添加剂对乙二胺湿法烟气脱硫的影响

采用自主设计的鼓泡吸收装置,以乙二胺溶液为脱硫剂,研究了盐酸、硫酸、磷酸、柠檬酸和硼酸作为添加剂对湿法烟气脱硫的影响。实验结果表明,加入酸添加剂后,提高了吸收液的有效吸收容量。其中,乙二胺/硼酸和乙二胺/磷酸的有效吸收容量较高,分别为266 mg/L和269 mg/L,pH值缓冲效果最佳。同时发现,乙二胺溶液的脱硫率随时间的延长而迅速减小;加入添加剂后,吸收液能在较长时间内保持较高脱硫率。10次吸收-解吸循环实验结果显示,乙二胺/硼酸、乙二胺/磷酸和乙二胺/柠檬酸的平均脱硫率均达99%,SO2解吸顺序为乙二胺/硼酸乙二胺/磷酸乙二胺/柠檬酸。硼酸和磷酸可强化乙二胺湿法烟气脱硫过程,是具有开发前景的添加剂。     

臭氧氧化结合湿法喷淋对玻璃窑炉烟气同时脱硫脱硝实验研究

采用臭氧氧化结合湿法喷淋对模拟玻璃窑炉烟气开展了同时脱硫脱硝实验研究.采用不同溶液(NaOH、Na₂S)进行了喷淋实验.结果表明,保证溶液pH值在10以上,NaOH浓度对NO_x脱除效率无影响,SO₂的存在促进了NO_x吸收.当O₃/NO物质的量比为1.6、溶液NaOH浓度为0.5%时,NO_x脱除效率可达70%,SO₂脱除效率在99%以上.往喷淋液中添加Na₂S,NO_x脱除效率随Na₂S浓度增加而提高,SO₂的存在对NO_x脱除效率无影响.当O₃/NO物质的量比为1.2、溶液中NaOH浓度为0.5%、添加剂Na₂S浓度为0.6%时,NO_x脱除效率可达70%,SO₂脱除效率在95%以上.60 min长时间运行实验证明,模拟烟气中的NO_x经碱液和添加剂吸收后主要以NO^-₂的形式存在于喷淋液中,且NO_x脱除效率不随溶液pH值的变化而变化.     

N,N-二甲基正辛胺/十六烷混合体系液液相变吸收SO2

为了克服传统脱硫工艺胺法脱硫中挥发的吸收剂污染空气以及吸收剂回收过程能耗巨大的缺点,开发了一种新型液液相变有机胺混合脱硫体系.将碱性较大的吸收剂N,N-二甲基正辛胺（DMOA）与沸点较高的溶剂十六烷混合形成均相溶液.其在吸收二氧化硫（SO₂）后自动分为两相,十六烷在上相,SO₂与DMOA反应的产物位于下相.上相十六烷可以直接进行循环利用,将下相溶液中的SO₂脱除即可实现DMOA再生.经核磁共振氢谱（¹H NMR）和傅里叶红外光谱（FTIR）表征发现,SO₂和DMOA的反应产物为电子转移产物.在压力为常压、温度为20℃的条件下,混合体系最多的摩尔吸收量为2.1 mol/mol,是同等条件下混合体系CO₂摩尔吸收量的38倍.该混合体系具有良好的循环吸收性能,在常压、120℃的条件下进行解吸操作基本可以完全循环再生DMOA.这些结果表明该混合体系用于吸收SO₂具有良好的前景.     

液相共存成分对氨法脱碳吸收液解吸CO2的影响研究

考察了烟气中SO₂、NO_x和CO₂与氨水的反应机理,研究了模拟解吸液解吸过程中主要液相共存成分,如(NH₄)₂SO₃、(NH₄)₂SO₄、NH₄NO₃、NaCl、NH₄Cl和(NH₄)₂CO₃对CO₂解吸的影响.研究表明,不同液相共存成分、质量分数、pH值、表面张力等对CO₂解吸产生一定影响,大部分液相共存成分的存在,会降低脱碳溶液CO₂的解吸量.质量分数低于10％的液相共存组分对脱碳吸收液CO₂解吸过程的制约作用依次为(NH₄)₂SO₃>NH₄NO₃>(NH₄)₂SO₄>NaCl>(NH₄)₂CO₃.因此,在碳捕集前应对烟气中的杂质成分进行脱除,减少其对解吸液理化特性的影响.     

臭氧氧化-生物炭吸附体系协同脱硫脱硝除汞研究全文替换

以O₃为氧化剂,玉米生物炭和椰壳活性炭为吸附剂,开展同时脱硫脱硝除汞研究。研究考察了温度、O₃/NO和吸附时间对玉米/椰壳炭脱硫脱硝除汞效率的影响,并对玉米/椰壳炭进行表征分析。结果表明,NO和Hg0氧化率随O₃/NO升高而升高,SO₂氧化率则先升高后略微降低;温度升高抑制NO氧化但促进Hg⁰和SO₂氧化;在140℃下,当O₃/NO为1.4时,NO、Hg⁰和SO₂氧化率分别达99%、78.6%和3.5%,随O₃/NO从0.4升至1.4,玉米炭对NO_x脱除效率从4.6%提升至93%,椰壳炭从4.5%提升至79%。玉米/椰壳炭会还原部分NO₂造成出口NO浓度上升,但玉米炭的NO_x吸附性能较椰壳炭强,而椰壳炭对Hg0和SO₂的吸附性能较强。椰壳炭较玉米炭具有更强的物理吸附能力;玉米炭表面含...     

利用硫酸氧钒制备钒炭催化剂用于烟气脱硫

利用硫酸氧钒制备钒炭催化剂用于烟气脱硫。研究发现,负载在活性炭上的硫酸氧钒极易被氧化为五价钒硫酸盐,这些五价钒硫酸盐具有很高的氧化SO₂的活性,极大地促进了SO₂在活性炭上的脱除。而且,通过煅烧可以将五价钒硫酸盐分解为五价钒氧化物,最佳煅烧温度为500℃,由于煅烧后用于储存硫酸的微孔孔容增加,SO₂的吸附容量得到了进一步提高,由此表明,利用硫酸氧钒可以制备传统的V₂O₅/AC催化剂。为了获得完全氧化的钒物种,对煅烧后的催化剂进行了空气中预氧化,但由于含氧官能团的形成、炭载体的烧蚀以及钒的还原,预氧化不利于脱硫。此外,研究中得到初步证据证明脱硫过程中V₂O₅/AC催化剂中五价钒氧化物转变成了五价钒硫酸盐,结合五价钒硫酸盐所表现出的氧化SO₂的能力,推测SO₂在V₂O₅/AC上的脱除遵循以下机理:五价钒氧化物先转变为五价钒硫酸盐,后者催化氧化SO₂为硫酸。     

烟气共存成分对微波辐照活性炭同时脱硫脱硝的影响研究

研究了O₂、CO₂以及水蒸气等各种烟气共存成分对微波辐照活性炭脱硫脱硝的影响。实验结果表明,SO₂对烟气脱硝有一定的抑制作用;烟气中水蒸气会抑制脱硫,低浓度水蒸气含量使脱硝效率上升,但高浓度水蒸气使脱硝效率下降;O₂和CO₂的存在可在一定程度上促进脱硫脱硝,但高浓度的O₂和CO₂会造成活性炭的损耗,从而抑制与脱硫和脱硝有关的还原反应。采用此方法可有效脱除烟气中SO₂和NO_{x,其脱除效率均在90%以上。}     

烟气脱硫活性炭微波再生特性的实验研究

研究了烟气脱硫活性炭的微波再生特性。通过扫描电镜、N₂吸附、元素分析、Boehm滴定表征微波再生对活性炭孔隙结构和表面化学性质的影响,分析微波再生对活性炭吸附烟气中SO₂的影响规律。结果表明,微波再生功率越高,SO₂再生曲线越窄,峰值浓度越高,有利于载硫活性炭的解吸和高浓度再生气的获取。微波再生对活性炭起到了活化作用,使活性炭的孔结构变狭长。随着微波再生功率的提高,活性炭的微孔比表面积、微孔孔容增加,酸性官能团含量上升,碱性官能团含量下降。100 W再生后,活性炭再生不完全,残留的H₂SO₄影响了活性炭的吸附,活性炭的SO₂吸附性能下降。200、300、400 W工况下,活性炭的SO₂吸附容量均得到提高,且随着再生功率的提高,活性炭的碱性官能团含量上升,微孔比表面积、微孔孔容增加,SO₂吸附性能逐渐增强。     

尿素/H2O2溶液同时脱硫脱硝机理研究

在填料塔上对尿素/H₂O₂溶液同时脱硫脱硝进行了实验研究。结果表明,尿素溶液对SO₂具有很高的去除效率,但对NO_x的去除受到多种因素的影响。实验主要研究了H₂O₂浓度、吸收反应温度、溶液pH值等因素对脱硝效率的影响,并确定了最佳实验条件,在此条件下脱硫脱硝效率分别达到100%和52.6%。同时,采用化学分析法和气相色谱法对尿素溶液同时脱硫脱硝的反应产物进行分析,推导出尿素/H₂O₂溶液同时脱硫脱硝的反应机理和总化学反应方程式。该技术可用于对现有湿法脱硫技术的改造,使其同时具有脱硫脱硝功能。     

脱硫废水蒸发增强电除尘脱除PM2.5和SO3实验研究

搭建燃煤热态实验系统,研究脱硫废水蒸发对电除尘和脱硫系统的影响;考察脱硫废水蒸发前后细颗粒粒径的变化、电除尘出口PM_2.5和SO₃浓度变化;分析增强电除尘脱除PM_2.5和SO₃机理。结果表明,脱硫废水蒸发后,蒸发室出口细颗粒粒径峰值由0.1 μm增大到1.1 μm,观察脱硫废水蒸发前后扫描电镜,明显观察到废水蒸发后颗粒团聚长大,颗粒间存在絮状物;采用脱硫废水烟道蒸发后,电除尘细颗粒脱除效率提高5%左右,PM_2.5数量浓度脱除效率提高25%左右;SO₃脱除效率为60%-80%,烟气中SO₃浓度对增强电除尘脱除PM_2.5和SO₃均有影响;脱硫废水蒸发对脱硫系统的效率和脱硫浆液的pH值没有影响。     

Flue Gas Desulfurization by Dielectric Barrier Discharge

There are many problems with flue gas desulfurization by traditional gas ionization discharge, including the large size of the plasma source, high energy consumption, and the need for a traditional desulfurization method. This paper introduces oxidization of SO₂ to sulfuric acid (H₂SO₄) in a duct by reactive oxygen species (O₂ ⁺, O₃) produced by strong ionization dielectric barrier discharge. The entire plasma reaction process is completed within the duct without the use of absorbents, catalysts, or large plasma source. The reactive oxygen species O₂ ⁺ reacts with gaseous H₂O in the flue gas to generate ·OH radicals, which can oxidize trace amounts of SO₂ in large volumes of the flue gas to produce H₂SO₄. Sulfuric acid is also produced by O₃ oxidation of SO₂ to SO₃, and SO₃ reacting with gaseous H₂O in the flue gas. Experimental results showed that with a gas temperature of 22 °C and reactive oxygen species injection rate of 0.84 mg/L, the SO₂ removal rate was 81.4 %, and the SO₄ ^2? concentration in the recovered liquid H₂SO₄ reached 53.8 g/L.     

Two-Step Electrodialysis Treatment of Monoethanolamine to Remove Heat Stable Salts

Electrodialysis technology was adapted to removal of heat stable salts from aqueous solutions of alkanolamine absorbents, with monoethanolamine as example. Removal of anions of heat stable salts by electrodialysis from a 30 wt % aqueous solution of monoethanolamine with the degree of carbonation of 0.2 mol of CO₂ per mole of monoethanolamine was studied. The two-step removal of heat stable salts by electrodialysis allows the monoethanolamine loss to be reduced and the concentration of residual CO₂ in the absorbent solution to be decreased. The suggested two-step electrodialysis treatment scheme allows the concentration of heat stable salts to be maintained on the required level from the viewpoint of their corrosion activity, the total volume of the concentrate to be decreased by 50%, and the monoethanolamine loss to be decreased by 30%. The treatment unit with the circulation volume of the monoethanol absorbent of 100 m³ h^–1 was calculated for confirming the efficiency of the two-step electrodialysis treatment scheme. As compared to the one-step electrodialysis treatment scheme, the two-step scheme ensures recovery of 50% of monoethanolamine at the same efficiency of the removal of heat stable salts.     

Stability of Sulfur(IV) Solutions in the Presence of Amines and the Tendency of Sulfite Ions to Disproportionate in Stock Solutions

Abstract

Several sulfite solutions at the level of 0.050 mol.L^?1 were kept at 25°C, in polyethylene flasks, in the presence and absence of air. The concentration of sulfite was periodically checked by the iodometric method. The presence of ethanolamine, ethylenediamine or tris(hydroximethyl)aminomethane, at 0.05 - 0.20 mol.L^?1 concentration levels, showed a remarkable stabilizing effect at pH values higher than 10.5. The amine ionization was supressed by the common ion effect by using OH^?, added as NaOH. The changes in the concentration of S(IV) solutions in the presence of amine were about 1 to 3 %, during the period of 85 days. The stabilizing effect depends only on the amine group and not on the mixed function alcohol/amine. It was shown that an adduct of R-NH₂.SO₂ type is not formed in aqueous medium. In the stock S(IV) solutions kept in highly alkaline medium a slow increase in pH was observed and disproportionation of sulfite ion was evidenced by formation of thiosulfate as revealed from ion chromatographic measurements. In the presence of oxygen dithionate ion is also formed.     

Oxidization of SO2 by Reactive Oxygen Species for Flue Gas Desulfurization and H2SO4 Production

A strong ionization dielectric barrier discharge was used to produce a high concentration of reactive oxygen species that were then injected into a simulated flue gas in a duct to remove SO₂ by oxidation. Sulfuric acid (H₂SO₄) was produced through the following two reactions: (1) O₃ oxidation of SO₂–SO₃, which then reacted with H₂O to produce H₂SO₄; and (2) reaction of O₂ ⁺ with H₂O to produce ·OH radicals, which then rapidly and non-selectively oxidized SO₂–H₂SO₄. When the molar ratio of reactive oxygen species to SO₂ was 4:1, the SO₂ removal efficiency was 94.6%, the energy consumption per cubic meter of flue gas was 13.3 Wh/m³, the concentration of recovered H₂SO₄ was 4.53 g/l, and the H₂SO₄ recovery efficiency was 28.8%. The H₂O volume fraction in the simulated flue gas affected the SO₂ removal efficiency, whereas the O₂ and CO₂ volume fractions did not. These results prove that oxidation by reactive oxygen species is a feasible method for flue gas desulfurization.     

Effect of medium acidity on the efficiency of oxidation of 2,4,6-trinitrotoluene to 2,4,6-trinitrobenzoic acid

An effect of boric acid additives on oxidation of 2,4,6-trinitrotoluene (TNT) to 2,4,6-trinitrobenzoic acid (TNBA) with chromic anhydride in concentrated (96—100%) H₂SO₄ has been studied. In the presence of tetrahydrosulfatoboric acid HB(HSO₄)₄ formed in situ (up to 5 mol.%) or added as a preliminary prepared solution (up to 1 mol. %), TNT is selectively oxidized to TNBA in the yields up to 95—99%. The mechanism including formation of TNT dication as a key step of its oxidation at the methyl group has been suggested.     

Preparation of γ-Al2O3 sorbents loaded with metal components and removal of thiophene from coking benzene

Series sorbents of Cu, Zn, Ni, Ce and Ag metal components supported on γ-Al₂O₃ carrier for removing thiophene from benzene were prepared by conventional and ultrasound-assisted incipient-wetness impregnation method. The static adsorption experiments were carried out in the thiophene-benzene solution with thiophene concentration of 500?mg/L. The results show that the desulfurization activity of all γ-Al₂O₃ sorbents modified by different metal components obviously increase, among which the sorbent modified by silver nitrate has the best performance. The active components of sorbents from Cu, Zn, Ni, Ce nitrates loaded on γ-Al₂O₃ carrier are their oxides. Besides Ag₂O, the products of silver nitrate thermal decomposition in sorbent prepared still have Ag⁰ and Ag–O–Al species. The assistant ultrasound in the process of sorbent preparation can not only shorten the impregnation time, but also enrich the pore structure of sorbent and improve the size and distribution of the Ag species, which is favorable to the removal of thiophene from benzene. The desulfurization capacity of sorbent changes with the Ag content loaded. The sorbent with 15?% quality content of Ag prepared by ultrasound-assisted impregnation method has the highest desulfurization efficiency. It could reduce the thiophene concentration to 1.7?mg/L from 500?mg/L at room temperature and ambient pressure, with the desulfurization efficiency of more than 99?%, when the ratio of sorbent to solution was 1:4?(g/mL).     

向日葵盘果胶对碳钢的缓蚀性能研究

以向日葵盘为原料,利用纤维素酶制备果胶(SFP)。采用静态失重、极化曲线和交流阻抗技术研究SFP在1mol/L HCl及0.5mol/L H_2SO_4溶液中对碳钢的缓蚀性能,并探讨其在碳钢表面的吸附机理。结果表明,缓蚀效率随SFP浓度增大而增大,随温度升高而降低。在HCl和H_2SO_4溶液中,SFP的吸附方式分别服从Langmuir和Temkin等温式,属于物理吸附;极化曲线测试显示SFP是一种混合型缓蚀剂。本文的研究表明,向日葵盘果胶是碳钢的绿色高效缓蚀剂,且在HCl溶液中的缓蚀性能优于在H_2SO_4溶液中。     

Preparation and SO2 Absorption/Desorption Properties of Crosslinked Poly(1,1,3,3‐Tetramethylguanidine Acrylate) Porous Particles

Summary: Novel crosslinked porous particles based on the ionic copolymer of 1,1,3,3‐tetramethylguanidine acrylate (TMGA) and N,N‐methylenebisacrylamide (MBA) were prepared via an inverse suspension polymerization using cyclohexane as continuous phase and Span 60 as the dispersant. The SO₂ absorption–desorption properties of the P(TMGA‐co‐MBA) particles were studied for the first time. The particles showed excellent SO₂ absorption properties: high capacity and rate. These absorption properties, as well as the particle volume, shape, and morphology, remained unchanged during the SO₂ absorption–desorption cycles. The material appeared to be a good candidate as SO₂ absorbent for fuel gas desulfurization (FGD) and purification of other SO₂‐containing gases.

Optical microscope image of the P(TMGA‐co‐MBA) porous particles.