榆林煤水蒸气气化条件下钾的迁移行为研究

韦兵; 陈倩; 王伟成; 张万祥; 陶睿旻; 窦艺帆; 王兴军

doi:10.1016/S1872-5813(22)60005-7

榆林煤水蒸气气化条件下钾的迁移行为研究

doi: 10.1016/S1872-5813(22)60005-7

韦兵^{1, 2,},
陈倩^{1, 2},
王伟成^{1, 2},
张万祥¹,
陶睿旻¹,
窦艺帆¹,
王兴军^{1, 2, ,}

1.
华东理工大学资源与环境工程学院, 上海 200237
2.
上海市煤气化工程技术研究中心, 上海 200237

基金项目: 国家自然科学基金（U21A20319）资助

详细信息

通讯作者:
Tel: 021- 64250192, E-mail: wxj@ecust.edu.cn

中图分类号: TQ54
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出版历程
- 收稿日期: 2021-12-31
- 修回日期: 2022-02-23
- 录用日期: 2022-02-28
- 网络出版日期: 2022-03-08
- 刊出日期: 2022-08-26

Migration behavior of potassium under condition of steam gasification of Yulin coal

WEI Bing^{1, 2
,},
CHEN Qian^{1, 2},
WANG Wei-cheng^{1, 2},
ZHANG Wan-xiang¹,
TAO Rui-min¹,
DOU Yi-fan¹,
WANG Xing-jun^{1, 2
, ,}

1.
School of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
Shanghai Engineering Research Center of Coal Gasification, Shanghai 200237, China

Funds: The project was supported by the National Natural Science Foundation of China (U21A20319)

More Information

Corresponding author: Tel: 021- 64250192, Email: wxj@ecust.edu.cn

摘要

摘要: 本研究利用固定床反应装置、原子吸收光谱、X射线衍射法(XRD)考察负载碳酸钾的榆林煤(ZA-K)、负载碳酸钾的榆林脱灰煤(ZA-THK)、负载碳酸钾的模拟灰(采用SiO₂、Al₂O₃、CaO、Fe₂O₃四种氧化物配置)气化反应后的钾迁移行为，采用傅里叶红外光谱、拉曼光谱，探究ZA-K及ZA-THK在热解过程中的结构演变对钾迁移行为的影响；实验结果表明，温度越高，气化反应残渣中水溶性钾回收效率越低；三次水洗可以回收总水溶性钾的94.06%−98.80%；不溶性钾的生成是因为钾与煤灰中硅铝生成钾的硅铝酸盐物相；ZA-THK比ZA-K中的钾在气化反应过程中更容易挥发，在700−850 ℃下，ZA-THK中的钾挥发比ZA-K高出10.28%−44.92%。主要原因是ZA-K中的灰分会将负载的钾固定在煤灰中；也是酸洗脱灰使煤的芳香聚合度降低，煤中出现更多的小环芳香结构(2−8环)。
- 催化气化 /
- 钾的迁移行为 /
- 回收效率
Abstract: A fixed bed reactor and atomic absorption spectroscopy were used to investigate potassium recovery efficiency of Yulin coal loaded with potassium carbonate (ZA-K), Yulin demineralized coal loaded with potassium carbonate (ZA-THK) and synthetic ash (Configurations of four oxides: SiO₂, Al₂O₃, CaO, Fe₂O₃) loaded with potassium carbonate after reaction. Fourier infrared spectroscopy and Raman spectroscopy were used to study influence of structural evolution of ZA-K and ZA-THK on migration of potassium during pyrolysis. The results show that the yield of water-soluble potassium decreases with increasing temperature. Three times water washing could recover 94.06%−98.80% of the total water-soluble potassium. Formation of insoluble potassium is due to the phase of potassium aluminosilicate formed by potassium, silicon and aluminum in the coal ash. Potassium is easier to volatilize from ZA-THK than that from ZA-K. At 700−850 ℃ potassium in ZA-THK is volatilized 10.28%−44.92% higher than that of ZA-K, resulting from that the ash in ZA-K would fix the loaded potassium in coal ash. Another reason may be caused by decrease in the degree of aromatic polymerization of ZA-THK through demineralization process, leading to more small-ring aromatic structures (2−8 rings) appearing in the coal.
- catalytic gasification /
- migration behavior of potassium /
- recovery efficiency

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FIG. 1763. FIG. 1763.

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图 1 实验流程示意图

Figure 1 Experimental flow diagram

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图 2 ZA和ZA-TH的傅里叶红外光谱谱图

Figure 2 FT-IR spectra of sample ZA and ZA-TH

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图 3 ZA-TH的红外拟合谱图

Figure 3 Curve-fitting FT-IR spectrum of ZA-TH

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图 4 不同温度下ZA-K与SYA-K的水洗次数与水溶性钾回收效率的关系

Figure 4 Relationship between washing times of ZA-K，SYA-K and the yield of water-soluble potassium at different temperatures

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图 5 三次水洗下可溶性钾的回收效率（η_1-3）占总水溶性钾（η_1-5）的百分比

Figure 5 Recovery efficiency of soluble potassium (η_1-3) as a percentage of the total water-soluble potassium (η_1-5) under three washings

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图 6 不同温度下ZA-K与SYA-K的水溶性钾总回收效率与不溶性钾回收效率

Figure 6 Total recovery efficiency of water-soluble potassium and the recovery efficiency of insoluble potassium of ZA-K and SYA-K at different temperatures

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图 7 800 ℃下ZA-K、SYA-K与SYA-K（Air）的XRD谱图

Figure 7 XRD patterns of ZA-K, SYA-K and SYA-K(Air) at 800 °C

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图 8 ZA-K、ZA-THK、SYA-K反应后钾的挥发量以及SYA-K-Factsage模拟

Figure 8 Volatilization of potassium in ZA-K, ZA-THK, SYA-K and after reactions and the results of SYA-K-Factsage simulation

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图 9 ZA-K（a）和ZA-THK（b）在不同温度下热解的拉曼光谱谱图

Figure 9 Raman spectra of ZA-K (left) and ZA-THK (right) pyrolysis at different temperatures

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图 10 ZA-THK 在600 ℃下热解的拉曼谱图分峰拟合

Figure 10 Raman spectrum curve-fitting of ZA-THK pyrolysis at 600 ℃

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图 11 不同热解温度下ZA-K和ZA-THK的I_D/I_G、I_D/$I_{({\rm{G}}_{\rm{R}}+{\rm{V}}_{\rm{R}}+{\rm{V}}_{\rm{L}})}$、I_S/I_G

Figure 11 I_D/I_G, I_D/$I_{({\rm{G}}_{\rm{R}}+{\rm{V}}_{\rm{R}}+{\rm{V}}_{\rm{L}})}$, I_S/I_G ratio of ZA-K and ZA-THK at different pyrolysis temperature

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图 12 煤热解和气化过程中钾迁移机理

Figure 12 Potassium migration mechanism diagram during pyrolysis and gasification

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表 1 ZA和ZA-TH的工业分析及元素分析

Table 1 Proximate and ultimate analyses of ZA and ZA-TH

Sample	Proximate analysis w_d/%			Ultimate analysis w_daf/%
Sample	A	V	FC	C	H	O^*	N	S
ZA	10.96	37.29	51.75	67.85	5.13	24.52	0.84	1.66
ZA-TH	1.44	29.58	68.98	66.76	5.43	25.60	0.63	1.58
*: by difference; d-dry basis；daf-dry and ash free basis

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表 2 ZA的灰成分分析

Table 2 Ash composition of ZA

Sample	SiO₂	Al₂O₃	CaO	Fe₂O₃	MgO	K₂O
w/%	48.88	19.21	12.19	9.87	1.61	1.80

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表 3 SYA的化学组成

Table 3 Chemical composition of SYA

Sample	SiO₂	Al₂O₃	CaO	Fe₂O₃
w/%	54.22	21.31	13.52	10.95

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表 4 ZA-TH的红外光谱拟合峰参数

Table 4 Infrared spectrum fitting peak parameters of ZA-TH

Peak#	Center/cm⁻¹	Hight	Width/cm⁻¹	Assignment	Area
1	3403.1	0.0027	97.2	stretching vibration of hydrogen-bond	0.2745
2	3318.3	0.0118	127.8	stretching vibration of −OH, −NH	1.6069
3	3217.3	0.0062	88.5	stretching vibration of hydrogen-bond	0.5799
4	3157.5	0.0040	81.7	stretching vibration of hydrogen-bond	0.3495
5	3040.9	0.0022	56.3	stretching vibration of CH in aromatic structures	0.1305
6	2955.0	0.0092	25.2	asymmetric stretching vibration of CH₃	0.2464
7	2923.4	0.0221	29.8	stretching vibration of CH in alkanes	0.7005
8	2896.5	0.0174	39.0	stretching vibration of CH in alkanes	0.7227
9	2849.4	0.0186	40.0	symmetric stretching vibration of CH₂ in alkanes	0.7892
10	1727.9	0.0128	35.8	stretching vibration of C=O in conjugated esters	0.4869
11	1697.6	0.0277	30.4	stretching vibration of C=O in carboxylic acids	0.8960
12	1592.9	0.0801	72.3	stretching vibration of C=C in aromatic rings	6.1682
13	1434.8	0.0190	46.2	asymmetric deformation vibration of CH₃	0.9361
14	1375.0	0.0044	16.8	asymmetric stretching vibration of C−O−C in aromatic ethers	0.0784
15	1255.5	0.0165	79.3	stretching vibration of C−OH in phenols	1.3938
16	1188.0	0.0354	112.6	stretching vibration of C−OH in phenols	4.2467
17	881.7	0.0040	15.6	out-of-plane deformation vibration of =C−H in aromatic structures with isolated aromatic hydrogens (1H)	0.0655
18	869.2	0.0046	9.1	out-of-plane deformation vibration of =C−H in aromatic structures with isolated aromatic hydrogens (1H)	0.0447
19	857.1	0.0035	11.9	out-of-plane deformation vibration of =C−H in aromatic structures with two adjacent hydrogens per ring (2H)	0.0442
20	839.0	0.0022	7.2	out-of-plane deformation vibration of =C−H in aromatic structures with two adjacent hydrogens per ring (2H)	0.0172
21	824.5	0.0019	5.4	out-of-plane deformation vibration of =C−H in aromatic structures with two adjacent hydrogens per ring (2H)	0.0108
22	813.9	0.0088	27.4	out-of-plane deformation vibration of =C−H in aromatic structures with three adjacent hydrogens per ring (3H)	0.2558
23	749.8	0.0115	27.1	out-of-plane deformation vibration of =C−H in aromatic structures with three adjacent hydrogens per ring (3H)	0.3319
24	720.3	0.0017	13.2	plane swing vibration of alkane (CH₂)_n ≥ 4	0.0236

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表 5 ZA和ZA-TH的红外结构参数

Table 5 Infrared structure parameters of ZA and ZA-TH

Sample	ƒ_a	A(CH₂)/A(CH₃)	I	‘C’	DOC
ZA	0.945	4.612	0.235	0.202	0.146
ZA-TH	0.946	2.843	0.323	0.183	0.128

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