加压热解气氛对碳酸钾催化煤热解过程中硫迁移的影响

刘方刚; 张永; 曲旋; 张荣; 毕继诚

加压热解气氛对碳酸钾催化煤热解过程中硫迁移的影响

刘方刚^{1, 2},
张永^{1, 2},
曲旋¹,
张荣¹,
毕继诚^1, ,

1.
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
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金（21576275）和国家重点基础研究发展规划（973计划，2011CB201305）资助

详细信息

通讯作者:
毕继诚, Tel:0531-4072379, E-mail:bijc@sxicc.ac.cn

中图分类号: TQ54
计量
- 文章访问数: 63
- HTML全文浏览量: 25
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2016-05-09
- 修回日期: 2016-08-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

Effects of different atmospheres on sulfur transformation during K₂CO₃ catalytic pressurized pyrolysis of coal

LIU Fang-gang^{1, 2},
ZHANG Yong^{1, 2},
QU Xuan¹,
ZHANG Rong¹,
BI Ji-cheng^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by the National Natural Science Foundation of China (21576275) and the Major State Basic Research Development Program of China (973 program, 2011CB201305)

摘要

摘要: 在加压热解装置上，考察了碳酸钾及热解气氛对煤热解过程中硫分布及其形态的影响。结果表明，碳酸钾通过捕获H₂S增加了半焦硫含量，同时可将煤焦表面活化，导致煤中有机质与黄铁矿分解产生的活泼硫结合形成新的有机硫。氢气能促进煤中硫的脱除，但是碳酸钾存在下热解释放的硫一部分以K₂S的形式固定于半焦中。水蒸气可显著促进煤中黄铁矿的分解，同时可与煤焦中的K₂S反应，降低半焦中的硫含量。两段床催化气化炉中，碳酸钾催化剂经热解后不影响其对煤焦的催化性能。
- 催化加压热解 /
- 碳酸钾 /
- 硫迁移
Abstract: The effects of K₂CO₃ and atmospheres on sulfur distribution and forms during pressurized coal pyrolysis were investigated in a lab-scale reactor. The results show that K₂CO₃ increases the sulfur remained in char by capturing H₂S during coal pyrolysis. The surface of the coal char is activated in the presence of K₂CO₃, and then the nascent sulfur releasing from the pyrite is captured by the organic matrix in coal to form new organic sulfur. Hydrogen shows positive effects on removal of pyrite and organic sulfur, and the released H₂S is partly fixed in char in the form of K₂S when K₂CO₃ was added. The decomposition of pyrite is enhanced in H₂O atmosphere. Meanwhile, K₂S in char can not exist due to effect of water vapour, so the sulfur remained in char is notably reduced. The catalytic property of K₂CO₃ on char gasification is not changed after pyrolysis in two-stage catalytic coal gasifier.
- pressured catalytic pyrolysis /
- potassium carbonate /
- sulfur transformation

HTML全文

图 1 煤催化气化两段炉示意图

Figure 1 Schematic diagram of two-stage pressurized fluidized catalytic coal gasifier

下载: 全尺寸图片幻灯片

图 2 煤加压热解装置示意图

Figure 2 Schematic diagram of the pressurized coal pyrolysis equipment

1: hopper; 2: electric furnace; 3: fixed-bed reactor; 4: thermocouple; 5: flange; 6: steam generator; 7: water storage tank; 8: high-pressure water pump; 9: mass flowmeter; 10: the primary cooler; 11: gas-liquid separator; 12: ethanediol; 13: circulating pump; 14: n-hexane second-stage cooler; 15: quenching trap; 16: micrometering valve; 17: wet type gas flowmeter; 18: gas bag

下载: 全尺寸图片幻灯片

图 3 半焦中水溶性硫化物测定的示意图

Figure 3 Schematic explanation for determination of sulfur forms in pyro-char

下载: 全尺寸图片幻灯片

图 4 不同温度下K₂CO₃对热解产物中硫分布的影响(3.5 MPa)

Figure 4 Effect of K₂CO₃ on sulfur distribution during pyrolysis in different temperatures (3.5 MPa)

下载: 全尺寸图片幻灯片

图 5 氢气对煤热解产物中硫分布的影响

Figure 5 Effect of H₂ on sulfur distribution during pyrolysis of coals

下载: 全尺寸图片幻灯片

图 6 脱无机硫煤样H₂S的逸出曲线

Figure 6 Evolution of H₂S in AP-TPR-MS analysis for de-inorganic-sulfured samples

下载: 全尺寸图片幻灯片

图 7 原煤中有机硫2p的XPS谱图

Figure 7 XPS organic sulfur 2p spectrum from raw coals

下载: 全尺寸图片幻灯片

图 8 煤中黄铁矿微粒的EDS谱图

Figure 8 EDS images showing pyrite grains and particles in coals

(a): BLG; (b): ND

下载: 全尺寸图片幻灯片

图 9 煤中黄铁矿微粒的SEM照片

Figure 9 SEM images showing pyrite grains and particles in coals

(a), (b): BLG; (c), (d): ND

下载: 全尺寸图片幻灯片

图 10 水蒸气对煤热解产物中硫分布的影响

Figure 10 Effect of water vapor on sulfur distribution during pyrolysis of coals

: S in gas; : S in tar; : S in char

下载: 全尺寸图片幻灯片

图 11 混合气氛对煤热解产物中硫分布的影响

Figure 11 Effect of mixed-atmosphere on sulfur distribution during pyrolysis of coals

下载: 全尺寸图片幻灯片

图 12 10%K₂CO₃-宁东煤加氢热解半焦XRD谱图

Figure 12 XRD spectrum of pyro-char from hydropyrolysis of 10%K₂CO₃-ND coal

下载: 全尺寸图片幻灯片

表 1 煤质分析

Table 1 Analysis of coals

Sample	Proximate analysis w_d/%			Ultimate analysis w_d/%			Sulfur forms w_d/%
Sample	A	V	FC	C	H	N	S_t	S_p	S_s	S_o
BLG	14.26	31.10	54.64	66.24	3.99	1.04	0.63	0.38	0.04	0.22
ND	17.42	32.41	50.17	64.14	4.25	0.75	2.36	1.18	0.42	0.67
BLG: Buliangou coal；ND: Ningdong coal；S_p: pyrite sulfur；S_s: sulfatic sulfur；S_o: orgnic sulfur

下载: 导出CSV

表 2 灰成分分析

Table 2 Analysis of coal ash

Sample	Content w/%
Sample	Al₂O₃	CaO	Fe₂O₃	K₂O	MgO	Na₂O	P₂O₅	SO₃	TiO₂	SiO₂
BLG	53.10	2.37	1.89	1.44	0.55	0.34	0.54	4.21	2.51	26.65
ND	15.58	12.01	9.40	1.91	2.96	2.17	0.08	13.57	0.71	38.52

下载: 导出CSV

表 3 碳酸钾及气氛对热解的影响

Table 3 Effect of K₂CO₃ and atmospheres on pyrolysis

Sample^#	Char yield w_d/%	Tar yield w_d/%
BLG-R-N	81.96	5.81
BLG-C-N	79.52	5.55
BLG-R-N (640 ℃)	76.89	5.43
BLG-C-N (640 ℃)	73.67	5.37
BLG-R-H	79.90	7.26
BLG-C-N	75.86	6.84
BLG-R-W	81.05	6.15
BLG-C-W	76.31	6.01
BLG-R-H+W	75.04	7.62
ND-C-N	79.24	4.81
ND-C-H	74.35	7.73
ND-C-W	75.73	5.75
ND-C-H+W	74.74	7.26
^#: sample code A-B-C means that the sample was obtained by pyrolysis of coal A (BLG=Buliangou coal, ND=Ningdong coal) in atmosphere C (N=N₂, H=H₂, W=H₂O, H+W=H₂+ H₂O) with the addition of B (R=raw coal, C=K₂CO₃)

下载: 导出CSV

表 4 不连沟煤热解半焦中的形态硫的分布(3.5 MPa)

Table 4 Distribution of sulfur forms in char of BLG coal (3.5 MPa)

Sample	Atmospheres	Temperature t/℃	S_p/S_t(%)	S_o/S_t(%)	S_sulfide/S_t(%)
BLG-coal	-	-	59.38	34.38	-
BLG-char	N₂	530	26.12	27.30	2.93
BLG+10%K₂CO₃-char	N₂	530	24.88	35.54	13.62
BLG-char	N₂	640	12.97	32.56	4.93
BLG+10%K₂CO₃-char	N₂	640	15.05	38.65	22.22
S_t: the total sulfur of feed stock (same below)

下载: 导出CSV

表 5 煤热解半焦中的形态硫分布(3.5 MPa-530 ℃)

Table 5 Distribution of sulfur forms in char of coals (3.5 MPa-530 ℃)

	Atmospheres	S_p/S_t(%)	S_o/S_t(%)	S_sulfide/S_t(%)
BLG-char	N₂	26.12	27.30	2.93
BLG-char	70%N₂+30%H₂	20.97	14.01	0.47
BLG+10%K₂CO₃-char	N₂	24.88	35.54	13.62
BLG+10%K₂CO₃-char	70%N₂+30%H₂	21.98	15.39	30.70
ND+10%K₂CO₃-char	N₂	31.11	36.34	11.65
ND+10%K₂CO₃-char	70%N₂+30%H₂	11.32	16.59	37.12

下载: 导出CSV

表 6 煤热解半焦中的形态硫分布(3.5 MPa-530 ℃)

Table 6 Distribution of sulfur forms in char of coals (3.5 MPa-530 ℃)

Sample	Atmospheres	S_p/S_t(%)	S_o/S_t(%)	S_sulfide/S_t(%)
BLG-char	N₂	26.12	27.30	2.93
BLG+10%K₂CO₃-char	N₂	24.88	35.54	13.62
BLG-char	70%N₂+30%H₂O	13.15	27.49	3.41
BLG+10%K₂CO₃-char	70%N₂+30%H₂O	19.12	27.62	0.31
ND+10%K₂CO₃-char	N₂	31.11	36.34	11.65
ND+10%K₂CO₃-char	70%N₂+30%H₂O	13.41	24.41	11.24

下载: 导出CSV

表 7 10%K₂CO₃-煤热解半焦中的形态硫的分布

Table 7 Distribution of sulfur forms in char of 10%K₂CO₃-coals

Sample	Atmospheres	S_p/S_t(%)	S_o/S_t(%)	S_sulfide/S_t(%)
BLG+10%K₂CO₃-char	N₂+30%H₂	19.12	27.62	0.31
BLG+10%K₂CO₃-char	N₂+21%H₂+30%H₂O	14.96	19.23	7.93
ND+10%K₂CO₃-char	N₂+30%H₂	13.41	24.41	11.24
ND+10%K₂CO₃-char	N₂+21%H₂+30%H₂O	10.19	17.83	14.54

下载: 导出CSV

表 8 10%K₂CO₃-宁东煤热解半焦中的硫化物

Table 8 Sulfide in char during pyrolysis of 10%K₂CO₃-ND coal

Sample	Atmospheres	S_sulfide/S_t(%)	K₂S/S_t(%)	FeS/S_t(%)
ND+10%K₂CO₃-char	N₂	11.65	2.15	9.50
ND+10%K₂CO₃-char	70%N₂+30%H₂	37.12	28.37	8.75

下载: 导出CSV

参考文献(19)

[1]	2015年我国天然气消费增速创10年最低[EB/OL]. http://news.xinhuanet.com/energy/2016-02/12/c_1118022736.htm.
[2]	毕继诚, 李克忠, 崔鑫, 祖静茹, 孙志强, 毛燕东, 康守国.一种联产合成气和煤焦油的方法:中国, CN102604683 A[P]. 2012-07-25. BI Ji-cheng, LI Ke-zhong, CUI Xin, ZU Jing-ru, SUN Zhi-qiang, MAO Yan-dogn, KANG Shou-guo. Method for co-production of synthetic gas and coal tar:CN, 102399595A[P]. 2012-04-04.
[3]	CHEN H K, LI B Q, YANG J L, ZHANG B J. Transformation of sulfur during pyrolysis and hydro-pyrolysis of coal[J]. Fuel, 1998, 77(6):487-493. doi: 10.1016/S0016-2361(97)00275-5
[4]	HUANG F, ZHANG L Q, YI B J, XIA Z J, ZHENG C G. Effect of H₂O on pyrite transformation behavior during oxy-fuel combustion[J]. Fuel Process Technol, 2015, 131:458-465. doi: 10.1016/j.fuproc.2014.12.027
[5]	LEVY J H, WHITE T J. The reaction of pyrite with water vapor[J]. Fuel, 1988, 67:1336-1339. doi: 10.1016/0016-2361(88)90114-7
[6]	SUGAWARA K, ABO K, SUGAWARA T, NISHYAMA Y, SHOLES M A. Dynamic behaviour of sulfur forms in rapid pyrolysis of coals with alkali treatment[J]. Fuel, 1995, 74:1823-1829. doi: 10.1016/0016-2361(95)80014-9
[7]	LIU Q R, HU H Q, ZHU S W, ZHOU Q, LI W Y, WEI X Y, XIE K C. Desulfurization of coal by pyrolysis and hydro-pyrolysis with addition of KOH/NaOH[J]. Energy Fuels, 2005, 19(4):1673-1678. doi: 10.1021/ef0497053
[8]	袁申富.煤加氢气化的气化特性实验研究[D].太原:中国科学院山西煤炭化学研究所, 2015. YUAN Shen-fu. Experimental study on gasification characteristics of coal hydrogasification[D]. Taiyuan:Institute of Coal Chemistry, 2015.
[9]	MOULDER J F, STICKLE W F, EOBOL P E. Handbook of X-ray Photoelectron Spectroscopy[M]. Eden Prairie:Perkin Elmer Corporation, 1992.
[10]	CLEYLE P J, CALEY W F, STEWART I, WHITEWAY S G. Decomposition of pyrite and trapping of sulfur in a coal matrix during pyrolysis of coal[J]. Fuel, 1984, 63:1579-1582. doi: 10.1016/0016-2361(84)90230-8
[11]	LBARRA J V, PALLCIOS J M, MOLINER R, BONET A. Evidence of reciprocal organic matter-pyrite interactions affecting sulfur removal during coal pyrolysis[J]. Fuel, 1994, 73(7):1046-1050. doi: 10.1016/0016-2361(94)90235-6
[12]	ČERNIČ-SIMIĆ S. A study of factors that influence the behaviour of coal sulfur during carbonization[J]. Fuel, 1962, 41:141-151.
[13]	HUHN F, KLEIN J, JÜNTGEN H. Investigations on the alkali-catalyzed steam gasification of coal:Kinetics and interactions of alkali catalyst with carbon[J]. Fuel, 1983, 62(2):196-199. doi: 10.1016/0016-2361(83)90197-7
[14]	MIMS C A, PABST J K. Role of surface salt complexes in alkali-catalyzed carbon gasification[J]. Fuel, 1983, 62:176-179. doi: 10.1016/0016-2361(83)90193-X
[15]	SNAPE E, MITCHELL S C, GARRCIA R, ISMALL K, BARTLE K D. Determination of organic sulfur forms in coals and coal derives by high pressure temperature-programmed reduction[J]. Fuel, 1993, 72(5):703-704. https://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/40_3_CHICAGO_08-95_0461.pdf
[16]	GARCIA R, MOINELO S, LAFFERTY C, SNAPE C E. Pyrolytic desulfurization of some high-sulfur coals[J]. Energy Fuels, 1991, 5(4):582-586. doi: 10.1021/ef00028a009
[17]	XU W C, KUMAGAI M. Sulfur transformation during rapid hydro-pyrolysis of coal under high pressure by using a continuous free fall pyrolyzer[J]. Fuel, 2003, 82:245-254. doi: 10.1016/S0016-2361(02)00290-9
[18]	MINKOVA V, RAZVIGOROVA M, GORANOVA M, LJUTZKANOV L, ANGELOVA G. Effect of water vapour on the pyrolysis of solid fuels 1. Effect of water vapour during the pyrolysis of solid fuels on the yield and composition of the liquid products[J]. Fuel, 1991, 70(6):713-719. doi: 10.1016/0016-2361(91)90067-K
[19]	LANG R J. Anion effects in alkali-catalyzed steam gasification[J]. Fuel, 1986, 65(10):1324-1329. doi: 10.1016/0016-2361(86)90097-9