富氮生物质原料热解过程中NO<sub><i>x</i></sub>前驱物释放特性研究

张晓鸿; 詹昊; 阴秀丽; 吴创之

富氮生物质原料热解过程中NO_x前驱物释放特性研究

张晓鸿^{1, 2},
詹昊^{1, 2},
阴秀丽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

详细信息

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2016-06-23
- 修回日期: 2016-09-15
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-12-10

Release characteristic of NO_x precursors during the pyrolysis of nitrogen-rich biomass

ZHANG Xiao-hong^{1, 2},
ZHAN Hao^{1, 2},
YIN Xiu-li¹,
WU Chuang-zhi^{1
, ,}

1.
Key Laboratory of Renewable Energy, CAS, Guangdong 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

More Information

Corresponding author: wucz@ms.giec.ac.cn

摘要

摘要: 利用热重分析-傅里叶红外光谱联用（TG-FTIR）和水平管式炉-X射线光电子能谱（XPS）研究了两种富氮生物质原料（大豆秸秆（SBS）和纤维板（FB））热解过程中NO_x前驱物（NH₃、HCN和HNCO）的释放特性，考察温度、升温速率及燃料含N物质结构对其NO_x前驱物释放行为的影响。结果表明，燃料中的N来源不同（天然固有与人工添加）造成其转化差异：SBS释放的NO_x前驱物主要为NH₃而FB为NH₃、HCN（快速）和HNCO（慢速）；FB气相N主要随挥发分析出，而SBS则相反，在二次反应阶段析出；两种燃料中N的转化随温度变化，低温下富集于半焦N，600℃以上时更多向非半焦N转移，NO_x前驱物以NH₃为主，高温及高升温速率利于HCN生成，若以减排NO_x为目的，热解温度控制在600℃为佳；两种燃料中N的结构均为胺类N（N-A），热解时部分N-A向半焦中杂环N转化，同时伴随杂环N分解；高温下吡啶N和吡咯N分解分别主要产生HCN和NH₃。
- 大豆秸秆 /
- 纤维板 /
- 热解 /
- NO_x前驱物 /
- 含氮结构
Abstract: The release of NO_x precursors (NH₃, HCN and HNCO) in the pyrolysis of two nitrogen-rich biomass materials, viz., soybean straw (SBS) and fiberboard (FB), were investigated by thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR, for slow pyrolysis) and horizontal tubular reactor-X-ray photoelectron spectroscopy (HTR-XPS, for rapid pyrolysis); the effects of final temperature, heating rate and nitrogen form in biomass on the release characteristic were considered. The results indicate that the evolution pathway is related to the form of nitrogen in biomass; nitrogen in SBS (SBS-N) is mainly converted to NH₃ during the secondary cracking reaction, whereas nitrogen in FB (FB-N) is transformed to NH₃, HCN (rapid) and HNCO (slow) during the primary pyrolysis reaction. Nitrogen in biomass (fuel-N) is inclined to convert to nitrogen in char (char-N) at low temperature and to nitrogen in tar (tar-N) or NO_x precursors at high temperature (>600℃), which suggests that a pyrolysis temperature below 600℃ can suppress the release of NO_x precursors. SBS-N and FB-N are characterized by protein and amide, respectively, which are partly converted to pyrrolic-N and pyridinic-N in char, forming preferably NH₃ and HCN, respectively.
- soybean straw /
- fiberboard /
- pyrolysis /
- NO_xprecursor /
- form of nitrogen

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图 1 SBS和FB结构示意图

Figure 1 Structure diagrams of SBS and FB

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图 2 快速热解实验装置示意图

Figure 2 Schematic diagram of the reactor for rapid pyrolysis

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图 3 SBS与FB热解失重曲线(升温速率： 40K/min)

Figure 3 Curves of weight and its derivative during the slow pyrolysis of SBS and FB with a heating rate of 40K/min

(a): weight change; (b): deriv.weight change

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图 4 SBS与FB慢速热解气相产物红外三维谱图 (升温速率： 40K/min)

Figure 4 3D FT-IR spectra of gaseous products during the slow pyrolysis of SBS and FB with a heating rate of 40K/min

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图 5 SBS与FB热解气相产物的红外光谱谱图

Figure 5 FT-IR spectra of gaseous products for the pyrolysis of SBS (a) and FB (b) at 360℃

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图 6 NH₃和HNCO吸光度随热解温度的变化

Figure 6 Absorbance profile of NH₃ and HNCO during the pyrolysis

(a): SBS-NH₃； (b): FB-NH₃； (c): FB-HNCO

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图 7 SBS与FB热解气相产物的红外光谱谱图

Figure 7 FT-IR spectra of gaseous pyrolysis products for SBS at 660℃ (a) and FB at 280℃(b)

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图 8 SBS与FB快速热解NH₃、 HCN产率随热解终温的变化

Figure 8 Yields of gaseous nitrogen-containing products during the rapid pyrolysis of SBS (a) and FB (b)

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图 9 FB与SBS快速热解N产物分布随热解温度变化

Figure 9 Nitrogen distribution in various products during the rapid pyrolysis of SBS (a) and FB (b)

Figure 9 : NO_x precurrsor; : other-N; : char-N

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图 10 原料及特征温度下半焦的N 1s谱图

Figure 10 N 1s XPS spectra of the biomass and derived char by pyrolysis

(a): raw-SBS; (b): SBS-char-500; (c): SBS-char-700; (d): raw-FB; (e): FB-char-500; (f): FB-char-700

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图 11 FB与SB热解过程各含N结构相对含量随温度的变化

Figure 11 Forms of nitrogen in the raw biomass and derived char during the rapid pyrolysis of (a) SBS and (b) FB

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图 12 氨基酸热解N转化路径示意图

Figure 12 Evolution of amino acid nitrogen duirng pyrolysis

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图 13 生物质热解半焦N转化路径示意图

Figure 13 Evolution of Char-N during the biomass pyrolysis

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表 1 豆秸与纤维板的元素分析与工业分析

Table 1 Ultimate and proximate analysis of soybean straw (SBS) and fiberboard (FB)

Sample	Ultimate analysis w/%(dry-ash free basis)					Proximate analysis w/%(dry basis)
Sample	C	H	N	S	O^*	V	FC	A
SBS	46.74	6.59	1.40	0.06	45.21	77.77	16.91	5.32
FB	44.79	6.16	7.49	0.01	41.55	83.56	16.13	0.30
^*: calculated by difference

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