SO2-Assisted Simultaneous Reduction of SO2 and NO by CO on SnO2-TiO2 Solid Solution

Sn_0.5Ti_0.5O₂ shows excellent catalytic performance both for the CO-SO₂ reaction and the CO-SO₂-NO reaction. At 350 ° C, 525 ppm SO₂/520 ppm NO/2085 ppm CO, SV = 3000 h^-1, the conversion of SO₂ is nearly complete in the CO-SO₂ reaction and above 89% in the CO-SO₂-NO reaction; NO conversion is above 98% in the latter reaction. The selectivities of S and N₂ are both close to 100%. SO₂ shows a significant promoting effect on the activity of the Sn_0.5Ti_0.5O₂ catalyst for NO reduction by CO. Combining transient response experiments, catalytic tests and TPD results, we propose a SO₂-assisted NO-CO reaction concept. The existence of a surface sulfur species, which was formed during the CO-SO₂ or CO-SO₂-NO reaction, is proved by XPS analysis. It is the active site for NO reduction in the CO-SO₂-NO reaction, and through which SO₂ accomplishes its promoter role. On the basis of the results obtained, the SO₂-assisted redox mechanism of simultaneous reduction of SO₂ and NO by CO is proposed.     

Role of ceria in the improvement of SO2 resistance of LaxCe1 − xFeO3 catalysts for catalytic reduction of NO with CO

Perovskite-type catalysts with LaFeO₃ and substituted La_xCe_1 − xFeO₃ compositions were prepared by sol–gel method. These catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), CO temperature-programmed reduction (CO-TPR), and SO₂ temperature-programmed desorption (SO₂-TPD). Catalytic reaction for NO reduction with CO in the presence of SO₂ has been investigated in this study. LaFeO₃ exhibited an excellent catalytic activity without SO₂, but decreased sharply when SO₂ gas was added to the CO + NO reaction system. In order to inhibit the effect of SO₂, substitution of Ce in the structure of LaFeO₃ perovskite has been investigated. It was found that La_0.6Ce_0.4FeO₃ showed the maximum SO₂ resistance among a series of La_xCe_1 − xFeO3 composite oxides.     

Catalytic removal of SO2, NO and HCl from incineration flue gas over activated carbon-supported metal oxides

Activated carbon-supported copper, iron, or vanadium oxide catalysts were exposed to incineration flue gas to investigate the simultaneous catalytic oxidation of sulfur dioxide/hydrogen chloride and selective catalytic reduction of nitrogen oxide by carbon monoxide. The results show that AC-supported catalysts exhibit higher activities for SO₂ and HCl oxidation than traditional γ-Al₂O₃-supported catalysts and the iron and vanadium catalysts act as catalysts instead of sorbents, and can decompose sulfate with evolution of SO₃ and then regenerate for more SO₂ adsorption to take place. The AC-supported catalysts also display a high activity for NO reduction with CO generated from a flue gas incineration process and the presence of SO₂ in the incineration flue gas can significantly promote catalytic activity. Using CO as the reducing agent for NO reduction is more effective than using NH₃, because NH₃ may be partially oxidized in the presence of excess O₂ (12 vol%. in the incineration flue gas used) to form N₂, which can decrease the overall extent of NO reduction.     

Catalytic properties of La2CuO4 in the CO + NO reaction

La₂CuO₄ is an active catalyst for the reduction of NO by CO. Under reaction conditions, the catalyst exhibits an activation which results in a lowering of the light‐off temperature by 80°C. XRD, TEM and EDX analysis carried out after the catalytic test indicate that the mixed oxide has been reduced to form a La₂O₃, Cu binary system. It seems that metallic copper species are the most active sites in the CO + NO reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nanosized CeO2-supported metal oxide catalysts for catalytic reduction of SO2 with CO as a reducing agent

Nanosized CeO₂ was synthesized by sol–gel method and used as the support to prepare six kinds of supported metal oxide catalysts by incipient wetness impregnation method. These catalysts were investigated for the catalytic reduction of SO₂ to elemental sulfur with CO as a reducing agent. Experimental results indicate that Cr₂O₃/nano-CeO₂ was the most active catalyst. Using this catalyst, a kinetic study was performed on the reduction of SO₂ and the optimal feed ratio of CO/SO₂ was found to be 2.5/1, and low concentrations of SO₂ and CO provide a high SO₂ conversion and sulfur yield. We also found that the catalyst presulfided by CO + SO₂ exhibits a higher performance than those pretreated with CO, SO₂ or He. The discrepancy in the stability and activity resulted in the pretreatment has been rationally explained. The temperature-programmed desorption patterns of SO₂ and CO illustrate that Cr₂O₃/nano-CeO₂ can adsorb and desorb SO₂ and CO more easily than can other catalysts. These results may properly explain why Cr₂O₃/nano-CeO₂ has a higher activity for the reduction of SO₂.     

Study on the Poisoning Mechanism of Sulfur Dioxide for Perovskite La0.9Sr0.1CoO3 Model Catalysts

The reaction and poisoning mechanism of SO₂ with La_0.9Sr_0.1CoO₃ model catalysts have been investigated. The structure and the chemical states of the model catalysts have been studied by using AES, XPS and XRD techniques. The results indicated that SO₂ diffused into the La_0.9Sr_0.1CoO₃ film during poisoning. La₂(SO₄)₃ species was formed on the surface of the film and La₂(SO₄)₃, La₂(SO₃)₃, La₂O₂SO₄ and CoO species were found in the interior. The perovskite structure of La_0.9Sr_0.1CoO₃ was destroyed by invasion of SO₂. The concentration of sulfur in the film layer was related to the reaction temperature and time. After the sample was poisoned for a fairly long time, the distribution of sulfur in the La_0.9Sr_0.1CoO₃ layer became homogeneous, suggesting that a dynamic equilibrium was achieved between the poisoning reaction and the decomposition of the sulfates. XRD and catalytic activity test results proved that the destruction of perovskite structure and the formation of sulfates were the main causes of deactivation.     

Simultaneous catalytic reduction of sulfur dioxide and nitric oxide

The present work reports a catalytic system for the simultaneous reduction of SO₂ and NO using CO as a reducing agent. The catalyst contains lanthanum oxysulfide and cobalt sulfides. Experimental results showed that at temperature above 450°C, SO₂ and NO conversions are greater than 98 and 99%, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Promotional effect of SO2 on the activity of Ir/SiO2 for NO reduction with CO under oxygen-rich conditions

The effect of coexisting SO₂ on the activity of silica-supported noble metal catalysts for the selective reduction of NO with CO in the presence of O₂ was investigated. Pt/SiO₂, Rh/SiO₂, and Pd/SiO₂ showed little catalytic activity for NO reduction, irrespective of coexisting SO₂. Although Ir/SiO₂ showed no NO reduction activity in the absence of SO₂, the presence of SO₂ drastically promoted NO reduction. A comparison of the catalytic performance of Ir/SiO₂ and Ir/Al₂O₃ in the presence of SO₂ showed that Ir supported on SiO₂ is more active than Ir on Al₂O₃. SiO₂ was found to be a more effective support than Al₂O₃. The most outstanding feature of the reaction on the Ir/SiO₂ catalyst was that the coexistence of SO₂ and O₂ is essential for NO reduction to occur. The role of coexisting SO₂ was considered to be not only to stabilize but also to create Ir⁰ sites in an oxidizing atmosphere. FT-IR measurements suggested that a cis-type coordinated species of NO and CO on one iridium atom (

) was an intermediate for NO reduction by CO. Although the

species completely disappeared with the addition of O₂ to the reaction gas, the presence of coexisting SO₂ caused a reappearance of the

species. A reaction mechanism in which N₂ and N₂O are produced via the recombination of dissociated N atoms (N_(a) + N_(a) → N₂) and the formation of dimer (NO)₂-type species (2NO → (NO)_2(a) → N₂O + O_(a)), respectively, is proposed.     

New thermochemical cycles for hydrogen production

The ease of decomposing some metal sulfates to oxides and sulfur trioxide is employed in the search for efficient closed cycle thermochemical methods for water splitting. The main features of the new processes are the production of O₂ through the decomposition of SO₂ and/or SO₃, the production of hydrogen by the decomposition of H₂S, reaction of H₂S with a metal, reaction of water with a metal, and/or reaction of water with sulfides.     

Sulfur production from smelter off-gas using CO–H2 gas mixture as the reducing agent over modified Fe/γ-Al2O3 catalysts

A series of modified γ-Al₂O₃ supported iron-based catalysts (M-Fe/γ-Al₂O₃) was developed to reduce SO₂ in actual smelter off-gases using CO–H₂ gas mixture as reducing agent for sulfur production. Used as modifiers, three metal additives — Ni, Co, and Ce were added to Fe/γ-Al₂O₃ catalysts. Changes in catalyst structure and active phase were characterized with X-ray diffraction, XPS, SEM, and EDS. The reduction ability of catalysts was exhibited via CO-TPR. The prepared catalysts only need to be pre-reacted for a period of time, eliminating the need for presulfidation treatment. Reaction conditions were optimized in a fixed bed reactor to achieve high SO₂ conversion and sulfur selectivity. XRD characterization was carried out to verify the resulting sulfur products. Combining in situ infrared characterization and catalyst evaluation of support and active component, the reaction mechanism was investigated and proposed.     

Thermally Stable CeO2–ZrO2–La2O3 Ternary Oxides Prepared by Deposition–Precipitation as Support of Rh Catalyst for Catalytic Reduction of NO by CO

The work mainly reported that CeO₂–ZrO₂–La₂O₃ mixed oxide was synthesized by deposition–precipitation method and used as support of Rh catalyst. The physicochemical properties of the resultant CeO₂–ZrO₂–La₂O₃ mixed oxides were characterized by X-ray powder diffraction (XRD), Vis-Raman, N₂ adsorption, transmission electron microscopy, temperature-programmed reduction, and oxygen storage capacity and the catalytic activities of Rh-loaded CeO₂–ZrO₂–La₂O₃ catalysts were evaluated by the reduction reaction of NO by CO. The combination of XRD and Raman results demonstrates that the resultant CeO₂–ZrO₂–La₂O₃ mixed oxides have a mixed phase comprised mainly of m-phase, c-phase, and t-phase. Compared with the counterpart prepared by co-precipitation method, Rh-loaded CeO₂–ZrO₂–La₂O₃ catalysts prepared by the deposition–precipitation method exhibited higher heat tolerance and better catalytic activity for the reduction of NO by CO as well as more uniform and discrete nanoparticles. The structural and textural characteristics caused by synthesis technique and the high dispersity of Rh on the materials are dominant contributors to the improvement of catalytic performance.     

Elemental sulfur production through regeneration of a SO2-adsorbed V2O5-CoO/AC in H2

H₂ regeneration of an activated carbon supported vanadium and cobalt oxides (V₂O₅-CoO/AC) catalyst–sorbent used for flue gas SO₂ removal is studied in this paper. Elemental sulfur is produced during the H₂-regeneration when effluent gas of the regeneration is recycled back to the reactor. The regeneration conditions affect the regeneration efficiency and the elemental sulfur yield. The regeneration efficiency is the highest at 330 °C, with SO₂ as the product. The production of elemental sulfur occurs at 350 °C and higher with the highest elemental sulfur yield of 9.8 mg-S/g-Cat. at 380 °C. A lower effluent gas recycle rate is beneficial to elemental sulfur production. Intermittent H₂ feeding strategy can be used to control H₂S concentration in the gas phase and increase the elemental sulfur yield. Two types of reactions occur in the regeneration, reduction of sulfuric acid to SO₂ by AC and reduction of SO₂ to elemental sulfur through Claus reaction. H₂S is an intermediate, which is important for elemental sulfur formation and for conversion of CoO to CoS that catalyzes the Claus reaction. The catalyst–sorbent exhibits good stability in SO₂ removal capacity and in elemental sulfur yield.     

Catalytic conversion of CO,NO and SO2 on the supported sulfide catalyst: I. Catalytic reduction of SO2 by CO

Catalytic reduction of SO₂ to elemental sulfur by CO has been systematically investigated over γ-Al₂O₃-supported sulfide catalysts of transition metals including Co, Mo, Fe, CoMo and FeMo with different loadings of the metals. The sulfided CoMo/Al₂O₃ exhibited outstanding activity: a complete conversion of SO₂ was achieved at a temperature of 300°C. The reaction proceeds catalytically and consistently over time and most efficiently at a molar feed ratio CO/SO₂ = 2. A precursor CoMo/Al₂O₃ oxide which experienced sulfurization through the CO–SO₂ reaction yielded a working sulfide catalyst having a yet lower activity than the CoMo catalyst sulfided before reaction (pre-sulfiding). The catalytic activity of various metal sulfides decreased in order of 4% Co 16% Mo > 4% Fe15% Mo > 16% Mo ≥ 25% Mo > 14% Co ≥ 4% Co > 4% Fe. A DRIFT study showed that CO adsorbs exclusively on CoMo phase and that SO₂ predominantly on γ-Al₂O₃. It is suggested that the Co–Mo–S structure is more adequate than the other metal-sulfur structures for the formation of a carbonyl sulfide (COS) intermediate because of the proper strength of metal–sulfur bond, and catalytically works with γ-Al₂O₃ for the COS–SO₂ reaction.     

CeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZSM-5 sorbents for high-temperature H<Subscript>2</Subscript>S removal

Performance of CeO₂-La₂O₃/ZSM-5 sorbents for sulfur removal was examined at temperature ranging from 500 oC to 700 oC. The sulfur capacity of 5Ce5La/ZSM-5 was much bigger than that of CeO₂/ZSM-5. H₂ had a negative impact on the sulfidation; however, CO had little influence on sulfur removal. The characterization results showed that CeO₂ and La₂O₃ were well dispersed on ZSM-5 because of the intimate admixing of La₂O₃ and CeO₂, the major sulfidation products were Ce₂O₂S and La₂O₂S, the XRD and SEM results revealed that ZSM-5 structure could remain intact during preparation and sulfidation process, the H₂-TPR showed that the reducibility of CeO₂ can be remarkably enhanced by addition of La.     

Simultaneous Removal of NO and SO2 from Flue Gas by UV/H2O2/CaO

The effects of several influencing factors (CaO and H₂O₂ concentration, gas flow, solution temperature, NO, SO₂, O₂ and CO₂ concentration) on the simultaneous removal of NO and SO₂ from flue gas by using a UV/H₂O₂/CaO process were studied. In addition, the anions in the liquid phase were measured by ion chromatography and the material balances for NO and SO₂ were calculated. It was found that, under all experimental conditions, this process achieved a SO₂ removal efficiency of 100 %. With the increase in CaO concentration, NO removal efficiency first increased and then remained almost unchanged. With the increase in H₂O₂ concentration, NO removal efficiency increased but the changes gradually became smaller. NO removal efficiency greatly decreased with increasing gas flow, NO concentration and CO₂ concentration. Slightly increasing the solution temperature and SO₂ concentration reduced NO removal efficiency. Increasing O₂ concentration can promote the removal of NO. The anions in the liquid phase were mainly SO₄^2– and NO₃^–. Most of the low valence nitrogen elements in NO and the low valence sulfur elements in SO₂ transformed into the high valence nitrogen element in NO₃^– and the high sulfur element in SO₄^2–.     

A study on the reactivity of Ce-based Claus catalysts and the mechanism of its catalysis for removal of H2S contained in coal gas

In this study, Claus reaction was applied for the selective removal of H₂S contained in the gasified coal gas, and the characteristics of Claus reaction over the Ce-based catalysts were investigated to propose the reaction mechanism. The Ce-based catalysts showed a high activity on Claus reaction. Specially, Ce_0.8Zr_0.2O₂ catalyst had a higher activity than CeO. On the basis of our experimental results, it was proposed that the selective oxidation of H₂S was carried out by the lattice oxygen in the Ce-based catalysts and that the reduction of SO₂ was performed by the lattice oxygen vacancy in the reduced catalyst. Since the mobility of the lattice oxygen in Ce_0.8Zr_0.2O₂ composite catalyst was better than the one in CeO₂, Ce_0.8Zr_0.2O₂ provided more lattice oxygen for the selective oxidation of H₂S. It was presumed that the reaction mechanism to convert H₂S and SO₂ into elemental sulphur over our prepared catalysts was different from the mechanism over the solid-acid catalysts. It is believed that Claus reaction over the Ce-based catalysts was carried out by the redox mechanism. Since the moisture was contained in the major components, CO and H, of the gasified fuel gas, the effects of CO and H₂O on the catalytic reaction were investigated over a Ce-based catalyst. The conversion of H₂S and SO₂ was decreased in Claus reaction over the Ce-based catalysts as the concentration of either H₂O or CO in the gasified coal gas was increased. Under the circumstances of the coexistence of both moisture and CO, however, the conversion was increased as the concentration of CO was increased. The reactivity of Claus reaction was varied in terms of the concentration ratio of CO to H₂O. The maximum conversion of H₂S and SO₂ was achieved in the condition of that the concentration of CO contained in the reacting gas was higher than the one of H₂O. The conversions of H₂S and SO₂ did not match to the stoichiometric ratios of Claus reaction. The higher conversion of H₂S was obtained in the higher concentration of H₂O, while the higher conversion of SO₂ was achieved in the higher concentration of CO. It was another evidence to indicate that the Claus reaction over the Ce-based catalysts was carried out by the redox mechanism.     

The effect of La2O3 on dynamic OSC over the Pd/OSC/Al2O3-based catalysts

In this study, fresh and aged Pd/(OSC–Al₂O₃) and Pd/(Al₂O₃–OSC–La₂O₃) metallic monoliths (OSC material Ce_0.75Zr_0.25O₂) were used to find out the effect of La₂O₃ on the catalyst behaviour in dynamic oxygen storage capacity (OSC) measurements. In addition, the interaction of CO, NO and O₂ reaction compounds over the studied catalysts was investigated in order to understand the effect of La₂O₃ in the oxidation and reduction reactions in lean automotive exhaust gas conditions. A FT-IR gas analyser was used to analyse the product gas composition. The presence of La₂O₃ on fresh and aged catalysts had negative effect on both the dynamic OSC and the activity of the catalyst. The reason for this is the different washcoat compositions between the studied catalysts which could explain the differences in BET surface areas.     

Activity and characterization of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for the SCR of NO with CO in the presence of SO2 and HCl

SO₂ and HCl are major pollutants emitted from waste incineration processes. Both pollutants are difficult to remove completely and can enter the catalytic reactor. In this work, the effects of SO₂ and HCl on the performance of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for NO removal were investigated in simulated waste incineration conditions. The characterizations of the catalysts were analyzed by BET, SEM/EDS, XRD, and ESCA. Experimental results indicated the 1%Rh/Al₂O₃ catalyst was significantly deactivated for NO and CO conversions when SO₂ and HCl coexisted in the flue gas. The addition of between 2 and 10 wt.% Na promoted the activity of the 1%Rh/Al₂O₃ catalyst for NO removal, but decreased the CO oxidation and BET surface area. The catalytic activity for NO removal was inhibited by HCl as a result of the formation of RhCl₃. Adding Na to the Rh/Al₂O₃ catalyst decreased the inhibition of SO₂ because of the formation of Na₂SO₄, which was observed in the XRD and ESCA analyses. SEM mapping/EDS showed that more S was residual on the surface of the Rh-Na/Al₂O₃ catalyst than Cl.     

SO_2对钙基吸收剂吸收NO的作用机理

针对低温条件下SO2对Ca(OH)2吸收NO的影响进行了实验研究,分析了烟气中O2和H2O对SO2促进Ca(OH)2吸收NO的影响。实验结果表明,当烟气不含SO2时,Ca(OH)2对NO基本无吸收作用;烟气中SO2的存在对NO吸收具有促进作用。H2O和O2对SO2促进NO吸收有显著影响;当烟气不含O2时,即使大量的SO2被吸收,NO吸收效率仍较低;只有SO2与O2和H2O共存才能促进NO吸收。脱硫产物CaSO3对NO无氧化作用;NO、H2O和SO2未在吸收剂表面产生可分解释放NO2的大分子中间配合物。分析认为在脱硫过程中产生了可以促进NO与O2反应的非稳定中间活性组分。     

Study on Olefin Alkylation of Thiophenic Sulfur in FCC Gasoline Using La2O3-Modified HY Zeolite

HY zeolite modified by La₂O₃ on olefin alkylation of thiophenic sulfur in fluid catalytic cracking (FCC) gasoline was studied in the micro fixed-bed reactor. Reaction pressure 1.5 MPa, reaction temperature 180 °C, WHSV 3.5 h^?1, using HY zeolite modified by 2% La₂O₃, the conversion of thiophene sulfur promoted nearly 10% with good selectivity, comparing with no-modified by La₂O₃. Acidity of modification of HY zeolite with La₂O₃ was tested in Pyridine–IR, it showed that increasing the amount of weak Bronsted (B) acid and the ratio of total B acid with total Lewis (L) acid could strengthen the hydrogen transfer activity of the catalyst, which leaded to improving the capacity of thiophene alkylation. The X-ray diffraction (XRD) results showed that the structure of catalysts could be optimized by loaded proper amount of La₂O₃ for promoting the acidic properties of HY zeolite.