Gaseous Elemental Mercury Removal Using Combined Metal Ions and Heat Activated Peroxymonosulfate/H2O2 Solutions

Several novel oxidation removal processes of elemental mercury (Hg⁰) from flue gas using combined Fe²⁺/Mn²⁺ and heat activated peroxymonosulfate (PMS)/H₂O₂ solutions in a bubbling reactor were proposed. The operating parameters (e.g., PMS/H₂O₂ concentration, Fe²⁺/Mn²⁺ concentration, solution pH, activation temperature, and Hg⁰/NO/SO₂/O₂/CO₂ concentration), mechanism and mass transfer-reaction kinetics of Hg⁰ removal were investigated. The results show that heat and Fe²⁺/Mn²⁺ have significant synergistic effect for activating PMS and PMS/H₂O₂ to produce free radicals to oxidize Hg⁰. Hg⁰ removal is strongly affected by PMS/H₂O₂ concentration, Fe²⁺/Mn²⁺ concentration, activation temperature, and solution pH. · and ·OH produced from combined heat and Fe²⁺/Mn²⁺ activated PMS/H₂O₂ play a leading role in Hg⁰ removal. Under optimized experimental conditions, Hg⁰ removal efficiencies reach 100, 94.9, 66.9, and 58.9% in heat/Fe²⁺/PMS/H₂O₂, heat/Mn²⁺/PMS/H₂O₂, heat/Fe²⁺/PMS, and heat/Mn²⁺/PMS systems, respectively. Hg⁰ removal processes in four systems belong to fast reaction and were controlled by mass transfer under optimized experimental conditions. © 2018 American Institute of Chemical Engineers AIChE J, 65: 161–174, 2019     

UV/H2O2氧化联合Ca(OH)2吸收同时脱硫脱硝

在小型紫外光-鼓泡床反应器中,对UV/H₂O₂氧化联合Ca(OH)₂吸收同时脱除燃煤烟气中NO与SO₂的主要影响因素[H₂O₂浓度、紫外光辐射强度、Ca(OH)₂浓度、NO浓度、溶液温度、烟气流量以及SO₂浓度]进行了考察。采用烟气分析仪和离子色谱仪分别对尾气中的NO₂和液相阴离子作了检测分析。结果显示:在本文所有实验条件下,SO₂均能实现完全脱除。随着H₂O₂浓度、紫外光辐射强度和Ca(OH)₂浓度的增加,NO的脱除效率均呈现先大幅度增加后轻微变化的趋势。NO脱除效率随烟气流量和NO浓度的增加均有大幅度下降。随着溶液温度和SO₂浓度的增加,NO脱除效率仅有微小的下降。离子色谱分析表明,反应产物主要是SO₄^2-和NO₃^-,同时有少量的NO₂^-产生。尾气中未能检测到有害气体NO₂。     

The oxidation of Fe(II) with Cu(II) in acidic sulfate solutions with air at elevated pressures

The oxidation of ferrous ions in acidic sulfate solutions in the presence of cupric ions at elevated air pressures was investigated in a high-intensity gas–liquid contactor. The study was required for the design of the regeneration steps of the novel Vitrisol^® desulphurization process. The effects of the Fe²⁺ concentration, Cu²⁺ concentration, Fe³⁺ concentration, initial H₂SO₄ concentration, and partial oxygen pressure on the reaction rate were determined at three different temperatures, i.e., T?=?50?°C, 70?°C, and 90?°C. Most of the experiments were determined to be affected by the mass transfer of oxygen, and therefore true intrinsic kinetics could not be fully determined. An increase in Fe²⁺ and Cu²⁺ concentrations, as well as the partial pressure of oxygen and temperature, increased the Fe²⁺ oxidation rate. H₂SO₄ did not influence the Fe²⁺ oxidation rate. An increase in Fe³⁺ concentration decreased the Fe²⁺ oxidation rate. Although determined from experiments partially affected by mass transfer, a first order of reaction in Fe²⁺ was observed, fractional orders in both Cu²⁺ and O₂ were measured, a zero order in H₂SO₄ was determined, and a negative, fractional order in Fe³⁺ was obtained. The activation energy was estimated to be 31.3?kJ/mol.     

Advanced Oxidative Removal of Nitric Oxide from Flue Gas by Homogeneous Photo‐Fenton in a Photochemical Reactor

In this work, advanced oxidation removal of nitric oxide (NO) from flue gas by homogeneous Photo‐Fenton was investigated in a photochemical reactor and the effects of several influencing factors on NO removal were evaluated. The gas‐liquid reaction products were determined. The reaction pathways of NO removal are also preliminarily discussed. It was found that with the increase of Fe²⁺ concentration, NO removal efficiency first increased and then decreased. Increasing H₂O₂ concentration and UV radiation intensity greatly increased NO removal efficiency, but the growth rates gradually became smaller. NO removal efficiency greatly reduced with the increase of gas flow and NO concentration, and only slightly decreased with the increase of solution temperature, but significantly increased with the increase of initial solution pH value. The main anion product in the liquid phase was NO₃^–. With respect to removal of NO using homogeneous Photo‐Fenton, ·OH oxidation was the main reaction pathway, and H₂O₂ oxidation was the secondary reaction pathway.     

Simultaneous removal of NO and SO2 using aqueous peroxymonosulfate with coactivation of Cu2+/Fe3+ and high temperature

A novel process on simultaneous removal of NO and SO₂ using aqueous peroxymonosulfate (PMS) with synergic activation of Cu²⁺/Fe³⁺ and high temperature in an impinging stream reactor is developed for the first time. Effects of PMS concentration, Cu²⁺/Fe³⁺ concentration, reaction temperature, solution pH, flue gas flow, liquid–gas ratio, gas components, and inorganic ions on NO/SO₂ removals were investigated. Active species and products were determined by electron spin resonance spectroscopy and ion chromatography. Removal pathways of NO/SO₂ were revealed, and mass transfer‐reaction kinetics of NO removal was studied. The optimal experimental conditions are obtained. H₂SO₄ and HNO₃ are the main products. It is found that there is a clear synergy between Cu²⁺/Fe³⁺ and high temperature for activating PMS. and ·OH are found to be the main oxidants for NO removal. NO removals belong to pseudo‐first fast reactions in the two investigated oxidation systems. Besides, the kinetic parameters are also measured. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1287–1302, 2017     

Removal of Hg0 from containing‐SO2/NO flue gas by ultraviolet/H2O2 process in a novel photochemical reactor

A novel photochemical spray reactor is first developed and is used to remove Hg⁰ and simultaneously remove Hg⁰/SO₂/NO from flue gas by ultraviolet (UV)/H₂O₂ process. The effects of several parameters (UV wavelength, UV power, H₂O₂ concentration, Hg⁰ inlet concentration, solution temperature, liquid–gas ratio, solution pH, SO₂ concentration, NO concentration, and O₂ concentration) on removal of Hg⁰ by UV/H₂O₂ process were investigated. Removal mechanism of Hg⁰ is proposed and simultaneous removal of Hg⁰, NO, and SO₂ is also studied. The results show that the parameters, UV wavelength, UV power, H₂O₂ concentration, liquid–gas ratio, solution pH, and O₂ concentration, have significant impact on removal of Hg⁰. However, the parameters, Hg⁰ inlet concentration, solution temperature, SO₂ concentration, and NO concentration, only have small effect on removal of Hg⁰. Hg²⁺ is the final product of Hg⁰ removal, and Hg⁰ is mainly removed by oxidations of H₂O₂, ·OH, · O, O₃, and photoexcitation of UV. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2275–2285, 2014     

Kinetic modeling of H2O2-enhanced oxidation of flue gas elemental mercury

Mercury emissions from coal-fired power plants account for 40% of the anthropogenic mercury emissions in the U.S. The speciation of mercury largely determines the amount of mercury capture in control equipments. Conversion of insoluble Hg⁰ into more soluble Hg²⁺ facilitates its removal in scrubbers. Past studies suggest that an added supply of OH radicals possibly enhance the mercury oxidation process. This study demonstrates that the application of H₂O₂, as source of OH radicals, accelerates the oxidation of Hg⁰ into Hg²⁺. A detailed kinetic reaction mechanism was compiled and the reaction pathways were established to analyze the effect of H₂O₂ addition. The optimum temperature range for the oxidation was 480–490 °C. The sensitivity analysis of the reaction mechanism indicates that the supply OH radicals increase the formation of atomic Cl, which accelerates the formation of HgCl₂ enhancing the oxidation process. Also, the pathway through HOCl radical, generated by the interactions between chlorine and H₂O₂ was prominent in the oxidation of Hg⁰. The flue gas NO was found to be inhibiting the Hg⁰ oxidation, since it competed for the supplied H₂O₂. Studying the interactions with the other flue gas components and the surface chemistry with particles in the flue gas could be important and may improve the insight into the post combustion transformation of mercury in a comprehensive way.     

Investigation on elemental mercury oxidation mechanism by non-thermal plasma treatment

Converting elemental mercury into divalent compound is one of the most important steps for mercury abatement from coal fired flue gas. The oxidation of elemental mercury was investigated in this paper using dielectric barrier discharge (DBD) non-thermal plasma (NTP) technology at room temperature. Effects of different flue gas components like oxygen, moisture, HCl, NO and SO₂ were investigated. Results indicate that active radicals including O, O₃ and OH all contribute to the oxidation of elemental mercury. Under the conditions of 5% O₂ in the simulated flue gas, about 90.2% of Hg⁰ was observed to be oxidized at 3.68 kV discharge voltage. The increase of discharge voltage, O₂ level and H₂O content can all improve the oxidation rate, individually. With O₂ and H₂O both existed, there is an optimal moisture level for the mercury oxidation during the NTP treatment. In this test, the observed optimal moisture level was around 0.74% by volume. Hydrogen chloride can promote the oxidation of mercury due to chlorine atoms produced in the plasma process. Both NO and SO₂ have inhibitory effects on mercury oxidation, which can be attributed to their competitive consumption of O₃ and O.     

Enhancement of NO absorption in ammonium-based solution using heterogeneous Fenton reaction at low H<Subscript>2</Subscript>O<Subscript>2</Subscript> consumption

A novel NO removal system is designed, where NO is initially oxidized by ?OH radicals from the decomposition of hydrogen peroxide (H₂O₂) over hematite and then absorbed by ammonium-based solution. According to the high performance liquid chromatography (HPLC) profile and the isopropanol injection experiments, the ?OH radicals are proved to play a critical role in NO removal. The NO removal efficiency primarily depends on H₂O₂ concentration, gas hourly space velocity (GHSV), H₂O₂ feeding rate and reaction temperature, while the flue gas temperature slightly affects the NO removal efficiency. The low H₂O₂ consumption makes this system a promising technique in NO removal process using wet-method. The evolution of catalyst in reaction is analyzed by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), Fourier Transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The nitrite ion and nitrate ion in aqueous solution are detected by the continuous phase flow analyzer. Finally, the macrokinetic parameters of the NO oxidation are obtained by using the initial rate method.     

Mercury removal from coal combustion by Fenton reactions – Part A: Bench-scale tests

This series of papers describes the development of technology to convert Hg(0) to Hg(II) in coal-derived flue gas based on the well-known Fenton reactions so that a Hg control strategy can be implemented in a wet scrubber. This effort consists of both bench-scale and pilot-scale work. This first paper reports on the bench-scale tests. The bench-scale results showed that Hg(0) oxidation can be achieved by the Fenton reactions and the oxidation rate is quantitatively dependent on the residence time of the Hg stream in the solution. An average of 75% oxidation of Hg(0) was achieved. Iron-based Fenton-type additives gave much more promising results compared to Cu-based Fenton-like additives for Hg(0) oxidation. The pH value of the sorbent solution also had a significant effect on the oxidation of Hg(0) and a suitable pH window was found to lie between 1.0 and 3.0 for this application. This may be attributed to the chain reaction mechanisms of Fe³⁺/H₂O₂ for Fenton reactions, i.e., the decomposition of H₂O₂ for the production of OOH radicals in the Fe³⁺/H₂O₂ system which is kinetically favoured under a wide range of conditions at pH values of 3 or less. At higher pH values, H₂O₂ is converted to H₂O instead of OOH radicals in the presence of Fe³⁺.     

Removal of high concentrations of H2S from simulated natural gas by Acidithiobacillus ferrooxidans immobilized on polyurethane foam

A chemo‐biochemical process for desulfurization of simulated natural gas containing hydrogen sulfide (H₂S) was investigated. The results showed that using polyurethane foam as a support for immobilization of Acidithiobacillus ferrooxidans obtained good biological oxidation performance and the maximum oxidation rate of ferrous iron was 4.12 kg m^?3 h^?1. Moreover, a semi‐empirical formula was set up for calculating theoretical ferrous oxidation rate as a function of influent Fe²⁺ and Fe²⁺ concentration in the bioreactor. The integrated chemical and biological process achieved removal efficiencies of about 80% when treating high concentrations of H₂S (15 000 ± 100 ppmv). © 2012 Society of Chemical Industry     

La‐hexaaluminate for synthesis gas generation by Chemical Looping Partial Oxidation of Methane Using CO2 as Sole Oxidant

Chemical looping partial oxidation of methane using a sole CO₂ oxidant (CL‐POM‐CO₂) is an emerging technology for synthesis gas generation and CO₂ utilization, which is highly dependent on an oxygen carrier (OC). In this work, Fe‐substituted La‐hexaaluminate as the OC was found to exhibit good reactivity and stability during 50 periodic CH₄/CO₂ redox cycles due to the formation of magnetoplumbite La‐hexaaluminate structure with the introduction of La. Deeper reduction for synthesis gas generation did not destroy the La‐hexaaluminate structure via a charge compensation mechanism, which increased CH₄ reactivity and further improved CO₂ utilization under subsequent re‐oxidation. In the La‐hexaaluminate structure, O₆‐Fe³⁺(Oh) was highly active for the total oxidation of methane, while O₅‐Fe³⁺(Tr) and O₄‐Fe³⁺(Th) selectively oxidized CH₄ to synthesis gas. The sole CO₂ oxidant only selectively recovered O₅‐Fe³⁺(Tr) and O₄‐Fe³⁺(Th), and thus is more favorable for improving synthesis gas selectivity than O₂/air, which offers an attractive opportunity for CO₂ utilization. © 2017 American Institute of Chemical Engineers AIChE J, 64: 550–563, 2018     

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–.     

Investigation of flue-gas treatment with O3 injection using NO and NO2 planar laser-induced fluorescence

Direct ozone (O₃) injection is a promising flue-gas treatment technology based on oxidation of NO and Hg into soluble species like NO₂, NO₃, N₂O₅, oxidized mercury, etc. These product gases are then effectively removed from the flue gases with the wet flue gas desulfurization system for SO₂. The kinetics and mixing behaviors of the oxidation process are important phenomena in development of practical applications. In this work, planar laser-induced fluorescence (PLIF) of NO and NO₂ was utilized to investigate the reaction structures between a turbulent O₃ jet (dry air with 2000 ppm O₃) and a laminar co-flow of simulated flue gas (containing 200 ppm NO), prepared in co-axial tubes. The shape of the reaction zone and the NO conversion rate along with the downstream length were determined from the NO-PLIF measurements. About 62% of NO was oxidized at 15d (d, jet orifice diameter) by a 30 m/s O₃ jet with an influence width of about 6d in radius. The NO₂ PLIF results support the conclusions deduced from the NO-PLIF measurements.     

Influence of the Metal Ions Cr3+, Fe3+, Ni2+ and Cu2+ on the Stability and Oxygen Consumption of Acrylic and Methacrylic Acid

For the safe and trouble‐free operation of a manufacturing plant and the safe storage of acrylic, as well as methacrylic monomers, it is important to know the polymerization stability as a function of the process parameters (temperature, oxygen concentration, and impurities, e.g., metal ions). Contamination with metal ions can be caused by the corrosion of steel units. Therefore, the influence of the metal ions Cr³⁺, Fe³⁺, Ni²⁺ and Cu²⁺ in the concentration range of 0–10 ppm (g g^–1) on the polymerization behavior and the oxygen consumption of acrylic and methacrylic acid were examined in this work. It was shown that Cr³⁺, Ni²⁺, and Cu²⁺ ions extend the inhibition period of acrylic acid (AA) and methacrylic acid (MAA) and reduce the O₂ consumption. Fe³⁺ ions, however, cause a decrease of the inhibition period and in the case of AA an increase of the O₂ consumption, which leads, in the end, to a faster unintentional polymerization. Therefore, alloys which contain iron should be avoided as far as possible in the construction of AA plants. Fe³⁺‐ions show the opposite influence towards MAA, here the presence of Fe³⁺ shows a stabilizing effect.     

Photooxidative removal of Hg0 from simulated flue gas using UV/H2O2 advanced oxidation process: Influence of operational parameters

Element mercury (Hg⁰) from flue gas is difficult to remove because of its low solubility in water and high volatility. A new technology for photooxidative removal of Hg⁰ with an ultraviolet (UV)/H₂O₂ advanced oxidation process is studied in an efficient laboratory-scale bubble column reactor. Influence of several key operational parameters on Hg⁰ removal efficiency is investigated. The results show that an increase in the UV light power, H₂O₂ initial concentration or H₂O₂ solution volume will enhance Hg⁰ removal. The Hg⁰ removal is inhibited by an increase of the Hg⁰ initial concentration. The solution initial pH and pH conditioning agent have a remarkable synergistic effect. The highest Hg⁰ removal efficiencies are achieved at the UV light power of 36W, H₂O₂ initial concentration of 0.125 mol/L, Hg⁰ initial concentration of 25.3 μg/Nm³, solution initial pH of 5, H₂O₂ solution volume of 600 ml, respectively. In addition, the O₂ percentage has little effect on the Hg⁰ removal efficiency. This study is beneficial for the potential practical application of Hg⁰ removal from coal-fired flue gas with UV/H₂O₂ advanced oxidation process.     

UV/H2O2氧化联合CaO吸收脱除NO的传质-反应动力学

在实验室规模的光化学反应器中,基于实验研究﹑动力学理论以及双膜理论,研究了UV/H₂O₂氧化联合CaO吸收(UV/H₂O₂-CaO工艺)脱除燃煤烟气中NO的传质-反应动力学。分析了NO吸收的传质-反应过程,明确了NO吸收过程的主要控制步骤和强化措施,测定了关键的动力学参数,推导了NO吸收过程的理论模型。结果表明:在实验范围内,NO吸收速率随着NO浓度的增加几乎呈线性增加。随着H₂O₂浓度和CaO浓度的增加,NO的吸收速率均呈现先增加后变缓的趋势。UV/H₂O₂-CaO工艺脱除NO是一个拟一级快速反应过程,强化气相主体扰动﹑增加气液接触面积和提高NO分压可有效提高NO的吸收速率。NO吸收速率方程的计算值和实验值具有较好的一致性。     

Competitive reaction pathway for photo and thermal catalytic removal of NO with hydrocarbon in flue gas under elevated temperatures

Three types of photocatalytic NO removal reaction including photo-assisted selective catalytic reduction (photo-SCR), photo-oxidation and photo-decomposition, were designated in the flue gas under elevated temperatures. The reliability of reaction pathways is supported by the excellent agreement of the change in the thermodynamic properties of individual catalytic reactions. The presence of O₂ could further effectively improve the photocatalytic activity at the low reaction temperature. However, an excess consumption of both O₂ and C₄H₁₀ was recognized by oxidation of C₄H₁₀ at the higher reaction temperature, resulting in the drop of the NO removal. This study provides the basis for designing the photocatalytic removal of NO with a hydrocarbon in the flue gas.     

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