Kinetic modeling and dynamic simulation for the catalytic wet air oxidation of aqueous ammonia to molecular nitrogen

A kinetic model for the catalytic wet air oxidation of aqueous ammonia over Ru/TiO₂ catalyst was developed considering the consecutive reaction steps as follows: (i) formation of active oxygen sites O* by the dissociative adsorption of aqueous O₂ on the catalyst, (ii) oxidation of aqueous NH₃ by the reaction with three O* sites to produce HNO₂, (iii) aqueous phase dissociation of HNO₂ into H⁺ and NO ₂ ^? , (iv) formation of NH ₄ ⁺ by the association of NH₃ with the HNO₂-dissociated H⁺, (v) formation of N₂ by the aqueous phase reaction between NO ₂ ^? and NH ₄ ⁺ , (vi) formation of NO₃ by the reaction of NO ₂ ^? with an O* site. For each reaction step, a rate equation was derived and its kinetic parameters were optimized by experimental data fitting. Activation energies for the reactions (ii), (v), and (vi) were 123.1, 76.7, and 54.5 kJ/mol, respectively, suggesting that the oxidation reaction of aqueous NH₃ to HNO₂ was a ratedetermining step. From the simulation using the kinetic parameters determined, the initial pH adjustment of the ammonia solution proved to be critical for determining the oxidation product selectivity between desirable N₂ and undesirable NO ₃ ^? as well as the degree of oxidation conversion of ammonia.     

Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water

Abstract

Some advanced oxidation processes (AOP's) such as Fenton H₂O₂/Fe²⁺, photo assisted Fenton UV/H₂O₂/Fe²⁺, UV photolysis, and photo assisted Fenton—like UV/O₂/Fe²⁺ have been tested for the degradation of Gemfibrozil in aqueous solution in a batch system and then in a membrane reactor. A nanofiltration/reverse osmosis type cross‐linked polyamide, UTC‐60 (Toray) membrane (19 cm²) was used. In the batch degradation tests, the gemfibrozil, used at 5 mg/L, was degraded by employing the four AOP's but numerous peaks of intermediates were observed at the HPLC. Indeed DOC analyses showed poor mineralization in the case of photolysis (3.1%) and UV/O₂/Fe (10%), while it was 62% using the photo assisted Fenton and 24% using the Fenton. Thus in the membrane reactor only the Fenton and the photo assisted Fenton were tested. Obtained results showed a drug degradation higher than 92%, a mineralization higher than 55%, and a membrane retention of the catalyst in solution higher than 95%.     

A comparative study of azo dye decolorization by electro‐Fenton in two common electrolytes

BACKGROUND: This study compared the decolorization behaviors of a model azo dye of methyl red in Na₂SO₄ and NaCl media by electro‐Fenton process, in which FeSO₄ was added into the solution, while H₂O₂ was efficiently generated on a graphite–polytetrafluoroethylene cathode. Parameters such as pH, cathodic potential, electrolyte concentration, and initial dye concentration as well as the treatment time were investigated to disclose different decolorization behaviour. RESULTS: Decolorization in NaCl medium had an advantage over that in Na₂SO₄ medium not only in performance but also in its suitability for application, which seemed less sensitive to variations in parameters and thus broadened the optimal performance range. In NaCl medium, indirect oxidation by active chlorine contributed greatly to the decolorization, and the removal of methyl red obeyed pseudo‐first‐order kinetics. CONCLUSION: Electro‐Fenton oxidation in the present system in the presence of NaCl would is a promising procedure for azo dye waste‐water treatment. Copyright © 2009 Society of Chemical Industry     

Advanced oxidation of catechol: A comparison among photocatalysis, Fenton and photo-Fenton processes

The aim of this work was to compare the behaviour of Fenton, photo-Fenton and photocatalysis processes to treat catechol solutions which are pollutants occurring in wastewaters from many industries. The effect of different process parameters, such as initial catechol concentration, H₂O₂/FeSO₄ ratio in Fenton and photo-Fenton oxidation, TiO₂ loadings in photocatalysis and irradiation times has been studied.Fenton and photo-Fenton (H₂O₂/FeSO₄ = 600/500 (w/w) and 30 min reaction time) processes allowed us to achieve a high efficiency in the mineralization of catechol (COD removals up to 83% and 96% respectively), and removal of aromaticity (UV₂₈₀) (up to 93% and 98% respectively), for an initial catechol concentration of 110 mg/l. On the opposite, photocatalysis was not effective in the removal of higher catechol concentrations (110 and 200 mg/l), whereas a significant removal of aromaticity versus time was observed for 50 mg/l. Gas chromatography-mass spectrometry analysis, performed under selected treatment conditions, showed that total removal of catechol can occur after Fenton (2000/500 w/w; 30 min), photo-Fenton (600/500 w/w; 30 min), and photocatalysis (3 g TiO₂/l; 240 min) treatments.     

Mineralization of the Pharmaceutical β-Blocker Atenolol by Means of Indirect Electrochemical Advanced Oxidation Process: Parametric and Kinetic Study

Atenolol is a β-blocker that can be found in urban wastewaters and which is not removed efficiently by conventional wastewater treatments. In the present study, electro-Fenton (EF) process was used to assess the degradation and mineralization of pharmaceutical atenolol in aqueous solutions. Electrolyses of 250 mL of atenolol solution (0.17 mM), at initial pH 3, were carried out in an undivided electrolytic cell in galvanostatic mode. Influence of material cathode (graphite, stainless steel, and platinized titanium), applied current (100–500 mA), sulfate dosage (0.01–0.5 M), and catalyst ferrous ions concentration (1–10 mM), on the oxidation efficiency was studied. Atenolol mineralization was monitored by COD dosage. Kinetic analysis indicated that atenolol mineralization followed a pseudo-first order model and the rate constant increased with rising current, ferrous ions concentration (up to 5 mM) and electrolyte concentration. Results showed that graphite cathode, 0.5 M Na₂SO₄ electrolyte, 0.3 A and 5 mM FeSO₄ catalyst were the best conditions for atenolol mineralization. In these optimal conditions, after 240 min more than 87% of the initial COD was removed. The corresponding current efficiency (CE) and specific energy consumption (SEC) were 22.33% and 0.194 kWh/kg COD, respectively. This latter corresponds to 0.078 kWh/m³ of treated wastewater.     

CoAl2O4 spinel catalyst for soot combustion with NOx/O2

Mesoporous and nanosized cobalt aluminate spinel with high specific surface area was prepared using microwave assisted glycothermal method and used as soot combustion catalyst in a NO_x + O₂ stream. For comparison, zinc aluminate spinel and alumina supported platinum catalysts were prepared and tested. All samples were characterised using XRD, (HR)TEM, N₂ adsorption–desorption measurements. The CoAl₂O₄ spinel was able to oxidise soot as fast as the reference Pt/Al₂O₃ catalyst. Its catalytic activity can be attributed to a high NO_x chemisorption on the surface of this spinel, which leads to the fast oxidation of NO to NO₂.     

Improved stability of Co-Ferrierite catalyst by Mn in dry–wet cycles of lean CH4-SCR of NOx

Ion-exchanged Co, Mn and Co,Mn-FER zeolite was tested as catalyst for the selective reduction of NO_x with CH₄ in the presence of O₂ under dry and wet (1 vol% H₂O) cycles. Under hydrothermal conditions Co-FER undergoes a progressive loss of activity, while Co,Mn-FER catalyst shows an increased water resistance. UV-VIS spectra of monometallic and bimetallic catalysts collected before and after dry–wet catalytic cycles show a change of Co species distribution within the zeolite upon heating and exposure to water. However, the presence of Mn prevents the decrease in the population of the most active Co²⁺ site in the presence of water and stabilises the catalytic activity, as evidenced in 80 h time on stream run.     

Relationship Between Gross Nitrogen Cycling and Nitrous Oxide Emissionin Grass-clover Pasture

Replacement of high-input N fertilized pastures with low-input grass-legume pastures may provide a mitigation option to reduce agricultural N₂O emissions. This study examined the relationship between N-cycling rates and N₂O production and evolution from the root zone of grass-clover pastures of various ages (production year 1, 2 and 8). The experimental approach included cross-labelling pasture monoliths with ¹⁵N-enriched substrates to identify sources of N₂O, in combination with assessment of gross N mineralization and nitrification. Nitrous oxide emissions were generally low, fluctuating between 82 and 136μg N₂O–N m⁻² d⁻¹, independent of pasture age. The ¹⁵N labelling indicated that at least 50% of the N₂O was derived from the soil NH₄⁺ pool, approaching 100% in June. In the two year old pasture the NH₄⁺ pool contributions to N₂O emissions varied significantly with sampling time. Emission rates of N₂O correlated positively with soil NH₄⁺ concentrations and the NH₄⁺ supply as expressed by gross mineralization. The N₂O emissions showed a significant inverse relationship with soil NO₃⁻, but was not correlated with the supply of NO₃⁻ as expressed by gross nitrification. The ratio N₂O vs. nitrification averaged 0.05% (range 0.004 to 0.29%) and varied with sampling time showing the lowest value in wet soil conditions.     

Response surface methodology approach for the optimization of tartrazine removal by heterogeneous photo-Fenton process using mesostructured Fe2O3-suppoted ZSM-5 prepared by chitin-templating

A statistical optimization of tartrazine dye removal process from aqueous solution by heterogeneous photo–Fenton process using Fe₂O₃-supported ZSM-5 catalyst was performed. ZSM-5 support was prepared by chitin-templating technique to obtain a mesoporous structure. Thereafter, Fe₂O₃ was supported on ZSM-5 through wet impregnation method. This material was characterized by different techniques and posteriorly evaluated as a catalyst for the removal of tartrazine from aqueous solution. A central composite rotational design coupled with response surface methodology approach was used to evaluate the influence of different reaction conditions on the decolorization of a solution containing tartrazine and to obtain the optimum conditions. Under the optimum experimental conditions of dye decolorization, a mineralization experiment was conducted through analysis of total organic carbon. In these conditions, 95% of decolorization was achieved at 30?min of reaction and a significant mineralization of 80% was observed at 180?min. Therefore, the photo-Fenton process using Fe₂O₃-supported ZSM-5 prepared by chitin-templating was proved to be feasible for both the decolorization and mineralization of tartrazine in aqueous solution.     

Sulfur‐replaced Fenton systems: can sulfate radical substitute hydroxyl radical for advanced oxidation technologies?

Sulfate radicals (SO₄^??) and hydroxy radicals (HO^?) are the major radicals used in advanced oxidation technologies (AOTs) for the removal of contaminants. Although SO₄^?? reacts with organic or inorganic compounds with rate constants comparatively lower than that of HO^?, AOTs based on SO₄^?? (abbreviated as SR‐AOTs) have gained lots of attention due to the selective oxidation and non‐pH‐dependence. A series of systems using persulfate (PS) or peroxymonosulfate (PMS) instead of H₂O₂ is designated as a sulfate radical‐Fenton system or sulfur‐replaced Fenton system (SR‐Fenton). Comparisons and analogies between Fenton (Fenton‐like) systems and SR‐Fenton systems are made and some new SR‐AOTs systems without PS or PMS are introduced. The possibility for the substitution of HO^? by SO₄^?? for AOTs is discussed. Most likely in the future, efforts will be concentrated on product‐oriented AOTs with the purpose of recovery of chemical products rather than mineralization of organic contaminants, producing greenhouse gas CO₂. Moreover, such SR‐Fenton system may be more atomically economical. © 2014 Society of Chemical Industry     

Numerical Study of NOx Abatement Using Ozone Injection Integrated with Wet Absorption

Nitrogen oxides emitted from power plants and the chemical industry are poisonous to humans and animals, contribute to ozone depletion, and cause acid rain. More than 90% of nitrogen oxides (NO_x) consist of nitric oxide (NO), which is insoluble in water. Among the various available techniques of NO_x abatement, ozone injection is a promising method in which NO is oxidized to higher-order nitrogen oxides (NO₃, N₂O₃, N₂O₄, and N₂O₅), which can easily be absorbed in a wet scrubber. In this article, the ozone injection process integrated with an absorber column is numerically modeled and simulated at various operating conditions. The predicted results of NO_x oxidation with ozone injection and absorption in water agree with the published experimental results. The ozone injection process is modeled using a plug flow reactor, while the wet absorption is based on a rigorous rate-based RateFrac model. Detailed kinetic mechanisms of O₃-NO_x oxidation and absorption of nitrogen oxides in water are incorporated in the model to simultaneously predict the performance efficiency of the ozone reactor and absorber column. Thermodynamic properties of the components are estimated using an Electrolyte NRTL model. The influence of performance parameters (such as feed gas flow rate, inlet gas temperature, reactor configurations, ozone concentration, and NO/NO₂ molar ratio) on the oxidation efficiency of NO_x in the reactor and absorber column is investigated to predict the optimal operating conditions.     

Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

High-stable CuPd–Cu2O/Ti-powder catalyst for low-temperature gas-phase selective oxidation of alcohols

The oxidation of alcohols to carbonyl compounds in gas-phase is of great importance in organic chemistry and industrial process. Herein, the catalyst CuPd–Cu₂O/Ti-powder is prepared by depositing Cu(NO₃)₂ and Pd(NO₃)₂ on Ti powder support followed by in-situ activation in reaction stream, which delivers high-performance for the gas-phase oxidation of alcohols. Compared with Cu/Ti-powder and Pd/Ti-powder, CuPd–Cu₂O/Ti-powder exhibits higher stability and activity in alcohol oxidation reaction. The catalyst is characterized by XRD, XPS, TEM and ICP. The results indicate that CuPd(alloy)–Cu₂O formed during the reaction contributes to the high activity and stability.     

Role of ceria-supported noble metal catalysts (Ru, Pd, Pt) in wet air oxidation of nitrogen and oxygen containing compounds

Catalytic wet air oxidation (CWAO) of aniline, phenol, carboxylic acids and ammonia was carried out in a batch reactor over noble metals (Ru, Pd, Pt) supported on ceria. Ruthenium is very active for the conversion of a wide range of organic compounds and selective into carbon dioxide. The ability of ceria to transfer oxygen is essential for good performances in CWAO. However, Ru/CeO₂ is not selective for ammonia oxidation into N₂. Addition of small amount of Pd enhances both activity and selectivity of Ru in this reaction. Finally, oxidation of nitrogenous organic compounds requires moderate temperature and oxygen pressure and needs to adjust the oxidizing capacity of the catalyst.     

Reduction of nitrogen oxides by ozonization-catalysis hybrid process

Treatment of nitrogen oxides (NO_x) by using a hybrid process consisting of ozonization and catalysis was investigated. The ozonization method may be an alternative for the oxidation of NO to NO₂. It was found that nitric oxide (NO) was easily oxidized to nitrogen dioxide (NO₂) in the ozonization chamber without using any hydrocarbon additive. In a temperature range of 443 to 503 K, the decomposition of ozone into molecular oxygen was not significant, and one mole of ozone approximately reacted with one mole of NO. A kinetic study revealed that the oxidation of NO to NO₂ by ozone was very fast, almost completed in a few tens of milliseconds. When the amount of ozone added was less than stoichiometric ratio with respect to the initial concentration of NO, negligible NO₃ and N₂O₅ were formed. The oxidation of a part of NO to NO₂ in the ozonization chamber enhanced the selective reduction of NO_x to N₂ by a catalyst (V₂O₅/TiO₂), indicating that the mixture of NO and NO₂ reacts faster than NO.     

Promotional effect of Ce on the activity of In/W–ZrO2 for selective reduction of NO x with methane

The Ce modified In/W–ZrO₂ catalysts were prepared by impregnation and mechanical mix method. Their activities for SCR of NO _x with methane were investigated. The activity of the In/W–ZrO₂ catalyst was enhanced by addition of Ce with both methods, while the promotional effect was more pronounced for catalyst prepared by mechanical mix method compared to impregnation method. The function of Ce was to improve the oxidation of NO to NO₂. The maximum NO _x conversion over the mechanical mixed catalyst can be stabilized at 74% at 450 °C in a dry gas flow and 37% at 500 °C in wet flow (24,000 h⁻¹). For the impregnated catalysts, Ce was found to compete with In to adsorb on strong acid site over W–ZrO₂ support and inhibited the formation of InO⁺, which resulted in the lower activity of these catalysts than mechanical mixed catalysts.     

A new reactor coupling heterogeneous Fenton‐like catalytic oxidation with membrane separation for degradation of organic pollutants

BACKGROUND: There is growing interest in employing heterogeneous Fenton‐like catalysts in slurry to obtain higher activity. However, fine size particles create problems associated with recovery from the treated water. Therefore, it is highly desirable to develop a novel Fenton‐like process that not only has high degradation efficiency of organic pollutants, but also allows for easily reusing the catalysts. RESULT: A new reactor was investigated by coupling the heterogeneous Fenton‐like oxidation with membrane separation. Results showed that the FeY catalyst could be almost filtrated by a submerged micro‐filtration membrane in the reactor to continuously activate H₂O₂. For a FeY dose of 1 g L^?1 and a residence time of 120 min, the degradation efficiency of AO II reached 97%. CONCLUSIONS: In the new reactor, degradation of AO II occurred continuously and efficiently without an additional FeY separation process. The treatment capacity of this FeY catalyst for wastewater containing 100 mg L^?1 AO II in the reactor was estimated to be 82 times that of a reactor in which the catalyst could not be reused. The distinguishing technical feature of this reactor was the reuse of the Fenton‐like catalyst. Copyright © 2011 Society of Chemical Industry     

Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

Selective reduction of NOx with hydrocarbons over Co/MFI prepared by sublimation of CoBr2 and other methods

Co/MFI catalysts were prepared by various methods, including wet-ion exchange (WIE), either as such or in combination with impregnation (IMP), solid-state ion exchange (SSI), and sublimation (SUB) of CoCl₂ (at 700°C) or CoBr₂ (at 600°C) onto H/MFI. The catalysts were tested for the reduction of NO_x with CH₄ or iso-C₄H₁₀ in excess O₂. Below 425°C the SUB catalysts show the highest NO_x reduction activity with CH₄ or iso-C₄H₁₀. Above 425°C, the best performance is given by WIE. Below the temperature of maximum N₂ yield, a mixture of Fe/FER and WIE is superior to either catalyst. Addition of 10% H₂O to the feed drastically decreases the N₂ yield in NO_x reduction with CH₄, but increases the activity with iso-C₄H₁₀ under some conditions. Permanent damage of the zeolite lattice as a potential cause for the adverse effect of H₂O in the tests with CH₄ is eliminated, as the original activity is fully restored after calcination. A 100 h test with a wet iso-C₄H₁₀ feed shows excellent stability with a SUB catalyst prepared from CoBr₂.Characterization by XRD, H₂-TPR, and FTIR reveals that WIE contains isolated Co²⁺ and (Co–OH)⁺ ions that are only reducible at 700°C. SUB catalysts show additional TPR peaks at low temperature, including a feature at 220–250°C, ascribed to multinuclear Co oxo-ions. The formation of an NO_y chemisorption complex is most rapid on these catalysts. No oxidation states between Co⁰ and Co²⁺ are detectable; the one-step reduction of Co²⁺ to Co⁰ clusters could be a cause for the unique propensity of Co/MFI to reduce NO_x with CH₄.     

亚甲基蓝光度法研究基于CaO2的Fenton反应条件

CaO₂作为原位Fenton 氧化修复中H₂O₂持续供源的作用逐渐受到关注。利用亚甲基蓝分光光度法评价了基于CaO₂的Fenton反应中催化剂种类、初始pH值、CaO₂用量、催化剂和CaO₂比例、磷酸缓冲溶液浓度对羟基自由基（HO·）产率的影响。结果表明,采用Fe²⁺作为催化剂,在pH值为4、CaO₂相似文献