化工进展 ›› 2025, Vol. 44 ›› Issue (7): 3879-3891.DOI: 10.16085/j.issn.1000-6613.2024-0856
• 工业催化 • 上一篇
基于金属离子改性的Cu-SSZ-13催化剂在NH3-SCR脱硝中的应用
张巍1,2(
), 梁垚城1,2, 伍乔1,2, 付业昊1,2, 尹艳山1,2, 成珊1,2, 阮敏1,2, 刘涛1,2, 周昭仪1,2, 张凯凯1,2, 李丹聪1,2
- 1.长沙理工大学能源与动力工程学院，湖南 长沙 410114
2.可再生能源电力技术湖南省重点实验室，湖南 长沙 410114
-
收稿日期:2024-05-26修回日期:2024-09-08出版日期:2025-07-25发布日期:2025-08-04 -
通讯作者:张巍 -
作者简介:张巍（1974—），男，博士，副教授，硕士生导师，研究方向为能源高效清洁利用。E-mail：weizhang@csust.edu.cn。 -
基金资助:国家自然科学基金(52006016);湖南省自然科学基金(2023JJ30047);湖南省自然科学基金(2021JJ40573);湖南省自然科学基金(2020JJ4098);湖南省教育厅科学研究重点项目(21A0216);湖南省教育厅优秀青年项目(20B041);湖南省教育厅优秀青年项目(22B0291);长沙理工大学青年教师成长计划(2019QJCZ044)
Metal ion modified Cu-SSZ-13 catalyst for NH3-selective catalytic reduction of NO x
ZHANG Wei1,2(), LIANG Yaocheng1,2, WU Qiao1,2, FU Yehao1,2, YIN Yanshan1,2, CHENG Shan1,2, RUAN Min1,2, LIU Tao1,2, ZHOU Zhaoyi1,2, ZHANG Kaikai1,2, LI Dancong1,2
- 1.College of Energy and Power Engineering, Changsha University of Science and Technology, Changsha 410114, Hunan, China
2.Key Laboratory of Renewable Energy and Electric Power Technology of Hunan Province, Changsha 410114, Hunan, China
-
Received:2024-05-26Revised:2024-09-08Online:2025-07-25Published:2025-08-04 -
Contact:ZHANG Wei
摘要：
选择性催化还原（NH3-SCR）技术是当前广泛应用的脱硝技术，其关键在于研发高效稳定的催化剂。Cu-SSZ-13分子筛脱硝催化剂因其优异的N2选择性和良好的催化活性备受研究人员关注。然而，Cu-SSZ-13分子筛催化剂存在的抗硫性和水热稳定性不足等问题严重限制了其工业应用。为了克服硫氧化物和水热老化对Cu-SSZ-13催化剂脱硝活性的影响，可通过向催化剂中引入不同的自由态金属离子来进行改性。本文综述了近年来有关碱（土）金属离子、过渡金属离子和稀土金属离子改性Cu-SSZ-13催化剂在NH3-SCR反应中的应用，并阐述了其抗硫机制和水热稳定性强化方法。展望了未来研究方向：综合利用不同金属离子的特点并结合离子之间的协同作用，制备具有优良抗硫性和水热稳定性的新型Cu-SSZ-13催化剂，明确金属离子在SSZ-13分子筛中的存在形式和相互作用机制，以及通过实验和计算相结合制备高效的金属离子改性Cu-SSZ-13催化剂以满足工业化应用。
中图分类号:
引用本文
张巍, 梁垚城, 伍乔, 付业昊, 尹艳山, 成珊, 阮敏, 刘涛, 周昭仪, 张凯凯, 李丹聪. 基于金属离子改性的Cu-SSZ-13催化剂在NH3-SCR脱硝中的应用[J]. 化工进展, 2025, 44(7): 3879-3891.
ZHANG Wei, LIANG Yaocheng, WU Qiao, FU Yehao, YIN Yanshan, CHENG Shan, RUAN Min, LIU Tao, ZHOU Zhaoyi, ZHANG Kaikai, LI Dancong. Metal ion modified Cu-SSZ-13 catalyst for NH3-selective catalytic reduction of NO x[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3879-3891.
图1 Ca2+对Cu-SSZ-13催化剂的影响机制[24]
图1 Ca2+对Cu-SSZ-13催化剂的影响机制[24]
表1 近年来文献报道较多的碱（土）金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 碱金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Li+ | >90% （200~500℃） | >90% （225~500℃） | 防止Brønsted酸位点水解 | NO=0.05L/min，O2=14%（体积分数），NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Na+ | >90% （180~500℃） | >90% （225~500℃） | 防止Brønsted酸位点水解 | NO=0.05L/min，O2=14%，NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Na+ | >95% （150~650℃） | >90%（ 200~600℃） | 增加催化剂的氧化还原能力，保留更多的骨架Al | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=80000h-1 | [ |
| Na+ | >80% （200~500℃） | — | 作为Lewis酸位点增加对NH3的吸附 | NO=0.036L/min，O2=14%，NH3=0.036L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| K+ | >90% （225~500℃） | — | 堵塞分子筛孔道，使催化剂内部的传质能力受到限制 | NO=0.05L/min，O2=14%，NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Mg2+ | >90% （250~450℃） | — | Brønsted酸位点和Cu2+减少，生成Cu x O y，堵塞沸石孔道 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=400000h-1 | [ |
| Ca2+ | >90% （250~400℃） | — | Brønsted酸位点和Cu2+减少，生成Cu x O y，堵塞沸石孔道，造成骨架结构崩溃 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=400000h-1 | [ |
表1 近年来文献报道较多的碱（土）金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 碱金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Li+ | >90% （200~500℃） | >90% （225~500℃） | 防止Brønsted酸位点水解 | NO=0.05L/min，O2=14%（体积分数），NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Na+ | >90% （180~500℃） | >90% （225~500℃） | 防止Brønsted酸位点水解 | NO=0.05L/min，O2=14%，NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Na+ | >95% （150~650℃） | >90%（ 200~600℃） | 增加催化剂的氧化还原能力，保留更多的骨架Al | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=80000h-1 | [ |
| Na+ | >80% （200~500℃） | — | 作为Lewis酸位点增加对NH3的吸附 | NO=0.036L/min，O2=14%，NH3=0.036L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| K+ | >90% （225~500℃） | — | 堵塞分子筛孔道，使催化剂内部的传质能力受到限制 | NO=0.05L/min，O2=14%，NH3=0.05L/min，N2作为平衡气，GHSV=100000h-1 | [ |
| Mg2+ | >90% （250~450℃） | — | Brønsted酸位点和Cu2+减少，生成Cu x O y，堵塞沸石孔道 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=400000h-1 | [ |
| Ca2+ | >90% （250~400℃） | — | Brønsted酸位点和Cu2+减少，生成Cu x O y，堵塞沸石孔道，造成骨架结构崩溃 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=400000h-1 | [ |
图2 NH3-SCR反应的E-R和L-H机制示意图[34]
图2 NH3-SCR反应的E-R和L-H机制示意图[34]
图3 低温下Cu-SSZ-13催化剂上SCR反应途径[7]
图3 低温下Cu-SSZ-13催化剂上SCR反应途径[7]
图4 双功能Pt-Cu-SSZ-13催化剂的NH3转化率和N2选择性[43]
图4 双功能Pt-Cu-SSZ-13催化剂的NH3转化率和N2选择性[43]
图5 Zr4+对Cu-SSZ-13催化剂低温活性的影响[46]
图5 Zr4+对Cu-SSZ-13催化剂低温活性的影响[46]
表2 近年来文献报道较多的过渡金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 过渡金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Fe3+ | >90% （175~450℃） | >90% （200~350℃） | 增加了新的活性位点，提高了催化剂的氧化还原能力 | NO=0.015L/min，O2=5%，NH3=0.015L/min，N2作为平衡气，总流量=0.3L/min，GHSV=150000h-1 | [ |
| Fe3+ | >80% （150~500℃） | — | 增加了活性位点的数量 | NO=0.015L/min，O2=5%，NH3=0.015L/min，N2作为平衡气，总流量=0.3L/min GHSV=120000h-1 | [ |
| Mn n+ | >90% （175~525℃） | >90% （200~500℃） | 提升了催化剂的氧化还原能力，抑制了脱铝和CuOx的生成 | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=30000h-1 | [ |
| Mn n+ | >90% （200~450℃） | >90% （300~400℃） | 提供了更多的活性位点，增强了对NO的吸附 | NO=0.01L/min，O2=3%，NH3=0.01L/min，N2作为平衡气，总流量=0.2mL/min，GHSV=300000h-1 | [ |
| Co2+ | >90% （275~450℃） | — | 控制Cu离子以[Cu(OH)]+-Z形式位于1Al位点，促进产生更多的活性更强的Lewis酸位点 | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=240000h-1 | [ |
| Nb5+ | >90% （200~625℃） | — | 增加了酸位点和活性位点数量，稳定了分子筛结构 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=60000h-1 | [ |
| Pt2+ | >90% （175~275℃） | — | 催化氧化NH3 | NO=0.05L/min，O2=5%，NH3=0.055L/min，N2作为平衡气，GHSV=200000h-1 | [ |
| Ti4+ | >95% （150~525℃） | >95% （200~450℃） | 增加活性位点 | NO=0.049L/min，NO2=0.001L/min，O2=5%，NH3=0.05L/min，Ar作为平衡气，GHSV=50000h-1 | [ |
| Zr4+ | >95% （200~400℃） | — | 调节催化剂表面Cu2+和Cu+的比例，从而提高Cu+的含量 | NO=0.01L/min，O2=5%，NH3=0.01L/min，N2作为平衡气，总流量=0.2mL/min，GHSV=24000h-1 | [ |
表2 近年来文献报道较多的过渡金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 过渡金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Fe3+ | >90% （175~450℃） | >90% （200~350℃） | 增加了新的活性位点，提高了催化剂的氧化还原能力 | NO=0.015L/min，O2=5%，NH3=0.015L/min，N2作为平衡气，总流量=0.3L/min，GHSV=150000h-1 | [ |
| Fe3+ | >80% （150~500℃） | — | 增加了活性位点的数量 | NO=0.015L/min，O2=5%，NH3=0.015L/min，N2作为平衡气，总流量=0.3L/min GHSV=120000h-1 | [ |
| Mn n+ | >90% （175~525℃） | >90% （200~500℃） | 提升了催化剂的氧化还原能力，抑制了脱铝和CuOx的生成 | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=30000h-1 | [ |
| Mn n+ | >90% （200~450℃） | >90% （300~400℃） | 提供了更多的活性位点，增强了对NO的吸附 | NO=0.01L/min，O2=3%，NH3=0.01L/min，N2作为平衡气，总流量=0.2mL/min，GHSV=300000h-1 | [ |
| Co2+ | >90% （275~450℃） | — | 控制Cu离子以[Cu(OH)]+-Z形式位于1Al位点，促进产生更多的活性更强的Lewis酸位点 | NO=0.05L/min，O2=10%，NH3=0.05L/min，N2作为平衡气，GHSV=240000h-1 | [ |
| Nb5+ | >90% （200~625℃） | — | 增加了酸位点和活性位点数量，稳定了分子筛结构 | NO=0.05L/min，O2=5%，NH3=0.05L/min，N2作为平衡气，GHSV=60000h-1 | [ |
| Pt2+ | >90% （175~275℃） | — | 催化氧化NH3 | NO=0.05L/min，O2=5%，NH3=0.055L/min，N2作为平衡气，GHSV=200000h-1 | [ |
| Ti4+ | >95% （150~525℃） | >95% （200~450℃） | 增加活性位点 | NO=0.049L/min，NO2=0.001L/min，O2=5%，NH3=0.05L/min，Ar作为平衡气，GHSV=50000h-1 | [ |
| Zr4+ | >95% （200~400℃） | — | 调节催化剂表面Cu2+和Cu+的比例，从而提高Cu+的含量 | NO=0.01L/min，O2=5%，NH3=0.01L/min，N2作为平衡气，总流量=0.2mL/min，GHSV=24000h-1 | [ |
图6 水热老化前后催化剂的SEM图像[52]（HA为水热老化）
图6 水热老化前后催化剂的SEM图像[52]（HA为水热老化）
表3 近年来文献报道较多的稀土金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 稀土金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Ce3+ | >85%（210~590℃） | >85%（220~540℃） | 稳定了活性位点Cu2+， 阻止脱铝 | NO=0.02L/min，O2=7%，H2O=10%，NH3=0.02L/min，Ar作为平衡气，总流量=0.4L/min，GHSV=40000h-1 | [ |
| Ce3+ | >95%（210~600℃） | >90%（210~600℃） | 增加酸位点数量，保护活性位点Cu2+和骨架Al | NO=0.05L/min，O2=5%，H2O=10%，NH3=0.05L/min，N2作为平衡气， GHSV=36000h-1 | [ |
| Sm3+ | >90%（200~550℃） | >80%（250~550℃） | 增加活性位点[Cu(OH)]+-Z的数量，抑制CuO x 的生成 | NO=0.05L/min，O2=5%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=200000h-1 | [ |
| Pr3+ | >80%（200~550℃） | >80%（225~550℃） | 抑制Z2 Cu2+在水热老化过程中的迁移和聚集 | NO=0.05L/min，O2=5%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=200000h-1 | [ |
| Y3+ | >80%（150~600℃） | >80%（150~580℃） | 保护活性位点， 稳定骨架Al | NO=0.05L/min，O2=10%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=40000h-1 | [ |
表3 近年来文献报道较多的稀土金属离子改性Cu-SSZ-13催化剂
| 改性离子 | 新鲜样品的最佳脱硝效率 | 水热老化样品的最佳脱硝效率 | 稀土金属改性的作用 | 反应条件 | 参考文献 |
|---|---|---|---|---|---|
| Ce3+ | >85%（210~590℃） | >85%（220~540℃） | 稳定了活性位点Cu2+， 阻止脱铝 | NO=0.02L/min，O2=7%，H2O=10%，NH3=0.02L/min，Ar作为平衡气，总流量=0.4L/min，GHSV=40000h-1 | [ |
| Ce3+ | >95%（210~600℃） | >90%（210~600℃） | 增加酸位点数量，保护活性位点Cu2+和骨架Al | NO=0.05L/min，O2=5%，H2O=10%，NH3=0.05L/min，N2作为平衡气， GHSV=36000h-1 | [ |
| Sm3+ | >90%（200~550℃） | >80%（250~550℃） | 增加活性位点[Cu(OH)]+-Z的数量，抑制CuO x 的生成 | NO=0.05L/min，O2=5%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=200000h-1 | [ |
| Pr3+ | >80%（200~550℃） | >80%（225~550℃） | 抑制Z2 Cu2+在水热老化过程中的迁移和聚集 | NO=0.05L/min，O2=5%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=200000h-1 | [ |
| Y3+ | >80%（150~600℃） | >80%（150~580℃） | 保护活性位点， 稳定骨架Al | NO=0.05L/min，O2=10%，H2O=5%，NH3=0.05L/min，N2作为平衡气， GHSV=40000h-1 | [ |
图7 Cu2+与[Cu(OH)]+活性位点上低温SO2中毒机理[57]
图7 Cu2+与[Cu(OH)]+活性位点上低温SO2中毒机理[57]
图8 Cu-SSZ-13分子筛水热老化处理下的脱铝机制[71]
图8 Cu-SSZ-13分子筛水热老化处理下的脱铝机制[71]
图9 一步水热合成法制备的Cu-Zn-SSZ-13催化剂的抗水热老化性能示意图[76]
图9 一步水热合成法制备的Cu-Zn-SSZ-13催化剂的抗水热老化性能示意图[76]
图10 4种催化剂在60000h-1的GHSV和850℃下用10% H2O水热老化10h后的SCR活性[78]
图10 4种催化剂在60000h-1的GHSV和850℃下用10% H2O水热老化10h后的SCR活性[78]
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