随着国家经济的飞速发展，对能源的消耗也随之增加。煤炭燃烧衍生的一系列环境问题，给人们的日常生活和身体健康造成了严重的影响。因此，环境部陆续出台了相关政策限制燃煤企业对氮氧化物的排放。选择性催化还原（SCR）技术是目前常用的一种脱硝技术。但由于催化剂在长期运行的过程中会受烟气中碱金属、重金属和SO2及锅炉内流场分布的影响导致其失活。失效的以TiO2为载体的钒基催化剂属于危险废弃物，同时其内部也含有一定量的钒、钨等战略性物资，因此，对失活催化剂进行再生达到回用要求具有一定的经济和环境意义。目前，失活催化剂常用清洗、活性负载加高温煅烧的工艺进行再生，再生后的催化剂比表较低，TiO2晶型部分转化为金红石，使用寿命无法满足24000 h。课题组着重对废钒基TiO2粉进行原位再生，然后通过湿式球磨法将稀土元素Ce、La加入再生钒基TiO2纳米粉对其改性，最终制备出了在催化性能，温度窗口，耐高温和抗水抗硫性上均高于商业催化剂V3.0W3.1的脱硝催化剂，采用一系列的物理化学表征技术研究再生催化剂的结构特征，物理化学特性以及其反应机理。该研究可为失效催化剂的再生提供新的思路。研究内容如下：
首先，考虑到TiO2纳米粉在脱硝催化剂中起到改善比表面积、增加内部活性点位和减少团聚现象等作用。选择均匀沉淀法、直接沉淀法以及溶胶凝胶法制备的TiO2与废钒基TiO2粉（3:7）经球磨法混合进行再生。结果表明：三种方法制备的TiO2均能提高废钒基TiO2粉的催化活性，其中，均匀沉淀法制备的TiO2纳米粉脱硝效率高于其它方法，在温度窗口为410 ~ 500 ℃时脱硝活性在80%以上。与废钒基TiO2粉相比，比表面积提高了18.81 m2/g，TiO2晶型为锐钛矿。同时其较高的拟合峰面积和Oα/(Oα+Oβ)比例说明其酸性点位的数量和浓度以及氧化还原能力得到了改善。表明载体在催化过程中发挥着重要作用。
其次，探究了载体再生阶段对脱硝性能影响的研究，结果表明：TiO2前驱体与废钒基TiO2粉（3:7）原位再生得到的TiO2粉表现出了优于其他阶段再生的催化活性，在385 ~ 550 ℃的温度区间内时，脱硝效率在80%以上。经多项表征分析发现，载体TiO2的晶型仍为锐钛矿型，孔径2-50 nm的介孔结构，且由前驱体与废钒基TiO2粉球磨法混合得到的样品比表面积为74.13 m2/g，高于其他阶段得到的样品，这意味着相同质量的样品表面可以承载着更多的活性物质。同时其更高的峰面积说明了中强酸位点和表面不饱和氧得到了提高。
最后，由于再生钒基TiO2粉的催化剂效率及温度窗口较低，无法满足脱硝需要，因此为了制备出能直接投入使用的宽温度窗口脱硝催化剂，采用球磨法引入稀土元素Ce和La对其进行改性再生，经测试发现：Ce5La2有着最佳的活性窗口，与商业钒基催化剂（V3.0W3.1）相比，在290 ~ 550 ℃的温度区间内，Ce5La2 的NO转化率均高于80%，且在380 ~ 512 ℃内的转化率可以维持在99%。同时Ce5La2再生催化剂在抗水、抗硫和耐高温方面与V3.0W3.1相比也展现出了较为优异的性质，在5 h的抗水抗硫性测试中，Ce5La2脱硝效率在80%以上，而V3.0W3.1从开始的95.8%迅速下降至44%；在550 ℃煅烧10天后，Ce5La2的NO转化率转化率未发生明显变化，在250~550 ℃内仍高于80%。表征分析发现，再生催化剂中独有的元素Ce由于具有良好的Ce3+/Ce4+变价能力，使再生催化剂表现出优于商业催化剂的氧化还原性，同时La的加入使得再生催化剂内的活性元素的分散度进一步提高，增强了CeO2与载体间的相互作用，为再生催化剂增加了表面活性氧物种以及增加了内部的中强酸量，同时观察到稀土元素的加入使得TiO2晶格条纹存在一定程度上相对紊乱且不连续情况，说明掺杂引起了部分缺陷，这些缺陷在催化反应中增加了NO的停留时间，使得催化反应得以更加充分的进行。Ce，La的加入与其本身存在的V形成了商业催化剂所没有的V-O-Ce/La短程化学键，从而在与V3.0W3.1的比较下，再生催化剂在中高温下表现出更加稳定和优异的脱硝性能。原位傅里叶红外分析发现，再生催化剂是在Brønsted酸点位起主导，Lewis酸点位协同进行的催化反应，符合Eley-Ridel机理

With the rapid development of the national economy, the consumption of energy has also increased. The series of environmental problems derived from coal combustion have caused serious impacts on people's daily life and physical health. Therefore, the Ministry of Environment has successively issued relevant policies to restrict NOx emissions from coal-fired enterprises. Selective catalytic reduction (SCR) technology is one of the commonly used denitrification technologies. However, the catalyst will become inactive due to the influence of alkali metals, heavy metals, SO2, and the distribution of fluid field in the boiler during long-term operation. The inactive TiO2-based vanadium catalyst is a hazardous waste, and it also contains certain amounts of strategic materials such as vanadium and tungsten. Therefore, the regeneration of inactive catalysts to meet reuse requirements has certain economic and environmental significance. Currently, the inactive catalysts are commonly regenerated by cleaning, active loading, and high-temperature calcination. The specific surface area of the regenerated catalyst is lower, and the TiO2 crystal phase is partially converted to anatase. The service life cannot meet the requirement of 24,000 h. The research group focuses on optimizing the regeneration method of waste vanadium-based TiO2 nanopowder, and then modifies the regenerated vanadium-based TiO2 nanopowder by wet ball milling method with rare earth elements Ce and La. Finally, the research group prepares a denitrification catalyst with higher catalytic performance, temperature window, resistance to high temperature and water and sulfur than commercial catalyst V3.0W3.1. A series of physical and chemical characterization techniques are used to study the structural features, physical and chemical properties, and reaction mechanism of the regenerated catalyst. This research can provide new ideas for the regeneration of inactive catalysts. The research content is as follows:
First, considering that TiO2 nanopowder plays an important role in improving the specific surface area, increasing the number of active sites and reducing agglomeration in the denitration catalyst. TiO2 prepared by uniform precipitation method, direct precipitation method and sol-gel method was mixed with the waste vanadium-based TiO2 powder (3:7) by ball milling method for regeneration. The results show that the TiO2 prepared by the three methods can improve the catalytic activity of the waste vanadium-based TiO2 powder. Among them, the TiO2 nanopowder prepared by uniform precipitation method has higher denitration efficiency than the other methods, with denitration activity of more than 80% at the temperature window of 410 ~ 500 ℃. Compared with the waste vanadium-based TiO2 powder, the specific surface area has increased by 18.81 m2/g, the TiO2 crystal structure is anatase, and the higher fitting peak area and Oα/(Oα+Oβ) ratio indicate that the number and concentration of acidic sites and oxidation-reduction ability have been improved. This shows that the carrier plays an important role in the catalytic process.
Secondly, the study on the influence of carrier regeneration stage on the denitration performance was conducted, the results show that the TiO2 precursor mixed with the waste vanadium-based TiO2 powder (3:7) in situ regenerated to obtain TiO2 powder has better catalytic activity than other regeneration stages, with denitration efficiency of more than 80% in the temperature range of 385 ~ 550 ℃. After multiple characterization analyses, it was found that the crystal phase of the carrier TiO2 was anatase, with a mesoporous structure of 2-50 nm pore size, and the specific surface area of the sample obtained by ball milling the precursor and waste vanadium-based TiO2 powder was 74.13 m2/g, higher than that of the samples obtained from other regeneration stages, which means that the same mass of the sample can carry more active substances on its surface. Meanwhile, its higher peak area indicates that the medium-strong acid sites and surface unsaturated oxygen have been improved.
Finally, due to the low catalytic efficiency and temperature window of the regenerated vanadium-based TiO2 powder catalyst, it cannot meet the requirements for NOx removal. Therefore, in order to prepare a wide-window NOx removal catalyst that can be directly put into use, the regenerated catalyst was modified by ball milling with rare earth elements Ce and La. After testing, it was found that Ce5La2 had the best activity window. Compared with the commercial vanadium-based catalyst (V3.0W3.1), the NO conversion rate of Ce5La2 was higher than 80% in the temperature range of 290 ~ 550 ℃, and the conversion rate could be maintained at 99% in the temperature range of 380 ~ 512 ℃. At the same time, the Ce5La2 regenerated catalyst also showed superior properties in terms of resistance to water, sulfur, and high temperature compared with V3.0W3.1. In the 5-hour test for water and sulfur resistance, the NOx removal efficiency of Ce5La2 was above 80%, while that of V3.0W3.1 dropped from 95.8% to 44% from the beginning. After being calcined at 550 ℃ for 10 days, the NO conversion rate of Ce5La2 did not change significantly, and it was still above 80% in the temperature range of 250 ~ 550 ℃.Characterization analysis reveals that the unique element Ce in the regenerated catalyst, due to its excellent Ce3+/Ce4+ redox ability, makes the regenerated catalyst exhibit superior oxidation-reduction properties compared to commercial catalysts. Meanwhile, the addition of La further enhances the dispersion of active elements in the regenerated catalyst, strengthens the interaction between CeO2 and the carrier, increases the surface active oxygen species and the internal medium-strong acid content, and observes that the addition of rare earth elements causes the TiO2 lattice stripes to exist to a certain extent of relative disorder and discontinuity, indicating that doping has caused some defects. These defects increase the NO residence time in the catalytic reaction, allowing the catalytic reaction to proceed more fully. The addition of Ce and La, together with the V present, forms a short-range chemical bond of V-O-Ce/La that is not present in commercial catalysts, thereby enabling the regenerated catalyst to exhibit more stable and superior denitration performance at medium and high temperatures compared to V3.0W3.1. In situ Fourier transform infrared analysis reveals that the regenerated catalyst undergoes a catalytic reaction dominated by Brønsted acid sites and coordinated by Lewis acid sites, consistent with the Eley-Ridel mechanism.
 

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