Preparation of MnO2/NaY composite and its performance inremoving SO2

doi:10.16085/j.issn.1000-6613.2018-1299

Chemical Industry and Engineering Progress ›› 2019, Vol. 38 ›› Issue (05): 2285-2293.DOI: 10.16085/j.issn.1000-6613.2018-1299

• Materials science and technology • Previous Articles Next Articles

Preparation of MnO₂/NaY composite and its performance inremoving SO₂

Lintao CHEN^1,^2,^5,⁶(),Yugo OSAKA³,Xuecheng LIU^1,^4,^5,⁶,Zhaohong HE^1,^5,⁶,Xing LI^1,^5,⁶,Hongyu HUANG^1,^5,⁶()

1. Guangzhou Institute of Energy Conversion，Chinese Academy of Sciences，Guangzhou 510640, Guangdong, China
2. University of Chinese Academy of Sciences，Beijing 100049，China
3. Kanazawa University，Kanazawa 9201192，Japan
4. Chongqing Technology and Business University，Chongqing 400000，China
5. CAS Key Laboratory of Renewable Energy，Guangzhou 510640，Guangdong, China
6. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development，Guangzhou 510640，Guangdong, China

Received:2018-06-22 Revised:2018-12-13 Online:2019-05-05 Published:2019-05-05
Contact: Hongyu HUANG

MnO₂/NaY复合材料的制备及其对SO₂脱除性能

陈林涛^1,^2,^5,⁶(),大坂侑吾³,刘学成^1,^4,^5,⁶,何兆红^1,^5,⁶,李兴^1,^5,⁶,黄宏宇^1,^5,⁶()

1. 中国科学院广州能源研究所，广东广州 510640
2. 中国科学院大学，北京 100049
3. 日本金泽大学，日本;金泽 9201192
4. 重庆工商大学，重庆 400000
5. 中国科学院可再生能源重点实验室，广东广州 510640
6. 广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640

通讯作者: 黄宏宇
作者简介:<named-content content-type="corresp-name">陈林涛</named-content>（1994—），男，硕士研究生，研究方向为干式脱硫技术。E-mail：<email>chenlt@ms.giec.ac.cn</email>。|黄宏宇，研究员，博士生导师，研究方向为节能与环保。E-mail：<email>huanghy@ms.giec.ac.cn</email>。
基金资助:
中国科学院前沿科学重点研究项目(QYZDY-SSW-JSC038);广东省省级科技计划(2016A050502040);广东省新能源和可再生能源研究开发与应用重点实验室项目(Y807S21001)

Abstract

Abstract:

MnO₂/NaY composite for desulfurization was prepared by precipitation method with NaY molecular sieve as the carrier and MnO₂ as the active component. The structure of the MnO₂/NaY composite was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), nitrogen adsorption desorption(N₂-adsorption desorption), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). The capacity method was used to test the desulfurization performance of the composite material and the influence of different loading capacity of MnO₂ and different reaction temperature were studied. The results showed that the larger the pore volume of MnO₂/NaY composite, the better the desulfurization performance. Porous coral MnO₂ has better desulphurization performance than rod-like MnO₂. The desulfurization performance of MnO₂/NaY increased first and then decreased with the increase of MnO₂ loading amount and reaction temperature. MnO₂/NaY-41% showed the best desulfurization performance at 400℃, and the desulfurization capacity reached 114.56mg $_{S O_{2}}$ /g_Materials in 1h. The decline in desulfurization performance at 500℃ is due to the decomposition of MnO₂ into Mn₃O₄ during the desulfurization process. The MnO₂/NaY showed better desulfurization performance than pure MnO₂. When the reaction temperature reached 300℃ and 400℃ respectively, the desulfurization performance of MnO₂/NaY-41% was higher than that of pure MnO₂ by 28.3% and 56.1% in 1h. The composite is expected to be applied in the desulfurization of marine exhaust gas.

Key words: flue gas, sulfur dioxide, adsorbents, manganese dioxide, molecular sieve

摘要：

以NaY分子筛为载体，MnO₂为活性组分，采用沉淀法制备MnO₂/NaY复合脱硫材料；通过X射线衍射（XRD）、扫描电子显微镜（SEM）、氮气吸附脱附法（N₂-吸附脱附）、X射线光电子能谱（XPS）、热重分析（TG）等手段进行材料的物理化学结构表征；使用容量法装置测试复合材料的脱硫性能；考察MnO₂不同负载量及不同反应温度对MnO₂/NaY复合材料脱硫性能的影响。结果表明：MnO₂/NaY复合材料的孔容越大，其脱硫性能越好；多孔珊瑚状MnO₂脱硫性能优于棒状MnO₂；随着MnO₂负载量及反应温度的增加，MnO₂/NaY的脱硫性能先增加后降低，MnO₂/NaY-41%在400℃时的脱硫性能最好，第1h脱硫量达到114.56mg ${_{S O}}_{_{2}}$ /g_材料；500℃时复合材料脱硫性能下降，是由于脱硫反应过程中MnO₂分解生成Mn₃O₄；MnO₂/NaY比纯MnO₂拥有更好的脱硫性能，反应温度为300℃和400℃时，MnO₂/NaY-41%较纯MnO₂的第1h脱硫量分别提高28.3%和56.1%。MnO₂/NaY-41%复合材料在中低温下的高效脱硫性能有望应用于船舶尾气的深度脱硫。

关键词: 烟道气, 二氧化硫, 吸附剂, 二氧化锰, 分子筛

CLC Number:

X511
X517

Lintao CHEN, Yugo OSAKA, Xuecheng LIU, Zhaohong HE, Xing LI, Hongyu HUANG. Preparation of MnO₂/NaY composite and its performance inremoving SO₂[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2285-2293.

陈林涛, 大坂侑吾, 刘学成, 何兆红, 李兴, 黄宏宇. MnO₂/NaY复合材料的制备及其对SO₂脱除性能[J]. 化工进展, 2019, 38(05): 2285-2293.

Figures/Tables 15

控制变量	数值
恒温室的温度/K	308.15
样品的反应温度/K	473.15~773.15
储气罐压力/Pa	37~41
样品质量/g	0.07~0.11
样品颗粒大小/目	≤100

样品	BET比表面积 /m²?g^-1	孔容/mL?g^-1	平均孔径/nm
纯MnO₂	91.75	0.5768	2.5148
NaY分子筛	897.72	0.4459	1.9866
MnO₂/NaY-20%	690.18	0.4511	2.6146
MnO₂/NaY-32%	569.64	0.6048	4.2472
MnO₂/NaY-41%	499.70	0.9660	7.7326
MnO₂/NaY-53%	389.68	0.7166	7.3555

样品	第1h平均脱硫速率（ $\overset{ˉ}{v}$ ） /mg $_{S O_{2}}$ ?g_材料 ^-1·h^-1	脱硫容量（吸附平衡） /mg $_{S O_{2}}$ ?g_材料 ^-1	MnO₂ 转化率/%
纯MnO₂	73.37	198.51	26.99
MnO₂/NaY-20%	72.11	104.63	71.11
MnO₂/NaY-32%	82.69	155.74	66.16
MnO₂/NaY-41%	114.56	206.11	68.33
MnO₂/NaY-53%	92.78	215.74	55.34

样品	第1h平均脱硫速率（ $\overset{ˉ}{v}$ ） /mg $_{S O_{2}}$ ?g_材料 ^-1·h^-1	脱硫容量（吸附平衡） /mg $_{S O_{2}}$ ?g_材料 ^-1	MnO₂ 转化率/%
纯MnO₂	73.37	198.51	26.99
MnO₂/NaY-20%	72.11	104.63	71.11
MnO₂/NaY-32%	82.69	155.74	66.16
MnO₂/NaY-41%	114.56	206.11	68.33
MnO₂/NaY-53%	92.78	215.74	55.34

温度/℃	第1h平均脱硫速率（ $\overset{ˉ}{v}$ ） /mg $_{S O_{2}}$ ·g_材料 ^-1·h^-1	脱硫容量（吸附平衡） /mg $_{S O_{2}}$ ·g_材料 ^-1	MnO₂转化率/%
200	23.87	33.92	11.25
300	31.82	45.62	15.13
400	114.56	206.11	68.34
500	58.27	132.38	43.89

温度/℃	第1h平均脱硫速率（ $\overset{ˉ}{v}$ ） /mg $_{S O_{2}}$ ·g_材料 ^-1·h^-1	脱硫容量（吸附平衡） /mg $_{S O_{2}}$ ·g_材料 ^-1	MnO₂转化率/%
200	23.87	33.92	11.25
300	31.82	45.62	15.13
400	114.56	206.11	68.34
500	58.27	132.38	43.89

材料	比表面积/m²?g^-1	脱硫容量/mg $_{S O_{2}}$ ?g_材料 ^-1	反应条件		最佳反应温度/℃
材料	比表面积/m²?g^-1	脱硫容量/mg $_{S O_{2}}$ ?g_材料 ^-1	SO₂浓度/μL?L^-1	平衡气	最佳反应温度/℃
CaO^[1]	10	36	250	空气	325
Ca(OH)₂ ^[1]	16.4	32	250	空气	325
MgO^[1]	143	20	250	空气	325
ZrO₂ ^[1]	95.7	16	250	空气	325
TiO₂ ^[5]	120	36	常压纯SO₂	无	室温
CuO-CeO₂ ^[31]	165	27	3600	氮气	500
CuO/AC^[32]	844	44	200	氮气	250
CuO/γ-Al₂O₃ ^[33]	166	115	1500	氩气	400
CuO/Y^[34]	—	160	3400	空气	450
MnO₂/AC^[16]	278	65.6	500	氮气	200
MnO₂/NaY-41%^[本文]	500	206	40Pa 纯SO₂	无	400

材料	比表面积/m²?g^-1	脱硫容量/mg $_{S O_{2}}$ ?g_材料 ^-1	反应条件		最佳反应温度/℃
材料	比表面积/m²?g^-1	脱硫容量/mg $_{S O_{2}}$ ?g_材料 ^-1	SO₂浓度/μL?L^-1	平衡气	最佳反应温度/℃
CaO^[1]	10	36	250	空气	325
Ca(OH)₂ ^[1]	16.4	32	250	空气	325
MgO^[1]	143	20	250	空气	325
ZrO₂ ^[1]	95.7	16	250	空气	325
TiO₂ ^[5]	120	36	常压纯SO₂	无	室温
CuO-CeO₂ ^[31]	165	27	3600	氮气	500
CuO/AC^[32]	844	44	200	氮气	250
CuO/γ-Al₂O₃ ^[33]	166	115	1500	氩气	400
CuO/Y^[34]	—	160	3400	空气	450
MnO₂/AC^[16]	278	65.6	500	氮气	200
MnO₂/NaY-41%^[本文]	500	206	40Pa 纯SO₂	无	400

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