CO2捕集回收技术研究

主要介绍了常用的胺化合物吸收法、钙基吸收剂法、金属氧化物法等CO2捕集回收技术的最新研究进展及存在的问题,综合对比了各种方法的优缺点:胺化合物吸收法吸收速率快,但再生能耗较高,因此开发"高效低耗"的复合吸收剂成为研究的重点;钙基吸收剂法在高温环境下对CO2的吸收有较好的效果,但吸收剂的碳酸化转化率及热稳定性是有待解决的关键问题;金属氧化物法具有高的CO2吸收效率,但成本较高.在此基础上,探索了CO2捕集回收技术改进工艺,提出改善吸收剂性能、开发高效低耗的CO2选择性吸收剂将成为今后CO2捕集回收技术的研究方向.     

柴油机尾气Fe(Ⅱ)EDTA络合-铁屑还原脱硝中试研究

采用Fe(Ⅱ)EDTA络合-铁屑还原脱硝工艺,针对功率175 k W的柴油机,搭建了处理量为640 m~3·h~(-1)的脱硫脱硝中试装置,系统研究了脱硝装置连续脱除柴油机尾气中NO的过程。结果表明:铁屑还原效果较好,连续运行时,Fe(Ⅱ)EDTA溶液对NO有很好的吸收效果;喷淋量、填料层高度及再生温度均会影响络合剂吸收NO的脱除效率,但功率的改变对络合剂吸收NO的脱除效率影响较小。长时间连续运行实验表明,系统的脱硝性能稳定,稳定运行时的脱硝效率连续7 d均保持在75%左右;系统运行过程中,络合液的pH逐渐上升,最终稳定在7.45左右。     

O3氧化结合化学吸收同时脱硫脱硝的动力学及热力学研究

构建了O3氧化多种污染物的反应机制,并对O3氧化SOx、NOx过程进行动力学模拟,然后利用热力学原理计算出Ca(OH)2和CaCO3湿法烟气同时脱硫脱硝吸收反应达到平衡时SOx和NOx的分压力.结果表明,Ca(OH)2作吸收剂湿法烟气同时脱硫脱硝比CaCO3作吸收剂效果好,而且两者几乎100％地去除烟气中的SOx和NO...     

EDTA-（NH4）2FeSO4络合剂脱除烟气中的氮氧化物

络合脱硝法是近年来新型的脱除氮氧化物的方法之一,其中EDTA金属络合剂受到了广泛关注,而亚铁络合剂又具有很好的脱除氮氧化物的效果。考查了硫酸亚铁铵与EDTA形成的Fe（II）EDTA这种比较常见的EDTA金属络合剂对NO的吸收容量,并考查温度、络合剂浓度等对Fe（II）EDTA吸收NO的影响。研究结果表明：在相同的实验环境和实验条件下,对于影响Fe（II）EDTA吸收NO的因素最重要的是温度,其余依次为络合剂浓度、气体流速、氧含量、吸收液pH,最适宜吸收条件是反应温度50℃、络合剂浓度0．1mol／L、进气流速600mL／min、氧含量2％、吸收液pH=6。     

氨-Fe(Ⅱ)EDTA法同步脱硫脱硝中试研究

在中试吸收塔反应器中,以氨基湿法烟气脱硫为基础,结合Fe(Ⅱ)EDTA络合吸收NO技术,实现同步脱硫脱硝;采用单一变量法研究了塔型、填料几何特性、填料层高度、液气比和Fe(Ⅱ)EDTA浓度等因素对同步脱硫脱硝的影响。结果表明,在相同的条件下,填料塔比空喷塔和鼓泡塔有利于同步脱硫脱硝;空隙率高、填料因子小的填料能明显提高脱硫脱硝效率,填料层高度从0 mm增加到900 mm,脱硫脱硝效率分别增大了4.49%和19.55%;液气比和Fe(Ⅱ)EDTA浓度越大,脱硝效率越高,但对SO_2的吸收没有影响。最佳工艺条件为:ф25 mm鲍尔环作填料且填料层高度为900 mm的填料塔、液气比为12 L/m~3、Fe(Ⅱ)EDTA浓度为0.05 mol/L,在此条件下,脱硫脱硝效率分别达到100%和51.55%。     

一种新型吸收剂吸收油气效果与影响因素分析

油气回收在倡导节约资源、保护环境的当今社会有着重要的意义。吸收法作为常见的油气回收手段,影响其吸收效果的关键因素之一是吸收剂的选用。分析了传统油气吸收剂的优缺点,在AbsFOV-97油气吸收剂基础上改进开发得到一种新型吸收剂,搭建了小试平台比较新型与传统吸收剂的吸收效果,并针对新型吸收剂,研究了影响吸收效果的因素,包括进塔油气浓度、吸收剂温度、吸收液喷淋量、进塔油气流量等,根据单因素小试实验设计了正交实验。结果表明,新型吸收剂回收率比改进前提高3.06%,进塔油气浓度为影响吸收效果的最大因素。     

N-甲基二乙醇胺/哌嗪/羟乙基乙二胺三元复合溶液捕集烟气中CO2中试研究

化学吸收法是目前烟气回收CO2技术的研究热点,其中一类重要的吸收剂就是醇胺复合溶液.醇胺复合溶液具有对CO2吸收速率快、吸收容量大及再生简单的特点,成为烟气CO2吸收剂的首选.采用中试连续实验装置,以N-甲基二乙醇胺(MDEA)/哌嗪(PZ)/羟乙基乙二胺(AEEA)(摩尔比为0.70:0.15:0.15)三元复合溶液为吸收剂对烟气中CO2进行吸收处理.研究结果表明,吸收剂最佳摩尔浓度为3.0 mol/L,最佳吸收温度为40℃,最佳液气比为10 L/m3;再沸器的热负荷随着吸收温度、吸收剂浓度以及液气比的增加而增大,脱碳率随着入口烟气中CO2浓度的增加而降低.     

喷动床半干式烟气脱硫脱硝实验研究

烟气脱硫脱硝一体化技术适合现阶段我国国情,具有良好的应用前景。以尿素为吸收剂,在喷动床实验装置中进行半干式烟气脱硫脱硝研究,考察了该方法的可行性及尿素与污染物摩尔比、近绝热饱和温差、进口烟气温度、进口污染物浓度等主要操作条件对脱硫效率和脱硝效率的影响。结果表明：该方法在适当的操作条件下可获得85%以上的脱硫效率和70%...     

草酸铁光催化协同络合铁脱硝剂再生过程

基于Fe(C_2O_4)_3的光化学性质,研究了Fe(C_2O_4)_3光催化协同络合铁脱硝剂再生的实验过程。实验考察了在50℃和Fe(Ⅱ)EDTA浓度为0.01 mol·L~(-1)以及NO进口浓度为530 mg·m-3的模拟烟气脱硝系统中,光催化再生模式、初始p H、Fe(C_2O_4)_3浓度及组成、氧气浓度对再生过程的影响。结果表明:Fe(C_2O_4)_3分开加入和分步光照是适合于本体系的反应方式;草酸钠与硫酸亚铁的最佳浓度比为3,浓度分别为0.06和0.02 mol·L~(-1),吸收液初始p H为5.3,有氧参与条件下,实现了络合剂有效再生,再生吸收液脱硝率最高可恢复到60%左右;氧在再生过程中表现出正协同效应。通过牺牲光敏性的草酸铁配体再生脱硝络合剂,建立了一种温和的光助低温湿式氨法同步脱硫脱硝过程。     

多循环CCRs法在分离燃煤锅炉尾部烟气中CO2方面的应用

随着温室效应和全球变暖的加剧,煤燃烧所排出的CO2作为引起温室效应的主要气体而引起人们的密切关注.由于燃煤锅炉所排放的尾气中所含的CO2的体积份额低、排放量大,而且处于微负压状态,因此目前控制和分离吸收CO2的方法,包括各类吸收法、吸附法、膜分离法和O2/CO2燃烧技术等,能够经济可行地适用于电力工业燃煤锅炉尾部烟气中CO2分离的方法非常少.与上述各类方法相比,钙基吸收剂CCRs(calcination/carbonation reactions)法是一种新兴的经济可行的分离燃煤锅炉尾部烟气中CO2的方法.对采用该法时,吸收剂的选择、吸收剂在多次CCRs过程中结构特点的变化、提高吸收剂对CO2的吸收容量以及防止吸收剂反应性的衰减等方面进行了详细的阐述.     

Removing nitric oxide from flue gas using iron(II) citrate chelate absorption with microbial regeneration

The addition of metal chelates such as Fe(II)EDTA or Fe(II)Cit to wet flue gas desulfurization systems has been shown to increase the amount of NO(x) absorption from gas streams containing SO(2). This paper attempts to demonstrate the advantage of not only using Fe(II)Cit chelate to absorb nitrogen oxides from flue gas but also the advantage gained from adding microorganisms to the system. Two distinct classes of microorganisms are needed: denitrifying and iron-reducing bacteria. The presence of oxygen in flue gas will affect the absorption efficiency of NO by Fe(II)Cit chelate. The oxidation of Fe(II) can be slowed with the help of bacteria in two ways: bacteria can serve to directly reduce Fe(III) to Fe(II) or they can serve to keep levels of dissolved oxygen in the solution low. As a result, after NO absorption, Fe(II)(Cit)NO will be reduced by denitrifying bacteria to Fe(II)Cit while Fe(III) is reduced by anaerobic bacteria back to Fe(II). Our experiments have shown that the implementation of our protocol allowed for an NO reduction rate constant increase from standard levels of 0.0222-0.100 m Mh(-1) with inlet NO changed from 250 to 1000 ppm. We have also found that total Fe concentration tends to decrease after prolonged periods of operation due to the loss of some Fe to the formation of Fe(OH)(3) that settles together with the sludge at the bottom of bioreactor tank.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

A review of the catalysts used in the reduction of NO by CO for gas purification

The reduction of NO by the CO produced by incomplete combustion in the flue gas can remove CO and NO simultaneously and economically. However, there are some problems and challenges in the industrial application which limit the application of this process. In this work, noble metal catalysts and transition metal catalysts used in the reduction of NO by CO in recent years are systematically reviewed, emphasizing the research progress on Ir-based catalysts and Cu-based catalysts with prospective applications. The effects of catalyst support, additives, pretreatment methods, and physicochemical properties of catalysts on catalytic activity are summarized. In addition, the effects of atmosphere conditions on the catalytic activity are discussed. Several kinds of reaction mechanisms are proposed for noble metal catalysts and transition metal catalysts. Ir-based catalysts have an excellent activity for NO reduction by CO in the presence of O₂. Cu-based bimetallic catalysts show better catalytic performance in the absence of O₂, in that the adsorption and dissociation of NO can occur on both oxygen vacancies and metal sites. Finally, the potential problems existing in the application of the reduction of NO by CO in industrial flue gas are analyzed and some promising solutions are put forward through this review.

     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

Effect of complexation with humic substances on diffusion of metal ions in water

Most studies on diffusion of metal ions in various water-rock systems have dealt with free ions (hydrated ions). However, it is often the case that metal ions are dissolved as complexed species such as with humic substances (HS) in natural waters. Hence, we need to study the diffusion behavior of these complexes in order to understand fully the diffusion phenomenon in natural. In this study, the diffusion coefficients of free metal ions (M(z+)) and their complexes with HS (M-HS) were compared to understand the effect of complexation with HS on the diffusion of metal ions such as Co(2+), Cd(2+), and rare earth elements (REE(3+)). Although the diffusion coefficients of free metal ions depend on ionic potential, such dependence was not observed in the presence of HS. Comparing the diffusion coefficients of metal complexes with ethylenediaminetetraacetate (EDTA), fulvic acid, and humic acid showed that the molecular weight (MW), or the size of the ligand, is of primary importance for the diffusion of M-HS. As a consequence, the diffusion coefficients of all REE(3+) were similar in the presence of HS, while they were different in the absence of HS due to the different size of each REE(3+). The similarity among the diffusion coefficients of REE-HS was caused by the much larger size of HS compared with each ion. However, the distribution coefficients of M-HS were not similar among REE(3+), Cd(2+), and Co(2+). REE(3+) and Cd(2+) which have higher affinities for larger MW fraction in HS diffused slower than Co(2+) which favors smaller MW fraction. The results show that the affinity for different MW fractions among HS controls the diffusion of M-HS, which must be important to predict precisely the diffusion behavior of metal ions bound to HS in natural systems.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

水吸收法处理低浓度氮氧化物废气的中试研究

对水在中试规模下吸收低浓度的氮氧化物废气进行了研究。分别研究了喷淋密度、温度、压力、气速以及氮氧化物浓度对吸收效果的影响,结果表明,综合考虑各种因素,喷淋密度在20 m3/（m2·h）,水温在15℃以下,气速小于0.28 m/s,废气浓度在400 mg/m3左右时,氮氧化物的平均脱除率可以达到50%左右;同时,随着压力的增大,吸收效率也增加。     

Differences in ability of NO2 absorption in various broad-leaved tree species

Absorption of nitrogen dioxide (NO(2)) by various broad-leaved tree species was determined by the (15)N dilution method. The tree seedlings were continuously exposed to 0.3 ppm (microl litre(-1)) NO(2) or the mixture of 0.3 ppm NO(2) and 0.1 ppm O(3) for 30 days. The total amount of NO(2)-nitrogen absorbed by a seedling during the 30-day exposure period primarily depended on the size of the seedling. Among the tested tree species, three cultivars of Populus showed the highest rate of NO(2) absorption per unit leaf area, reaching as much as 0.3 mg N per dm(2) per day. The absorption rates for Populus cultivars were more than four times greater than those for Viburnum or Cinnamomum which had the lowest rate. A highly significant correlation was recognised between the rate of NO(2) absorption and the stomatal conductance among the species. Three cultivars of Populus which had the highest rates of NO(2) absorption were most susceptible to the mixture of NO(2) and O(3). On the contrary, Cinnamomum, Viburnum and Quercus, which showed the lowest rate of NO(2) absorption, were very tolerant to the mixed gas. These results indicate that the species difference in susceptibility to the mixture of NO(2) and O(3) was mainly determined by the difference in rate of absorption of these gases. Exposure to NO(2) alone had no detrimental effect on the tested tree species.     

CeO_x/AC催化剂NH_3选择性催化还原NO

以用不同浓度的HNO3预处理后的椰壳活性炭为载体,负载铈制备SCR催化剂。利用比表面积分析仪（BET）、X射线衍射（XRD）、扫描电镜（SEM）和催化剂活性实验,探讨了不同变量如金属离子的分布、焙烧温度和载体属性对催化活性的影响。结果表明,HNO3处理后,经500℃焙烧金属铈负载量为7%的催化剂表现出优良的催化性能。在90℃时,NO转化率在90%以上,随温度升高,达到接近100%的NO转化率。     

Investigation of trace metal binding properties of lignin by diffusive gradients in thin films

The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid + 40 μM lignin at an ionic strength of 0.01 M (NaNO₃) and pH = 7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb⁺² > Cu⁺² > Cd⁺² > Ni⁺² > Co⁺² > Mn⁺². Stability constants (Log K) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.