苏鲁豫皖四省毗邻地区天然焦特征及燃烧特性

秦云虎; 王双美; 朱士飞; 吴国强; 权巨涛; 毛礼鑫

doi:10.12363/issn.1001-1986.21.09.0501

苏鲁豫皖四省毗邻地区天然焦特征及燃烧特性

1.
江苏地质矿产设计研究院，江苏徐州 221006
2.
中国煤炭地质总局，北京 100038
3.
中国煤炭地质总局第一勘探局，河北邯郸 056004

基金项目: 中国地质调查局地质调查标准修订与升级推广工作子项目(12120115053401)；徐州市科技局重点研发计划专项(KC21147)

详细信息

作者简介:
秦云虎，1962年生，男，江苏无锡人，教授级高级工程师，从事煤田地质勘查、科研及岩土工程勘察工作.E-mail：1403270328@qq.com

中图分类号: P618.11；TD98
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出版历程
- 收稿日期: 2021-09-13
- 修回日期: 2021-11-14
- 网络出版日期: 2022-05-06
- 发布日期: 2022-05-24

Specific properties and combustion characteristics of natural coke from adjacent areas of Jiangsu, Shandong, Henan and Anhui provinces

1.
Jiangsu Design Institute of Geology for Mineral Resources, Xuzhou 221006, China
2.
China National Administration of Coal Geology, Beijing 100038, China
3.
First Exploration Bureau, China National Administration of Coal Geology, Handan 056004, China

摘要

摘要: 碳达峰碳中和背景下提高资源利用效率尤为重要，然而天然焦长久以来并未得到应有的重视。我国天然焦资源丰富，在苏鲁豫皖四省毗邻地区的煤矿开采中经常发现由于岩浆岩侵入，煤层受到烘烤而变质为天然焦的现象。广泛采集苏鲁豫皖四省毗邻地区天然焦样品，在描述天然焦宏观及显微特征的基础上，对天然焦开展工业分析、地球化学特征、自燃倾向性和焦尘爆炸性等方面的测试与分析，采用美国TA2100热分析仪测试典型样品的燃烧特性。结果表明：天然焦的宏观物理特性、显微组分特性与煤具有明显的差异性；总体上各项分析指标与无烟煤没有明显的界线，天然焦与同地的残留煤相比，其挥发分产率降低、C/H比大幅提高；天然焦变质程度达到或高于无烟煤阶段，不易自燃、焦尘无爆炸性。燃烧特性测试结果表明山东菏泽赵楼天然焦样品具有较强的反应活性，并根据天然焦的特性探讨了利用方向，认为其在制作型煤、合成氨、碳材料、生产水泥以及CO₂地质封存等方面具有利用价值或潜力。
- 天然焦特征 /
- 燃烧特性 /
- 煤岩学 /
- 微量元素
Abstract: It is particularly important to improve resource utilization efficiency against the background of carbon peak and carbon neutrality, but the natural coke has not been paid enough attention for a long time. The natural coke is abundant in China and is often found in the mining of coal mines in neighboring areas of Shandong, Henan and Anhui provinces. Due to the intrusion of magmatic rock, the original coal seam is baked and transformed into natural coke. In this study, samples of natural coke from various areas were collected to study its macroscopic and microscopic characteristics. The industrial analysis, geochemical parameters, spontaneous combustion tendency and coke dust explosive were studied. At the same time, typical samples were selected to analyze the combustion characteristics by American TA2100 thermal analyzer. The results show that the macroscopic physical properties and maceral properties of natural coke are obviously different from those of coal. On the whole, there is no obvious boundary about the analysis indexes of natural coke and anthracite. The index of volatile yield and C/H values for natural coke and the residual coal in the same place is significantly decreased by the former, and greatly increased by the latter. The metamorphic degree of natural coke is generally reached or higher than that of anthracite, and it is not easy to spontaneous combustion with its coke dust non-explosive. The analysis of combustion characteristics shows that the natural coke sample has strong reactivity. Furthermore, the utilization direction of natural coke was discussed according to its characteristics, and there is value or potential in the production of briquette, ammonia synthesis, carbon materials, cement production and CO₂ geological storage.
- characteristic of natural coke /
- combustion characteristic /
- coal petrology /
- trace element

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图 1 天然焦样品照片

Fig. 1 Photographs of the selected samples

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图 2 天然焦中的石墨小球体和显微片状结构

Fig. 2 Graphite spherules and microflake structure in the natural coke

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图 3 天然焦样品元素组成测试结果

Fig. 3 Test results of elemental composition of the selected samples

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图 4 天然焦样品与中国煤的有害元素和微量元素对比

Fig. 4 Content of harmful elements and trace elements in natural coke and Chinese coal

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图 5 天然焦样品密度与反射率

Fig. 5 Density and reflectance of natural coke

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图 6 天然焦燃烧TG−DTG曲线

Fig. 6 The TG-DTG curves of the selected natural coke

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表 1 天然焦样品煤质分析测试结果

Table 1 Test results of natural coke samples

样品编号	勘探地区	煤层	采样深度/m	工业分析ω/%				焦渣 (1—8)	全水 ω(M_t) /%	全硫 ω(S_t,d)/%	各种形态硫ω/%			Q_gr,d/ (MJ∙kg⁻¹)
样品编号	勘探地区	煤层	采样深度/m	水分M_ad	灰分A_d	挥发分 V_daf	固定碳FC_d	焦渣 (1—8)	全水 ω(M_t) /%	全硫 ω(S_t,d)/%	S_p,d	S_s,d	S_o,d	Q_gr,d/ (MJ∙kg⁻¹)
1	江苏孔庄煤矿	7	831.6	1.49	20.87	16.11	66.38	2		0.63	0.25	0	0.38	26.49
2	安徽淮北金石	3	415.0	3.19	16.38	6.39	78.28	1	4.62	0.38	0.09	0	0.29	27.91
3	山东官桥夏庄煤矿	3	425.0	4.38	8.28	6.42	85.83	1		0.97	0.20	0.02	0.75	30.81
4	安徽淮北金石	3	676.0	3.24	13.70	5.89	81.21	2		0.41				28.65
5	河南永城新桥	二₂	454.0	1.94	15.79	8.45	77.10	2	8.49	1.94	0.70	0.02	1.22	27.32
6	山东微山昭阳	3_上	410.0	2.45	15.13	5.42	80.27	2	5.99	0.99	0.66	0.02	0.31	28.09
7	安徽关帝庙勘探区	10	985.0	1.30	19.21	6.06	75.90	1	2.81	0.47	0.26	0.02	0.19	26.00
8	山东菏泽赵楼	3_下	910.0	2.28	15.93	5.99	79.03	2	2.37	0.28	0.18	0.02	0.07	26.90
9	河南车集煤矿	二₂	784.0	1.80	19.94	8.46	73.29	1	1.97	0.14	0.10	0.01	0.03	25.24
10	山东菏泽赵楼	3_上	910.0	3.14	12.30	5.96	82.48	2	3.30	0.31	0.19	0.02	0.10	28.67

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表 3 样品灰熔融性测试结果

Table 3 Results of fusibility of sample ash 单位：℃

样品编号	DT	ST	HT	FT
2	1 360	1 420	>1 500	>1 500
3	>1 500	>1 500	>1 500	>1 500
4	1 380	1 440	>1 500	>1 500
5	1 280	1 300	1 310	1 320
6	1 260	1 300	1 320	1 340
7	1 240	1 250	1 260	1 270
8	1 220	1 240	1 250	1 260
9	1 240	1 250	1 260	1 270
10	1 230	1 240	1 270	1 280

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表 2 样品灰成分测试结果

Table 2 Test results of ash composition of the selected samples

样品编号	灰成分ω/%										碱酸比
样品编号	K₂O	Na₂O	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	SO₃	TiO₂	MnO₂	碱酸比
1	0.68	0.52	42.58	29.04	4.53	7.78	4.83	6.09	1.26	0.050	0.252
2	3.43	0.90	44.32	34.78	3.34	3.47	1.42	1.54	2.29	0.010	0.154
3	2.08	0.69	47.52	37.49	4.92	1.42	1.02	0.65	1.23	0.009	0.117
4	2.74	0.76	46.42	33.08	8.04	1.90	1.29	1.10	1.77	0.096	0.181
5	1.94	0.92	26.86	20.54	5.71	24.38	1.52	14.61	0.60	0.656	0.718
6	1.17	0.78	47.42	25.33	10.66	4.33	1.50	4.25	1.73	0.179	0.248
7	2.16	1.32	43.21	27.24	12.08	4.70	3.74	2.78	1.66	0.140	0.333
8	1.54	1.36	35.03	26.71	6.17	17.55	2.81	3.88	2.19	0.201	0.460
9	0.68	0.71	42.16	21.58	5.85	20.04	3.32	2.85	0.84	0.148	0.474
10	0.68	1.94	28.62	24.32	8.02	23.38	3.27	5.82	1.79	0.296	0.681
烟煤^[20]	0.68~ 3.52	0.57~ 2.57	39.10~ 59.88	19.77~34.65	1.81~14.88	0.57~ 10.11	0.45~3.29	2.39~19.89	1.13~2.49

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表 4 天然焦自燃倾向性和焦尘爆炸性测试结果

Table 4 Results of spontaneous combustion tendency and coke dust explosive of natural coke

样品编号	自燃倾向		焦尘爆炸
样品编号	吸氧量/ (cm³∙g⁻¹)	自燃等级 (Ⅰ/Ⅱ/Ⅲ)	火焰长度/ mm	岩粉质量分数/%	有无爆炸
2	0.87	Ⅲ	无火	0	无
3	0.60	Ⅲ	无火	0	无
5	0.90	Ⅲ	无火	0	无
6	0.48	Ⅲ	无火	0	无
7	0.50	Ⅲ	无火	0	无
8	0.37	Ⅲ	无火	0	无
9	0.44	Ⅲ	无火	0	无
10	0.42	Ⅲ	无火	0	无

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表 5 测试结果及学者研究结果^[26-28]

Table 5 Test results of the selected natural coke and previous studies

样品	着火温度/ K	燃尽温度/ K	燃烧峰温/ K	最大失重速率/ (%∙min⁻¹)	S/ (10⁻¹¹ K ⁻³∙min⁻²)	R_w/ min⁻¹	活化能E/(kJ∙mol⁻¹)
天然焦	763	1 023	844	4.55	8.44	2.73	97.25
煤泥^[26]	720	843	777	7.10	0.83	1.63	248.50
油页岩^[27]				2.95	6.40
原煤1^[26]	709	812	763	13.30	2.14	1.69	109.10
原煤2^[27]				13.90	160.00
原煤3^[28]	609	871	678	9.43	8.92		44.07
原煤4^[28]	693	1 026	794	5.93	2.03		55.90

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