吡啶萃取对烟煤热解过程焦油生成特性的影响

LUO An-qi; ZHANG Dan; ZHU Ping; QU Xuan; ZHANG Jin-li; ZHANG Jian-shu

吡啶萃取对烟煤热解过程焦油生成特性的影响

骆安琪¹,
张丹¹,
朱平¹,
曲旋²,
张金利^{1, 3},
张建树^1, ,

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, 煤炭转化重点实验室, 山西太原 030001
3.
天津大学化工学院, 天津 300072

基金项目:

the National Natural Science Foundation of China 21566033

the National Natural Science Foundation of China 21106087

the Start-Up Foundation for Young Scientists of Shihezi University rczx201013

详细信息

中图分类号: TQ530.2
计量
- 文章访问数: 74
- HTML全文浏览量: 24
- PDF下载量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2017-06-14
- 修回日期: 2017-09-22
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-11-10

Effect of pyridine extraction on the tar characteristics during pyrolysis of bituminous coal

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 21106087

the Start-Up Foundation for Young Scientists of Shihezi University rczx201013

More Information

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

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).

摘要

摘要: 煤中含有以非共价键结合的可萃取物，煤的萃取物和萃余物热解反应性不同。本研究首先用醋酸消除煤中静电作用力，再以吡啶萃取消除氢键作用力，通过热重和固定床研究了煤萃取物和萃余物的热解特性。相对于原煤，萃取物（E1）的H/C原子比较高，而萃余物（R1）比原煤的孔径有所增大。热重实验表明，萃取物热分解温度低，失重率大；萃余物在485℃之前失重大于原煤，温度高于485℃小于原煤。固定床氮气热解表明，萃取物（E1）的焦油产率和气体比原煤高；萃余物（R1）的焦油产率低于原煤焦油产率。而氢气气氛下，萃取残渣的焦油产率明显高于原煤，这是由于吡啶萃余物具有更开放的孔结构，有利于加氢热解过程氢向孔内扩散，减少了缩聚反应。
- 煤 /
- 萃取 /
- 热解 /
- 焦油 /
- 非共价键
Abstract: Extensive research has shown that coal has an extractable small molecular compound, which was associated with non-covalent bonding coal molecules. In addition, the reactivity of coal extract and residue is different. In this work, a bituminous coal was acid washed and extracted by pyridine to destroy the electrostatic interactions and hydrogen bonds. The pyrolysis behavior of the extracts and residue was studied by thermogravimetry (TG) and a fixed bed reactor. The H/C atomic ratio for the pyridine extract was significantly higher than that of raw coal, indicating hydrogen-rich components. The pyridine extract (E1) gave a higher tar yield of 44.41%, as well as more gas, while the tar yield of residue (R1) was lower than raw coal in an N₂ atmosphere. However, the residue gave more than two times the amount of tar under H₂ than that of N₂ because developed porous structure was formed by pyridine extraction, which would facilitate hydrogen diffusion into the pore structure and reduce the polycondensation reaction.
- coal /
- extraction /
- pyrolysis /
- tar /
- non-covalent bonding
本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).
注释:

HTML全文

Figure 1 Relation between n-alkane retention time and carbon number by GC

下载: 全尺寸图片幻灯片

Figure 2 Carbon number distribution of HS

下载: 全尺寸图片幻灯片

Figure 3 Thermogravimetric of coal and coal-derived materials

下载: 全尺寸图片幻灯片

Figure 4 Tar and char yields of coal and coal-derived materials

下载: 全尺寸图片幻灯片

Figure 5 The gas volume of coal and coal-derived materials

下载: 全尺寸图片幻灯片

Figure 6 Proportion of maltene and asphaltene in tar

: maltene; : asphaltene

下载: 全尺寸图片幻灯片

Figure 7 Pyrolysis products of sample under N₂ at different temperatures

下载: 全尺寸图片幻灯片

Figure 8 Pyrolysis products of sample under H₂ at different temperatures

下载: 全尺寸图片幻灯片

Table 1 Proximate and ultimate analyses of SHZ coal sample

Coal sample	Proximate analysis w_ad/%				Ultimate analysis w_daf/%
Coal sample	M	A	V	F	C	H	N	S	O
SHZ coal	3.07	5.63	32.99	58.31	79.94	4.76	1.25	0.41	13.64

下载: 导出CSV

Table 2 Yield of each fraction obtained from solvent extracts

Sample	Extract fraction w_daf/%
Sample	HS	TS	TI
E1	25.57	61.30	13.13

下载: 导出CSV

Table 3 Ultimate analyses of raw coal, extracts and residues

Coal sample	Ultimate analysis w_daf/%					Atomic ratio
Coal sample	C	S	H	N	O^a	H/C	O/H
Raw coal	79.94	0.41	4.76	1.25	13.64	0.71	0.14
AC	78.54	0.27	4.60	1.20	15.39	0.70	0.15
R1	79.03	0.23	4.65	2.00	14.09	0.70	0.13
E1	81.17	0.26	6.95	1.28	10.34	1.02	0.10
^a: by difference

下载: 导出CSV

Table 4 Porous structure of raw coal, AC and R1

Analysis item		Raw coal	AC	R1
BET	surface area A/(m²·g^-1)	0.90	0.69	0.10
	pore size d/nm	12.80	15.69	60.63
MIP	pore area A/(m²·g^-1)	7.30	7.23	7.03
	intrusion volume v/(mL·g^-1)	0.70	0.70	0.78
	average pore diameter d/nm	38.14	38.77	44.23
	porosity /%	49.76	49.95	51.99
	Iodine numbers	70.2	60.2	192.0

下载: 导出CSV

参考文献(22)

[1]	AMIN M N, LI Y, LU X, ZHANG S. In situ catalytic pyrolysis of low rank coal for the conversion of heavy oils into light oils[J]. Adv Mater Sci Eng, 2017, 2017:1-8 https://www.hindawi.com/journals/amse/2017/5612852/
[2]	ZOU L, JIN L J, WANG X, HU H. Pyrolysis of Huolinhe lignite extract by in-situ pyrolysis-time of flight mass spectrometry[J]. Fuel Process Technol, 2015, 135:52-59. doi: 10.1016/j.fuproc.2014.10.011
[3]	GIVEN P H. The distribution of hydrogen in coals and its relation to coal structure[J]. Fuel, 1960, 39(7):147-153.
[4]	GIVEN P H, MARZEC A, BARTON W A, LYNCH L J, GERSTEIN B C. The concept of a mobile or molecular phase within the macromolecular network of coals:A debate[J]. Fuel, 1986, 65(2):155-163. doi: 10.1016/0016-2361(86)90001-3
[5]	NISHIOKA M. The associated molecular nature of bituminous coal[J]. Fuel, 1992, 71(8):941-948. doi: 10.1016/0016-2361(92)90246-K
[6]	CODY G D, DAVIS A, HATCHER P G. Physical structural characterization of bituminous coals:Stress-strain analysis in the pyridine-dilated state[J]. Energy Fuels, 1993, 7(4):455-462. doi: 10.1021/ef00040a003
[7]	CODY G D, DAVIS A, HATCHER P G. The dynamic nature of coal's macromolecular structure:Viscoelastic analysis of solvent-swollen coals[J]. Energy Fuels, 1993, 7(4):463-468. doi: 10.1021/ef00040a004
[8]	PANT L M, HUANG H, SECANELL M, LARTER S, MITRA S K. Multi scale characterization of coal structure for mass transport[J]. Fuel, 2015, 159:315-323. doi: 10.1016/j.fuel.2015.06.089
[9]	PAN J, LV M, BAI H, HOU Q, LI M. Effects of metamorphism and deformation on the coal macromolecular structure by laser Raman spectroscopy[J]. Energy Fuels, 2017, 31(2):1136-1146. doi: 10.1021/acs.energyfuels.6b02176
[10]	ⅡNO M. Network structure of coals and association behavior of coal-derived materials[J]. Fuel Process Technol, 2000, 62(2):89-101. doi: 10.1007/s00216-010-4328-x
[11]	SUZUKI M, NORINAGA K, ⅡNO M. Macroscopic observation of thermal behavior of concentrated solution of coal extracts[J]. Fuel, 2004, 83(16):2177-2182. doi: 10.1016/j.fuel.2004.06.006
[12]	HE W, LIU Z, LIU Q, SHI L, SHI X. Behavior of radicals during solvent extraction of three low rank bituminous coals[J]. Fuel Process Technol, 2017, 156:221-227. doi: 10.1016/j.fuproc.2016.10.029
[13]	LI Z K, WEI X Y, YANG Z S, YAN H L, WEI Z H. Characterization of extracts from geting bituminous coal[J]. Anal Lett, 2015, 48(9):1494-1501. doi: 10.1080/00032719.2014.989529
[14]	KIM K, CHO H, LEE S, MUN M, LEE D. Coal and solvent properties and their correlation with extraction yield under mild conditions[J]. Korean J Chem Eng, 2016, 33(7):2142-2159. doi: 10.1007/s11814-016-0062-1
[15]	AND D L W, SMITH E R. On the molecular-level interactions between pittsburgh No. 8 coal and several organic liquids[J]. Energy Fuels, 2003, 17(6):1423-1428. doi: 10.1021/ef030076r
[16]	NISHIOKA M, GEBHARD L A, SILBERNAGEL B G. Evidence for charge-transfer complexes in high-volatile bituminous coal[J]. Fuel, 1991, 70(3):341-348. doi: 10.1016/0016-2361(91)90120-Y
[17]	NISHIOKA M. Multistep extraction of coal[J]. Fuel, 1991, 70(12):1413-1419. doi: 10.1016/0016-2361(91)90007-W
[18]	WANG S K, WEI X Y, WANG Y G, ZHAN-KU LI, CHEN Y X. Compositional features of extracts from Shenmu char powder[J]. J Fuel Chem Technol, 2016, 44(1):1-6. doi: 10.1016/S1872-5813(16)30005-6
[19]	LI C, TOSHIMASA TAKANOHASHI A, SAITO I, AND HA, MASHIMO K. Elucidation of mechanisms involved in acid pretreatment and thermal extraction during ashless coal production[J]. Energy Fuels, 2004, 18(1):97-101. doi: 10.1021/ef0340054
[20]	BUSCH A, GENSTERBLUM Y. CBM and CO₂-ECBM related sorption processes in coal:A review[J]. Int J Coal Geol, 2011, 87(2):49-71. doi: 10.1016/j.coal.2011.04.011
[21]	JI H, LI Z, YANG Y, HU S, PENG Y. Effects of organic micromolecules in coal on its pore structure and gas diffusion characteristics[J]. Transport Porous Med, 2015, 107(2):419-433. doi: 10.1007/s11242-014-0446-9
[22]	JI H, LI Z, PENG Y, YANG Y, TANG Y. Pore structures and methane sorption characteristics of coal after extraction with tetrahydrofuran[J]. J Nat Gas Sci Eng, 2014, 19(7):287-294.