橄榄废弃物低温热解过程中氯的析出规律

doi:10.11949/j.issn.0438-1157.20180176

化工学报 ›› 2018, Vol. 69 ›› Issue (8): 3693-3700.DOI: 10.11949/j.issn.0438-1157.20180176

橄榄废弃物低温热解过程中氯的析出规律

谢敏¹, 程健¹, 陈刚², 张蕾³, 任霄汉⁴

1 哈尔滨电气股份有限公司, 黑龙江哈尔滨 150028;
2 中国船舶重工集团公司第七〇三研究所, 黑龙江哈尔滨 150078;
3 哈尔滨工业大学能源科学与工程学院, 黑龙江哈尔滨 150001;
4 山东大学热科学与工程研究中心, 山东济南 250061

收稿日期:2018-02-07 修回日期:2018-04-20 出版日期:2018-08-05 发布日期:2018-08-05
通讯作者: 任霄汉
基金资助:
国家自然科学基金项目（51476046）。

Chlorine release during low-temperature pyrolysis of olive residue

XIE Min¹, CHENG Jian¹, CHEN Gang², ZHANG Lei³, REN Xiaohan⁴

1 Harbin Electric Company Limited, Harbin 150028, Heilongjiang, China;
2 China Shipbuilding Industry Corporation No. 703 Research Institute, Harbin 150078, Heilongjiang, China;
3 School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China;
4 Institute of Thermal Science and Technology, Shandong University, Jinan 250061, Shandong, China

Received:2018-02-07 Revised:2018-04-20 Online:2018-08-05 Published:2018-08-05
Supported by:
supported by the National Natural Science Foundation of China (51476046).

摘要/Abstract

摘要：

生物质直燃是生物质能利用的主要方式，而含氯化合物的释放则影响了生物质锅炉的结渣与腐蚀。低温热解作为一种有效的预处理手段可以解决由氯化物导致的锅炉结渣、腐蚀问题。利用水平管式炉试验系统，测量了不同热解温度下橄榄废弃物HCl、CH₃Cl等含氯物质的释放情况，分析了不同热解温度下上述污染物的释放规律。通过分析发现：HCl和CH₃Cl是生物质热解过程中氯的主要析出产物，热解温度的升高有助于氯等元素分别向HCl和CH₃Cl的转化，低温热解条件下氯的释放主要以CH₃Cl为主，随着温度的升高，二者的差距逐渐减小，当温度达到400℃时，HCl取代CH₃Cl成为生物质热解过程中主要的含氯气态产物。

关键词: 生物质, 生物燃料, 低温热解, 氯释放, HCl, CH₃Cl

Abstract:

Biomass direct combustion is the main way of biomass energy utilization. Chlorine plays an important role in boiler slagging and corrosion during the combustion of high-chlorine biomass. Low-temperature pyrolysis could make chlorine release and get the low chlorine content biomass. We assessed the effect of the low-temperature pyrolysis intensity on the chlorine content of residual biomass and of the released gaseous species. For this purpose, olive residue was subjected to low-temperature pyrolysis (mild pyrolysis) at furnace temperatures, in the range of 250-400℃ in an inert nitrogen atmosphere. The major chlorinated species in the evolving pyrolysis gas (torgas) were identified as HCl and CH₃Cl, and quantified. HCl and CH₃Cl will compete Cl which is released during biomass low-temperature pyrolysis and low temperature will promote the conversion of Cl to CH₃Cl. When the temperature is below 350℃, CH₃Cl is the main product of Cl release and when the temperature arrives at 400℃, HCl will replace CH₃Cl to become the main product during low-temperature pyrolysis.

Key words: biomass, biofuel, low-temperature pyrolysis, chlorine release, HCl, CH₃Cl

中图分类号:

谢敏, 程健, 陈刚, 张蕾, 任霄汉. 橄榄废弃物低温热解过程中氯的析出规律[J]. 化工学报, 2018, 69(8): 3693-3700.

XIE Min, CHENG Jian, CHEN Gang, ZHANG Lei, REN Xiaohan. Chlorine release during low-temperature pyrolysis of olive residue[J]. CIESC Journal, 2018, 69(8): 3693-3700.

参考文献 31

[1]	中国国家发展和改革委员会. 国际可再生能源现状与展望[M]. 北京:中国环境科学出版社, 2007. National Development and Reform Commission. International Renewable Energy Current Status and Future Outlook[M]. Beijing:China Environmental Science Press, 2007.
[2]	IRENA. Biomass for heat and power[DB/OL]. http://www.irena.org/DocumentDownloads/Publications/IRENA-ETSAP_Tech_Brief_E05_Biomass%20for%20Heat%20and%20Power.pdf.
[3]	ROMEO L M, GARETA R. Fouling control in biomass boilers[J]. Biomass & Bioenergy, 2009, 33(5):854-861.
[4]	伊晓路, 孙立, 郭东彦, 等. 生物质秸秆预处理技术[J]. 可再生能源, 2005, (2):31-33. YI X L, SUN L, GUO D Y, et al. Pretreatment technology of raw biomass stalks[J]. Renewable Energy, 2005, (2):31-33.
[5]	REN X H, SUN R, MENG X X, et al. Carbon, sulfur and nitrogen oxide emissions from combustion of pulverized raw and torrefied biomass[J]. Fuel, 2017, 188:310-323.
[6]	REN X H, SUN R, CHI H H, et al. Hydrogen chloride emissions from combustion of raw and torrefied biomass[J]. Fuel, 2017, 200:37-46.
[7]	USLU A, FAAJJ A P C, BERGMAN P C A. Pre-treatment technologies, and their effect on international bioenergy supply chain logistics. Techno-economic evaluation of torrefaction, fast pyrolysis and pelletisation[J]. Energy, 2008, 33(8):1206-1223.
[8]	KASSMAN H, BROSTRÖM M, BERG M, et al. Measures to reduce chlorine in deposits:application in a large-scale circulating fluidised bed boiler firing biomass[J]. Fuel, 2011, 90(4):1325-1334.
[9]	NIELSEN H P, FRANDSEN F J, DAM-JOHANSEN K, et al. The implications of chlorine-associated corrosion on the operation of biomass-fired boilers[J]. Progress in Energy & Combustion Science, 2000, 26(3):283-298
[10]	BJÖRKMAN E, STRÖMBERG B. Release of chlorine from biomass at pyrolysis and gasification conditions[J]. Energy & Fuels, 2014, 11(5):1026-1032.
[11]	吴鹏, 余春江, 柏继松, 等. 生物质热解氯的析出机制研究[J]. 中国电机工程学报, 2013, 33:1-7. WU P, YU C J, BAI J S, et al. Mechanism study of chlorine release during biomass pyrolysis[J]. Proceedings of the CSEE, 2013, 33:1-7.
[12]	杜胜磊, 陈汉平, 杨海平, 等. 生物质热解过程中F和Cl的迁徙行为研究[J]. 中国电机工程学报, 2010, 30(14):115-120. DU S L, CHEN H P, YANG H P, et al. Transformation behavior of F and Cl during biomass pyrolysis[J]. Proceedings of the CSEE, 2010, 30(14):115-120.
[13]	陈安合, 杨学民, 林伟刚.生物质热解和气化过程Cl及碱金属逸出行为的化学热力学平衡分析[J].燃料化学学报, 2007, 35(5):539-547. CHEN A H, YANG X M, LIN W G. Release characteristics of chlorine and alkali metals during pyrolysis and gasification of biomass by thermodynamical equilibrium analysis[J]. Journal of Fuel Chemistry and Technology, 2007, 35(5):539-547.
[14]	郭献军. 生物质燃烧氯的析出与控制研究[D]. 武汉:华中科技大学, 2009. GUO X J. Study on release and control of chlorine during biomass combustion[D]. Wuhan:Huazhong University of Science and Technology, 2009.
[15]	喻敏, 董勇, 王鹏, 等. 氯元素对燃煤烟气脱汞的影响研究进展[J]. 化工进展, 2012, 31(7):1610-1614. YU M, DONG Y, WANG P, et al. Progress of effects of chloride on mercury removal for coal-fired flue gas[J]. Chemical Industry and Engineering Progress, 2012, 31(7):1610-1614.
[16]	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.
[17]	陆强, 张栋, 朱锡锋. 四种金属氯化物对纤维素快速热解的影响(Ⅰ):Py-GC/MS实验[J]. 化工学报, 2010, 61(4):1018-1024. LU Q, ZHANG D, ZHU X F. Catalytic effects of four metal chlorides of fast pyrolysis of cellulose (Ⅰ):Py-GC/MS experiments[J]. CIESC Journal, 2010, 61(4):1018-1024.
[18]	孟晓晓, 孙锐, 袁皓, 等. 不同热解温度下玉米秸秆中碱金属K和Na的释放及半焦中赋存特性[J]. 化工学报, 2017, 68(4):1600-1607. MENG X X, SUN R, YUAN H, et al. Effect of different pyrolysis temperature on alkali metal K and Na emission and existence in semi-char[J]. CIESC Journal, 2017, 68(4):1600-1607.
[19]	SALEH S B, 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.
[20]	SHANG L, AHRENFELDT J, HOLM J K, et al. Intrinsic kinetics and devolatilization of wheat straw during torrefaction[J]. Journal of Analytical & Applied Pyrolysis, 2013, 100(5):145-152.
[21]	邓丛静, 于小飞, 陈军, 等. 橄榄油加工工艺及品质评价[J]. 林产工业, 2011, 38(1):62-63. DENG C J, YU X F, CHEN J, et al. The processing and evaluation of olive oil production[J]. China Forest Products Industry, 2011, 38(1):62-63.
[22]	李聚桢. 我国油橄榄产业发展的探讨[J]. 粮油食品科技, 2012, 20(2):23-26. LI J Z. The investigation of industrial development of olive in China[J]. Science and Technology of Cereals, Oils and Foods, 2012, 20(2):23-26.
[23]	LIANG L G, SUN R, FEI J, et al. Experimental study on effects of moisture content on combustion characteristics of simulated municipal solid wastes in a fixed bed[J]. Bioresource Technology, 2008, 99(15):7238-7246.
[24]	REN X H, ROKNI E, SUN R, et al. Evolution of chlorine-bearing gases during corn straw torrefaction at different temperatures[J]. Energy&Fuel, 2017, 31:13713-13723.
[25]	KEIPI T, TOLVANEN H, KOKKO L, et al. The effect of torrefaction on the chlorine content and heating value of eight woody biomass samples[J]. Biomass and Bioenergy, 2014, 66:232-239.
[26]	KNUDSEN J N, JENSEN P A, DAMJOHANSEN 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.
[27]	CHEN H, CHEN X, QIAO Z, et al. Release and transformation behavior of Cl during pyrolysis of torrefied rice straw[J]. Fuel, 2016, 183:145-154.
[28]	PALMER T Y. Combustion sources of atmospheric chlorine[J]. Nature, 1976, 263(5572):44-46.
[29]	EKLUND G, PEDERSEN J R, STRÖMBERG B. Methane, hydrogen chloride and oxygen form a wide range of chlorinated organic species in the temperature range 400℃-950℃[J]. Chemosphere, 1988, 17(3):575-586
[30]	BAXTER L L, MILES T R, JENKINSC B M, et al. The behavior of inorganic material in biomass-fired power boilers:field and laboratory experiences[J]. Fuel Processing Technology, 1998, 54(1/2/3):47-78.
[31]	JENSEN P A, FRANDSEN F J, DAMJOHANSEN 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.

橄榄废弃物低温热解过程中氯的析出规律

Chlorine release during low-temperature pyrolysis of olive residue

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