High-throughput technology for novel SO2 oxidation catalysts

Abstract

We review the state of the art and explain the need for better SO₂ oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO₂ to SO₃. High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO₂ oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO₂ conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO₃ from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations.     

Effects of particulates, heavy metals and acid gas on the removals of NO and PAHs by V2O5–WO3 catalysts in waste incineration system

This study investigated the activities of prepared and commercial V₂O₅–WO₃ catalysts for simultaneous removals of NO and polycyclic aromatic hydrocarbons (PAHs) and the influences of particulates, heavy metals, SO₂, and HCl on the performances of catalysts. The experiments were carried out in a laboratory-scale waste incineration system equipped with a catalyst reactor. The DREs of PAHs by prepared and commercial V₂O₅–WO₃ catalysts were 64% and 72%, respectively. Increasing the particulate concentrations in flue gas suppressed the DRE of PAHs, but increasing the carbon content on surface of catalysts promotes the NO conversions. The DRE of PAHs by the catalysts was significantly decreased by the increased concentrations of heavy metal Cd, but was promoted by high concentration of Pb. The influence level of SO₂ was higher than HCl on the performances of V₂O₅–WO₃ catalysts for PAHs removal, but was lower than HCl for NO removal. Prepared and commercial V₂O₅–WO₃ catalysts have similar trends on the effects of particulates, heavy metals, SO₂, and HCl. The results of ESCA analysis reveal that the presences of these pollutants on the surface of catalysts did not change the chemical state of V and W.     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

A chemiluminescence-based analyzer of NO_x gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NO_x analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al₂O₃ substrate was tested for the efficiency of NO_x removal using a home-built 64-channel parallel and sequential tubular reactor. The NO_x concentrations measured by the NO_x analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al₂O₃. Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NO_x analyzer allowed to select Pt-Ce_(X) (X=1–3) and Pt–Fe₍₂₎ as the optimal catalysts for NO_x removal: 73% NO_x conversion was achieved with the Pt–Fe₍₂₎ alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Visible light-induced degradation of acetone over SO4/MoOx/MgF2 catalysts

A visible light active photodegration catalyst was prepared by doping MoO₃ into MgF₂ matrix. The addition of SO₄²⁻ into MoO_x/MgF₂ could improve the catalytic activity greatly and an acetone conversion of 96.1% under visible light was obtained on the SO₄²⁻/5% MoO_x/MgF₂ (SMM) catalyst. By BET, XRD, Raman, FT-IR, XPS, UV–vis technology the specific area, structure and photoadsorption ability of the catalysts were characterized. The high photocatlaytic activity of the SMM catalyst is attributed to its large specific area, the high dispersal of MoO₃ domains in MgF₂ and the inhibiting effect of MgF₂ matrix on the electron–hole pair recombination.     

燃煤烟气中单质汞的催化氧化技术研究进展

针对燃煤电厂烟气中汞的脱除问题,综述了单质汞氧化催化剂与催化氧化机理的研究现状;着重阐述了碳基、金属及金属氧化物催化剂和选择性催化还原(SCR)催化剂对单质汞的催化氧化性能,分析了活性组分、烟气条件等对各催化剂氧化单质汞性能的影响;指出异相反应是单质汞氧化的重要途径,不同催化剂、不同烟气气氛下氧化机理不同;最后结合我国燃煤电厂的现状,提出深入研究单质汞的催化氧化机理,进一步提高SCR催化剂的催化氧化单质汞活性、抗硫性及稳定性将是燃煤烟气汞污染控制技术的重点发展方向。     

Effect of hydrometallurgical process parameters on the Mn2O3 nano catalysts derived from spent batteries used in the plasma catalytic oxidation of BTX

Manganese oxide catalysts have been synthesized from the used batteries via hydrometallurgical method and effect of hydrometallurgical parameters such as the effect of acid type (H₂SO₄, HNO₃, HCl), acid concentration (0.5, 1, 1.5, 2 %v/v) and powder to acid ratio (1/50, 1/60, 1/70, 1/80) were in detail investigated. The physico-chemical properties of as-prepared catalysts were characterized by FT-IR, XRD, FESEM, EDX, BET, TEM, and TPR-H₂ analysis. The activity of as-prepared catalysts were investigated towards the oxidation of benzene, toluene, and xylene (BTX) in a plasma-catalytic process. The results show that benzene and toluene conversion were almost constant in the range of 97–98% in case of various acid types, acid concentrations and solid to liquid ratios. However, the xylene conversion were varied in case of different hydrometallurgical factors. The highest xylene conversion was obtained in the presence of MnS0.5–60, which was prepared using H₂SO₄ with concentration of 0.5%v/v and solid to liquid ratio of 1/60. The effect of the input voltage and BTX flow rate on the BTX conversion was also investigated using MnS0.5–60 catalyst in detail.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

Abstract

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Nitrogen and europium doped TiO2 anodized films with applications in photocatalysis

Micro-arc oxidation method is a useful process for mesoporous titanium dioxide films. In order to improve the photocatalytic activity of the TiO₂ film, N-Eu co-doped titania catalyst was synthesized by micro-arc oxidation in the H₂SO₄/Eu(NO₃)₃ mixture solution.The specific surface area and the roughness of the anodic titania film fabricated in the H₂SO₄/Eu(NO₃)₃ electrolyte, were increased compared to that of the anodic TiO₂ film prepared in H₂SO₄ solution. The absorbance response of N-Eu titania film shows a higher adsorption onset toward visible light region, and the incorporated N and Eu ions during anodization as a dopant in the anodic TiO₂ film significantly enhanced the photocatalytic activity for dye degradation. After dye decomposition test for 3 h, dye removal rates for the anodic TiO₂ film were 60.7% and 90.1% for the N-Eu doped titania film. The improvement of the photocatalytic activity was ascribed to the synergistic effects of the surface enlargement and the new electronic state of the TiO₂ band gap by N and Eu co-doping.     

Effect of different acid oxidation on morphology,dispersion and optical band-gap of multi-walled carbon nanotubes

In this paper the effect of different acid oxidation on morphology, dispersion and optical band gap of multi-walled carbon nanotubes (CNTs) is reported. Oxidation of CVD synthesized MWCNTs were carried out in 8M HNO₃, 8M H₂SO₄, 8M HNO₃/H₂O₂ and 8M H₂SO₄/HNO₃. Oxidized nanotubes sample were characterized by XRD, SEM, FT-IR, TGA, UV-Vis spectroscopy and Raman analysis. Oxidized-nanotubes show a lower shift in XRD peak and an increase in d-spacing, which implies deterioration of MWNTs. New peaks in FT-IR spectra of oxidized-nanotube samples at around 1742 cm^?1 confirms the presence of carbonyl groups. Optical bandgap, molar absorptivity coefficient is estimated for pristine and oxidized nanotubes sample using UV-Vis spectroscopy data and Tauc plot. It is observed that optical bandgap decreases on oxidation and lowest bandgap 2.92 eV is observed for H₂SO₄ treated MWNTs. The information on the optical bandgap of the MWNTs is of great importance for the development of optoelectronic devices.     

Efficient mineralization of dimethyl phthalate by catalytic ozonation using TiO2/Al2O3 catalyst

The removal of dimethyl phthalate (DMP), which is a pollutant of concern in water environments, was carried out by catalytic ozonation with TiO₂/Al₂O₃ catalysts. The heterogeneous catalytic ozonation was an ozonation process combined with the catalytic and adsorptive properties of the TiO₂/Al₂O₃ catalysts to significantly accelerate the mineralization efficiency. Semi-batch ozonation was performed under various experimental conditions including the fed ozone concentration, catalyst type, catalyst dosage, and ultraviolet radiation on the degradation of DMP. The complete removal of DMP was efficiently achieved by both sole and catalytic ozonation; meanwhile, the presence of the catalysts slightly accelerated the elimination rate of DMP. On the other hand, the mineralization efficiency, in terms of total organic carbon (TOC) removal, was substantially enhanced by employing the TiO₂/Al₂O₃ catalyst. The mineralization efficiency using the TiO₂/Al₂O₃ catalyst was the highest, followed in decreasing order by the Al₂O₃ catalyst, the TiO₂ catalyst, and sole ozonation. In addition, the use of the TiO₂/Al₂O₃ catalyst would increase the utilization efficiency of the fed ozone, especially in the late ozonation period. Furthermore, the decrease in the catalytic activity of the TiO₂/Al₂O₃ catalyst after multi-run experiments can be mostly recovered by an incineration process at a high temperature.     

Chemiluminescence analyzer of NOx as a high-throughput screening tool in selective catalytic reduction of NO

Abstract

A chemiluminescence-based analyzer of NO_x gas species has been applied for high-throughput screening of a library of catalytic materials. The applicability of the commercial NO_x analyzer as a rapid screening tool was evaluated using selective catalytic reduction of NO gas. A library of 60 binary alloys composed of Pt and Co, Zr, La, Ce, Fe or W on Al₂O₃ substrate was tested for the efficiency of NO_x removal using a home-built 64-channel parallel and sequential tubular reactor. The NO_x concentrations measured by the NO_x analyzer agreed well with the results obtained using micro gas chromatography for a reference catalyst consisting of 1 wt% Pt on γ-Al₂O₃. Most alloys showed high efficiency at 275 °C, which is typical of Pt-based catalysts for selective catalytic reduction of NO. The screening with NO_x analyzer allowed to select Pt-Ce_(X) (X=1–3) and Pt–Fe₍₂₎ as the optimal catalysts for NO_x removal: 73% NO_x conversion was achieved with the Pt–Fe₍₂₎ alloy, which was much better than the results for the reference catalyst and the other library alloys. This study demonstrates a sequential high-throughput method of practical evaluation of catalysts for the selective reduction of NO.     

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al₂O₃ catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al₂O₃ and 10%Ni-9.5%Mo/Al₂O₃ were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al₂O₃ catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.     

A novel application of iron oxide nanoparticles for detection of hydrogen peroxide in acid rain

Determining the concentration of hydrogen peroxide (H₂O₂) is of great importance in food, pharmaceutical, environmental and clinical analyses. Horseradish peroxidase (HRP), an enzyme specifically catalyzing the oxidative reaction of H₂O₂ to develop color reaction, has been widely used for measuring H₂O₂ concentration. However, owing to the instability and high cost of this enzyme, discovering efficient mimics of peroxidase has been important to conquer these disadvantages of protein catalyst. Recently we have found that Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) possess intrinsic peroxidase-like activity, which can catalyze oxidation of various peroxidase substrates in the presence of H₂O₂. Based on this finding, we developed a spectrometric method using Fe₃O₄ MNPs as a catalyst to determine H₂O₂ in rainwater. Our data show that the Fe₃O₄ MNPs are efficient catalysts to determine H₂O₂ in rainwater. Compared to HRP, the Fe₃O₄ MNPs are reusable and economical and these characteristics make the particles a board range of applications in determining H₂O₂ in the rainwater.     

The Cu-Co-Fe oxide system applied to carbon nanotubes synthesized on Fe2O3

The paper addresses the catalytic activity of oxygen-containing Cu-Co-Fe catalysts applied onto carbon nanotubes in the CO oxidation reaction. The carbon nanotubes were synthesized on an Fe₂O₃catalyst. The activity of oxide-containing Cu-Co-Fe catalysts is shown to depend on the treatment of metal-carbon precursor material, amount of the active component and method of its application. According to the X-ray phase analysis, thermal desorption mass spectroscopy, and transmission electron microscopy, the active component is a mixture of Cu₂(OH)₃NO₃ and CuO phases whose ratio and distribution depend on the catalyst optimal synthesis conditions, which provide the structural formation of active sites in the CO oxidation reaction. The presence of an active Cu-Co-Fe oxide component in the surface layer, which is produced by a single application of the active component to carbon nanotubes, results in a higher activity of the catalysts in the CO oxidation in comparison to the catalysts prepared by a step-wise application of the active component.     

离子液体中阴阳离子的特性对其吸收二氧化硫的影响

SO_2是一种无色、有强烈刺激性气味的气体,弥散在空气中的SO_2对人体健康、生态环境有着严重的危害,是导致空气质量不断恶化的主要大气污染物之一。人为造成的SO_2污染物的主要来源有燃料燃烧、工业生产、交通运输等,其中燃料燃烧占70%。因此,削减和控制燃料燃烧所产生的SO_2的排放是我国能源利用和环保领域的重要研究方向,烟气脱硫是应对烟气中SO_2排放的有效途径。湿法烟气脱硫是目前应用最广泛的方法,占世界安装烟气脱硫机组总容量的85%,采用该方法处理的烟气占总处理量的80%。在湿法烟气脱硫技术中比较实用的主要包括钙法脱硫、有机胺脱硫、海水脱硫。其中,钙法脱硫的脱硫效率高,对煤种的适应性较强,但是脱硫会产生CaSO_4沉淀,降低经济效益;有机胺脱硫的系统腐蚀性小,副产品可生产硫酸,但是胺易挥发,造成吸收剂损失和环境污染;海水法脱硫的工艺简单、运行可靠,但其应用受到地域的影响,并且对环境也会产生一定的影响。离子液体是一种新兴的绿色介质,它具有环保、可再生、结构可调控的优点,为解决传统工艺中的污染问题提供了新方案。在离子液体吸收气体的过程中,吸收液不会因其挥发性而蒸发进入气相,并且可以在较低的温度下完成吸收解吸循环。离子液体的这些优良特性使其在SO_2吸收方面有着极广阔的应用前景。目前,研究者们已合成了一系列胍盐类、咪唑类、醇胺类、吡啶类等离子液体,探究其吸收SO_2的性能与机理,并根据其结构可设计的特点,在离子液体中的阴阳离子上引入各类官能团(如氰基、醚基、氨基、卤素),合成满足特定需求的离子液体,使其高效、可逆、低耗地吸收SO_2。本文总结了近年来各类离子液体吸收SO_2的性能和机理,为系统地认识离子液体在SO_2分离领域的应用提供了帮助;重点阐明了离子液体中阴阳离子的种类、官能化,尤其是酸碱性对其吸收SO_2的影响,这为调整离子液体酸碱性、合理设计离子液体的结构,探索离子液体吸收SO_2的机理,改善其对SO_2的吸收性能有着重要的价值。最后指出了目前研究中存在的问题并且对未来新型离子液体的合成进行了展望。     

In2O3 nanowires for gas sensors: morphology and sensing characterisation

Thin and densely packed In₂O₃ nanowires have been synthesised on alumina substrates via transport and condensation method, starting from nanoparticles of indium or palladium as catalysts for the condensation process. Indium catalyst promoted wires growth according to vapour-solid (VS) mechanism, while palladium catalyst leads to wires formation based on vapour-liquid-solid (VLS) condensation. Electron microscopy and related diffraction analysis demonstrated that the wires are monocrystalline, with atomically sharp termination of the lateral sides, and are free from extended defects. The sensing properties of nanowires bundles have been tested to acetone using the flow through technique in the temperature range between 100 and 500 °C.     

Synthesis and characterization of novel nanostructured fishbone-like Cu(OH)2 and CuO from Cu4SO4(OH)6

The Cu₄SO₄(OH)₆ was synthesized by a simple hydrothermal reaction with a yield of ~ 90%. Using Cu₄SO₄(OH)₆ as the starting material, novel fishbone-like Cu(OH)₂ was produced by a direct reaction of Cu₄SO₄(OH)₆ with NaOH solution. The Cu(OH)₂ consists of many needle-like nanorods parallel to each other and perpendicular to the direction of backbone, forming fishbone-like structure. Using the fishbone-like Cu(OH)₂ as the sacrificial precursor, CuO with similar size and morphology was obtained through a simple heat treatment. X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, X-ray photoelectron spectroscopy, BET nitrogen adsorption, and UV-Vis absorption spectroscopy were employed to characterize the as-prepared samples. The conversion of the Cu₄SO₄(OH)₆ to the fishbone-like Cu(OH)₂ was visualized by time-dependent SEM images. A mechanism was also proposed based on the observed results.     

Promotional effects of carbon nanotubes on V2O5/TiO2 for NOX removal

A series of V₂O₅/TiO₂-carbon nanotube (CNT) catalysts were synthesized by sol-gel method, and their activities for NO_X removal were compared. A catalytic promotional effect was observed by adding CNTs to V₂O₅/TiO₂. The catalyst V₂O₅/TiO₂-CNTs (10 wt.%) showed an NO_X removal efficiency of 89% at 300 °C under a GHSV of 22,500 h⁻¹. Based on X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, NH₃-temperature-programmed desorption, temperature-programmed reduction, Brunauer-Emmett-Teller surface area measurements, differential scanning calorimetry, and thermogravimetric analysis, the increased acidity and reducibility, which could promote NH₃ adsorption and oxidation of NO to NO₂, respectively, contributed to this promotion.