膜法氨水吸收脱除烟气中CO2的研究

以氨水为吸收剂,对聚丙烯中空纤维膜分离烟气中CO2进行了实验研究.结果表明:随着气体流量和入口CO2浓度的增加,CO2去除率下降而传质速率增加;随着氨水浓度和氨水流量的增加,CO2去除率和传质速率均显著增加,但当氨水浓度大于2.5 mol·L-1,吸收液流量大于80m L·min-1后,膜接触器对CO2去除率和传质速率基本保持不变;膜接触器连续运行15 d后其吸收性能显著下降,CO2去除率、传质速率、总传质系数均下降约40%~50%.接触角测量、SEM及XPS表征结果表明:随着操作的进行,聚丙烯膜在吸收液环境中接触角逐渐降低,疏水性减弱,造成膜孔润湿;同时碳酸盐在膜孔形成结晶,堵塞膜孔,使得传质阻力进一步增加,从而造成膜接触器吸收性能的下降.     

Response surface method for modeling the removal of carbon dioxide from a simulated gas using water absorption enhanced with a liquid-film-forming device

This paper presents the results from using a physical absorption process to absorb gaseous CO_2mixed with N_2using water by producing tiny bubbles via a liquid-film-forming device(LFFD)that improves the solubility of CO_2in water.The influence of various parameters—pressure,initial CO_2concentration,gas-to-liquid ratios,and temperature—on the CO_2removal efficiency and its absorption rate in water were investigated and estimated thoroughly by statistical polynomial models obtained by the utilization of the response surface method(RSM)with a central composite design(CCD).Based on the analysis,a high efficiency of CO_2capture can be reached in conditions such as low pressure,high CO_2concentration at the inlet,low gas/liquid ratio,and low temperature.For instance,the highest removal efficiency in the RSM–CCD experimental matrix of nearly 80%occurred for run number 20,which was conducted at 0.30 MPa,CO_2concentration of 35%,gas/liquid ratio of 0.71,and temperature of 15°C.Furthermore,the coefficients of determination,R~2,were 0.996 for the removal rate and 0.982 for the absorption rate,implying that the predicted values computed by the constructed models correlate strongly and fit well with the experimental values.The results obtained provide essential information for implementing this method properly and effectively and contribute a promising approach to the problem of CO_2capture in air pollution treatment.     

超低排放下燃煤电厂氨排放特征

燃煤电厂采用SCR(选择性催化还原)脱硝过程消耗大量的氨,同时存在氨逃逸和氨排放问题.为了掌握超低排放燃煤机组的氨排放程度、脱硝氨逃逸情况以及各环保设施对氨的协同脱除能力,为燃煤电厂氨减排政策制定和氨减排技术研发提供支持.在京津冀大气污染传输通道城市中选取11个城市中的14台机组,采用例如DL/T 260—2012《燃煤电厂烟含脱硝装置性能验收试验规范》的标准方法用稀硫酸吸收烟气中的氨再结合分光光度测试方法,对环保设施多个位置的烟气中氨进行浓度测试.结果表明:①氨排放浓度介于0.05~3.27 mg/m3之间,平均约0.95 mg/m3,通过烟气排入大气中氨的浓度不高;②测试的14台机组中有7台机组(约50%)脱硝氨逃逸值高于设计值(2.28 mg/m3),说明脱硝氨逃逸超过设计值呈普遍现象,个别电厂脱硝氨逃逸严重,氨逃逸亟待解决;③环保设施对逃逸氨具有较好的协同脱除能力,平均脱除率约为64.86%.建议对于SCR脱硝氨逃逸严重的机组,对SCR出口烟道截面氮氧化物(NO_x)实施网格式测试,在此基础上实施精细化精准喷氨、优化流场、提高SCR脱硝运行水平(或采用专业化运维),从源头上减少氨耗量,降低系统能耗和氨排放.      

Comparison of CO2 emission between COREX and blast furnace iron-making system

Steel works faced increasing demand to minimize the emission of GHGs. The CO₂ emissions of COREX and blast furnace iron-making system were compared. It is point out that COREX contribute little to CO₂ emission reduction. Comparing to conventional blast furnace iron-making system, direct CO₂ emissions of COREX is higher. Considering the credits of export gases for power generation, the total CO₂ emission of COREX have advantages only when the COREX is joined with high-efficiency generating units which efficiency is greater than 45% and CO₂ emission factor of the grid is higher than 0.9 kgCO₂/kWh.     

Absorption characteristics of new solvent based on a blend of AMP and 1,8-diamino-p-menthane for CO2 absorption

Aqueous 1,8-diamino-p-menthane (KIER-C3) and commercially available amine solutions were tested for CO₂ absorption. A 2-amino- 2-methyl-1-propanol (AMP) solution with an addition of KIER-C3 showed 9.3% and 31.6% higher absorption rate for CO₂ than the AMP solution with an addition of monoethanolamine (MEA) and ammonia (NH₃), respectively. The reaction rate constant for CO₂ absorption by the AMP/KIER-C3 solution was determined by the following equation: k_2,AMP/C3 = 7.702×10⁶ exp (-2248.03/T). A CO₂ loading ratio of the AMP/KIER-C3 solution was also 2 and 3.4-times higher than that of the AMP/NH3 solution and the AMP/MEA solution, respectively. Based on the experimental results, KIER-C3 may be used as an excellent additive to increase CO₂ absorption capability of AMP.     

Microalgae: a promising tool for carbon sequestration

Increasing trends in global warming already evident, the likelihood of further rise continuing, and their impacts give urgency to addressing carbon sequestration technologies more coherently and effectively. Carbon dioxide (CO₂) is responsible for over half the warming potential of all greenhouse gases (GHG), due to the dependence of world economies on fossil fuels. The processes involving CO₂ capture and storage (CCS) are gaining attention as an alternative for reducing CO₂ concentration in the ambient air. However, these technologies are considered as short-term solutions, as there are still concerns about the environmental sustainability of these processes. A promising technology could be the biological capture of CO₂ using microalgae due to its unmatched advantages over higher plants and ocean fertilization. Microalgae are phototrophic microorganisms with simple nutritional requirements, and comprising the major primary producers on this planet. Specific pathways include autotrophic production via both open pond or closed photobioreactor (PBR) systems. Photosynthetic efficiency of microalgae ranged from 10?C20 % in comparison with 1?C2 % of most terrestrial plants. Some algal species, during their exponential growth, can double their biomass in periods as short as 3.5 hours. Moreover, advantage of being tolerant of high concentration of CO₂ (flue gas), low light intensity requirements, environmentally sustainable, and co-producing added value products put these as the favoured organisms. Advantages of microalgae in comparison with other sequestration methodologies are discussed, which includes the cultivation systems, the key process parameters, wastewater treatment, harvesting and the novel bio-products produced by microalgal biomass.     

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction (SCR) denitration may increase the emission of NH₄⁺ and NH₃. The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization (WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system. The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH₄⁺ will generate new ammonium-containing particles and gaseous ammonia. The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation. Therefore, even if the concentration of NH₄⁺ in the desulfurization slurry is quite low, a high level of NH₄⁺ was still contained in the fine particles at the outlet of the scrubber. When the accumulated NH₄⁺ in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH₃ to NH₄⁺ and increased the additional emission of primary NH₄⁺ aerosols. With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH₄⁺ emitted from entrainment and evaporation of the desulfurization slurry decreased. In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH₄⁺ concentration and pH values of the slurry.     

基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究

富氧燃煤烟气压缩液化CO2的高压低温工况为NO氧化为易溶于水的NO2提供了十分有利的条件.基于小型高压吸收试验装置,采用配制的富氧燃煤模拟烟气,在高压常温下进行了NO、SO2、O2与H2O的吸收反应试验.根据反应前后的气液产物分析,测定了不同组分比例与不同压力下混合气体中NO与SO2的转化率.NO氧化与吸收试验表明,NO转化为HNO3的比率随压力升高而增加,在0.5 ～2 MPa之间增加很快,在2 ～3 MPa之间增速趋丁平缓,压力达3 MPa以上时,90％以上的NO均转化为稀硝酸,且初始NO浓度越高,NO的转化率越大.混合气体中同时存在5O2与NO的联合吸收试验发现,只有少量的NO转化成了NO3-,SO2向H2SO4的转化率随压力升高而增加,初始SO2浓度越大,转化率越高.分析表明,SO2与NO同时存在时SO2先行转化为SO3,NO充当了催化剂,但SO2转化为SO3的一次转化率小于35％,反应酸液产物的多次循环能使SO2的转化率达到90％以上.建议的工艺流程中需采用两座吸收反应塔顺序脱除SO2与NO并回收稀酸溶液,有望在富氧燃煤发电捕集CO2系统中降低脱硫脱硝成本,部分地弥补富氧燃烧机组发电成本的增加.     

氨水混合吸收剂脱除CO2实验研究

氨水作为一种很有应用前景的CO2化学吸收剂,存在吸收速率慢的问题.使用湿壁塔实验台,考察了不同种类的添加剂(MEA、PZ、1-MPZ、2-MPZ)对氨水吸收CO2速率的影响.结果表明,4种添加剂均能明显提高氨水吸收CO2的速率,其中PZ具有最好的促进效果.0、0.1、0.3和0.5 mol·mol-1负荷下,3 mol·L-1NH3+0.3 mol·L-1PZ溶液的总传质系数(KG)分别是3 mol·L-1NH3溶液在相应负荷下的3、3.2、3.2和2.9倍.改变反应温度、添加剂量、PZ浓度等条件对基于NH3/PZ混合吸收剂吸收CO2的反应过程进行实验,得到了其在不同条件下的KG,初步探讨CO2吸收的反应机制,并计算出准一级反应速率常数为42.7 m3·(mol·s)-1.     

燃煤电厂产生和排放的PM2.5中水溶性离子特征

为了认识我国燃煤电厂一次PM2.5排放特征,并定量评估大规模开展烟气脱硫与脱硝对其影响,本研究选取了国内一个煤粉炉电厂和一个循环流化床电厂,对其产生和排放的PM2.5进行现场测试,并进行水溶性离子组分的分析.结果表明,在所测的这两个电厂中,循环流化床电厂产生的PM2.5的质量浓度高于煤粉炉电厂产生的PM2.5的质量浓度,但是这两个电厂排放的PM2.5的质量浓度相当.产生此结果的主要原因是该循环流化床电厂配备的电袋复合除尘器比煤粉炉电厂的普通电除尘器对PM2.5去除效率更高.煤粉炉电厂产生PM2.5中水溶性离子浓度低于循环流化床电厂,但是煤粉炉电厂排放PM2.5中水溶性离子浓度却远远高于循环流化床电厂,表明煤粉炉电厂排放的PM2.5受脱硫和脱硝设施的影响较大.煤粉炉烟气脱硝过程中可能形成硫酸雾,烟气中的部分硫酸雾和过剩的NH3反应生成NH4HSO4进入颗粒相,同时降低了PM2.5的p H值;而脱硫过程中脱硫液的夹带也会导致NH+4和SO2-4进入PM2.5.所以,虽然两个电厂产生的PM2.5中水溶性离子均以Ca2+和SO2-4为主,但煤粉炉排放PM2.5中的水溶性离子则以NH+4和SO2-4为主.     

中国城镇污水处理厂温室气体排放时空分布特征

城镇污水处理厂由于运行过程中能够大量产生二氧化碳(CO_2)、甲烷(CH_4)和氧化亚氮(N_2O),而被视为重要的人为温室气体释放源.采用基于污染物削减量的排放因子法建立了2014年中国城镇污水处理厂温室气体(CO_2、CH_4和N_2O)排放清单,并分析温室气体排放的时空分布和影响因素.结果表明,2014年中国城镇污水处理厂温室气体排放总量(以CO_2-eq计)为7 348.60 Gg,CO_2、CH_4和N_2O排放量分别为6 054.57 Gg、27.47 Gg(769.08 Gg,以CO_2-eq计)和1.98 Gg(524.95 Gg,以CO_2-eq计);各省份间排放量差异明显,华东地区排放量较高,西北地区排放量较低,西藏几乎没有排放,2005~2014年这10年间中国通过城镇污水处理厂排放的温室气体总量增长了229.4%,CO_2、CH_4和N_2O的涨幅分别为217.9%、217.9%和520.3%;地区经济的发展水平和污水处理量与当地城镇污水厂温室气体释放量相关性最大,人均蛋白质供应量与城镇污水厂N_2O产生量密切相关.     

包气带水气二相流CO2运移规律

利用土柱实验装置模拟CO₂在土壤中的迁移转化规律,重点研究湿润峰处水、气二相间污染物转化实验土柱长1m,过饱和CO2溶液浓度为748mg/L.分析表明水相运移受对流、弥散、反应及水-气质量传输机制控制,气相运移受对流、扩散和水-气质量传输机制控制.对土柱中水气二相动态条件下的取样方法进行了探索,确定了CO₂在渗透湿润峰水-气二相间分配系数为0.00061,表明水相向气相有一定传输,但不显著.可进一步为低中水平放射性废物地质处置安全评价及固体废物填埋处置环境影响评价提供定量科学依据.     

Simultaneous transfer across an air-water interface of gases that interact through acid-base reactions

Theory is developed to describe how the transfer of gas across an air-water interface may be influenced by the simultaneous transfer of a different gas with which it interacts through acid-base reactions. The theory is applied to the problem of NH₃ loss from lowland rice-field flood water as influenced by the simultaneous loss fo CO₂. It uses a two-thin-layer model of the interface and describes the diffusion and reaction of gases and dissolved species, and of acids and bases that move in response to the pH changes that result from gas diffusion and reaction. Reaction kinetics are allowed for. In the rice-field system, NH₃ loss tends to make the solution more acidic, whereas CO₂ loss makes it more alkaline. Over the range of conditions found in rice fields, NH₃ loss may be limited by diffusion in both air and solution; CO₂ loss is always limited by diffusion in solution. When the equilibration between CO₂ species is uncatalysed, acidification resulting from NH₃ loss dominates alkalinization resulting from CO₂ loss, and the pH at the air-water boundary may be as much as one unit lower than that in the bulk solution. But in the presence of carbonic anhydrase, the situation is reversed and the boundary pH may be considerably greater than that in the bulk, especially at high CO₂ pressures.     

Effects of amine, amine salt and amide on the behaviour of carbon dioxide absorption into calcium hydroxide suspension to precipitate calcium carbonate

The amount of carbon dioxide （CO2） absorption and calcium ion （Ca^2＋） concentration besides the pH of aqueous solution were observed during the COz absorption to precipitate calcium carbonate （CaCO3） from calcium hydroxide （Ca（OH）2）. A reaction rate-limiting effect of an amount of CO2 absorption without any organic additives in the early stage of the precipitation was observed, which was attributed to an interruption effect of bicarbonate ion （HCO3） on the precipitation of CaCO3. The improvement for the reaction rate was achieved not only by amine additives but also by neutral additives such as ε-caprolactam or amine salt. When the hexamethylene diamine was dissolved in the solution, successive change of crystal forms of CaCO3 aragonite to calcite in aqueous suspensions, confirmed by Ca^2＋ concentration change and X-ray diffraction, was concluded that a local environment around the amine group in aqueous solution and an interaction of the diamine with precipitated CaCO3 particles were important factors for these reactions.     

A novel gas purification system for biologically produced gases

A novel gas purification system employing membrane contactors with dense membranes in the absorption as well as the desorption unit has been tested concerning the separation efficiency of CO₂. The separation efficiency of potassium carbonate (K₂CO₃) promoted by piperazine (PZ) as absorption medium has been tested in the absorption unit. Since the absorbent will be regenerated in the desorption unit, the influence of temperature, sweep flow rate and absorbent type (0.5 M K₂CO₃ and 0.5 M K₂CO₃/0.5 M PZ) on the separation efficiency of CO₂ in the desorption unit has been investigated. Desorption by vacuum has been considered as well.In addition experimental results of the coupling of a bioreactor producing hydrogen by anoxygenic photosynthesis (low and fluctuating product gas flow rates and fluctuating compositions) with a membrane contactor for gas purification are reported. This was done in order to show the applicability of this system to processes producing biogases.     

Comparison of absorption rates and absorption capacity of ammonia solvents with MEA and MDEA aqueous blends for CO2 capture

In this work we present the experimental results of absorption rates and absorption capacity for the CO₂ absorption by ammonia (NH₃) aqueous solutions. Experiments are carried out in a thermoregulated Lewis-type cell reactor and are achieved in temperature and concentration ranges of 278–303 K and 2–5wt.% NH₃ respectively. The obtained values for absorption kinetic rates and absorption capacity are compared with those available for alkanolamine solvents, commonly used to absorb CO₂. In order to achieve this comparison, data available in studies about alkanolamine solvents at 303–333 K and 5–50wt.% for alkanolamines solutions were considered. Results show that CO₂ absorption by NH₃ is faster than the one carried out by MDEA, except for 2wt.% NH₃ at 288 K. At 278 K and using aqueous solutions of 3wt.% NH₃, the absorption rate is almost identical to the one reached with MDEA solvent. The highest absorption capacity, also compared with alkanolamine solution, is reached with aqueous solutions of 5wt.% NH₃ at 278 K and 303 K.     

脉冲放电条件下用高炉煤气洗涤水脱硫的研究

采用自行设计的针-针式电极结构的等离子体反应器装置,在脉冲电晕放电作用下利用武汉钢铁(集团)公司2#焦炉的高炉煤气洗涤水进行了烟气脱硫模拟试验,考察了喷淋水种类、循环次数、液气比、电压峰值对SO2去除效果的影响,并对脱硫的产物进行了分析;考察了脉冲放电、SO2对氰化物去除效果的影响.研究结果表明:高炉煤气洗涤水具有较好...     

Ca(OH)2解吸并固定混合吸收液中CO2的实验研究

CO₂化学吸收法分离纯度高,技术成熟,但能耗过高及成本是困扰该技术发展的瓶颈.在常压条件下对利用Ca（OH）₂直接矿物碳酸化固定MDEA/PZ混合吸收富液中CO₂进行了一系列实验研究,考察了吸收液负荷、Ca（OH）₂投加量、pH、温度及搅拌速率等因素对解吸率的影响,并利用动态吸收-解吸循环实验研究了其CO₂吸收性能和循环使用稳定性,最后对碳酸化反应产物进行了XRD、TEM分析.结果表明,在常压条件下,Ca（OH）₂可以通过液相直接矿物碳酸化对CO₂进行直接固定,并实现吸收富液的再生;随着负荷的升高及Ca（OH）₂投加量、pH、搅拌速率的增大,解吸率随之增加;随着溶液温度升高,解吸率下降;经过5次动态吸收-解吸循环实验后CO₂吸收量可以达到并保持在0.57 mol·L^-1,显示出了良好的循环稳定性.     

Synthesis of highly effective absorbents with waste quenching blast furnace slag to remove Methyl Orange from aqueous solution

Water quenching blast furnace slag(WQBFS) is widely produced in the blast furnace iron making process. It is mainly composed of CaO, MgO, Al_2O_3, and SiO_2 with low contents of other metal elements such as Fe, Mn, Ti, K and Na. In this study, WQBFS was treated with grinding, hydrochloric acid acidification, filtration, filtrate extraction by alkali liquor and a hydration reaction. Then BFS micropowder(BFSMP), BFS acidified solid(BFSAS) and BFS acid-alkali precipitate(BFSAP) were obtained, which were characterized by X-ray diffraction, scanning electron microscopy, X-ray fluorescence and Brunauer-Emmet-Teller(BET)specific surface area. The decoloration efficiency for Methyl Orange(MO) was used to evaluate the adsorptive ability of the three absorbents. The effects of adsorptive reaction conditions(p H and temperature of solution, reaction time, sorbent dosage and initial concentration) on MO removal were also investigated in detail. The results indicated that BFSAP performed better in MO removal than the other two absorbents. When the p H value of MO solutions was in the range 3.0–13.0, the degradation efficiency of a solution with initial MO concentration of 25 mg/L reached 99.97% for a reaction time of 25 min at 25°C.The maximum adsorption capacity of BFSAP for MO was 167 mg/g. Based on optimized experiments, the results conformed with the Langmuir adsorption isotherm and pseudo-second-order kinetics. Among inorganic anions, SO_4~(2-)and PO_4~(3-)had significant inhibitory effects on MO removal in BFSAP treatment due to ion-exchange adsorption.     

Pilot study on bromate reduction in ozonation of water with low carbonate alkalinities by carbon dioxide

A pilot study was carried out to explore the application of carbon dioxide for pH depression in a bubble column and its ability to inhibit bromate formation for water with a low alkalinity. Results showed that in the absence of ammonia, CO2 was capable of reducing bromate 38.0%–65.4% with one-unit pH depression. CO2 caused a slightly lower bromate reduction (4.2%) than did H2SO4 when the pH was depressed to 7.4, and a more a pronounced lower reduction (8.8%) when the pH was depressed to 6.9. In the presence of 0.20 mg/L-N ammonia, bromate was largely inhibited with 73.9% reduction. When the pH was depressed to 7.4, CO2 and H2SO4 showed an 11.3% and 23.5% bromate reduction respectively, demonstrating that the joint use of CO2 and ammonia might be a plausible strategy of blocking all three bromate formation pathways. CO2 could be applied through the aeration diffuser together with ozone gas, resulting in a similar bromate reduction compared with the premixing method through Venturi mixer.