松木颗粒流态化两段气化制备清洁燃气的工艺稳定性验证

doi:10.16085/j.issn.1000-6613.2023-2028

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2576-2586.DOI: 10.16085/j.issn.1000-6613.2023-2028

• 新能源与可再生能源 • 上一篇

松木颗粒流态化两段气化制备清洁燃气的工艺稳定性验证

王欣宇¹^,²(), 王超¹^,²(), 张梦娟¹^,²(), 刘方正¹^,², 李晗旸¹^,², 王正林¹^,², 贾鑫¹^,², 宋兴飞¹^,², 许光文¹^,², 韩振南¹^,²()

^1.特色资源化工与材料教育部重点实验室，辽宁沈阳 110142
^2.沈阳化工大学能源与化工产业技术研究院，辽宁沈阳 110142

收稿日期:2023-11-21 修回日期:2024-03-05 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 王超,张梦娟,韩振南
作者简介:王欣宇（1997—），女，硕士研究生，研究方向为生物质气化。E-mail：13032460986@163.com。
基金资助:
国家自然科学基金新疆联合基金(U190310);国家自然科学基金青年科学基金(22108175);辽宁省教育厅高校基本科研项目(LJKMZ20220798)

Process stability verification of the two-stage fluidized bed gasification for pine particles to produce clean gas

WANG Xinyu¹^,²(), WANG Chao¹^,²(), ZHANG Mengjuan¹^,²(), LIU Fangzheng¹^,², LI Hanyang¹^,², WANG Zhenglin¹^,², JIA Xin¹^,², SONG Xingfei¹^,², XU Guangwen¹^,², HAN Zhennan¹^,²()

^1.Key Laboratory of Resources Chemicals and Materials (Shenyang University of Chemical Technology), Ministry of Education, Shenyang 110142, Liaoning, China.
^2.Institute of Energy and Chemical Industry Technology, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2023-11-21 Revised:2024-03-05 Online:2024-05-15 Published:2024-06-15
Contact: WANG Chao, ZHANG Mengjuan, HAN Zhennan

摘要/Abstract

摘要：

为了验证流态化两段气化工艺的长时间运行稳定性，本实验采用商用果木炭半焦作为松木流态化两段气化制备清洁燃气的催化床料。实验前期通过形成稳定的有效催化半焦床层，减少半焦在系统内的积累周期，以实现系统快速达到高效脱除焦油的目的。实验中，保持过量空气系数（ER）为0.35，提升管气速为3m/s，并逐渐调整流化介质中的氧气浓度，逐步增大生物质处理量。结果显示，随着松木颗粒的进料量从1kg/h增大到3kg/h，产品气中CO和H₂体积分数分别从7.71%和3.13%增长至16.15%和12.60%，CH₄的体积分数略微下降。气体收率（标准）也从0.90m³/kg增长至1.36m³/kg，相应的产品气热值（标准）从3.26MJ/m³增加至4.80MJ/m³。通过多次人为启停和改变运行参数等操作，在整个12h运行周期内，流态化两段气化产生的半焦与消耗的半焦速度相匹配，温度和压力表现出良好的运行稳定性。这一结果证明了流态化两段气化工艺在生物质制气中具有技术先进性和长时间运行稳定性。

关键词: 流态化, 两段气化, 循环流化床, 低焦油合成气, 生物质, 反应解耦

Abstract:

In order to verify the long-term operation stability of the two-stage fluidized bed gasification process, commercial fruit charcoal semi-coke is used as the catalytic bed material for the preparation of clean gas by pine fluidized two-stage gasification in this experiment. In the early stage of the experiment, a stable and effective catalytic semi-coke bed layer is formed to reduce the accumulation period of semi-coke, so as to quickly reach high-efficiency tar removal in the system. The excess air coefficient (ER) is maintained at 0.35, the gas velocity in the riser is 3m/s, and the oxygen concentration in the fluidization medium is gradually adjusted to gradually increase the biomass processing capacity. The results show that as the feed rate of pine particles increases from 1kg/h to 3kg/h, the volume percentages of CO and H₂ in the product gas increase from 7.71% and 3.13% to 16.15% and 12.60%, respectively, while the volume percentage of CH₄ slightly decreases. The gas yield also increases from 0.90m³/kg to 1.36m³/kg, and the corresponding calorific value of the product gas increases from 3.26MJ/m³ to 4.80MJ/m³. Through multiple manual start-stop and change of operating parameters, during the entire 12h operating cycle, the semi-coke produced by the fluidized two-stage gasification matches the speed of semi-coke consumption, and the temperature and pressure show good operating stability. This result proves that the two-stage fluidized bed gasification process has technological advancement and long-term operation stability in the production of gas from biomass.

Key words: fluidized, two-stage gasification, circulating fluidized bed, low-tar syngas, biomass, reaction decoupling

中图分类号:

TQ546.2

王欣宇, 王超, 张梦娟, 刘方正, 李晗旸, 王正林, 贾鑫, 宋兴飞, 许光文, 韩振南. 松木颗粒流态化两段气化制备清洁燃气的工艺稳定性验证[J]. 化工进展, 2024, 43(5): 2576-2586.

WANG Xinyu, WANG Chao, ZHANG Mengjuan, LIU Fangzheng, LI Hanyang, WANG Zhenglin, JIA Xin, SONG Xingfei, XU Guangwen, HAN Zhennan. Process stability verification of the two-stage fluidized bed gasification for pine particles to produce clean gas[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2576-2586.

图/表 13

图1 两级流化床反应器中果木炭辅助松木颗粒气化示意图

图2 用于生物质气化实验的两级流化床反应器示意图

图3 原料的照片和粒径分布

表1 原材料的元素分析和工业分析

样本	元素分析^②/%（质量分数）					低品位热值/MJ·kg^-1	工业分析^②/%（质量分数）
样本	C	H	O^①	N	S	低品位热值/MJ·kg^-1	挥发分	灰分	水分	固定碳^①
松木屑	50.31	5.86	42.86	0.18	0	19.84	84.19	0.79	7.67	7.35
外加半焦	75.96	3.72	11.33	0.54	0	32.15	32.42	8.45	2.33	56.80

图4 空气气氛下松木颗粒和外加半焦的TG和DTA曲线

表2 气化实验的实验条件及其关键操作数据

条件参数		实验 1	实验 2	实验 3
热载体	Al₂O₃	添加热载体质量/kg	6
ER	0.35	电炉（T0）温度/℃	950
外加半焦	商用果木炭	添加商用果木炭质量/kg	1.6
从物料平衡得到的理论提升管反应器气速/m·s^-1	3
生物质进料速率/kg·h^-1		1	2	3
O₂体积分数/%		8.9	17.8	26.6
N₂体积分数/%		91.1	82.2	73.4
气化器（T3）温度/℃		826.7	831.1	851.8
热解器（T1）温度/℃		649.3	688.1	690.3
气体收率（标准）/m³·kg^-1		0.90	0.94	1.36
产生气体低品位热值（标准）/MJ·m^-3		3.26	3.86	4.80
实际提升管气速/m·s^-1		2.77	3.34	4.62
平均焦油含量（标准）/g·m^-3		0.37

图5 预实验期间热解器和气化器的温度和压力的变化

图6 气化实验中热解器和气化器的温度和压力的变化

图7 不同情况下气体成分的时间序列变化

图8 不同情况下生产气的组成和相应的低热值

图9 不同情况的产气率和焦油产率的时间序列变化

图10 所得焦油样品的GC-MS表征1—2,6,6-四甲基-4-哌啶酮；2—蔡；3—2-甲基蔡萘；4—联苯；5—联苯；6—联苯；7—二苯并呋喃；8—芴；9—十七烷；10—9H芴、9-亚甲基；11—1-苯基萘；12—4H环戊并[deq]菲；13—邻苯二甲酸二丁酯；14—荧蔥；15—二十三烷；16—二十四烷；17—邻苯二甲酸二(2-乙基己基)酯

图11 原料和生成焦炭的形态特征

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松木颗粒流态化两段气化制备清洁燃气的工艺稳定性验证

Process stability verification of the two-stage fluidized bed gasification for pine particles to produce clean gas

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