生物质燃烧和热解中钾的释放规律研究进展

doi:10.16085/j.issn.1000-6613.2019-1155

摘要/Abstract

摘要：

生物质中碱金属钾的含量较高，钾在燃烧和热解过程中释放到炉内，会造成积灰、结渣、腐蚀等问题，影响锅炉安全、经济运行。本文通过对文献进行比较和分析，介绍了生物质中钾的含量和赋存形式，碱金属的定量检测方法，生物质中钾在不同条件下热解和燃烧过程中的释放规律，以及燃料成分和粒径、反应温度和升温速率、反应器类型等因素对钾释放规律的影响。结果表明，生物质燃料中钾的赋存形式包括有机钾、无机钾和含钾矿物质等；有机钾分解所释放出的一次产物，最终会经过不同路径的二次反应以其他形式释放或留在灰中；钾的最终释放形式与释放过程中发生的二次反应密切相关，主要包括KCl、K₂SO₄、KOH和含钾矿物质。

关键词: 生物质, 燃烧, 热解, 钾, 释放

Abstract:

The high content of alkali metal potassium in biomass and its release into furnace during combustion and pyrolysis may cause problems such as ash accumulation, slagging, corrosion, etc, affecting the safe and economic operation of the boiler. By comparing and analyzing literatures, the paper introduces the content and form of potassium in biomass, the quantitative detection methods of alkali metal, and the release mechanism of potassium under different conditions in pyrolysis and combustion. The effects of fuel composition, particle size, reaction temperature, heating rate, reactor type and other factors on the release of potassium are also discussed. The occurrence forms of potassium in biomass fuels include organic potassium, inorganic potassium and potassium-containing minerals. The primary products released by the decomposition of organic potassium will eventually be released in other forms or left in the ash through secondary reactions of different paths. The final release form of potassiumis closely related to the secondary reaction that occurs during the release process, including KCl, K₂SO₄, KOH and potassium-containing minerals.

Key words: biomass, combustion, pyrolysis, potassium, release

中图分类号:

TQ51

王洋,董长青. 生物质燃烧和热解中钾的释放规律研究进展[J]. 化工进展, 2020, 39(4): 1292-1301.

Yang WANG,Changqing DONG. Release of K during biomass combustion and pyrolysis: a review[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1292-1301.

图/表 8

参考文献 53

1	蒋剑春. 生物质能源应用研究现状与发展前景[J]. 林产化学与工业, 2002, 22(2): 75-80.
	JIANG J C.Prospect on research and development ofbiomass energy utilization[J]. Chemistry and Industry of Forest Products, 2002, 22(2): 75-80.
2	RAGLAND K W, AERTS D J, BAKER A J. Properties of wood for combustion analysis[J]. Bioresource Technology, 1991, 37(2):161-168.
3	MILLER R N. A geochemical study of the inorganic constituents in some low-rank coals[J]. Thesis Pennsylvania State Univ., 1978,13(1):146-149.
4	MILLER R N, GIVEN P H. The association of major, minor and trace inorganic elements with lignites. I. Experimental approach and study of a North Dakota lignite[J]. Geochimica et Cosmochimica Acta, 1986, 50(9): 2033-2043.
5	JENKINS B M, BAXTER L L, JR T R M, et al. Combustion properties of biomass[J]. Fuel Processing Technology, 1998, 54(1/2/3): 17-46.
6	ZEVENHOVEN O M. Ash-forming matter in biomass fuels[M]. Åbo/Turku, Finland: ÅboAkademi, 2001: 2-3.
7	WERKELIN J, SKRIFVARS B J, ZEVENHOVEN O M, et al. Chemical forms of ash-forming elements in woody biomass fuels[J]. Fuel, 2010, 89(2): 481-493.
8	FORSBERG C, BROSTRÖO M, BACKMAN R, et al. Principle, calibration, and application of the in situ alkali chloride monitor[J]. Review of Scientific Instruments, 2009, 80(2): 153-168.
9	HAYRINEN V, HERNBERG R, AHO M. Demonstration of plasma excited atomic resonance line spectroscopy for on-line measurement of alkali metals in a 20kW bubbling fluidized bed[J]. Fuel, 2004, 83(7): 791-797.
10	韩雨佳, 杨燕梅, 许开龙, 等. 准东煤射流火焰碱金属析出在线测量研究[J]. 工程热物理学报, 2017, 38(6): 1351-1356.
	HAN Y J, YANG Y M, XU K L, et al. On-line measurement of alkali metal released from the jet flames of Zhundong coal[J]. Journal of Engineering Thermophisics, 2017, 38(6): 1351-1356.
11	朱燕群, 钟厦, 何勇, 等. 准东煤化学处理后碱金属含量的激光测量研究[J]. 激光技术, 2017, 41(1): 101-105.
	ZHU Y Q, ZHONG X, HE Y, et al. Measurement of alkali content in Zhundong coal after chemical fractionation treatment by LIBS method[J]. Laser Technology, 2017, 41(1): 101-105.
12	朱川. 高碱煤中碱金属含量测定及应用进展[J]. 洁净煤技术, 2018, 24(5): 20-25, 32.
	ZHU C. Determination of alkali metal content in high alkali coal and its application[J]. Clean Coal Technology, 2018, 24(5): 20-25, 32.
13	杨光. 生物质燃烧过程中碱金属迁移研究[D]. 广州: 华南理工大学, 2012.
	YANG G. Study on the alkali transformation behavior of straw combusiton[D]. Guangzhou: South China University of Technology, 2012.
14	田艳飞. 含碱金属燃烧火焰的发射光谱检测与分析[D]. 武汉: 华中科技大学, 2016.
	TIAN Y F. Measurement and analysis of emission spectra from flames containing alkali metals[D]. Wuhan: Huazhong University of Science and Technology, 2016.
15	杨涛, 胡松, 向军, 等. 生物质热能利用过程中碱/碱土金属特性及检测技术研究进展[J]. 生物质化学工程, 2008, 42(6): 49-54.
	YANG T, HU S, XIANG J, et al. Review on characteristics and detection technology of the alkali/alkaline earth metal during biomass thermal utilizaiton[J]. Biomass Chemical Engineering, 2008, 42(6): 49-54.
16	GOTTWALD U, MONKHOUSE P. Single-port optical access for spectroscopic measurements in industrial flue gas ducts[J]. Applied Physics B, 1999, 69(2): 151-154.
17	MONKHOUSE P. On-line diagnostic methods for metal species in industrial process gas[J]. Progress in Energy and Combustion Science, 2002, 28(4): 331-381.
18	HELBLE J J, SRINIVASACHAR S, BONI A A, et al. Measurement and modeling of vapor-phase sodium chloride formed during pulverized coal combustion[J]. Combustion Science and Technology, 1992, 81(4-6): 193-205.
19	GOTTWALD U, MONKHOUSE P, WULGARIS N, et al. In-situ study of the effect of operating conditions and additives on alkali emissions in fluidised bed combustion[J]. Fuel Processing Technology, 2002, 75(3): 215-226.
20	FRENCH R J, DAYTON D C, MILNE T A. The direct observation of alkali vapor species in biomass combustion and gasification[R]. Golden, CO (United States): National Renewable Energy Lab., 1994-01-20.
21	DAYTON D C, FRENCH R J, MILNE T A. Direct observation of alkali vapor release during biomass combustion and gasification. 1. Aapplication of molecular beam/mass spectrometry to switchgrass combustion[J]. Energy & Fuels, 1995, 9(5): 855-865.
22	BLASING M, MULLER M. Mass spectrometric investigations on the release of inorganic species during gasification and combustion of Rhenish lignite[J]. Fuel, 2010, 89(9): 2417-2424.
23	ZARCHY A S. An alkali metal detector for use in fluidized bed combustor effluent streams[C]//5th Symp. on Instrumentation and Control for Fossil Energy Processes, USA,1981.
24	DAVIDSSON K O, STOJKOVA B J, PETTERSSON J B C. Alkali emission from birchwood particles during rapid pyrolysis[J]. Energy & Fuels, 2002, 16(5): 1033-1039.
25	DAVIDSSON K O, ENGVALL K, HAGSTRÖM M, et al. A surface ionization instrument for on-line measurements of alkali metal components in combustion: instrument description and applications[J]. Energy &Fuels, 2002, 16(6): 1369-1377.
26	LIAW S B, WU H. Leaching characteristics of organic and inorganic matter from biomass by water: differences between batch and semi-continuous operations[J]. Industrial & Engineering Chemistry Research, 2013, 52(11): 4280-4289.
27	ZHANG Z H, SONG Q, ALWAHABI Z T, et al. Temporal release of potassium from pinewood particles during combustion[J]. Combustion and Flame, 2015, 162(2): 496-505.
28	FATEHI H, HESAMEDDIN Y, WANG Z, et al. LIBS measurements and numerical studies of potassium release during biomass gasification[J]. Proceedings of the Combustion Institute, 2015, 35(2): 2389-2396.
29	FATEHI H, LI Z S, BAI X S, et al. Modeling of alkali metal release during biomass pyrolysis[J]. Proceedings of the Combustion Institute, 2017, 36(2): 2243-2251.
30	HUPAM M. Ash-related issues in fluidized-bed combustion of biomasses: recent research highlights[J]. Energy & Fuels, 2011, 26(1): 4-14.
31	JENSEN P A, FRANDSEN F J, DAM-JOHANSEN K, et al. Experimental investigation of the transformation and release to gas phase of potassium and chlorine during straw pyrolysis[J]. Energy & Fuels, 2000, 14(6): 1280-1285.
32	KNUDSEN J N, JENSEN P A, DAM-JOHANSEN K. Transformation and release to the gas phase of Cl, K, and S during combustion of annual biomass[J]. Energy & Fuels, 2004, 18(5): 1385-1399.
33	KNUDSEN J N, JENSEN P A, LIN W, et al. Secondary capture of chlorine and sulfur during thermal conversion of biomass[J]. Energy & Fuels, 2005, 19(2): 606-617.
34	VAN-LITH S C, ALONSO-RAMÍREZ V, JENSEN P A, et al. Release to the gas phase of inorganic elements during wood combustion. part 1: Development and evaluation of quantification methods[J]. Energy &Fuels, 2006, 20(3): 964-978.
35	VAN-LITH S C, JENSEN P A, FRANDSEN F J, et al. Release to the gas phase of inorganic elements during wood combustion. part 2: Influence of fuel composition[J]. Energy & Fuels, 2008, 22(3): 1598-1609.
36	OKUNO T, SONOYAMA N, HAYASHI J, et al. Primary release of alkali and alkaline earth metallic species during the pyrolysis of pulverized biomass[J]. Energy & Fuels, 2005, 19(5): 2164-2171.
37	KEOWN D M, FAVAS G, HAYASHI J, et al. Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash[J]. Bioresource Technology, 2005, 96(14): 1570-1577.
38	ZINTL F, STRÖMBERG B, BJÖRKMAN E. Release of chlorine from biomass at gasification conditions[C]//Biomass for energy and Industry, 10th European Conference and Technology Exhibition, Germany, 1998, 1608.
39	BRIDGWATER A V. Progress in thermochemical biomass conversion[M]. Britain: Blackwell Science, 2001: 1234-1245.
40	HAMILTON J T G, MCROBERTSS W C, KEPPLER F, et al. Chloride methylation by plant pectin: an efficient environmentally significant process[J]. Science, 2003, 301(5630): 206-209.
41	SALEH S,FLENSBORG J P, SHOULAIFAR T K, et al. Release of chlorine and sulfur during biomass torrefaction and pyrolysis[J]. Energy & Fuels, 2014, 28(6): 3738-3746.
42	SAILAUKHANULY Y,SÁROSSY Z, CARLSEN L, et al. Mechanistic aspects of the nucleophilic substitution of pectin on the formation of chloromethane[J]. Chemosphere, 2014, 111: 575-579.
43	CZÉGÉNY Z, JAKAB E, BOZI J, et al. Pyrolysis of wood-PVC mixtures. formation of chloromethane from lignocellulosic materials in the presence of PVC[J]. Journal of Analytical and Applied Pyrolysis, 2015, 113: 123-132.
44	DAYTON D C, JENKINS B M, TURN S Q, et al. Release of inorganic constituents from leached biomass during thermal conversion[J]. Energy & Fuels, 1999, 13(4): 860-870.
45	WIGMANS T, ELFRING R, MOULIJN J A. On the mechanism of the potassium carbonate catalysed gasification of activated carbon: the influence of the catalyst concentration on the reactivity and selectivity at low steam pressures[J]. Carbon, 1983, 21(1): 1-12.
46	HASHIMOTO K, MIURA K, XU J J, et al. Relation between the gasification rate of carbons supporting alkali metal salts and the amount of oxygen trapped by the metal[J]. Fuel, 1986, 65(4): 489-494.
47	LI X, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. part VIII. Catalysis and changes in char structure during gasification in steam[J]. Fuel, 2006, 85(10): 1518-1525.
48	WU H, QUYN D M, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. part III. The importance of the interactions between volatiles and char at high temperature[J]. Fuel, 2002, 81(8): 1033-1039.
49	LI X, WU H, HAYASHI J, et al. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. part VI. Further investigation into the effects of volatile-char interactions[J]. Fuel, 2004, 83(10): 1273-1279.
50	JOHANSEN J M, JAKOBSEN J G, FRANDSEN F J, et al. Release of K, Cl, and S during pyrolysis and combustion of high-chlorine biomass[J]. Energy & Fuels, 2011, 25(11): 4961-4971.
51	OLSSON J G, JÄGLID U, PETTERSSON J B C, et al. Alkali metal emission during pyrolysis of biomass[J]. Energy & Fuels, 1997, 11(4): 779-784.
52	DAYTON D C, MILNE T A. Applications of advanced technology to ash-related problems in boilers[M]. US: Springer US, 1996: 161-185.
53	MISRA M K, RAGLAND K W, BAKER A J. Wood ash composition as a function of furnace temperature[J]. Biomass and Bioenergy, 1993, 4(2): 103-116.

生物质	质量分数/%
生物质	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	Na₂O	K₂O	TiO₂	SO₃	P₂O₅
红橡木	49.00	9.50	8.50	17.50	1.10	0.50	9.50	—	2.60	1.80
麦秸秆	55.32	1.88	0.73	6.14	1.06	1.71	25.60	0.08	4.40	1.26
榛子壳	33.70	3.10	3.80	15.40	7.90	1.30	30.40	0.10	1.10	3.20
杏仁壳	23.50	2.70	2.80	10.50	5.20	1.60	48.50	0.10	0.80	4.50

生物质	质量分数/%
生物质	SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	Na₂O	K₂O	TiO₂	SO₃	P₂O₅
红橡木	49.00	9.50	8.50	17.50	1.10	0.50	9.50	—	2.60	1.80
麦秸秆	55.32	1.88	0.73	6.14	1.06	1.71	25.60	0.08	4.40	1.26
榛子壳	33.70	3.10	3.80	15.40	7.90	1.30	30.40	0.10	1.10	3.20
杏仁壳	23.50	2.70	2.80	10.50	5.20	1.60	48.50	0.10	0.80	4.50

分析方法	原理	检测类型	检测的物质	检测精度	其他
IACM	光谱学	在线原位检测	KC、NaCl	1～50μg·g^-1	检测碱金属氯化物
TDLAS	光谱学	在线原位检测	原子K、Na	>7.5ng·kg^-1	仅气态
PEARLS	光谱学	在线取样检测	原子、Na	μg·kg^-1	不区分相态
LIBS	光谱学	在线原位检测	原子K、Na	μg·g^-1	不区分相态
ELIF	光谱学	在线原位检测	原子K、Na	μg·kg^-1	仅气态
SI	电离作用	在线取样检测	K⁺、Na⁺	μg·kg^-1	离子，不区分相态
MBMS	质谱学	在线取样检测	KCl、KOH等	μg·g^-1	分子，不区分相态
ICP-AES	光谱学	非在线检测	原子K、Na	μg·kg^-1	不区分相态

分析方法	原理	检测类型	检测的物质	检测精度	其他
IACM	光谱学	在线原位检测	KC、NaCl	1～50μg·g^-1	检测碱金属氯化物
TDLAS	光谱学	在线原位检测	原子K、Na	>7.5ng·kg^-1	仅气态
PEARLS	光谱学	在线取样检测	原子、Na	μg·kg^-1	不区分相态
LIBS	光谱学	在线原位检测	原子K、Na	μg·g^-1	不区分相态
ELIF	光谱学	在线原位检测	原子K、Na	μg·kg^-1	仅气态
SI	电离作用	在线取样检测	K⁺、Na⁺	μg·kg^-1	离子，不区分相态
MBMS	质谱学	在线取样检测	KCl、KOH等	μg·g^-1	分子，不区分相态
ICP-AES	光谱学	非在线检测	原子K、Na	μg·kg^-1	不区分相态

[1]	李宁, 李金科, 董金善. 乙烯裂解炉多孔介质燃烧器的研究与开发[J]. 化工进展, 2023, 42(S1): 73-83.
[2]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[3]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[4]	邵志国, 任雯, 许世佩, 聂凡, 许毓, 刘龙杰, 谢水祥, 李兴春, 王庆吉, 谢加才. 终温对油基钻屑热解产物分布和特性影响[J]. 化工进展, 2023, 42(9): 4929-4938.
[5]	李志远, 黄亚继, 赵佳琪, 于梦竹, 朱志成, 程好强, 时浩, 王圣. 污泥与聚氯乙烯共热解重金属特性[J]. 化工进展, 2023, 42(9): 4947-4956.
[6]	王帅晴, 杨思文, 李娜, 孙占英, 安浩然. 元素掺杂生物质炭材料在电化学储能中的研究进展[J]. 化工进展, 2023, 42(8): 4296-4306.
[7]	吴亚, 赵丹, 方荣苗, 李婧瑶, 常娜娜, 杜春保, 王文珍, 史俊. 用于复杂原油乳液的高效破乳剂开发及应用研究进展[J]. 化工进展, 2023, 42(8): 4398-4413.
[8]	郑梦启, 王成业, 汪炎, 王伟, 袁守军, 胡真虎, 何春华, 王杰, 梅红. 菌藻共生技术在工业废水零排放中的应用与展望[J]. 化工进展, 2023, 42(8): 4424-4431.
[9]	李海东, 杨远坤, 郭姝姝, 汪本金, 岳婷婷, 傅开彬, 王哲, 何守琴, 姚俊, 谌书. 炭化与焙烧温度对植物基铁碳微电解材料去除As(Ⅲ)性能的影响[J]. 化工进展, 2023, 42(7): 3652-3663.
[10]	关红玲, 杨辉, 井红权, 刘玉琼, 谷守玉, 王好斌, 侯翠红. 木质素基控释材料及其在药物输送和肥料控释中的应用[J]. 化工进展, 2023, 42(7): 3695-3707.
[11]	姚丽铭, 王亚琢, 范洪刚, 顾菁, 袁浩然, 陈勇. 餐厨垃圾处理现状及其热解技术研究进展[J]. 化工进展, 2023, 42(7): 3791-3801.
[12]	张杉, 仲兆平, 杨宇轩, 杜浩然, 李骞. 磷酸盐改性高岭土对生活垃圾热解过程中重金属的富集[J]. 化工进展, 2023, 42(7): 3893-3903.
[13]	于丁一, 李圆圆, 王晨钰, 纪永升. pH响应性木质素水凝胶的制备及药物控释[J]. 化工进展, 2023, 42(6): 3138-3146.
[14]	侯殿保, 贺茂勇, 陈育刚, 杨海云, 李海民. 资源优化配置与循环经济在钾资源开发利用中的应用[J]. 化工进展, 2023, 42(6): 3197-3208.
[15]	修浩然, 王云刚, 白彦渊, 邹立, 刘阳. 准东煤/市政污泥混燃燃烧特性及灰熔融行为分析[J]. 化工进展, 2023, 42(6): 3242-3252.