寸圖片幻燈片

圖 7 分子表面的屏蔽導體電荷密度分布σ-profile圖(a)和化學勢曲線σ-potential圖(b)

Figure 7. Charge density distribution σ-profile diagram (a) and chemical potential curve σ-potential diagram (b) of the shielded conductor on the molecular surface

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表 1 干燥煤的工業分析和元素分析（質量分數）

Table 1. Industrial analysis and elemental analysis of dry coal （mass fraction） %

Sample	M_ad	A_ad	V_ad	FC_ad	S_T,C	S_{Raw, O, C}	S_{Raw, I, C}
Air-dried raw coal	2.79	4.64	39.37	53.20	2.19	1.29	0.9

下載: 導出CSV

表 2 同一反應時間煤中的硫含量和光催化煤脫硫率

Table 2. Sulfur content in coal and photocatalytic coal desulfurization rate at the same reaction time

Items	Sample	The mass ratio of each component in the sample	S_{T, C}/%	D_{R, O, C}/%	D_{R, I, C}/%	D_S /%
1^#	Raw coal		2.19
2^#	Raw coal–[HO₂MMim][HSO₄]–H₂O₂ （Avoid light）	3∶1∶10	1.87	6.20	26.67	14.61
3^#	Raw coal–[HO₂MMim][HSO₄]–H₂O₂	3∶1∶10	1.82	6.98	31.11	16.89
4^#	Raw coal–[HO₂MMim][HSO₄]–H₂O₂–TiO₂	3∶1∶10∶4	1.68	10.08	42.22	23.29
		3∶5∶10∶4	1.86	12.40	18.89	15.07
		3∶10∶10∶4	1.9	9.30	18.89	13.24
5^#	Raw coal–[HO₂MMim][HSO₄]–H₂O–TiO₂	3∶5∶10∶4	1.97	11.63	8.89	10.50
6^#	Raw coal–H₂O₂–TiO₂ (light time 3 h)	3∶10∶4	2.03	6.98	7.78	7.31
	Raw coal–H₂O₂–TiO₂		1.84	10.85	23.33	15.98
	Raw coal–H₂O₂–TiO₂ (light time 9 h)		1.85	6.20	28.89	15.53
7^#	Raw coal–H₂O–H₂O₂–TiO₂	3∶1∶10∶4	1.86	7.75	25.56	15.07
		3∶5∶10∶4	1.91	10.85	15.56	12.79
		3∶10∶10∶4	1.83	6.98	30.00	16.44
8^#	Raw coal–[HO₂MMim][HSO₄]–H₂O–H₂O₂–TiO₂	3∶5∶5∶10∶4	1.83	10.85	24.44	16.44
8^#	Raw coal–[HO₂MMim][HSO₄]–H₂O–H₂O₂–TiO₂	3∶5∶10∶10∶4	1.87	8.53	23.33	14.61

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表 3 溶質在溶劑中的溶解度、化學勢、靜電能、氫鍵能和范德華力

Table 3. Solubility, chemical potential, electrostatic energy, hydrogen bond energy, and van der Waals force of solute in solvent

Solute	Solvent	Solubility， Log₁₀x	Chemical potential/ (kJ· mol^?1)	Electrostatic energy/ (kJ· mol^?1)	Hydrogen bond/ (kJ· mol^?1)	Van der Waals forces/ (kJ· mol^?1)
Thiophene	[HO₂MMim][HSO₄]	?5.5490	11.8715	11.9531	0.0130	?62.4057252
Thiophene	H₂O₂	?9.8911	17.7725	18.0919	0	?56.2682
Sulfone	[HO₂MMim][HSO₄]	?1.9457	15.5087	13.7912	?2.5133	?72.4048
Sulfone	H₂O₂	?8.9631	12.2277	13.8393	?9.8744	?64.5552

下載: 導出CSV

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