In-situ sulfur fixation performance of Ca-Fe composite metal oxides during gasification of combustible municipal solid waste

doi:10.16085/j.issn.1000-6613.2022-0023

Abstract

Abstract:

Gasification technology can effectively alleviate the environmental threat caused by the increasing combustible municipal solid waste, but the H₂S and SO₂ produced by gasification still need to be removed to reduce the sulfur emission. The complex composition of combustible municipal solid waste requires suitable sulfur fixation reagent to remove H₂S and SO₂ simultaneously. In-situ sulfur fixation refers to the co-occurrence of gasification and sulfur removal after premixing raw materials and sulfur fixation reagent, and the sulfur pollutants are fixed in the ash. In this work, the typical components such as polystyrene particles and sawdust were mixed to simulate the combustible municipal solid waste and CO₂ was used as gasification agent. A series of Ca-Fe composite metal oxides were prepared by ball milling method and their in-situ sulfur fixation performance were further studied. The results showed that at 600℃, CaO/Fe₂O₃ mass ratio in Ca-Fe composite metal oxides has affected on the sulfur fixation rate. The sulfur fixation rate reached 82.65% when 1∶1 Ca-Fe composite metal oxides were used, better than other CaO/Fe₂O₃ mass ratios. In contrast, the sulfur fixation rates of using CaO and Fe₂O₃ solely were only 65.57% and 74.12% respectively. BET and SEM analysis showed the interactions between CaO and Fe₂O₃ during the composite metal oxides formation by ball milling, which affected the physico-chemical properties such as particle size distribution (PSD), pore size and specific surface area. Besides, the sintering phenomenon was much alleviated. Therefore, the best comprehensive performance was for the CaO/Fe₂O₃mass ratio of 1∶1.

Key words: municipal solid waste, gasification, in-situ sulfur fixation, composite metal oxide, ball milling method

摘要：

气化技术可有效缓解因可燃生活垃圾产量不断增加而衍生的环境问题，但仍需要对气化产生的H₂S和SO₂进行脱除以降低硫污染物排放风险。可燃生活垃圾组成的复杂性决定了需要开发适宜的双效固硫剂以对H₂S和SO₂一步脱除。原位固硫指将气化原料与固硫剂预先混合，气化与硫脱除同时进行且硫污染物被固定于灰渣中。本文使用聚苯乙烯颗粒、木屑等典型组分配制可燃生活垃圾作为气化原料，以CO₂为气化剂，采用球磨法制备了一系列Ca-Fe复合金属氧化物作为固硫剂并对其原位固硫性能进行了研究。结果表明，在600℃气化温度下，Ca-Fe复合金属氧化物中的CaO/Fe₂O₃比例对固硫率产生影响，且两者质量比为1∶1时固硫性能最佳，固硫率可达82.65%。作为对比，CaO和Fe₂O₃单一组分固硫率仅分别为65.57%和74.12%。BET、SEM等分析表明CaO、Fe₂O₃球磨形成复合金属氧化物时产生相互作用并影响粒径分布、孔径、比表面积等物化性质，且能够改善固硫剂的烧结现象，质量比为1∶1时综合作用效果最优。

关键词: 生活垃圾, 气化, 原位固硫, 复合金属氧化物, 球磨法

CLC Number:

X705

LIU Yang, HUANG Yaji, DONG Xinxin, DING Xueyu, YANG Xiaoyu, WANG Xinyu, ZHANG Zhenrong, CAO Gehan, LI Zhiyuan, TIAN Xinqi. In-situ sulfur fixation performance of Ca-Fe composite metal oxides during gasification of combustible municipal solid waste[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5677-5684.

刘洋, 黄亚继, 董新新, 丁雪宇, 杨晓域, 王新宇, 张臻荣, 曹歌瀚, 李志远, 田新启. 可燃生活垃圾气化Ca-Fe复合金属氧化物的原位固硫性能[J]. 化工进展, 2022, 41(10): 5677-5684.

Figures/Tables 11

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名称	工业分析/%				元素分析/%
名称	水分M_ad	灰分A_ad	挥发分V_ad	固定碳FC_ad	C_ad	H_ad	O_ad	N_ad	S_ad
橡胶	0.90	5.50	91.62	1.98	77.35	8.79	5.98	6.78	0.781
纸类	10.05	0.41	76.78	12.76	45.31	6.10	45.99	0.17	0.155
塑料	0.01	0.01	99.77	0.21	91.62	7.61	1.54	0.09	0.015
织物	5.73	0.24	86.98	7.05	42.30	6.19	50.37	0.24	0.056
木屑	18.31	1.40	68.79	11.05	41.94	5.48	42.69	0.17	0.043
厨余	13.10	0.41	77.12	9.37	39.42	6.57	50.02	1.19	0.085
混合样	6.21	0.61	85.57	5.91	61.05	6.91	29.61	0.86	0.103

名称	工业分析/%				元素分析/%
名称	水分M_ad	灰分A_ad	挥发分V_ad	固定碳FC_ad	C_ad	H_ad	O_ad	N_ad	S_ad
橡胶	0.90	5.50	91.62	1.98	77.35	8.79	5.98	6.78	0.781
纸类	10.05	0.41	76.78	12.76	45.31	6.10	45.99	0.17	0.155
塑料	0.01	0.01	99.77	0.21	91.62	7.61	1.54	0.09	0.015
织物	5.73	0.24	86.98	7.05	42.30	6.19	50.37	0.24	0.056
木屑	18.31	1.40	68.79	11.05	41.94	5.48	42.69	0.17	0.043
厨余	13.10	0.41	77.12	9.37	39.42	6.57	50.02	1.19	0.085
混合样	6.21	0.61	85.57	5.91	61.05	6.91	29.61	0.86	0.103

CaO∶Fe₂O₃	BET比表面积/m²·g^-1	孔体积/cm³·g^-1	平均孔径/nm
1∶1	8.0936	0.0361	29.7107
2∶1	7.6769	0.0476	26.2253
3∶1	5.4052	0.0505	25.8667
1∶2	5.8046	0.0285	20.1726
1∶3	3.7019	0.0180	22.0413

CaO∶Fe₂O₃	BET比表面积/m²·g^-1	孔体积/cm³·g^-1	平均孔径/nm
1∶1	8.0936	0.0361	29.7107
2∶1	7.6769	0.0476	26.2253
3∶1	5.4052	0.0505	25.8667
1∶2	5.8046	0.0285	20.1726
1∶3	3.7019	0.0180	22.0413

编号	停留时间/min	组分名称	化学式
a	11.688	phenol（苯酚）	C₆H₅OH
b	13.709	naphthalene（萘）	C₁₀H₈
c	15.598	naphthalene，1-methyl-（1-甲基萘）	C₁₁H₁₀
d	15.891	naphthalene，2-methyl-（2-甲基萘）	C₁₁H₁₀
e	16.822	biphenyl（联苯）	C₁₂H₁₀
f	17.595	diphenylemthane（二苯基甲烷）	C₁₃H₁₂
1	19.291	bibenzyl（联苄）	C₁₄H₁₄
2	19.721	benzene，1,1′-(1-methyl-1,2-ethanediyl)bis- (1,2-二苯基丙烷）	C₁₅H₁₆
3	21.624	benzene，1,1′-(1,3-propanediyl)bis- （1,3-二苯基丙烷）	C₁₅H₁₆
4	22.742	N-benzyl-1H-benzimidazole （N-苄基苯并咪唑）	C₁₄H₁₂N₂
5	23.258	(E)-stilbene [(E)-二苯乙烯]	C₁₄H₁₂
6	25.444	phenanthrene（菲）	C₁₄H₁₀
7	25.832	naphthalene，1-phenyl-（1-苯基萘）	C₁₆H₁₂
8	29.989	naphthalene，2-phenyl-（2-苯基萘)	C₁₆H₁₂