载Na胜利褐煤热解过程中氮的迁移转化

郑盼盼; 王永刚; 武欣; 刘宸; 白艳萍; 林雄超

载Na胜利褐煤热解过程中氮的迁移转化

中国矿业大学 (北京) 化学与环境工程学院, 北京 100083

基金项目:

国家自然科学基金 21406261

国家科技支撑计划 2012BAA04B02

详细信息

通讯作者:
王永刚, Tel:010-62339882, E-mail:wyg1960@126.com

中图分类号: TQ541
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- 文章访问数: 100
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- PDF下载量: 10
- 被引次数: 0
出版历程
- 收稿日期: 2016-12-17
- 修回日期: 2017-03-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-04-10

Transformation of nitrogen during pyrolysis of Na-loaded Shengli brown coal

School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

Funds:

the National Natural Science Foundation of China 21406261

the Plan of National Science and Technology Support 2012BAA04B02

摘要

摘要: 采用具有流化床/固定床特征的石英反应器进行不同Na负载量的胜利褐煤热解实验，考察不同Na负载量对煤热解过程中氮迁移的影响。用紫外可见分光光度计分析气相的NH₃和HCN，用X光电子能谱仪（XPS）表征固体半焦中有机氮的存在形式。结果表明，低温热解时，增加Na的含量对煤中氮转化为NH₃起促进作用；高温热解时，Na抑制煤中氮转化为NH₃。Na对煤中氮转化为HCN表现为抑制作用，这种影响规律不随温度而变化。载Na量增加降低半焦氮含量，促进半焦中季氮的生成，但这种影响在低温时不明显。
- 褐煤 /
- 热解 /
- Na /
- 氮
Abstract: The impact of Na content on nitrogen transformation during the pyrolysis of Shengli raw coal and the Na-loaded coal in a fixed-bed/fluidized-bed quartz reactor was investigated. The quantification of NH₃ and HCN in gas product was carried out using an ultraviolet-visible spectrophotometer while the occurrence modes of nitrogen in the solid chars were detected by X-ray photoelectron spectroscopy (XPS). The results indicate that the transformation of coal-N to NH₃ can be catalytically enhanced by certain amount of Na at low temperature. When the final pyrolysis temperature is relatively high, the presence of Na appears to inhibit the formation of NH₃. Meanwhile, for any given pyrolysis temperature, the production of HCN will be suppressed by Na. When the pyrolysis temperature is high, the increase of Na content in coal causes the reduction of nitrogen remaining in char and promotes quaternary nitrogen formation, whereas, the effect is negligible at low temperature.
- brown coal /
- pyrolysis /
- Na /
- nitrogen

HTML全文

图 1 流化床/固定床反应器热解实验装置流程示意图^[18]

Figure 1 Schematic diagram of coal pyrolysis reaction system

1: argon; 2: flow rate controller; 3: coal feeder; 4: coal; 5: electrical furnace; 6: fluidized-bed/fixed-bed reactor; 7: NaOH or H₂SO₄ solution in absorption bottles

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图 2 不同载Na量煤样热解过程中NH₃在升温段和恒温段的分配规律

Figure 2 Distribution of NH₃ at heating stage and constant temperature stage during the pyrolysis of coal with different sodium contents

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图 3 热解过程中煤中氮转化为NH₃的路径示意图

Figure 3 Schematic diagram of coal-N's conversion into NH₃ during pyrolysis

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图 4 不同载Na量煤样热解过程中HCN的生成

Figure 4 Formation of HCN during the pyrolysis of coal with different sodium content

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图 5 热解过程中煤中氮转化为HCN的路径示意图

Figure 5 Schematic diagram of coal-N's conversion into HCN during pyrolysis

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图 6 不同温度下Na含量对半焦氮的影响

Figure 6 Effect of Na contents on the char-N at different temperatures

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图 7 胜利褐煤1 073 K半焦的XPS谱图

Figure 7 XPS spectrum (N 1s) of the char from Shengli brown coal pyrolysis at 1 073 K

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表 1 煤样的工业分析和元素分析

Table 1 Proximate and ultimate analysis of coal samples

Coal sample	Proximate analysis w/%				Ultimate analysis w_daf/%
Coal sample	M_ad	A_d	V_daf	FC_daf	C	H	O^*	N	S
Na0	6.44	8.54	45.93	54.07	60.55	4.66	33.28	0.95	0.56
Na1	6.08	9.73	40.57	59.43	60.38	5.11	32.74	1.18	0.59
Na2	6.30	10.91	41.09	58.91	60.37	4.97	33.04	1.15	0.47
Na3	6.76	11.7	41.39	58.61	59.60	5.01	33.92	1.15	0.44
Na6	13.07	17.77	35.90	64.10	50.64	5.12	42.72	1.10	0.42
^*: by difference；Na0, Na1, Na2, Na3 and Na6 represent coal loaded with 1%Na, 2%Na, 3%Na and 6%Na respectively

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表 2 煤样的碱金属及碱土金属分析

Table 2 Alkali and alkaline earth metal analysis of coal samples

Coal sample	Content w/%
Coal sample	Na	Ca	Mg
Na0	1.51	0.563	0.137
Na1	1.99	0.555	0.280
Na2	3.07	0.660	0.173
Na3	3.85	0.728	0.334
Na6	6.37	0.761	0.347

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表 3 不同氮形态的结合能

Table 3 Binding energy of different nitrogen morphologies

Nitrogen morphology	Binding energy E/eV
Pyridine-N	398.7±0.4
Pyrrole-N	400.5±0.3
Quaternary-N	401.1±0.3

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表 4 不同Na含量煤1 073 K热解半焦中氮官能团的相对含量

Table 4 Distribution (relative percentage) of nitrogen functional groups in chars from pyrolysis of coal with different sodium contents at 1 073 K

Char	Content w/%
Char	N-6	N-5	N-Q
Na0 char	33.43	55.69	10.87
Na1 char	33.59	53.14	13.27
Na2 char	32.84	52.83	14.33
Na3 char	24.82	42.77	32.41

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