Mn-HAP基低温SCR催化剂的制备及抗硫中毒性能

doi:10.15541/jim20220020

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1065-1072.DOI: 10.15541/jim20220020 CSTR: 32189.14.10.15541/jim20220020

Mn-HAP基低温SCR催化剂的制备及抗硫中毒性能

陈亚玲¹^,²(), 舒松¹^,², 王劭鑫¹^,², 李建军¹^,²()

1.四川大学建筑与环境学院, 成都 610000
2.国家烟气脱硫工程技术研究中心, 成都 610000

收稿日期:2022-01-13 修回日期:2022-04-14 出版日期:2022-10-20 网络出版日期:2022-04-26
通讯作者: 李建军, 教授. E-mail: jjli@scu.edu.cn
作者简介:陈亚玲(1997-), 女, 硕士研究生. E-mail: chenyaling@stu.scu.edu.cn
基金资助:
国家重点研发计划(2019YFC0214404);四川省重大科技专项(2019KJT0067-2018SZDZX0019);中国石油化工有限公司项目(320033);四川大学遂宁市校市战略合作专项资金(2020CDSN-12)

Mn-HAP SCR Catalyst: Preparation and Sulfur Resistance

CHEN Yaling¹^,²(), SHU Song¹^,², WANG Shaoxin¹^,², LI Jianjun¹^,²()

1. College of Architecture and Environment, Sichuan University, Chengdu 610000, China
2. National Engineering Research Center for FGD, Chengdu 610000, China

Received:2022-01-13 Revised:2022-04-14 Published:2022-10-20 Online:2022-04-26
Contact: LI Jianjun, professor. E-mail: jjli@scu.edu.cn
About author:CHEN Yaling (1997-), female, Master candidate. E-mail: chenyaling@stu.scu.edu.cn
Supported by:
National Key Research and Development Program of China(2019YFC0214404);Major Science and Technology Special Project of Sichuan Province(2019KJT0067-2018SZDZX0019);China Petroleum & Chemical Corporation Project(320033);Special Fund Project for School-city Strategic Cooperation of SuiNing, Sichuan University(2020CDSN-12)

摘要/Abstract

摘要：

低温选择性催化还原(SCR)脱硝是工业烟气末端治理的重要技术, 强化催化剂硫抗性是低温SCR领域内亟待解决的问题。本研究以羟基磷灰石(HAP)为载体、Mn为活性组分通过共沉淀法成功合成了Mn-HAP低温(100~200℃)脱硝催化剂, 探究了其脱硝性能及金属硫酸盐和硫酸铵的中毒特性。结果表明: 以HAP作为活性组分Mn的载体能一定程度上提高催化剂的抗硫性。当反应温度为140 ℃时, SCR催化剂脱硝效率达到100%, 金属硫酸盐相较硫酸铵对催化剂低温脱硝活性的影响更显著, 120 ℃时脱硝效率分别降低37.40%和8.83%。不同手段分析表明, 不同表面硫物种均会不同程度地降低催化剂比表面积并改变活性Mn氧化态。金属硫酸盐显著降低Mn⁴⁺/Mn比例是造成催化剂失活的主要原因。

关键词: 羟基磷灰石, 低温NH₃-SCR, SO₂抗性, 金属硫酸盐, 硫酸铵

Abstract:

Low-temperature selective catalytic reduction (SCR) denitrification is an important technology for the end treatment of flue gas and enhancing sulfur resistance of catalysts is a challenge demanding prompt solution in the field of low-temperature SCR. Here, a Mn-HAP catalyst for nitrogen removal at low temperature (100-200 ℃) was successfully synthesized by co-precipitation method using hydroxyapatite (HAP) as carrier and Mn as an active component, and then its denitrification performance and resistance to fight against metal sulfate and ammonium sulfate poisoning were studied. The results showed that the sulfur resistance of the catalyst could be improved to a certain extent by using HAP as Mn active substance carrier. When the reaction temperature was 140 ℃, the denitrification efficiency of the SCR catalyst reached 100%. Meanwhile, the effect of metal sulfate on the denitrification activity at low temperature was more significant than that of ammonium sulfate, and the denitrification efficiency under the two sulfate species at 120 ℃ was reduced by 37.40% and 8.83%, respectively, as compared with that of fresh catalyst. Different characterization analysis indicated that different surface sulfur species could reduce the specific surface area and change the oxidation state of active Mn to various degrees. The main reason for catalysts deactivation is that the metal sulfate can significantly decrease the proportion and oxidation-reduction performance of Mn⁴⁺. Therefore, this study provides an important direction for improving the sulfur resistance of SCR catalysts.

Key words: hydroxyapatite, low-temperature NH₃-SCR, SO₂ resistance, metal sulfate, ammonium sulfate

中图分类号:

TB34

陈亚玲, 舒松, 王劭鑫, 李建军. Mn-HAP基低温SCR催化剂的制备及抗硫中毒性能[J]. 无机材料学报, 2022, 37(10): 1065-1072.

CHEN Yaling, SHU Song, WANG Shaoxin, LI Jianjun. Mn-HAP SCR Catalyst: Preparation and Sulfur Resistance[J]. Journal of Inorganic Materials, 2022, 37(10): 1065-1072.

图/表 10

图1 催化剂制备与中毒示意图

Fig. 1 Schematic illustration for preparing and poisoning catalysts

图2 脱硝活性评价装置示意图

Fig. 2 Schematic illustration of denitration activity evaluation device

图3 (a)CPF、CPM、CPA和HAP的SCR活性以及CPF的抗硫性测试和(b)CPF稳定性测试图

Fig. 3 (a) SCR activity of CPF, CPM, CPA, and HAP, and sulfur resistance test of CPF and (b) stability test of CPF Colorful figures are available on website

表1 不同催化剂活性对比

Table 1 Activity comparison of different catalysts

Catalyst	Preparation method	NO conversion/%	Temperature and condition	Ref.
Mn-HAP	Co-preparation	62.60	140 ℃, 200×10^-6 SO₂, 2 h	This research
NB-C-P	Hydrothermal	45.00	150 ℃, 250×10^-6 SO₂, 2 h	[20]
MnO₂	Oxalic acid co-precipitation	17.65	150 ℃, 200×10^-6 SO₂, 2 h	[21]
MnCrO_x	Hydrothermal redox reaction	37.46	150 ℃, 50×10^-6 SO₂, 2 h	[22]

图4 催化剂的(a)XRD图谱和(b)DTG曲线

Fig. 4 (a) XRD patterns and (b) DTG curves of catalysts

图5 CPF、CPM和CPA的(a)N2吸脱附等温线和(b)孔径分布图

Fig. 5 (a) N2 adsorption-desorption isotherms and (b) pore size distributions of CPF, CPM, and CP

表2 新鲜催化剂与中毒催化剂物理参数

Table 2 Physical parameters of fresh catalysts and toxic catalysts

Sample	Specific area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore size/nm
CPF	153.6	0.5500	13.49
CPM	117.3	0.4600	14.11
CPA	133.2	0.4300	11.57

图6 CPF、CPM和CPA的(a)Mn2p和(b)O1s的XPS图谱

Fig. 6 (a) Mn2p and (b) O1s XPS spectra of CPF, CPM and CPA

表3 新鲜催化剂与中毒催化剂表面Mn和O的XPS分析结果

Table 3 XPS results of Mn and O on the surface of fresh catalysts and toxic catalysts

Sample	O			Mn
Sample	O_latt/O	O_ads/O	O_ads/O_latt	Mn²⁺/Mn	Mn³⁺/Mn	Mn⁴⁺/Mn
CPF	0.9050	0.0950	0.1050	0.06510	0.1670	0.7300
CPM	0.9210	0.0790	0.0860	0.10000	0.5900	0.3100
CPA	0.8760	0.1230	0.1410	0.13500	0.2240	0.6410

图7 CPF、CPM和CPA的(a)H2-TPR曲线和(b)NH3-TPD曲线

Fig. 7 (a) H2-TPR and (b) NH3-TPD curves of CPF, CPM and CPA

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Mn-HAP基低温SCR催化剂的制备及抗硫中毒性能

Mn-HAP SCR Catalyst: Preparation and Sulfur Resistance

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