二氧化碳和水气氛对高钠煤转化过程中钠迁移的影响

骆安琪; 朱平; 张建树; 曲旋; 张荣; 毕继诚; 张金利

二氧化碳和水气氛对高钠煤转化过程中钠迁移的影响

骆安琪¹,
朱平¹,
张建树^1, ,,
曲旋²,
张荣²,
毕继诚²,
张金利^{1, 3}

1.
石河子大学化学化工学院新疆兵团化工绿色过程重点实验室省部共建国家重点实验室培育基地, 新疆石河子 832003
2.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
3.
天津大学化工学院, 天津 300072

基金项目:

国家自然科学基金 21566033

国家自然科学基金 U1703253

详细信息

中图分类号: TQ530.2
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- 被引次数: 0
出版历程
- 收稿日期: 2018-01-18
- 修回日期: 2018-03-28
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-05-10

Effect of atmosphere on sodium migration during conversion of high sodium coals

1.
School of Chemistry and Chemical Engineering, Key Laboratory for Green Process of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, Shihezi 832003, China
2.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Funds:

the National Natural Science Foundation of China 21566033

the National Natural Science Foundation of China U1703253

More Information

Corresponding author: ZHANG Jian-shu, E-mail: zjschem@163.com

摘要

摘要: 对新疆的两种高钠煤（伊犁煤YL、呼图壁煤HTB）进行了N₂、CO₂和H₂O气氛和不同温度下钠迁移的研究。采用逐级萃取和湿法消解法确定了原煤、半焦中钠的赋存形态，定量研究了两种煤中钠的挥发及迁移规律。结果表明，YL煤的形态钠中水溶钠占80.08%，HTB煤的形态钠中不溶钠占61.54%。不同气氛下，升高温度都可促进两种煤中钠的挥发，半焦中水溶钠比例减小，醋酸铵可溶钠比例会出现先增加后减少现象，盐酸可溶钠比例呈增加趋势。对于YL煤，CO₂气氛可抑制钠的挥发，H₂O蒸气可促进钠的挥发；900℃时，YL煤CO₂气氛下钠挥发仅为N₂气氛下的50.25%，而H₂O气氛钠挥发为N₂气氛下的111.45%。对于HTB煤，CO₂气氛也可抑制钠的挥发，900℃时CO₂气氛下钠挥发为N₂气氛的80.91%；HTB煤在H₂O蒸气下，800℃之前钠挥发高于N₂，当900℃时，钠挥发略低于N₂气氛。YL煤形态钠中以水溶钠为主，其挥发的同时会向盐酸可溶钠及不溶钠转变。而HTB煤形态钠中以不溶钠为主，其次是水溶钠，CO₂和H₂O气氛能促进不溶钠向其他可溶态钠转变。
- 钠金属 /
- 迁移 /
- 萃取 /
- 热解 /
- 气化
Abstract: The sodium release and transformation of Yili (YL) and Hutubi (HTB) coal were examined at different temperatures under N₂, CO₂ and H₂O atmospheres. By using sequential extraction and wet digestion separately, the occurrence mode and content of sodium in raw coal and chars were measured. The migration of sodium in two coals was studied qualitatively and quantitatively. The results show that water soluble sodium in YL coal accounts for 80.08%, while in HTB, insoluble sodium is 61.54%. The volatilization of sodium in two coals increases with increasing temperature. Water soluble sodium in semi coke shows a decrease trend; ammonium acetate soluble sodium increases and then decreases; hydrochloric acid soluble sodium exhibits an increasing tendency. For YL volatilization of sodium is inhibited by CO₂ while it is promoted by H₂O compared with N₂. At 900℃ volatilization of sodium under CO₂ and H₂O is 50.25% and 111.45%, respectively, of that under N₂. CO₂ atmosphere can inhibit volatilization of sodium in HTB. At 900℃ volatilized sodium under CO₂ is 80.91% of that under N₂. In H₂O atmosphere, volatilization of sodium is higher than that in N₂ before 800℃ and slightly lower than that in N₂ at 900℃. The predominant sodium in YL coal is water soluble which volatilized during increasing temperature and transformed to hydrochloric acid soluble and insoluble sodium simultaneously. While for HTB, insoluble sodium is the dominant occurrence mode, followed by water soluble one. CO₂ and H₂O can promote transformation of insoluble sodium to soluble one in HTB coal.
- sodium /
- migration /
- extraction /
- pyrolysis /
- gasification

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图 1 固定床反应器实验示意图

Figure 1 Schematic diagram of the fixed bed reactor

1: gas cylinder; 2: flowmeter; 3: tube furnace; 4: temperature control; 5: absorption bottle; 6: coil; 7: absorption bottle; 8: cold trap

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图 2 YL和HTB煤灰的XRD谱图

Figure 2 XRD patrerns of YL and HTB coals ash

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图 3 N₂气氛下YL煤焦不同温度下钠的存在形式

Figure 3 Variation of occurrence modes of sodium as YL coal chars devolatilized in N₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

图 4 CO₂气氛下YL煤焦不同温度下钠的存在形式

Figure 4 Variation of occurrence modes of sodium as YL coal chars devolatilized in CO₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

图 5 H₂O气氛下YL煤焦不同温度下钠的存在形式

Figure 5 Variation of occurrence modes of sodium as YL coal chars devolatilized in 80% H₂O+20% N₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

图 6 N₂气氛下HTB煤焦不同温度下钠的存在形式

Figure 6 Variation of occurrence modes of sodium as HTB coal chars devolatilized in N₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

图 7 CO₂气氛下HTB煤焦不同温度下钠的存在形式

Figure 7 Variation of occurrence modes of sodium as HTB coal chars devolatilized in CO₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

图 8 H₂O气氛下HTB煤焦不同温度下钠的存在形式

Figure 8 Variation of occurrence modes of sodium as HTB coal chars devolatilized in 80% H₂O+20% N₂ atmosphere at different temperatures

(a): content of various sodium forms in chars; (b): fraction of various sodium forms in chars
: H₂O soluble; : NH₄AC soluble; : HCl soluble; : insoluble; : volatilized

下载: 全尺寸图片幻灯片

表 1 YL和HTB煤的工业分析和元素分析

Table 1 Proximate and ultimate analysis of YL and HTB

Sample	Proximate analysis w/%			Ultimate analysis w_daf /%
Sample	M_ad	A_d	V_daf	C	H	O^*	N	S
YL	10.55	9.30	30.02	67.61	4.28	25.70	1.11	1.30
HTB	2.67	6.12	30.46	76.62	4.37	17.71	0.97	0.33
^*：by difference

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表 2 YL和HTB煤的灰成分分析

Table 2 Composition of coal ash

Sample	Composition w/%
Sample	Al₂O₃	CaO	Fe₂O₃	K₂O	MgO	Na₂O	P₂O₅	SO₃	TiO₂	SiO₂
YL	13.23	9.95	12.56	2.91	2.81	2.93	0.05	10.50	0.48	44.43
HTB	13.73	22.17	8.60	3.09	4.81	4.10	0.12	1.88	0.63	39.34

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表 3 原煤中钠的存在形式

Table 3 Modes of occurrence of sodium in raw coal

Sample	Total sodium w/(μg·g^-1)	H₂O soluble/%	NH₄AC soluble/%	HCl soluble/%	Insoluble/%
YL coal	1900.63	80.08	6.63	5.84	7.45
HTB coal	1746.98	27.91	4.83	5.72	61.54

下载: 导出CSV

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