秸秆烘焙过程氯、硫释放及AAEMs迁徙转化特性研究

doi:10.11949/0438-1157.20200628

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5785-5792.DOI: 10.11949/0438-1157.20200628

秸秆烘焙过程氯、硫释放及AAEMs迁徙转化特性研究

蒋好^1,²(),朱有健^1,³(),刘恒¹,邵敬爱^1,⁴,成伟¹,杨鹏¹,吴贵豪¹,杨海平¹(),陈汉平^1,⁴

^1.华中科技大学能源与动力工程学院煤燃烧国家重点实验室，湖北武汉 430074
^2.华中科技大学中欧清洁与可再生能源学院，湖北武汉 430074
^3.郑州轻工业大学能源与动力工程学院，河南郑州 450002
^4.华中科技大学能源与动力工程学院新能源科学与工程系，湖北武汉 430074

收稿日期:2020-05-22 修回日期:2020-08-05 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 朱有健,杨海平
作者简介:蒋好（1994—），男，硕士研究生，jiang_hao@hust.edu.cn
基金资助:
国家自然科学基金项目(51706210)

Release and transformation characteristics of chlorine, sulfur and AAEMs during cornstalk torrefaction

JIANG Hao^1,²(),ZHU Youjian^1,³(),LIU Heng¹,SHAO Jing'ai^1,⁴,CHENG Wei¹,YANG Peng¹,WU Guihao¹,YANG Haiping¹(),CHEN Hanping^1,⁴

^1.State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^2.China-EU Institute for Clean and Renewable Energy, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^3.School of Energy and Power Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, Henan, China
^4.Department of New Energy Science and Engineering, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2020-05-22 Revised:2020-08-05 Online:2020-12-05 Published:2020-12-05
Contact: ZHU Youjian,YANG Haiping

摘要/Abstract

摘要：

利用固定床管式炉研究了玉米秆中氯、硫、碱及碱土金属（AAEMs）在不同烘焙温度下的释放和迁徙转化规律。研究发现氯、硫的释放率随烘焙温度升高呈递增趋势，在220~300℃范围内氯和硫的释放率分别为10%~40%和27%~60%。烘焙后样品中氯的绝对含量相比原样有所增加，并且以碱金属氯化物形式存在的无机氯占比减少，有机氯占比增加；硫的绝对含量显著降低，烘焙后可达到Ⅰ级成型燃料中硫含量要求。AAEMs在烘焙过程中释放率均较低，但赋存形态发生一定变化，主要表现为水溶性AAEMs含量降低，有机结合态AAEMs含量增加，此外盐酸酸溶性和不溶性Ca、Mg的占比也有一定程度增加。

关键词: 玉米秆, 烘焙, 无机组分, 碱及碱土金属, 释放, 迁徙转化

Abstract:

A fixed-bed tube furnace was used to study the release and migration and transformation of chlorine, sulfur, alkali and alkaline earth metals (AAEMs) in corn stalks at different baking temperatures. It was found that the release ratios of chlorine and sulfur, which increased continuously with temperature in the range of 220—300℃, were 10%—40% and 27%—60%, respectively. However, the absolute content of chlorine increased after torrefaction with the decreased ratio of alkali metal chloride and increased ratio of organochlorine (C—Cl). The absolute content of sulfur decreased significantly after torrefaction, meeting the sulfur requirement of commercial biomass pellets. In addition, the proportion of acid-soluble and insoluble Ca and Mg in hydrochloric acid also increased to a certain extent.

Key words: cornstalk, torrefaction, inorganic species, alkali and alkaline earth metallic species, release, migration and transformation

中图分类号:

TK 6

蒋好,朱有健,刘恒,邵敬爱,成伟,杨鹏,吴贵豪,杨海平,陈汉平. 秸秆烘焙过程氯、硫释放及AAEMs迁徙转化特性研究[J]. 化工学报, 2020, 71(12): 5785-5792.

JIANG Hao,ZHU Youjian,LIU Heng,SHAO Jing'ai,CHENG Wei,YANG Peng,WU Guihao,YANG Haiping,CHEN Hanping. Release and transformation characteristics of chlorine, sulfur and AAEMs during cornstalk torrefaction[J]. CIESC Journal, 2020, 71(12): 5785-5792.

图/表 8

表1 玉米秆（CS）和烘焙玉米秆（TCS）的性质分析

Table 1 Properties of raw and torrefied cornstalk

样品	工业分析^①/%(mass)			元素分析^①/%(mass)					O/C 原子比	H/C 原子比	LHV/ (MJ/kg)	固体产率/%	能量产率/%
样品	灰分	挥发分	固定碳	C	H	O^②	N	S	O/C 原子比	H/C 原子比	LHV/ (MJ/kg)	固体产率/%	能量产率/%
CS	8.69	73.87	17.44	43.06	5.72	41.67	0.74	0.123	0.73	1.58	16.17	—	—
TCS₂₂₀	9.47	71.53	19.00	44.67	5.56	39.16	1.04	0.097	0.66	1.48	16.54	93.02	95.15
TCS₂₆₀	10.55	62.59	26.86	46.86	5.32	36.14	1.05	0.084	0.58	1.35	17.02	79.23	83.39
TCS₃₀₀	11.29	45.45	43.26	55.42	4.61	27.42	1.16	0.098	0.37	0.99	19.08	49.60	58.53

表2 玉米秆灰元素组成分析

Table 2 Ash chemical composition of cornstalk

氧化物	含量/%(mass)
Na₂O	3.56
MgO	8.09
Al₂O₃	3.23
SiO₂	26.79
P₂O₅	4.57
SO₃	8.61
K₂O	35.96
CaO	8.4
MnO	0.14
Fe₂O₃	0.65

图1 玉米秆烘焙实验装置1—氮气；2—质量流量计；3—冷却区；4—石英管反应器；5—温度控制器；6—电热炉体；7—准备区；8—尾气吸收装置；9—进样杆；10—陶瓷坩埚；11—反应区

Fig.1 Schematic diagram of cornstalk torrefaction

图2 烘焙过程氯、硫释放率及样品中绝对含量

Fig.2 Release ratio and absolute concentration of chlorine and sulfur during cornstalk torrefaction

图3 氯、硫的释放率与样品失重率

Fig.3 Release ratio of chlorine and sulfur versus mass loss during cornstalk torrefaction

表3 玉米秆烘焙碱和碱土金属含量及释放率

Table 3 Concentration and release rate of AAEMs during cornstalk torrefaction

元素	含量/(mg/g)		释放率/%
元素	玉米秆	300℃烘焙玉米秆	释放率/%
K	14.32	25.77	10.71
Na	0.33	0.58	12.82
Ca	4.29	7.44	13.92
Mg	3.67	6.46	12.79

图4 玉米秆Cl 2p XPS谱图和曲线拟合结果

Fig.4 Chlorine 2p XPS spectra with curve-fitting result

图5 玉米秆和300℃烘焙玉米秆中AAEMs的赋存形态R—玉米秆；T—300℃烘焙玉米秆

Fig.5 Speciation and distribution of AAEMs extracted from CS and TCS300

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秸秆烘焙过程氯、硫释放及AAEMs迁徙转化特性研究

Release and transformation characteristics of chlorine, sulfur and AAEMs during cornstalk torrefaction

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