脱硝协同汞氧化聚苯硫醚四元催化滤料制备方法及理化特性

doi:10.16085/j.issn.1000-6613.2019-0636

摘要/Abstract

摘要：

采用原位氧化法（ISM）、浸渍煅烧法（ICM）和涂覆法（CM）制备聚苯硫醚（PPS）双效催化滤料，在模拟烟气固定床系统中考察了滤料低温NO_x催化协同Hg⁰氧化性能，深入分析了原位氧化滤料表面形貌、元素分布、晶态结构和Hg及NO_x赋存形态。结果表明：在相同条件下，3种制备方法对应滤料催化活性大小顺序为Mn-Ce-Fe-Co-O_x/PPS@ISM＞Mn-Ce-Fe-Co-O_x/PPS@ICM＞Mn-Ce-Fe-Co-O_x/PPS@CM。ISM对应PPS单层饱和负载量约为0.9，活性反应温度窗口为110~210℃，其中170℃时Mn-Ce-Fe-Co-O_x/PPS@ISM的非均相NO氧化、NO_x还原和Hg⁰氧化效率最高分别达到8.6%、84.6%和93.2%。程序升温脱附实验结果表明：(0.9)Mn-Ce-Fe-Co-O_x/PPS@ ISM表面NO_x吸附活性位点中弱碱位数量占优，而中碱位化学吸附NO主要以NO_y（y=2或3）结构存在，歧化态NO₂次之。同时，Hg与NO在氧气条件下以非均相反应途径转化为HgO和Hg(NO₃)₂/Hg₂(NO₃)₂。表征结果表明：ISM制备的MnO_x、CeO_x、CoO_x和Fe₂O₃复合氧化物呈弱晶相、高度分散团絮状结构赋存于PPS@ISM纤维。

关键词: 复合材料, 聚合物, 原位氧化法, 浸渍煅烧法, 涂覆法, 汞氧化, 选择催化还原

Abstract:

Catalytic polyphenylene sulfide（PPS） filters were prepared by using in-situ method(ISM), impregnation calcination method（ICM） and coating method（CM）, respectively. The catalytic activities for NO_x and Hg⁰ oxidation of the catalysts at low temperature were investigated in a fixed bed system to determine the best preparation method and related basic operation parameters. In addition, the surface morphology, crystalline structure and NO_x occurrence morphology of (0.9)Mn-Ce-Fe-Co-O_x/PPS@ISM were analyzed. The experimental results showed that the maximum NO_x and Hg⁰ conversions decreased in the sequence of Mn-Ce-Fe-Co-O_x/PPS@ISM > Mn-Ce-Fe-Co-O_x/PPS@ICM > Mn-Ce-Fe-Co-O_x/PPS@CM. The maximum efficiencies of NO oxidation, NO_x reduction and Hg⁰ oxidation on (0.9)Mn-Ce-Fe-Co-O_x/PPS@ISM at 170℃ were 8.6%, 84.6% and 93.2%, respectively. The results of temperature programmed desorption showed that the NO interaction types were mainly in the form of nitrite/nitrate, followed by the adsorption state NO₂. Besides, the mercury on the catalyst mainly existed in the form of HgO and Hg(NO₃)₂/Hg₂(NO₃)₂ in the presence of NO. The results of characterizations showed that MnO_x, CeO_x, CoO_x and Fe₂O₃ were in the form of amorphous phase and well dispersed on PPS@ISM in a flocculent structure.

Key words: composites, polymers, in-situ method, impregnation calcination method, coating method, Hg⁰ oxidation, selective catalytic reduction (SCR)

中图分类号:

X511

李银生,刘猛,段钰锋,陈聪,李娜,吕剑虹. 脱硝协同汞氧化聚苯硫醚四元催化滤料制备方法及理化特性[J]. 化工进展, 2020, 39(1): 267-277.

Yinsheng LI,Meng LIU,Yufeng DUAN,Cong CHEN,Na LI,Jianhong LÜ. Optimal preparation of quaternary catalytic functional PPS filter materials and their chemical properties[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 267-277.

图/表 17

图1 催化滤料性能测试固定床系统

图2 NO程序升温脱附实验系统

表1 实验工况表

工况	反应温度/℃	初始Hg⁰浓度/μg·m^-3	活性负载量	O₂/%	NO/μL?L^-1	NH₃/μL?L^-1	过滤风速/m·min^-1	评价类型
工况	反应温度/℃	初始Hg⁰浓度/μg·m^-3	活性负载量	O₂/%	NO/μL?L^-1	NH₃/μL?L^-1	过滤风速/m·min^-1	0～1h	1～3.5h
1	170	45.1	0.9	5.0	300	300	1.0	NO_x还原	Hg⁰氧化
2	170	45.1	0.7	5.0	300	300	1.0
3	170	45.1	0.8	5.0	300	300	1.0
4	170	45.1	1.0	5.0	300	300	1.0
5	170	45.1	1.1	5.0	300	300	1.0
6	170	45.1	1.2	5.0	300	300	1.0
7	170	45.1	1.3	5.0	300	300	1.0
8	120	45.1	0.9	5.0	300	300	1.0
9	250	45.1	0.9	5.0	300	300	1.0
10	300	45.1	0.9	5.0	300	300	1.0
11	130	45.1	0.9	5.0	300	0	1.0	NO氧化
12	150	45.1	0.9	5.0	300	0	1.0
13	170	45.1	0.9	5.0	300	0	1.0
14	190	45.1	0.9	5.0	300	0	1.0
15	210	45.1	0.9	5.0	300	0	1.0

图3 Mn-Ce-Fe-Co-Ox/PPS@(ISM/ICM/CM)滤料最佳脱硝协同汞氧化性能

图4 Mn-Ce-Fe-Co-Ox/PPS@CM涂覆滤料0～3.5h内脱硝性能和汞氧化性能

图5 活性负载量对Mn-Ce-Fe-Co-Ox/PPS@ISM脱硝协同汞氧化性能的影响

图6 不同反应温度下(0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料的双效催化性能

图7 不同反应温度下(0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料的NO氧化活性

图8 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM表面碱性位点种类及数量

图9 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料NO-TPD脱附

图10 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料Hg-TPD脱附

表2 几种标准汞化合物分解温度区间[27]

纯汞化合物	脱附峰温/℃	分解温度/℃
HgO	308±1；471±1	200~360；370~530
Hg(NO₃)₂·H₂O	215±4；280±13；460±25	150~370；375~520
Hg₂(NO₃)₂·2H₂O	264±35；427±19	120~375；376~500

图11 催化滤料NOx催化及Hg0氧化反应途径

图12 单位温度梯度下滤料性能降低幅值κ

图13 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料的SEM微观形貌

图14 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM滤料EDX能谱及元素分布

图15 (0.9)Mn-Ce-Fe-Co-Ox/PPS@ISM活性组分的XRD谱图

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