松木屑与废橡胶化学链共气化特性试验

doi:10.16085/j.issn.1000-6613.2019-1067

摘要/Abstract

摘要：

在自行设计的两级固定床反应器上，对以天然贫铁矿石为载氧体的松木屑与废橡胶化学链共气化特性进行了研究。考察了载氧体的存在、废橡胶掺混比例、一级反应器温度、水蒸气流量等因素对生物质化学链共气化过程的影响。结果表明：载氧体的存在能显著改善气化效果；掺混一定量的废橡胶可以显著提高低位热值和碳转化率，并且呈现协同效应。本试验中最佳的废橡胶掺混比例为20%；共气化过程中的产气率、碳转化率均随温度的增加（750～950℃）而逐渐升高，但热值随温度的升高而有所下降；水蒸气流量的增加能显著提高合成气中H₂的含量，进水流量保持在0.66g/min时，能实现生物质共气化过程产气率、碳转化率、低位热值等各项指标的最佳平衡。通过扫描电镜（SEM）、X射线衍射（XRD）等表征分析，发现天然贫铁矿石在长时间运行中表现良好的反应性和耐磨损性。

关键词: 生物质, 贫铁矿石, 化学链, 合成气, H₂/CO比

Abstract:

The chemical loopingco-gasification process of sawdust and waste tires with natural lean iron ore as oxygen carrier was studied on a self-designed two-stage fixed-bed reactor. The effects of the presence of oxygen carrier, blending ratio of waste tires, the temperature of first-stage reactor and water flow rate on the chemical loopingco-gasification process of biomass were investigated. The results showed that the presence of oxygen carrier could significantly improve the gasification effect and increase the gas yield; blending a certain amount of waste tires could significantly improve low calorific value and carbon conversion efficiency, and exhibited synergistic effect, the best blending ratio of waste tires in this experiment was 20%; the gas yield and carbon conversion efficiency in theco-gasification process rose with the increase of temperature, and the synergistic effect was gradually enhanced, but the lower calorific value decreased with the increase of temperature; the rise of water flow rate could significantly increase the content of H₂ in the synthesis gas, and when the water flow rate was maintained at 0.66g/min, the optimum balance of the gas yield, carbon conversion efficiency and low calorific value and other indicators of the biomassco-gasification process could be realized. Characterization and analysis by scanning electron microscopy (SEM) and X-ray diffraction (XRD) showed that natural lean iron ore exhibited good reactivity and wear resistance during long-term operation.

Key words: biomass, natural lean iron ore, chemical looping gasification, syngas, H₂/CO ratio

中图分类号:

汪德成,金保昇,金朝阳,吴畏,周正. 松木屑与废橡胶化学链共气化特性试验[J]. 化工进展, 2020, 39(3): 956-965.

Decheng WANG,Baosheng JIN,Zhaoyang JIN,Wei WU,Zheng ZHOU. High hydrogen syngas production from chemical loopingco-gasification of sawdust and waste tires[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 956-965.

图/表 17

表1 试验物料工业分析与元素分析（空干基）

物料	工业分析				元素分析(质量分数)/%
物料	M/%	V/%	FC/%	A/%	C	H	O	N	S
松木屑	6.34	78.76	14.24	0.66	47.62	6.75	43.10	0.48	0.26
废橡胶	0.74	56.28	17.34	25.64	62.85	4.92	9.50	0.52	2.30

表2 天然贫铁矿石组分分析

成分	质量分数/%
Fe₂O₃	44.16
SiO₂	18.93
Al₂O₃	2.98
CaO	17.09
MgO	7.43
SO₃	2.35
其他	7.06

图1 两级固定床反应器示意图1—加料器；2—固定床；3—电炉；4—热电偶；5—温控箱；6—冰水浴；7—蠕动泵；8—蒸汽发生器；9—烟气分析仪

图2 载氧体存在对气体产物体积的影响（850℃）

图3 不同床料对产物气体组分的影响随时间变化规律

图4 废橡胶掺混比例对产物气体组分的影响

图5 掺混比例对碳转换率和低位热值的影响

图6 协同效应对碳转化率的影响

图7 温度对产物气体组分的影响

表3 不同温度条件下的试验结果

一级反应器温度/℃	产气率/m³·kg^-1	低位发热量/kJ·m^-3	碳转换率/%
750	0.43	13165	29
800	0.67	13070	42
850	0.83	12144	48
900	1.15	12749	67
950	1.38	12057	74

图8 水蒸气流量对产物气体组分的影响

图9 水蒸气流量对H2/CO的影响

图10 水蒸气流量对合成气热值和效率的影响

图11 水蒸气流量对碳转化率的影响

图12 载氧体反应前后的SEM形貌分析

图13 载氧体反应前后的EDS分析

图14 载氧体反应前后的XRD分析

A―Fe2O3；B―Fe3O4；C―FeO；D―SiO2

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