Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

Study on the denitrification performance of FexLayOz/activated coke for NH3-SCR and the effect of CO escaped from activated coke at mid-high temperature on catalytic activity

Currently, activated coke is widely used in the removal of multiple pollutants from industrial flue gas. In this paper, a series of novel Fe_xLa_yO_z/AC catalysts was prepared by the incipient wetness impregnation for NH₃-SCR denitrification reaction. The introduction of Fe-La bimetal oxides significantly improved the denitrification performance of activated coke at mid-high temperature, and 4% Fe_0.3La_0.7O_1.5/AC exhibited a superior NO_x conversion efficiency of 90.1% at 400 °C. The catalysts were further characterized by BET, SEM, XRD, Raman, EPR, XPS, FTIR, NH₃-TPD, H₂-TPR, et al., whose results showed that the perovskite-type oxide of LaFeO₃ and oxygen vacancies were produced on the catalysts’ surfaces during roasting. Fe-La doping enhanced the amount of acid sites (mainly Lewis and other stronger acid sites) and the content of multifarious oxygen species, which were beneficial for NO_x removal at mid-high temperature. Moreover, it was investigated that the effect of released CO from activated coke at mid-high temperature on the NO_x removal through the lifetime test, in which it was found that a large amount of CO produced by pyrolysis of activated coke could promote the NO_x removal, and long-term escaping of CO on the activated coke carrier did not have a significant negative impact on catalytic performance. The results of the TG-IR test showed that volatile matter is released from the activated coke while TG results showed that the weight loss rate of 4% Fe_0.3La_0.7O_1.5/AC only was 0.0015~0.007%/min at 300–400 °C. Hence, 4% Fe_0.3La_0.7O_1.5/AC had excellent thermal stability and denitrification performance to be continuously used at mid-high temperature. Finally, the mechanisms were proposed on the basis of experiments and characterization results.

     

蚯蚓-稻壳炭联合堆肥对工业污泥中重金属的影响研究

蚯蚓堆肥相关研究多集中在生活污泥方面,对工业污泥的探索较少。该研究以马鞍山某钢铁污水处理站污泥为例,添加不同比例稻壳炭(2%、4%、8%),设置污泥单独堆肥、稻壳炭与污泥堆肥以及蚯蚓-稻壳炭联合污泥堆肥试验,探索蚯蚓与稻壳炭联合堆肥对工业污泥中重金属形态和生物有效性的影响。研究表明,(1)相比污泥单独堆肥,稻壳炭联合污泥堆肥能增加污泥pH、EC、TP和降低TOC、TN,而蚯蚓联合稻壳炭堆肥污泥可增加TN,并进一步增加污泥EC、TP,显著降低污泥的pH、TOC。(2)稻壳炭堆肥中重金属Zn、Cu、Pb、Cd含量因浓缩效应而上升;而蚯蚓联合稻壳炭堆肥,重金属含量显著下降,添加4%稻壳炭时,重金属Zn、Cu、Pb、Cd质量分数达到最小值,分别为856.64、137.10、158.92、15.48mg·kg-1。(3)重金属形态分析表明,随着稻壳炭比例增加,稻壳炭堆肥中重金属Zn、Cu、Pb、Cd的交换态和碳酸盐结合态转化为残渣态及铁锰氧化态的比例增大,添加8%稻壳炭时DTPA提取的有效态重金属质量分数最低,分别为705.72、47.95、50.43、4.47 mg·kg-1;蚯蚓-稻壳炭联合堆肥会使得污泥中重金属交换态、碳酸盐结合态、铁锰结合态和有机结合态均向残渣态转化,添加4%稻壳炭与蚯蚓的协同转化能力最大,Zn、Cu、Pb、Cd有效态重金属质量分数分别为629.84、38.63、36.76、1.63mg·kg-1,说明稻壳炭添加入蚯蚓堆肥可进一步降低工业污泥中重金属有效性,使重金属钝化。本研究可为稻壳炭联合蚯蚓堆肥处理工业污泥提供参考和科学依据。     

Multi-process and multi-pollutant control technology for ultra-low emissions in the iron and steel industry

The iron and steel industry is not only an important foundation of the national economy, but also the largest source of industrial air pollution. Due to the current status of emissions in the iron and steel industry, ultra-low pollutant emission control technology has been researched and developed. Liquid-phase proportion control technology has been developed for magnesian fluxed pellets, and a blast furnace smelting demonstration project has been established to use a high proportion of fluxed pellets (80%) for the first time in China to realize source emission reduction of SO₂ and NO_x. Based on the characteristics of high NO_x concentrations and the coexistence of multiple pollutants in coke oven flue gas, low-NO_x combustion coupled with multi-pollutant cooperative control technology with activated carbon was developed to achieve efficient removal of multiple pollutants and resource utilization of sulfur. Based on the characteristics of co-existing multiple pollutants in pellet flue gas, selective non-catalytic reduction (SNCR) coupled with ozone oxidation and spray drying adsorption (SDA) was developed, which significantly reduces the operating cost of the system. In the light of the high humidity and high alkalinity in flue gas, filter materials with high humidity resistance and corrosion resistance were manufactured, and an integrated pre-charged bag dust collector device was developed, which realized ultra-low emission of fine particles and reduced filtration resistance and energy consumption in the system. Through source emission reduction, process control and end-treatment technologies, five demonstration projects were built, providing a full set of technical solutions for ultra-low emissions of dust, SO₂, NO_x, SO₃, mercury and other pollutants, and offering technical support for the green development of the iron and steel industry.     

造纸黑液木素在肥料中的应用

综述了造纸黑液木素功能性肥料的研究动态及作者的研究成果 ,指出了造纸黑液木素肥料资源化的应用前景     

壳聚糖的絮凝性能及其在废水脱色处理中的应用

介绍了壳聚糖的理化性质及其作为絮凝剂的优点,探讨了壳聚糖的絮凝机理,分析了壳聚糖絮凝效果的影响因素(包括废水p H、絮凝温度、搅拌转速及时间、壳聚糖投加量、壳聚糖脱乙酰度及相对分子质量、废水浊度),总结了壳聚糖改性和复合后在废水脱色处理中的应用。指出:未来还需更深入地研究絮凝机理,同时也需进一步研究影响絮凝效果的因素;新型壳聚糖絮凝剂将向更高效、成本更低且环境友好的方向发展。     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites(Na A, Na X, HZSM-5)impregnated with iron(Ⅲ) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy, and temperature programmed desorption(TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury(Hg0)into oxidized mercury(Hg2+). The crystallization of Na Cl due to the ion exchange effect during the impregnation of Na A and Na X reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of Fe Cl3–HZSM-5 was mainly in the form of mercuric chloride(Hg Cl2), while on Fe Cl3–Na X and Fe Cl3–Na A it was mainly mercuric oxide(Hg O).     

Hg removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg^2 +). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃–HZSM-5 was mainly in the form of mercuric chloride (HgCl₂), while on FeCl₃–NaX and FeCl₃–NaA it was mainly mercuric oxide (HgO).