Experimental and Theoretical Studies on Desulfurization Efficiency of Dual-alkali FGD System in a RST Scrubber

The effects of operating parameters on desulfurization efficiency of a dual-alkali FGD process in a rotating-stream-tray (RST) scrubber are investigated. A dimensionless factor, e, is proposed in this study to predict desulfurization efficiency of this dual-alkali FGD system. e represents the desulfurization ability of a dual alkali FGD system, determined by five main operating parameters such as sodium ion concentration, ratio of absorbent flow rate to flue gas flow rate, pH value of absorbent solution, ratio of sulfate ion to total sulfur ion in absorbent solution, and sulfur dioxide concentration of inlet flue gas. The empirical expression for predicting desulfurization efficiency at different temperatures is obtained through the experimental study and theoretical calculation. It provides useful guide for engineering design.     

Optimum conditions for preparation of flue gas desulfurization absorbent from rice husk ash

Several previous studies have reported the preparation of absorbents from coal fly ash variations as a source of siliceous material for the preparation of absorbents for flue gas desulfurization. On the other hand, this study presents findings from an experimental investigation of the preparation of absorbents from rice husk ash as the source of the siliceous material. The effect of various absorbent preparation variables such as hydration period, amount of rice husk ash, amount of calcium sulfate (CaSO₄) and hydration temperature on the BET (Brunner–Emmett–Teller) specific surface area of the absorbent were investigated. Based on the Central Composite Design (CCD) of experiments, a third order mathematical model was developed to correlate the absorbent preparation variables to the surface area of the absorbent. The predicted surface area was found to agree satisfactory with the experimental values. The model indicated that lower hydration period and temperature favor the formation of absorbent with higher surface area. Sulfation activity test on the absorbent revealed that the absorbent prepared from rice husk ash does have a high capacity in sulfur dioxide (SO₂) absorption.     

Investigation of the Degradation of Chelate Complexes in Liquid Redox Desulfurization Processes

Metal complexes such as Fe-EDTA, which are used as pseudo-catalysts or oxygen carriers in wet oxidative desulfurization processes, are subject to a degradation mechanism that significantly influences the economics of such processes. Therefore, this study presents a methodology for determining the degree of degradation during the reactive hydrogen sulfide absorption in a Fe-EDTA solution within a continuously operating semi-batch reactor system. For this purpose, the reactive conversion of H₂S in the liquid phase was used as a reference, and a clear dependence of the degradation on the pH could be shown. In addition, indicators are introduced that evaluate the observed pH dependency of the degradation and distinguish pH-induced effects such as the pH-dependent absorption performance of H₂S.     

Fe2+液相催化氧化脱除烟气中SO2

提出了一种烟气脱硫新工艺。实验选用水作脱硫剂 ,在只以Fe为催化剂的条件下进行。加入吸收液槽中的铁屑可与脱硫产生的稀硫酸进行反应 ,不仅可维持较高的吸收液pH值 ,而且产生的Fe2 + 引发了液相催化氧化SO2 反应。连续运行实验结果表明脱硫过程在不同阶段分别受SO2 溶解、Fe2 + 液相催化氧化SO2 反应、气相中SO2 扩散和铁屑与酸反应控制。吸收液中Fe2 + 质量浓度的变化和初始Fe2 + 质量浓度对脱硫率及吸收液pH值影响显示 ,可直接由清水制取高浓度硫酸亚铁溶液。实验还调查了SO2 入口质量浓度、液气比、空塔气速和吸收温度对脱硫率和吸收液pH值的影响     

超重力烟气脱硫的实验研究

超重力旋转床(RPB)是一种高效强化传质的设备.以亚硫酸钠溶液为吸收剂,采用并流操作方式在 RPB 中进行了模拟烟气脱硫的实验研究,考察了吸收液中钠离子浓度、旋转床转子的转速、气液比(l=G/L)等工艺参数对二氧化硫脱除率的影响.实验结果表明:当钠离子浓度小于0.20 mol·L-1时.SO2的脱除率随钠离子浓度的升高...     

Desulfurization matching with coal poly-generation system based on dual gas resources

The coal poly-generation system for the production of alcohol and ether fuels as well as power is one of advanced coal utilization techniques. The team leaded by Professor Xie Kechang is carrying out the research on the poly-generation system to produce the syngas from the combination of gasified and pyrolyzed coal gas (dual gas resources) for the alcohol ether synthesis. Gas desulfurization is one of the key technologies for this system. The desulfurization matching with dual gas resources based poly-generation system for the production of alcohol and ether fuels as well as power is presented according to gas components, sulfur content, sulfur species and desulfurization accuracy in this technology. This matching desulfurization is classified into hot gas desulfurization, normal gas desulfurization, warm gas desulfurization and organic sulfur catalytic conversion. The preparation of H₂S removal sorbents, organic sulfur hydrolysis catalyst and the evaluation of their activities involved in the system were investigated. The H₂S removal efficiencies of the crude and fine desulfurization sorbents prepared for hot gas desulfurization are 90% and 99% at 500 °C in simulating coal gas, and their sulfur capacities are 21.85 wt.% and 24.91 wt.%, respectively. The organic sulfur catalyst shows the high hydrolysis activity, and the hydrolysis conversion of COS is more than that of CS₂ on the same catalyst. The research will provide necessary information for the matching desulfurization technology in the demonstration project on dual gas resources coal poly-generation system.     

改良络合铁法脱硫的研究

本文介绍了一种新型的络合铁法脱硫新工艺,此吸收剂系碱性溶液中的络合Ｆｅ＾２／Ｆｅ＾３＋的变价体系。     

Sulfur removal in coal tar pitch by oxidation with hydrogen peroxide catalyzed by trichloroacetic acid and ultrasonic waves

A procedure for the desulfurization of coal tar pitch (CTP) by oxidation with hydrogen peroxide (H₂O₂) was developed, in which trichloroacetic acid (TCA) was used as a catalyst combined with ultrasonic waves. For comparison, the effects of H₂O₂ combined with different catalysts on sulfur removal were also investigated. The oxidative system composed of H₂O₂ and TCA is highly effective for sulfur removal from CTP. The reaction conditions such as type of solvent used, temperature, and CTP-to-TCA ratio considerably influence sulfur removal when the same oxidant is used. The desulfurization efficiency for CTP with 0.9 wt.% sulfur content reaches 91.1 wt.% at a xylene-to-CTP volume ratio of 2.5, a CTP-to-TCA mass ratio of 0.5, an ultrasonic treatment duration of 60 min, a reaction temperature of 70 °C, and with an extraction liquid containing methanol and sodium hydroxyl. The experiment confirms that the addition of surface active agent has no beneficial effect on sulfur removal.     

气流床烟气干法脱硫技术的初步试验研究

介绍了新型燃煤烟气干法脱硫并回收硫技术的工艺流程概念。其特点是利用可再生煤基脱硫剂细粉进行干法连续脱硫, 脱硫过程在下喷式气流床中完成; 采用间接换热式脱硫剂热再生, 生成含高浓度二氧化硫的再生气体; 加压、冷却再生尾气, 其中的二氧化硫液化并与其它气体组分相分离, 进而生产液体二氧化硫副产品; 并介绍了烟气脱硫、脱硫炭再生和再生尾气液化的单元试验研究结果。     

High temperature desulfurization over nano-scale high surface area ceria for application in SOFC

In the present work, suitable absorbent material for high temperature desulfurization was investigated in order to apply internally in solid oxide fuel cells (SOFC). It was found that nano-scale high surface area CeO₂ has useful desulfurization activity and enables efficient removal of H2S from feed gas between 500 to 850°C. In this range of temperature, compared to the conventional low surface area CeO₂, 80–85% of H2S was removed by nano-scale high surface area CeO₂, whereas only 30–32% of H2S was removed by conventional low surface area CeO₂. According to the XRD studies, the product formed after desulfurization over nano-scale high surface area CeO₂ was Ce₂O₂S. EDS mapping also suggested the uniform distribution of sulfur on the surface of CeO₂. Regeneration experiments were then conducted by temperature programmed oxidation (TPO) experiment. Ce₂O₂S can be recovered to CeO₂ after exposure in the oxidation condition at temperature above 600°C. It should be noted that SO₂ is the product from this regeneration process. According to the SEM/EDS and XRD measurements, all Ce₂O₂S forming is converted to CeO₂ after oxidative regeneration. As the final step, a deactivation model considering the concentration and temperature dependencies on the desulfurization activity of CeO₂ was applied and the experimental results were fitted in this model for later application in the SOFC model.     

常温氧化锌精脱硫在联醇生产中的应用

该文介绍了我国开发的852型COS水解催化剂串KT310常温ZnO脱硫剂精脱硫新工艺在联醇生产中的应用.     

Modeling of ammonia-based wet flue gas desulfurization in the spray scrubber

A mathematical model of ammonia-based wet flue gas desulfurization process was developed based on the double film theory. The calculated results of the desulfurization system for two 220 t·h⁻¹ boilers per unit by this model were compared to that of corresponding measured data. It was found that the calculated results agree well with the measured data for the operating conditions of pH, liquid/gas ratio and SO₂ concentration. This model can provide predictions of the absorption performance of an ammonia-based wet flue gas desulfurization process and appears to be helpful for designing scrubbers for SO₂ absorption with ammonia absorbent.     

Oil Palm Ash/Ca(OH)2/CaSO4 Absorbent for Flue Gas Desulfurization

The preparation, optimization and activity of active absorbent prepared from oil palm ash for the removal of SO₂ in flue gas from combustion systems were investigated. The absorbent was prepared from oil palm ash, calcium hydroxide and calcium sulfate using a water hydration process. A Central Composite Design (CCD) was used to study the influence of various absorbent preparation variables – hydration period, amount of oil palm ash, and amount of CaSO₄ – on the BET (Brunauer‐Emmett‐Teller) specific surface area of the resulting absorbent. The surface areas of the absorbents obtained were in the range of 18.7–147.2 m²/g. It was found that all three absorbent preparation variables studied have a significant positive influence on the BET surface area of the resulting absorbent. An empirical model was then developed to correlate the three absorbent preparation variables to the BET surface area of the resulting absorbent. The model showed significance at a confidence level of 95 % using Analysis of Variance (ANOVA). Based on the empirical model, a maximum specific surface area of 128.6 m²/g exists within the range of the experimental variables investigated. The hydration conditions that result in the maximum surface area are a hydration period of 10 h, amount of oil palm ash 15.0 g, and amount of CaSO₄ 2.7 g. Experimental validations of these predicted optimum hydration conditions gave surface areas in the range of 125.9–129.5 m²/g. These results are in excellent agreement with the predicted value. In addition, desulfurization activity tests showed that the absorbent derived from oil palm ash/Ca(OH)₂/CaSO₄ exhibited a higher desulfurization capacity compared to its starting materials.     

新型钡基高温燃烧固硫剂的研究与应用

引　言燃烧脱硫技术是在高温燃烧过程中将煤中的硫转化为硫酸盐或硫化物 ,因而其固硫率与硫酸盐或硫化物的热力学形成过程密切相关 .据文献报道 ,ＣａＳＯ3和ＣａＳＯ4 分别在 10 0 4℃[1] 和 1195～ 12 14℃[2 ] 就已开始分解 .纯ＣａＳＯ4 在 12 5 0℃高温下的分解率为 85 % .纯ＢａＳＯ4 的分解温度为 15 80℃[3] ,大大高于ＣａＳＯ4 ,显示较高的热稳定性 .根据元素周期表递变规律 ,位于第 6周期的Ｂａ较位Ｆｉｇ .1　Ｓｃｈｅｍａｔｉｃｏｆｉｎｔｅｌｌｉｇｅｎｔｓｕｌｆｕｒｄｅｔｅｒｍｉｎａｔｉｏｎ1—ｍａｉｎｆｒａｍｅｏｆｉｎ…     

氮氧化物在湿法烟气脱硫过程中的作用

采用了气液鼓泡床反应器,以NaOH溶液为吸收液,在模拟烟气条件下对氮氧化物在湿法烟气脱硫过程中的作用进行了实验研究.结果表明,在吸收液为碱性的环境下,NO2的存在对脱硫率略有促进,SO2的存在则可显著增加脱硝率;在吸收液变乏且已呈酸性的环境下,NO2和SO2互相抑制彼此的脱除率;无论酸碱环境,NO和SO2对彼此脱除率的影响都很微弱.NO和NO2的存在对脱硫产物影响显著,NO2的存在促进了脱硫产物中硫酸盐的生成,碱性环境下尤其显著,而NO的存在抑制了脱硫产物中硫酸盐的生成.     

铁基脱硫渣再生制备铁酸钠及其循环脱硫

用Fe2O3与Na2CO3制备铁酸钠用于脱除含硫铝酸钠溶液中的硫,采用氧化焙烧及水浸方式对铁基脱硫渣(NaFeS2?2H2O)进行再生,研究了其循环脱硫效果. 结果表明,铁基脱硫渣于950℃下在氧化性气氛中焙烧1 h,可除去脱硫渣中70%的硫;将焙烧渣水浸,硫含量降至0.2%以下,总硫去除率达99%. 将除硫后的浸出渣再制备铁酸钠用于循环脱硫,脱硫率可达67.65%,与初始脱硫剂的脱硫率(69.09%)相当,可实现铁基脱硫剂的再生循环. 焙烧时渣中硫主要以SO2气体排出,剩余可溶性Na2SO4则在水浸过程中进入溶液而被除去.     

Chemical desulfurization of petroleum fractions for ultra-low sulfur fuels

An improved desulfurization process for removing sulfur from hydro treated diesel oil based on the oxidation of thiophenic type sulfur-containing compounds with H₂O₂ and acetic acid (AcOH) using H₂SO₄ as catalyst has been studied. The experimental results show that the sulfone content in the oxidation product increased rapidly with an increase in acetic acid and sulfuric acid ratios from 1:0 to 2:1 mole ratios. The maximum DBT conversion (wt.%) was at 2:1 mole ratio of acetic acid/sulfuric acid. This oxidation process is found to be capable of removing up to 90% of the sulfur compounds in hydro treated real fuels and can provide an alternative way to meet the future sulfur environmental requirements.     

Microwave-assisted extractive catalytic-oxidative desulfurization of diesel fuel via a VO(acac)2/ionic liquid system with H2O2 and H2SO4 as oxidizing agents

The removal of sulfur compounds from transportation fuel is an important aspect for protecting environment and for fuel cell applications. On the other hand, an innovative way to remove the sulfur is necessary because clean low-sulfur diesel is more widely used in the world today. In this work, we studied the effect of microwave irradiation power and time on the extractive catalytic oxidative desulfurization (ECODS) process of diesel fuel model (40 mL with initial S-content of 450 ppm), using vanadyl acetylacetonate (VO(acac)₂) as a catalyst and N-carboxymethylpyridine hydrosulphate ionic liquid ([CH₂COOHPy][HSO₄] IL) as an extractant, and hydrogen peroxide (H₂O₂) as an oxidant agent. The optimal microwave-assisted extractive catalytic – oxidative desulfurization (MECODS) experimental conditions were as follows: microwave irradiation power?=?500?W, microwave irradiation time?=?90?s, IL/diesel volume ratio?=?1:10, VO(acaca)₂/diesel mass ratio?=?0.5?wt%, and H₂O₂ volume?=?1 mL. Under these conditions, the sulfur content in commercial diesel fuel was reduced from 450 to 60?ppm (sulfur removal efficiency of 86.67%), which was superior to that of the simple oxidation with no IL (22.6%) or oxidation with not including catalyst (11.3%), and without affecting the physicochemical properties of diesel fuel. The catalytic system VO(acac)₂/IL can be recycled 5 times with merely a negligible loss in activity. Based on these experimental results, a MECODS mechanism was proposed. Ultra-deep desulfurization with 99.1% of sulfur removal efficiency was reached, using MECODS reaction under optimum conditions by adding 3?mL of H₂SO₄ (0.1?N) to the main reaction. This highest sulfur removal efficiency can be attributed to the synergetic effect between microwave activation heating energy and the additional protonation, which multiplied the sulfones’ (BTO₂s and DBTO₂s) formation pathways and thus accelerated the desulfurization reactions.     

An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide–acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe²⁺/H₂O₂ 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 μg/g to 9.50 μg/g.     

中温条件下氧化铁对氧化钙脱硫的活化作用

运用热重分析仪对石灰与氧化铁混合物的固硫效果进行了分析.发现氧化铁在200～700 ℃和二氧化硫不发生反应.石灰的固硫效果随温度的提高而有所改善：500 ℃以下基本不能固硫,600 ℃、700 ℃有一定的硫化效果.加入氧化铁后,石灰固硫特性随温度变化的趋势没有改变,但石灰的钙利用率不仅大大提高,而且随氧化铁的混合配比单调递增.氧化铁对石灰中温烟气脱硫反应并没有传统意义上的催化作用.氧化铁所起的是改变石灰颗粒表层产物生成方式的活化作用,使反应生成物不会形成一个致密的外壳,而以氧化铁为活性中心进行硫化反应,形成了分散的硫酸钙产物堆积,改善了硫化过程中的表面孔隙结构,减少了石灰颗粒表面硫化产物层对反应气体向石灰颗粒内部扩散的阻力.