抗生素菌渣热解N官能团变化特征及其与NO<sub><i>x</i></sub>前驱物关系研究

詹昊; 林均衡; 黄艳琴; 阴秀丽; 刘华财; 袁洪友; 吴创之

抗生素菌渣热解N官能团变化特征及其与NO_x前驱物关系研究

詹昊^{1, 2},
林均衡^{1, 2},
黄艳琴¹,
阴秀丽¹,
刘华财¹,
袁洪友¹,
吴创之^1, ,

1.
中国科学院广州能源研究所中国科学院可再生能源重点实验室, 广东省新能源和可再生能源重点实验室, 广东广州 510640
2.
中国科学院大学, 北京 100049

基金项目:

国家自然科学基金 51676195

国家自然科学基金 51661145022

详细信息

通讯作者:
吴创之, E-mail:wucz@ms.giec.ac.cn

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2017-05-25
- 修回日期: 2017-08-13
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Evolution of nitrogen functionalities and their relation to NO_x precursors during pyrolysis of antibiotic mycelia wastes

1.
Key Laboratory of Renewable Energy, CAS, Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

The project was supported by the National Natural Science Foundation of China 51676195

The project was supported by the National Natural Science Foundation of China 51661145022

摘要

摘要: 以青霉素菌渣（PMW）和土霉素菌渣（TMW）为对象，在水平管式反应器中进行快速热解，采用X射线光电子能谱（XPS）表征和化学吸收-分光光度定量分析方法，研究了抗生素菌渣热解N官能团变化特征及其与NO_x前驱物的关系。结果表明，菌渣燃料N官能团分为无机N（N-IN）和蛋白质及其水解产物N（N-A）两种。决定菌渣NO_x前驱物以NH₃-N为主，N官能团主要为N-A，PMW占81.1%、TMW占59.0%。在低温区间，N-IN在150-250℃分解和N-A在250-450℃转化，为NH₃-N主要来源；PMW和TMW产率分别为20.9%和25.6%，而HCN-N产率小于2%，基本与燃料N官能团特征无关；该阶段伴随吡啶N（N-6）和吡咯N（N-5）的生成及转化，峰值在350-400℃。在高温区间，半焦N反应，主要是N-6和N-5的转化，为NH₃-N和部分HCN-N的来源；该阶段伴随少量更稳定质子化吡啶N（N-Q）和氮氧化物N（N-X）生成。由于N-IN和不稳定N-A低温下会快速分解，250-300℃下菌渣半焦N去除高达40%、能量损失可控制在25%，因此，采用合适低温热解处理菌渣，在保证能量前提下可有效去除燃料中的N。
- 抗生素菌渣 /
- N官能团 /
- NO_x前驱物 /
- 低温热解 /
- N去除
Abstract: On the basis of rapid pyrolysis of two antibiotic mycelial wastes (AMWs), viz., penicillin mycelia waste (PMW) and terramycinmycelial waste (TMW), in a horizontal tubular quartz reactor, evolution of nitrogen functionalities and their relation to NO_x precursors were investigated with the help of XPS and chemical absorption-spectrophotometry methods.The results indicate that inorganic-N (N-IN) and amide-N/amine-N/amino-N (N-A) are two kinds of nitrogen functionalities in the raw AMWs samples, determining the predominance of NH₃-N among NO_x precursors. N-A is found to be the main one with the proportion of 81.1% and 59.0% for PMW and TMW, respectively. At low temperatures, the decomposition of N-IN and the conversion of N-A mainly occur at 150-250℃ and 250-450℃, respectively, which are two routes for most NH₃-N with yields of 20.9% (PMW) and 25.6% (TMW). While HCN-N is produced with a small amount less than 2%, having no relationship with the characteristics of nitrogen functionalities in fuels. Besides, pyridinic-N (N-6) and pyrrolic-N (N-5) are also formed and then converted with peak values at 350-400℃. At high temperatures, the conversion of N-6 and N-5 is prevailing, leading to the basically equal increments on NH₃-N and HCN-N. Simultaneously, a minor amount of more stable quaternary nitrogen (N-Q) and N-oxide (N-X) is produced. Typically, due to the rapid decomposition of N-IN and labile N-A at low-temperature pyrolysis, nitrogen removal can reach up to 40% while energy loss can be controlled within 25% when pyrolyzing at 250-300℃. As a result, low-temperature pyrolysis could be an effective method for nitrogen removal whereas preserving the energy in AMWs.
- AMWs /
- nitrogen functionalities /
- NO_x precursors /
- low-temperature pyrolysis /
- nitrogen removal

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图 1 实验流程示意图

Figure 1 Schematic diagram of the experimental system

下载: 全尺寸图片幻灯片

图 2 抗生素菌渣的TG和DTG曲线

Figure 2 TG and DTG curves of AMWs at 15 ℃/min under Ar atmosphere

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图 3 低温热解菌渣原料及各温度半焦的XPS(N 1s)谱图

(N0: N-IN；N1: N-A；N2: N-6；N3: N-5)

Figure 3 N 1s XPS spectra of AMWs and AMWs-derived chars generated at low-temperature ranging from 150 to 450℃

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图 4 低温热解各N官能团比例随温度的变化

(a): PMW; (b): TMW

Figure 4 Fraction of various nitrogen functionalities vs. the pyrolysis temperature in low temperature region

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图 5 高温区间两菌渣各温度半焦的XPS(N 1s)谱图

(N2: N-6；N3: N-5；N4: N-Q；N5: N-X)

Figure 5 N 1s XPS spectra of AMWs-derived chars produced at high-temperature ranging from 500 to 800℃

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图 6 快速热解高温下各N官能团比例随温度的变化

(a): PMW; (b): TMW

Figure 6 Fraction of various nitrogen functionalities vs. the pyrolysis temperature in high temperature region

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图 7 快速热解固相N官能团产率(a，b)、NO_x前驱物组分产率(c)及比例(d)随热解终温的变化

Figure 7 Yield of various nitrogen functionalities in solid phase ((a): PMW, (b): TMW), yields (c) and ratio (d) of NO_x precursors vs. the pyrolysis temperature

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图 8 热解过程燃料半焦Y_{N_rem}及Y_{q_loss}随温度的变化

Figure 8 Changes of Y_{N_rem} and Y_{q_loss} in chars vs. the temperature during rapid pyrolysis process

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表 1 抗生素菌渣的工业分析及元素分析

Table 1 Proximate and ultimate analyses of antibiotic mycelial wastes (AMWs)

AMW	PMW	TMW
	Proximate analysis w_db/%
Ash	8.09	14.85
Volatile matter	78.51	73.90
Fixed carbon	13.40	11.25
HHV Q /(MJ·kg^-1)	19.28	19.33
	Ultimate analysis w_daf/%
Carbon	48.07	50.60
Hydrogen	6.96	7.17
Nitrogen	8.04	10.93
Sulfur	0.57	0.81
Oxygen (by difference)	36.36	30.49

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参考文献(32)

[1]	贡丽鹏, 郭斌, 任爱玲, 刘仁平, 宋汉宁.抗生素菌渣理化特性[J].河北科技大学学报, 2012, 33(2):190-196. doi: 10.7535/hbkd.2012yx02023 GONG Li-peng, GUO Bin, REN Ai-ling, LIU Ren-ping, SONG Han-ning. Physical and chemical properties of antibiotics bacterial residue[J]. J Heibei Univ Sci Technol, 2012, 33(2):190-196. doi: 10.7535/hbkd.2012yx02023
[2]	许光文, 纪文峰, 刘周恩, 万印华, 张小勇.轻工生物质过程残渣高值化利用必要性与技术路线分析[J].过程工程学报, 2009, 9(3):618-624. http://www.cnki.com.cn/Article/CJFDTOTAL-HGYJ200903037.htm XU Guang-wen, JI Wen-feng, LIU Zhou-en, WAN Yin-hua, ZHANG Xiao-yong. Necessity and technical route of value-added utilization of biomass process residues in light industry[J]. Chin J Process Eng, 2009, 9(3):618-624. http://www.cnki.com.cn/Article/CJFDTOTAL-HGYJ200903037.htm
[3]	GUO B, GONG L, DUAN E, LIU R, REN A, HAN J, ZHAO W. Characteristics of penicillin bacterial residue[J]. J Air Waste Manage, 2012, 62(4):485-8. doi: 10.1080/10962247.2012.658956
[4]	ZHANG G Y, MA D C, PENG C N, LIU X X, XU G W. Process characteristics of hydrothermal treatment of antibiotic residue for solid biofuel[J]. Chem Eng J, 2014, 252(252):230-238. https://www.cabdirect.org/cabdirect/abstract/20143295251
[5]	Ma D C, Zhang G Y, Zhao P T, AREEPRASERT C, SHEN Y F, YOSHIKAWA K, XU G W. Hydrothermal treatment of antibiotic mycelial dreg:More understanding from fuel characteristics[J]. Chem Eng J, 2015, 273(8):147-155. http://www.irgrid.ac.cn/handle/1471x/975435
[6]	尤占平, 郝长生, 焦永刚, 赵亮, 封春红.两种抗生素菌渣热解及燃烧特性对比研究[J].工业安全与环保, 2016, 42(05):41-43. doi: 10.3969/j.issn.1001-425X.2016.05.012 YOU Zhan-ping, HAO Chang-sheng, JIAO Yong-gang, ZHAO Liang, FENG Chun-hong. Pyrolysis and combustion characteristics comparison studies of two kinds of antibiotic residues[J]. Ind Safety Environ Prot, 2016, 42(05):41-43. doi: 10.3969/j.issn.1001-425X.2016.05.012
[7]	贡丽鹏. 土霉素菌渣热解技术的研究[D]. 石家庄: 河北科技大学, 2012. GONG Li-peng. Research on pyrolysis technology of terramycin bacterial residue[D]. Shijiazhuang:Hebei University of Science & Technology, 2012.
[8]	ZHOU B H, GAO Q, WANG H H, DUAN E H, GUO B, ZHU N. Preparation, characterization, and phenol adsorption of activated carbons from oxytetracycline bacterial residue[J]. J Air Waste Manage, 2012, 62(12):1394-1402. doi: 10.1080/10962247.2012.716013
[9]	YANG S J, ZHU X D, WANG J S, XING J, LIU Y C, FENG Q, ZHANG S C, CHEN J M. Combustion of hazardous biological waste derived from the fermentation of antibiotics using TG-FTIR and Py-GC/MS techniques[J]. Bioresource Technol, 2015, 193:156-163. doi: 10.1016/j.biortech.2015.06.083
[10]	DU Y Y, JIANG X G, MA X J, LIU X D, LÜ G J, JIN Y Q, WANG F, CHI Y, YAN J H. Evaluation of cofiring bioferment residue with coal at different proportions:Combustion characteristics and kinetics[J]. Energy Fuels, 2013, 27(10):6295-6303. doi: 10.1021/ef401536b
[11]	BALAT M, BALAT M, KIRTAY E, BALAT H. Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1:Pyrolysis systems[J]. Energy Convers Manage, 2009, 50(12):3147-3157. doi: 10.1016/j.enconman.2009.08.014
[12]	HANSSON K M, SAMUELSSON J, TULLIN C, AMAND L E. Formation of HNCO, HCN, and NH₃ from the pyrolysis of bark and nitrogen-containing model compounds[J]. Combust Flame, 2004, 137(3):265-277. doi: 10.1016/j.combustflame.2004.01.005
[13]	CAO J J, SHEN Z X, CHOW J C, WATSON J G, LEE S C, TIE X X, HO K F, WANG G H, HAN Y M. Winter and summer PM_2.5 chemical compositions in fourteen chinese cities[J]. J Air Waste Manage, 2012, 62(10):1214-1226. doi: 10.1080/10962247.2012.701193
[14]	TIAN F J, LI B Q, CHEN Y, LI C Z. Formation of NO_x precursors during the pyrolysis of coal and biomass. Part Ⅴ. Pyrolysis of a sewage sludge[J]. Fuel, 2002, 81(17):2203-2208. doi: 10.1016/S0016-2361(02)00139-4
[15]	TIAN F J, YU J L, MCKENZIE L J, HAYASHI J I, CHIBA T, LI C Z. Formation of NO_x precursors during the pyrolysis of coal and biomass. Part Ⅶ. Pyrolysis and gasification of cane trash with steam[J]. Fuel, 2005, 84(4):371-376. doi: 10.1016/j.fuel.2004.09.018
[16]	CAO J P, LI L Y, MORISHITA K, XIAO X B, ZHAO X Y, WEI X Y, TAKARADA T. Nitrogen transformations during fast pyrolysis of sewage sludge[J]. Fuel, 2013, 104:1-6. doi: 10.1016/j.fuel.2010.08.015
[17]	TIAN Y, ZHANG J, ZUO W, CHEN L, CUI Y N, TAN T. Nitrogen conversion in relation to NH₃ and HCN during microwave pyrolysis of sewage sludge[J]. Environ Sci Technol, 2013, 47(7):3498-3505. doi: 10.1021/es304248j
[18]	WEI L H, WEN L, YANG T H, ZHANG N. Nitrogen transformation during sewage sludge pyrolysis[J]. Energy Fuels, 2015, 29(8):5088-5094. doi: 10.1021/acs.energyfuels.5b00792
[19]	成建华, 张文莉.抗生素菌渣处理工艺设计[J].化工与医药工程, 2003, 24(2):31-34. http://www.cnki.com.cn/Article/CJFDTOTAL-YGCJ200302014.htm CHENG J H, ZHANG W L. Technological design of antibiotic residue treatment[J]. Chem Pharm Eng, 2003, 24(2):31-34. http://www.cnki.com.cn/Article/CJFDTOTAL-YGCJ200302014.htm
[20]	MA D C, ZHANG G Y, AREEPRASERT C, LI C X, SHEN Y F, YOSHIKAWA K, XU G W. Characterization of NO emission in combustion of hydrothermally treated antibiotic mycelial residue[J]. Chem Eng J, 2016, 284(1):708-715. https://www.deepdyve.com/lp/elsevier/characterization-of-no-emission-in-combustion-of-hydrothermally-5KziAkwD9K
[21]	ZHU X D, YANG S J, WANG L, LIU Y C, QIAN F, YAO W Q, ZHANG S C, CHEN J M. Tracking the conversion of nitrogen during pyrolysis of antibiotic mycelial fermentation residues using XPS and TG-FTIR-MS technology[J]. Environ Pollut, 2016, 211:20-27. doi: 10.1016/j.envpol.2015.12.032
[22]	CHEN H F, WANG Y, XU G W, YOSHIKAWA K. Fuel-N evolution during the pyrolysis of industrial biomass wastes with high nitrogen content[J]. Energies, 2012, 5(12):5418-5438. doi: 10.3390/en5125418
[23]	ZHAN H, YIN X L, Huang Y Q, Zhang X H, Yuan H Y, Xie J J, Wu C Z. Characteristics of NO_x precursors and their formation mechanism during pyrolysis of herb residues[J]. J Fuel Chem Technol, 2017, 45(3):279-288. doi: 10.1016/S1872-5813(17)30017-8
[24]	KELEMEN S R, AFEWORKI M, GORBATY M L, KWIATEK P J, SANSONE M, WALTERS C C, COHEN A D. Thermal transformations of nitrogen and sulfur forms in peat related to coalification[J]. Energy Fuels, 2006, 20(2):635-652. doi: 10.1021/ef050307p
[25]	TIAN K, LIU W J, QIAN T T, JIANG H, YU H Q. Investigation on the evolution of N-containing organic compounds during pyrolysis of sewage sludge[J]. Environ Sci Technol, 2014, 48(18):10888-10896. doi: 10.1021/es5022137
[26]	李梅, 杨俊和, 张启锋, 常海洲, 孙慧.用XPS研究新西兰高硫煤热解过程中氮、硫官能团的转变规律[J].燃料化学学报, 2013, 41(11):1287-1293. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18287.shtml LI Mei, YANG Jun-he, ZHANG Qi-feng, CHANG Hai-zhou, SUN Hui. XPS study on transformation of N-and S-functionalgroups during pyrolysis of high sulfur New Zealand coal[J]. J Fuel Chem Technol, 2013, 41(11):1287-1293. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18287.shtml
[27]	郭斌, 贡丽鹏, 刘仁平, 任爱玲, 宋汉宁.土霉素菌渣的热解特性及动力学研究[J].太阳能学报, 2013, 34(9):1504-1508. http://www.cnki.com.cn/Article/CJFDTOTAL-TYLX201309003.htm GUO Bin, GONG Li-peng, LIU Ren-ping, REN Ai-ling, SONG Han-ling. Study on pyrolysis characteristics and kinetics of terramycin bacterial residue[J]. Acta Energi Sin, 2013, 34(9):1504-1508. http://www.cnki.com.cn/Article/CJFDTOTAL-TYLX201309003.htm
[28]	詹昊, 张晓鸿, 阴秀丽, 吴创之.生物质热化学转化过程含N污染物形成研究进展[J].化学进展, 2016, 28(12):1880-1890. doi: 10.7536/PC160438 ZHAN Hao, ZHANG Xiao-hong, YIN Xiu-li, WU Chuang-zhi. Formation of nitrogenous pollutants during biomass thermo-chemical conversion[J]. Prog Chem, 2016, 28(12):1880-1890. doi: 10.7536/PC160438
[29]	CHEN H F, NAMIOKA T, YOSHIKAWA K. Characteristics of tar, NO_x precursors and their absorption performance with different scrubbing solvents during the pyrolysis of sewage sludge[J]. Appl Energ, 2011, 88(12):5032-5041. doi: 10.1016/j.apenergy.2011.07.007
[30]	HANSSON K M, AMAND L E, HABERMANN A, WINTER F. Pyrolysis of poly-L-leucine under combustion-like conditions[J]. Fuel, 2003, 82(6):653-660. doi: 10.1016/S0016-2361(02)00357-5
[31]	刘海明, 张军营, 郑楚光, 孟韵.煤中吡咯型和吡啶型氮热解稳定性研究[J].华中科技大学学报:自然科学版, 2004, 32(11):13-15. http://www.cnki.com.cn/Article/CJFDTOTAL-HZLG200411004.htm LIU Hai-ming, ZHANG Jun-ying, ZHENG Chu-guang, MENG Yun. Quantum chemical study of the pyrolysis stability of pyrrolic nitrogen and pyridinic nitrogen in coal[J]. J Huazhong Univ Sci Technol:Nat Sci Ed, 2004, 32(11):13-15. http://www.cnki.com.cn/Article/CJFDTOTAL-HZLG200411004.htm
[32]	XIE Z L, FENG J, ZHAO W, XIE K C, PRATT K C, LI C Z. Formation of NO_x and SO_x precursors during the pyrolysis of coal and biomass. Part Ⅳ. Pyrolysis of a set of Australian and Chinese coals[J]. Fuel, 2001, 80(15):2131-2138. doi: 10.1016/S0016-2361(01)00103-X