糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用

doi:10.11949/0438-1157.20211028

化工学报 ›› 2021, Vol. 72 ›› Issue (11): 5770-5778.DOI: 10.11949/0438-1157.20211028

糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用

王文燕^1,³(),张光义^2,³(),孟辉波¹,朱新宇^1,³,张建岭³,许光文¹

^1.沈阳化工大学机械与动力工程学院，辽宁沈阳 110142
^2.北京工商大学生态环境学院，北京 100048
^3.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190

收稿日期:2021-07-23 修回日期:2021-09-06 出版日期:2021-11-05 发布日期:2021-11-12
通讯作者: 张光义
作者简介:王文燕（1995—），女，硕士研究生，wywang2121@163.com
基金资助:
国家重点研发计划项目(2019YFC1906805)

Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NO_x emission from its combustion flue gas

Wenyan WANG^1,³(),Guangyi ZHANG^2,³(),Huibo MENG¹,Xinyu ZHU^1,³,Jianling ZHANG³,Guangwen XU¹

^1.School of Mechanical and Power Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China
^2.School of Ecology and Environment, Beijing Technology and Business University, Beijing 100048, China
^3.State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2021-07-23 Revised:2021-09-06 Online:2021-11-05 Published:2021-11-12
Contact: Guangyi ZHANG

摘要/Abstract

摘要：

通常，具有高含氮资源禀赋生物质在能源化利用过程中需控制NO_x排放。解耦燃烧是可适用于高含水、高含氮燃料的低NO_x燃烧技术，其对NO_x生成的抑制效果优于其他燃烧技术。为揭示解耦燃烧中热解挥发产物的原位控氮潜力、发展双流化床解耦燃烧技术，以糠醛渣为原料，借助固定床装置和双流化床装置，分别开展其热解特性和双流化床解耦燃烧近实际工况模拟研究。具体地，首先在固定床反应器中考察糠醛渣在不同温度下的热解产物分布，继而借助双流化床反应器考察了热解在线挥发产物对热解半焦同步燃烧烟气中NO_x的还原效果。结果表明：在500~700℃热解温度区间内，随温度的升高，半焦产率逐渐减少，从45.2%下降到39.8%；气体产率呈明显上升趋势，从12.4%上升到22.5%，CO、CH₄、H₂等还原性组分产率增加显著；焦油产率略有降低，从15.9%降低到12.9%；水分产率变化不大。双流化床解耦燃烧实验中，糠醛渣热解挥发产物对热解半焦同步燃烧所产烟气控氮效果良好，热解挥发产物对半焦燃烧烟气NO_x减排效果主要受热解温度、二次风占比影响，总过量空气系数ER=1.3，热解温度600℃、二次风过量空气系数ER₂=0.5时，糠醛渣热解挥发产物对相同热解条件下生成的半焦燃烧（900℃，过量空气系数ER₁=0.8）所产烟气原位控氮效果达到最优，NO_x减排率为54.80%。这表明，可通过控制热解挥发分产物产率、氧化程度，充分发挥挥发分的NO_x还原能力，从而明显改善解耦燃烧原位控氮效果。

关键词: 糠醛渣, 热解, 解耦燃烧, NO_x排放, 原位控氮

Abstract:

Generally, biomass with high nitrogen resource endowments needs to control NO_x emissions in the process of energy utilization. Decoupled combustion falls within low-NO_x combustion technologies, which is suitable for high-water, high-nitrogen fuels and has better effects on suppressing NO_x formation compared to other combustion technologies. In order to make clear the potential of pyrolysis volatile for in-situ nitrogen control in decoupled combustion and to develop the dual fluidized bed decoupled combustion technology, with furfural residue as the material, a fixed-bed reactor and a dual fluidized bed combustion apparatus were respectively employed for studying its pyrolysis characteristics and simulating its decoupled combustion in the dual fluidized bed at approximately actual working conditions in this paper. Concretely, the product distribution of furfural residue pyrolysis at different temperatures was first investigated in the fixed-bed reactor, and then the effects of the on-line pyrolysis products on in-situ control of NO_x emission from synchronous combustion of the resulting pyrolysis char of the raw material in the dual fluidized bed combustion apparatus were revealed. The results showed that: in the pyrolysis temperature range of 500—700℃, with the increase of temperature, the semi-coke yield gradually decreased, from 45.2% to 39.8%; the gas yield showed an obvious upward trend, rising from 12.4% to 22.5%, the yield of reducing components such as CO, CH₄, and H₂ increased significantly; the yield of tar decreased slightly, from 15.9% to 12.9%; the yield of water did not change much. During the decoupling combustion experiments using the double fluidized bed, it was found that the volatiles produced by pyrolysis from furfural residue exhibited a good effect on in-situ nitrogen control for the combustion flue gas from its resulting pyrolysis char. The NO_x control effect of the pyrolysis volatiles for the char combustion flue gas depended heavily on the pyrolysis temperature and the proportion of secondary air. When the total excess air factor ER was 1.3, the pyrolysis temperature 600℃ and the secondary excess air factor ER₂=0.5, the effect of the volatiles from furfural residue pyrolysis on the in-situ nitrogen control for the flue gas from combustion (at 900℃ with the first excess air factor ER₁=0.8) of the char produced by pyrolysis at the same conditions reached the best, and the NO_x emission reduction ratio was high as 54.80%. These indicated that the yields and oxidation degrees of pyrolysis volatile products can be regulated to bring their potential for NO_x reduction into full play, thus visibly improving the in-situ nitrogen control effect for decoupled combustion.

Key words: furfural residue, pyrolysis, decoupled combustion, NO_x emission, in-situ nitrogen control

中图分类号:

TK 6

王文燕, 张光义, 孟辉波, 朱新宇, 张建岭, 许光文. 糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用[J]. 化工学报, 2021, 72(11): 5770-5778.

Wenyan WANG, Guangyi ZHANG, Huibo MENG, Xinyu ZHU, Jianling ZHANG, Guangwen XU. Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NO_x emission from its combustion flue gas[J]. CIESC Journal, 2021, 72(11): 5770-5778.

图/表 10

表1 糠醛渣的工业分析和元素分析

Table 1 Proximate and ultimate analyses of furfural residues

Proximate analysis/%(mass, dry)			Ultimate analysis/%(mass, dry)
Ash	Volatile	Fixed carbon	C	H	O^①	N	S
21.93	64.61	13.46	42.74	4.46	38.23	0.58	0.53

图1 糠醛渣固定床热解装置流程图1—high pressure nitrogen cylinder; 2—pressure reducing valve; 3—pressure gauge; 4—mass flowmeter; 5—temperature transmitter; 6—temperature controller; 7—fixed bed gold furnace; 8—condenser; 9—temperature circulator; 10—filter flask; 11—cold trap tank; 12—tar collecting bottle; 13—saturated sodium bicarbonate bottle; 14—color-changing silicone bottle; 15—wet flowmeter; 16—gas bag

Fig.1 Schematic diagram of the fixed bed reactor for furfural residue pyrolysis

图2 双流化床燃烧装置流程示意图1—high pressure nitrogen cylinder; 2—high pressure air cylinder; 3—pressure reducing valve; 4—rotor flow meter;5—two-stage electric heating furnace; 6—lower fluidized bed; 7—upper fluidized bed; 8—feed inlet

Fig.2 Flow diagram of the dual fluidized bed combustion apparatus

图3 糠醛渣不同温度下热解产物产率

Fig.3 Yields of the products from furfural residue pyrolysis at different temperatures

图4 糠醛渣在不同温度下热解气体产率

Fig.4 Yields of gas products from furfural residue pyrolysis at different temperatures

图5 糠醛渣900℃燃烧过程中NOx排放浓度随时间的变化

Fig.5 Temporal variation of the NOx emission concentration during furfural residue combustion at 900℃

图6 糠醛渣不同温度热解挥发分在900℃燃烧烟气NOx排放浓度和N转化率

Fig.6 NOx emission concentration and the N conversion rate during/after combustion (at 900℃) of the volatiles from furfural residue pyrolysis at different temperatures

图7 半焦层对糠醛渣挥发分燃烧NOx的减排效果

Fig.7 Effects of semi-coke layer on reducing the NOx emission from combustion of the furfural residue volatiles

图8 不同热解温度挥发分与半焦耦合燃烧NOx排放浓度与减排率

Fig.8 NOx emission concentration and NOx reduction rate during coupled combustion of volatiles and semi-cokes prepared at different pyrolysis temperatures

图9 一、二次风比对挥发分与半焦耦合燃烧NOx排放浓度、N转化率及NOx减排率的影响

Fig.9 Effects of the primary and secondary air ratios on the NOx emission concentration, the N conversion rate and the NOx reduction rate for coupled combustion of volatiles and semi-coke

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糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用

Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NO_x emission from its combustion flue gas

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糠醛渣热解特性及热解挥发产物对其燃烧烟气原位控氮作用

Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NOx emission from its combustion flue gas

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Furfural residue pyrolysis characteristics and the effect of its pyrolysis products on in-situ control of NO_x emission from its combustion flue gas