Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

The removal system for the absorption of CO₂ with amines and NH₃ is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO₂ by amines and NH₃ solutions was performed in this study to derive the reaction kinetics. The absorption of CO₂ as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH₃ was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O₂ concentration and pH value. The absorption efficiency of MEA is better than that of NH₃ and DEA, but the absorption capacity of NH₃ is the best. The active energies of the MEA and NH₃ with CO₂ are 33.19 and 40.09 kJ/mol, respectively.     

混合有机胺吸收烟道气中CO2的实验研究

以工业应用为背景,采用双搅拌釜反应器,对DETA(二乙烯三胺) MDEA(N-甲基二乙醇胺)、TETA(三乙烯四胺） MDEA混和有机胺水溶液吸收模拟烟道气中CO2进行研究。结果显示,在MDEA中加入少量烯胺DETA、TETA,可显著提高CO2吸收速率和吸收容量,增强传质效果。其吸收CO2的效果优于常用的MEA(-乙醇胺)和DEA(二乙醇胺)。     

混合胺MEA＋DETA吸收CO2的影响因素

以MEA为主体,DETA为添加剂,考察1h内,在温度298～338K,压力300～700kPa,混合胺溶液初始浓度（质量分数）4％～20％范围内,MEA＋DETA不同配比的混合吸收剂吸收CO2的特性。获得MEA＋DETA混合胺吸收CO2的最佳吸收条件为：308K、500kPa、总胺质量浓度为20％,MEA与DETA的配比为8：2。     

Chemical absorption process for degradation of VOC gas using heterogeneous gas-liquid photocatalytic oxidation: toluene degradation by photo-Fenton reaction

A novel process for degradation of toluene in the gas-phase using heterogeneous gas-liquid photocatalytic oxidation has been developed. The degradation of toluene gas by photo-Fenton reaction in the liquid-phase has experimentally examined. The photo-Fenton reaction in the liquid-phase could improve the overall toluene absorption rate by increasing the driving force for mass transfer and as a result enhance the removal of toluene in the exhaust gas. The toluene concentrations in the inlet gas were varied in the range from 0.0968 to 8.69gm(-3) with initial hydrogen peroxide concentration of 400mgl(-1) and Fe dose of 5.0mgl(-1). It was found that toluene in the inlet gas was almost completely dissolved into water and degraded in the liquid-phase for the inlet toluene gas concentration of less than 0.42gm(-3). The dynamic process of toluene gas degradation by the photo-Fenton reaction providing information for reaction kinetics and mass transfer rate was examined. Toluene removal kinetic analysis indicated that photo-Fenton degradation was significantly affected by H(2)O(2) concentration. The experimental results were satisfactorily described by the predictions simulated using the simplified tanks-in-series model combined with toluene removal kinetic analysis. The present results showed that the proposed chemical absorption process using the photo-Fenton heterogeneous gas-liquid photocatalytic oxidation is very effective for degradation of volatile organic gases.     

鼓泡反应器中液相络合催化同时脱硫脱硝的研究

在鼓泡反应器中考察了[Co(en)3]2+同时吸收去除SO2和NO的影响因素,实验结果表明,pH值和脱硫剂种类是影响乙二胺合钴同时脱除NO和SO2的最重要影响因素,烟气中的氧促进乙二胺合钴吸收NO和SO2,烟气中的SO2,CO2和NO2对乙二胺合钴吸收NO具有抑制作用。在实验条件温度为20℃,pH为13.0,[Co(en)3]2+浓度为0.025 mol/L,加入1 g NH3.H2O的脱硝率更好,连续吸收60 min,脱硝率均保持在93.5%,加入NaOH和NH3.H2O的脱硫效果最好。乙二胺合钴络合同时脱除NO和SO2完全可以在一个装置中完成。     

捕集低浓度二氧化碳的化学吸收工艺及其综合比较

目前CO₂捕集成为减缓全球变暖的重要技术,但是迄今为止没有一种技术能够大规模商业化运行。在现有技术中,化学吸收法最具前景,而化学吸收法中研究最集中的吸收剂为单乙醇胺、哌嗪碳酸钾溶液、离子液和氨水。为了了解各个化学吸收工艺的特点和应用情况,有必要对上述工艺进行综合比较。通过各种吸收剂的特性、工艺特点、研究进展和能耗等方面的比较,显示单乙醇胺工艺成熟度较高,联合氨法工艺前景非常好,而离子液和哌嗪碳酸钾工艺需要进一步研究。     

填料塔中Na2CO3吸收高浓度H2S的传质特性

在填料吸收塔中考察了Na2CO3溶液吸收高浓度H2S气体的气液传质特性。通过测量填料塔进出口气体中H2S浓度计算了Na2CO3溶液吸收高浓度H2S气体的总体积传质系数（KGa）,并研究了进气流速、吸收液流量、吸收温度和吸收液浓度对KGa的影响。结果表明,KGa随Na2CO3浓度、吸收液流量的增加而增加,随吸收温度、进气流速的升高而降低;在高浓度H2S吸收过程中液相传质阻力不能忽略。     

混合胺MEA+DETA吸收CO2的影响因素

以MEA为主体,DETA 为添加剂,考察1 h内,在温度298~338 K,压力300~700 kPa,混合胺溶液初始浓度(质量分数)4%~20%范围内,MEA+DETA不同配比的混合吸收剂吸收CO₂的特性。获得MEA+DETA混合胺吸收CO₂的最佳吸收条件为:308 K、500 kPa、总胺质量浓度为20%,MEA与DETA 的配比为8:2。     

旋转填充床吸收模拟工业废气中SO2的研究

选择3%SO2作为模拟工业废气,一乙醇胺（MEA）作为吸收剂在超重力条件下对模拟工业废气中脱硫工艺进行了实验研究,考察了旋转填充床转速、气液比、吸收剂入口温度以及吸收剂浓度对脱硫率的影响,确定了MEA作为吸收剂时适宜的操作条件。同时在旋转填充床中考察了几种不同吸收剂对3%SO2脱除率的影响。研究表明,1 mol/L哌嗪（PZ）的脱除率最优,1 mol/L N-甲基乙醇胺（MDEA）的脱除率最低。     

氧化镁烟气脱硫反应特性研究

利用实验室规模的鼓泡式反应装置,对比了碳酸钙、氧化镁和氧化镁/硫酸镁脱硫剂的反应活性,证实脱硫液中高浓度硫酸镁的存在是保证镁法脱硫效率高于钙法的重要因素,并考察了硫酸镁浓度、脱硫剂(氧化镁)浓度、烟气量、SO2浓度和吸收液温度等因素对脱硫效率的影响。结果表明,脱硫反应可以根据pH分为2个不同阶段;反应过程中脱硫效率随着硫酸镁浓度的增加而显著升高;烟气量增加将会导致脱硫效率有所下降;入口SO2浓度升高,脱硫效率下降;氧化镁浓度、温度对脱硫效率影响不显著。结合实验现象进行推断,氧化镁脱硫的反应过程受SO2在气液两相界面的传质扩散和其水解产物在液相的扩散控制。     

Bio-syngas production with low concentrations of CO2 and CH4 from microwave-induced pyrolysis of wet and dried sewage sludge

This paper assesses the feasibility of producing syngas from sewage sludge via two pyrolysis processes: microwave-induced pyrolysis (MWP) and conventional pyrolysis (CP). The changes in the composition of the produced gas as a function of the pyrolysis treatment and the initial moisture content of the sludge were evaluated. It was found that MWP produced a gas with a higher concentration of syngas than CP, reaching values of up to 94vol%. Moreover, this gas showed a CO2 and CH4 concentration around 50% and 70%, respectively, lower than that obtained in the gas from CP. With respect to the effect of moisture on gas composition, this was more pronounced in CP than in MWP. Thus, the presence of moisture increases the concentration of H2 and CO2 and decreases that of CO, especially when CP was used. In order to elucidate the behaviour of CO2 during the pyrolysis, the CO2 gasification kinetics of the char obtained from the pyrolysis were investigated. It was established that in microwave heating the gasification reaction is much more favoured than in conventional heating. Therefore, the low concentration of CO2 and the high concentration of CO in the microwave pyrolysis gas could be due to the self-gasification of the residue by the CO2 produced during the devolatilization of the sewage sludge in the pyrolysis process.     

氨水土壤混合物脱除CO2温室气体的实验研究

为了脱除CO2温室气体,提出了利用氨水土壤混合物去除CO2的新方法.分别考察了土壤颗粒粒径、CO2初始流量、氨水浓度(质量比)和温度对CO2脱除量和脱除率的影响.实验结果表明,该方法去除CO2的量较土壤物理吸附量和氨水化学吸收量的总和提高了大约15%;随着氨水浓度的增大,CO2的脱除率和脱除量都增大;随着土壤颗粒粒径和CO2初始流量的增大,CO2的脱除率和脱除量都减小;当温度由22℃升高到31℃,CO2的脱除率随着温度的升高而增大,但是继续升高温度到40 ℃,CO2的脱除率反而下降.     

Bench-scale biofilter for removing ammonia from poultry house exhaust

A bench-scale biofilter was evaluated for removing ammonia (NH3) from poultry house exhaust. The biofilter system was equipped with a compost filter to remove NH3 and calcium oxide (CaO) filter to remove carbon dioxide (CO2). Removal of NH3 and CO2 from poultry house exhaust could allow treated air with residual heat to be recirculated back into the poultry house to conserve energy during winter months. Apart from its use as a plant nutrient, NH3 removal from poultry house exhaust could lessen the adverse environmental impacts of NH3 emissions. Ammonia and CO2 were measured daily with gas detector tubes while temperatures in the poultry pen and compost filter were monitored to evaluate the thermal impact of the biofilter on treated air. During the first 37 days of the 54-day study, exhaust air from 33 birds housed in a pen was treated in the biofilter; for the final 17 days, NH3-laden exhaust, obtained by applying urea to the empty pen was treated in the biofilter. The biofilter system provided near-complete attenuation of a maximum short-term NH3 concentration of 73 ppm. During the last 17 days, with a mean influent NH3 concentration of 26 ppm, the biofilter provided 97% attenuation. The CaO filter was effective in attenuating CO2. Compared with a biofilter sized only for NH3 removal, an oversized biofilter would be required to provide supplemental heat to the treated air through exothermic biochemical reactions in the compost. The biofilter could conserve energy in poultry production and capture NH3 for use as plant nutrient. Based on this study, a house for 27,000 broilers would require a compost filter with a volume of approximately 34 m3.     

氨水土壤混合物脱除CO2温室气体的实验研究

为了脱除CO2温室气体,提出了利用氨水土壤混合物去除CO2的新方法。分别考察了土壤颗粒粒径、CO2初始流量、氨水浓度（质量比）和温度对CO2脱除量和脱除率的影响。实验结果表明,该方法去除CO2的量较土壤物理吸附量和氨水化学吸收量的总和提高了大约15%;随着氨水浓度的增大,CO2的脱除率和脱除量都增大;随着土壤颗粒粒径和CO2初始流量的增大,CO2的脱除率和脱除量都减小;当温度由22℃升高到31℃,CO2的脱除率随着温度的升高而增大,但是继续升高温度到40℃,CO2的脱除率反而下降。     

旋转填充床吸收模拟工业废气中SO2的研究

选择3%SO2作为模拟工业废气,一乙醇胺(MEA)作为吸收剂在超重力条件下对模拟工业废气中脱硫工艺进行了实验研究,考察了旋转填充床转速、气液比、吸收剂入口温度以及吸收剂浓度对脱硫率的影响,确定了MEA作为吸收剂时适宜的操作条件.同时在旋转填充床中考察了几种不同吸收剂对3%SO2脱除率的影响.研究表明,1 mol/L哌嗪...     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

Biotreatment of H2S- and NH3-containing waste gases by co-immobilized cells biofilter

Gas mixture of H2S and NH3 in this study has been the focus in the research area concerning gases generated from the animal husbandry and the anaerobic wastewater lagoons used for their treatment. A specific microflora (mixture of Thiobacillus thioparus CH11 for H2S and Nitrosomonas europaea for NH3) was immobilized with Ca-alginate and packed inside a glass column to decompose H2S and NH3. The biofilter packed with co-immobilized cells was continuously supplied with H2S and NH3 gas mixtures of various ratios, and the removal efficiency, removal kinetics, and pressure drop in the biofilter was monitored. The results showed that the efficiency remained above 95% regardless of the ratios of H2S and NH3 used. The NH3 concentration has little effect on H2S removal efficiency, however, both high NH3 and H2S concentrations significantly suppress the NH3 removal. Through product analysis, we found that controlling the inlet ratio of the H2S/NH3 could prevent the biofilter from acidification, and, therefore, enhance the operational stability. Conclusions from bioaerosol analysis and pressure drop in the biofilter suggest that the immobilized cell technique creates less environmental impact and improves pure culture operational stability. The criteria for the biofilter operation to meet the current H2S and NH3 emission standards were also established. To reach Taiwan's current ambient air standards of H2S and NH3 (0.1 and 1 ppm, respectively), the maximum inlet concentrations should not exceed 58 ppm for H2S and 164 ppm for NH3, and the residence time be kept at 72 s.     

异养硝化细菌Alcaligenes sp.S3除氮特性及动力学

从湘江生活污水排污口分离纯化的一株菌Alcaligenes sp.S3,在氨氮浓度为400 mg/L时,经过192 h的降解,氨氮的去除率达到88%,并且NH2OH和NO2--N并没出现积累。在对不同浓度的氨氮进行一级动力学拟合时发现,只有氨氮浓度较高时才很好地符合,浓度为500 mg/L时R2达到0.9923。酸性环境对Alcaligenes sp.S3生长有抑制作用,在pH7.5～10生长较好。摇床转速对Alcaligenes sp.S3除氮影响不大,C/N过低或过高对Alcaligenes sp.S3除氮都有影响。     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Selective catalytic oxidation of ammonia over copper-cerium composite catalyst

This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).