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.     

Vaporization reduction characteristics of aqueous ammonia solutions by the addition of ethylene glycol, glycerol and glycine to the CO2 absorption process

Aqueous ammonia (NH₃) solution can be used as an alternative absorption for the control of CO₂ emitted from flue gases due to its high absorption capacity, fast absorption rate and low corrosion problem. The emission of CO₂ from iron and steel plants requires much attention, as they are higher than those emitted from power plants at a single point source. In the present work, low concentration ammonia liquor, 9 wt.%, was used with various additives to obtain the kinetic properties using the blast furnace gas model. Although a solution with a high ammonia concentration enables high CO₂ absorption efficiency, ammonium ions are lost as ammonia vapor, resulting in reduced CO₂ absorption due to the lower concentration of the ammonia absorbent. To decrease the vaporization of ammonia, ethylene glycol, glycerol and glycine, which contain more than one hydroxyl radical, were chosen. The experiments were conducted at 313 K similar to the CO₂ absorption conditions for the blast furnace gas model.     

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.     

Sorbents with high efficiency for CO2 capture based on amines-supported carbon for biogas upgrading

Sorbents for CO_2 capture have been prepared by wet impregnation of a commercial active carbon(Ketjen-black, Akzo Nobel) with two CO_2-philic compounds, polyethylenimine(PEI)and tetraethylenepentamine(TEPA), respectively. The effects of amine amount(from 10 to70 wt.%), CO_2 concentration in the feed, sorption temperature and gas hourly space velocity on the CO_2 capture performance have been investigated. The sorption capacity has been evaluated using the breakthrough method, with a fixed bed reactor equipped with on line gas chromatograph. The samples have been characterized by N_2 adsorption–desorption,scanning electron microscopy and energy dispersive X-ray(SEM/EDX). A promising CO_2 sorption capacity of 6.90 mmol/gsorbenthas been obtained with 70 wt.% of supported TEPA at 70℃ under a stream containing 80 vol% of CO_2. Sorption tests, carried out with simulated biogas compositions(CH_4/CO_2mixtures), have revealed an appreciable CO_2 separation selectivity; stable performance was maintained for 20 adsorption–desorption cycles.     

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.     

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.     

Gas separation using porous cement membrane

Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.     

固定化碳酸酐酶在立式反应器催化吸收模拟烟气中CO2的实验研究

利用海藻酸钠包埋和戊二醛交联法固定碳酸酐酶,并在立式反应器进行了固定化酶吸收CO2的特性实验.实验结果表明:固定化酶的酶活力回收率是56.3%;固定化酶显著加快模拟烟气中CO2的吸收;载酶量小时,气体流量是影响吸收CO2效果的主要因素,气体流量增大,载酶量成为主要因素;气体流量增大,载酶量对反应终止p H的影响减小;载酶量增大,气体流量对反应终止p H的影响减小;气体流量增大,CO2吸收效率下降,载酶量提高,CO2吸收效率上升;气体流量为650 m L·min-1和载酶量为1 mg时,固定化酶催化吸收CO2效果显著;固定化酶具有较高的操作稳定性;SEM显示反应后的固定化酶表面出现大量形状不规则的小孔,空隙结构变得发达.     

Simultaneous removal of CO2, NOx and SOx using single stage absorption column

Capturing flue gases often require multiple stages of scrubbing, increasing the capital and operating costs. So far, no attempt has been made to study the absorption characteristics of all the three gases (NO, SO₂ and CO₂) in a single stage absorption unit at alkaline pH conditions. We have attempted to capture all the three gases with a single wet scrubbing column. The absorption of all three gases with sodium carbonate solution promoted with oxidizers was investigated in a tall absorption column. The absorbance was found to be 100% for CO₂, 30% for NO and 95% for SO₂ respectively. The capture efficiency of sodium carbonate solution was increased by 40% for CO₂ loading, with the addition of oxidizer. Absorption kinetics and reaction pathways of all the three gases were discussed individually in detail.     

Capture of carbon dioxide from flue gas on TEPA-grafted metal-organic framework Mg2(dobdc)

Carbon dioxide （CO2） adsorption on a standard metal-organic framework Mg2（dobdc） （Mg/DOBDC or Mg-MOF-74） and a tetraethylenepentamine （TEPA） modified Mgz（dobdc） （TEPA-Mg/DOBDC） were investigated and compared. The structural information, surface chemistry and thermal behavior of the adsorbent samples were characterized by X-ray powder diffraction （XRD）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. CO2 adsorption capacity was measured by dynamic adsorption experiments with N2-CO2 mixed gases at 60℃. Results showed that the CO2 adsorption capacity of Mg/DOBDC was significantly improved after amine modification, with an increase from 2.67 to 6.06 mmol CO2/g adsorbent. Moreover, CO2 adsorption on the TEPA-Mg/DOBDC adsorbent was promoted by water vapor, and the adsorption capacity was enhanced to 8.31 mmol CO2/g absorbent. The adsorption capacity of the TEPA-Mg/DOBDC adsorbent dropped only 3% after 5 consecutive adsorption]desorption cycles. Therefore, this kind of adsorbent can be considered as a promising material for the capture of CO2 from flue gas.     

钙法解吸并固定乙醇胺富液中CO2

针对醇胺类吸收剂富液中CO_2的解吸及后续处置所存在的不足,提出一种新型解吸方案——钙法.通过CO_2负荷试验和Ca(OH)_2投加量试验确定了该法理想处理负荷为0.84 mol·L-1,理想投加比例为C∶Ca=1∶1(摩尔比),此条件下反应15 min和30 min的解吸率达到52.17%和55.02%,这表明钙法矿化解吸乙醇胺富液中CO_2是可行的.在此基础上,进一步研究了pH、温度和搅拌强度对CO_2解吸固定效果的影响.试验结果表明,CO_2解吸率随着pH和搅拌强度的增加而增大,但当pH和搅拌强度增大到一定程度后,解吸率增长放缓甚至出现下降.较高的解吸温度尽管解吸率更大,但高温条件下无法达到矿化固定CO_2的目的.CO_2二次吸收负荷试验表明经钙法解吸后的MEA再生液具有良好的可重复使用性.     

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study

CO₂ is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO₂. Membrane gas separation is a fast growing CO₂ capture technique, particularly gas separation by composite membranes. The separation of CO₂ by a membrane is not just a process to physically sieve out of CO₂ through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO₂. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO₂ in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO₂ through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO₂) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO₂ membrane adsorbed more quantity of CO₂ gas as compared to pure CA membrane. The high CO₂ adsorption capacity may enhance the diffusion and solubility of CO₂ in the CA-TiO₂ composite membrane, which results in a better CO₂ separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R², the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion.     

KrBr*准分子灯直接光解一甲胺气体

研究了正弦电源驱动的207 nm KrBr*准分子灯光解气相中的一甲胺(MA).考察了降解的影响因素(气体流速、初始浓度、输入功率),测定了灯的输入功率和辐射光谱.为了评价光解过程,对去除效率、能率、碳平衡和CO2的选择性这4个参数进行了研究.结果表明,去除率随着灯的输入功率升高、气体流速的降低以及气体初始浓度的升高而升高.能率与一甲胺初始浓度呈正相关性,输入功率为65.1 W时能率最高.输入功率升高,气体流速下降,碳平衡和CO2选择性都略有升高.当灯的输入功率为79.8 W,气体流速9.0 m3·h-1,初始浓度为2 897 mg·m-3,一甲胺去除率为56.8%,能率为185.6g·(kW·h)-1,相应的碳平衡和CO2选择性为16.8%和10.3%.最后,利用气质联用仪测定了一甲胺降解的产物,结合一甲胺的吸收光谱,推测了一甲胺的光解机制.     

陶瓷膜接触器在润湿模式下吸收SO2的传质强化

将平均孔径为100 nm的Al_2O_3陶瓷膜组装成膜接触器,以单乙醇胺(MEA)为吸收剂,在考察吸收剂浓度对膜吸收过程影响的基础上,深入比较了陶瓷膜在润湿和非润湿模式下脱除SO_2的传质性能.实验结果表明,当MEA浓度大于0.26 mol·L~(-1)时,润湿模式下SO_2的脱除率和传质系数均高于非润湿模式.根据膜理论和阻力串联模型建立了陶瓷膜吸收SO_2的传质方程,理论计算表明,润湿模式下膜相传质阻力因瞬间化学反应的存在大幅降低,润湿模式更适用于脱除烟气中低浓度的SO_2.本研究结果可为陶瓷膜接触器在膜吸收领域的工业化应用和进一步传质优化提供参考.     

N,N’-二(2-羟丙基)哌嗪-H2SO4水溶液吸收SO2动力学

在鼓泡式反应器中,以N,N’-二(2-羟丙基)哌嗪(HPP)-硫酸水溶液为吸收剂,利用初始速率法探讨了SO2吸收反应动力学.结果表明:HPP-H2SO4水溶液吸收SO2为快速反应;吸收速率NA随着SO2进口体积浓度yA和吸收剂浓度CN的增大而增大,随着吸收温度T的升高而降低;吸收速率对CN是0.5级反应,对yA为0.85级反应.同时,建立了HPP-H2 SO4水溶液吸收SO2的吸收速率NA与CN、yA及T之间的经验关系式,发现该经验关系式的预测值与实验值符合较好,可用于工程设计计算.     

Avoiding CO2 capture effort and cost for negative CO2 emissions using industrial waste in chemical-looping combustion/gasification of biomass

Chemical-looping combustion (CLC) is a combustion process with inherent separation of carbon dioxide (CO₂), which is achieved by oxidizing the fuel with a solid oxygen carrier rather than with air. As fuel and combustion air are never mixed, no gas separation is necessary and, consequently, there is no direct cost or energy penalty for the separation of gases. The most common form of design of chemical-looping combustion systems uses circulating fluidized beds, which is an established and widely spread technology. Experiments were conducted in two different laboratory-scale CLC reactors with continuous fuel feeding and nominal fuel inputs of 300 W_th and 10 kW_th, respectively. As an oxygen carrier material, ground steel converter slag from the Linz–Donawitz process was used. This material is the second largest flow in an integrated steel mill and it is available in huge quantities, for which there is currently limited demand. Steel converter slag consists mainly of oxides of calcium (Ca), magnesium (Mg), iron (Fe), silicon (Si), and manganese (Mn). In the 300 W unit, chemical-looping combustion experiments were conducted with model fuels syngas (50 vol% hydrogen (H₂) in carbon monoxide (CO)) and methane (CH₄) at varied reactor temperature, fuel input, and oxygen-carrier circulation. Further, the ability of the oxygen-carrier material to release oxygen to the gas phase was investigated. In the 10 kW unit, the fuels used for combustion tests were steam-exploded pellets and wood char. The purpose of these experiments was to study more realistic biomass fuels and to assess the lifetime of the slag when employed as oxygen carrier. In addition, chemical-looping gasification was investigated in the 10 kW unit using both steam-exploded pellets and regular wood pellets as fuels. In the 300 W unit, up to 99.9% of syngas conversion was achieved at 280 kg/MW_th and 900 °C, while the highest conversion achieved with methane was 60% at 280 kg/MW_th and 950 °C. The material’s ability to release oxygen to the gas phase, i.e., CLOU property, was developed during the initial hours with fuel operation and the activated material released 1–2 vol% of O₂ into a flow of argon between 850 and 950 °C. The material’s initial low density decreased somewhat during CLC operation. In the 10 kW, CO₂ yields of 75–82% were achieved with all three fuels tested in CLC conditions, while carbon leakage was very low in most cases, i.e., below 1%. With wood char as fuel, at a fuel input of 1.8 kW_th, a CO₂ yield of 92% could be achieved. The carbon fraction of C₂-species was usually below 2.5% and no C₃-species were detected. During chemical-looping gasification investigation a raw gas was produced that contained mostly H₂. The oxygen carrier lifetime was estimated to be about 110–170 h. However, due to its high availability and potentially low cost, this type of slag could be suitable for large-scale operation. The study also includes a discussion on the potential advantages of this technology over other technologies available for Bio-Energy Carbon Capture and Storage, BECCS. Furthermore, the paper calls for the use of adequate policy instruments to foster the development of this kind of technologies, with great potential for cost reduction but presently without commercial application because of lack of incentives.

     

Removal of phosphorus and sulfur from yellow phosphorus off-gas by metal-modified activated carbon

In order to provide comprehensive utilization of high concentration CO for mono-carbon (C1) chemical industry, the purification of yellow phosphorus off-gas is of great concern. In this research, activated carbon (AC) modified by different impregnants were used for removal of PH₃, H₂S, SO₂, COS, and CS₂ in yellow phosphorus off-gas. For the removal of PH₃, AC impregnated with 0.10 mol L⁻¹ CuAc₂ was proved to be the best adsorbent. And removal efficiency of H₂S could be significantly enhanced by AC impregnated with 7% Na₂CO₃. The results of plant experiments suggested that the total concentration of the impurities in yellow phosphorus off-gas was less than 1 mg Nm⁻³ after purification operation. The metal-modified activated carbon (MMAC) was systematically characterized in terms of XPS, TGA, and DTA. The adsorption reaction mechanism was also investigated. As a result, the yellow phosphorus off-gas purified in this study can be used as a raw material gas in the C1 chemical industry.     

Desulfurizing absorbent for flue gas and its absorption mechanism

A new desulfurizing absorbent for flue gas,i.e.,an organic physical solvent of DMSO(dimethyl sulfoxide) mixed with a relatively small amount of chemical solvent(Mn^2 ) was studied.Compared with pure physical solvent of DMSO,the purification efficiency of the new absorbent was improved .And its absorption and reaction mechanism are discussed.     

中空纤维膜接触器分离烟气中CO2

在中空纤维膜接触器试验台上利用模拟烟气进行CO2的分离试验,采用MDEA与MEA和MDEA与氨基酸盐2种混合吸收液,考察吸收液种类、浓度、CO2负荷和烟气CO2含量对脱除效率和传质速率的影响.结果表明,在MDEA水溶液中加入MEA或氨基酸盐作为添加剂,大大提高了脱除效率,改善了传质速率,相对于单一的MDEA吸收液,混合吸收液的脱除效率平均提高了200%,传质速率提高了238%,其中以MEA作为添加剂的混合吸收液的传质速率在2种混合吸收液中最好,传质速率最高可以达到1.7 mol·m-2·h-1.     

电吸附技术去除水中磷酸盐离子的研究

水体富营养化是世界各国面临的重大环境污染问题.水中的磷酸盐作为水体富营养化的关键因素,如何有效去除日益引起研究者的关注.本研究利用电吸附技术处理水中PO_4~(3-)、HPO_4~(2-)和H_2PO_4~- 3种常见磷酸盐离子,并分析电吸附和脱附的特性及机理.实验得到电吸附处理K_3PO_4时,离子去除率最大,但脱附率最差,这严重影响电吸附电极的再生性.K_3PO_4溶液中存在大量的OH~-,炭电极对KOH产生物理吸附,该吸附类型比电吸附的双电层吸附难脱附.添加少量HCl调节磷酸盐的pH,减少OH~-,将溶液中PO_4~(3-)转化为HPO_4~(2-)和H_2PO_4~-,可以提高电极的脱附率,增加电极的循环使用效率,同时可增加溶液中磷含量的去除率.炭电极电吸附K_3PO_4+HCl溶液时,电极的再生性良好,连续循环四次,离子去除率由28.7%降为26.6%.