Enhancement of CO2 capture in the MDEA solution by introducing TETA or TETA-AEP mixtures as an activator

TETA or TETA-AEP mixtures were used as an activator to enhance CO₂ capture in the MDEA solution. The effect of amount and type of activators, and the viscosity of absorbents on CO₂ capture were discussed. The results showed that the positive effect of TETA-AEP mixtures on CO₂ capture in the MDEA solution was greater than that of TETA. The optimal absorbent was No. V, whose CO₂ absorption capacity/desorption efficiency was 3.08 times/1.18 times of No. ?. The viscosity had a little influence on CO₂ absorption and an obvious effect on CO₂ desorption.     

Absorption of carbon dioxide in piperazine activated concentrated aqueous 2-amino-2-methyl-1-propanol solvent

In this work new experimental data on the rate of absorption of CO₂ into piperazine (PZ) activated concentrated aqueous solutions of 2-amino-2-methyl-1-propanol (AMP) over the temperature range 303–323 K are presented. The absorption experiments have been carried out in a wetted wall contactor over CO₂ partial pressure range of 5–15 kPa. PZ is used as a rate activator with a concentration ranging from 2 to 8 wt% keeping the total amine concentration in the solution at 40 wt%. The physical properties such as density and viscosity of concentrated aqueous AMP+PZ, as well as physical solubility of CO₂ in concentrated aqueous AMP+PZ, are also measured. New experimental data on vapor liquid equilibrium (VLE) of CO₂ in these concentrated aqueous solutions of AMP+PZ in the temperature range of 303–323 K have also been presented. The VLE measurements are carried out in an equilibrium cell in CO₂ pressure range of 0.1–140 kPa. A thermodynamic model based on electrolyte non-random two-liquid (eNRTL) theory is used to represent the VLE of CO₂ in aqueous AMP+PZ. Liquid phase speciations are estimated considering the nonideality of concentrated solutions of the amines and the calculated activity coefficients by eNRTL model. The CO₂ absorption in the aqueous amine solutions is described by a combined mass transfer-reaction kinetics model developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental results of the rates of absorptions of CO₂ into aqueous AMP+PZ.     

Kinetics of carbon dioxide absorption in aqueous solution of diethylenetriamine (DETA)

A string of discs contactor was used to measure the kinetics CO₂ absorption in unloaded aqueous solution with the diethylenetriamine (DETA) concentrations ranging between 1.0 and 2.9 kmol m⁻³ and at temperatures ranging between 298.1 and 332.3 K. The reaction rates strongly increase as the increasing the concentrations and temperatures. Both the termolecular and the zwitterion models were applied to interpret the experimental data and gave identical results for all practical purposes. The reaction order with respect to the DETA concentration is found to vary slightly with temperature between 1.71 and 1.76 with an average of about 1.73. Both DETA and water contribute as a base in carbamate formation. It was found that fitting of experimental data to the termolecular mechanism gave statistically more robust results than fitting to the zwitterion mechanism.     

Initial evaluation of the impact of post-combustion capture of carbon dioxide on supercritical pulverised coal power plant part load performance

Pulverised coal-fired plants often play an important role in electricity grids as mid-merit plants that can operate flexibly in response to changes in supply and demand. As a consequence, these plants are required to operate over a wide output range. This paper presents an initial evaluation of some potential impacts of adding post-combustion CO₂ capture on the part load performance of pulverised coal-fired plants. Preliminary results for ideal cases analysed using a simple high-level model indicate that post-combustion CO₂ capture could increase the options available to power plant operators. In particular, solvent storage could allow higher effective plant load factors to be achieved to assist with capital recovery while still permitting flexible operation for grid support. A number of areas for more detailed analysis are identified.     

Reusable poly(allylamine)-based solid materials for carbon dioxide capture under continuous flow of ambient air

Poly(allylamine) (PAA) is prepared via free-radical polymerization and physically impregnated on fumed silica at various amine loadings. The PAA-silica composites were found to have significant potential as trace carbon dioxide adsorbents under ambient conditions. The sorbent materials are shown to have high adsorption capacities with desirable adsorption-desorption characteristics. The effects of temperature and humidity on adsorption capacity and kinetics were studied at near-ambient conditions. Sorbent regenerative ability was confirmed within around 8% change following subsequent adsorption-desorption cycles and thermogravimetric analysis.     

Dynamic modeling of CO2 absorption from coal-fired power plants into an aqueous monoethanolamine solution

Among carbon capture and storage (CCS), the post-combustion capture of carbon dioxide (CO₂) by means of chemical absorption is actually the most developed process. Steady state process simulation turned out as a powerful tool for the design of such CO₂ scrubbers. Besides steady state modeling, transient process simulations deliver valuable information on the dynamic behavior of the system. Dynamic interactions of the power plant with the CO₂ separation plant can be described by such models. Within this work a dynamic process simulation model of the absorption unit of a CO₂ separation plant was developed. For describing the chemical absorption of CO₂ into an aqueous monoethanolamine solution a rate based approach was used. All models were developed within the Aspen Custom Modeler^® simulation environment. Thermo physical properties as well as transport properties were taken from the electrolyte non-random-two-liquid model provided by the Aspen Properties^® database. Within this work two simulation cases are presented. In a first simulation the inlet temperature of the flue gas and the lean solvent into the absorber column was changed. The results were validated by using experimental data from the CO₂SEPPL test rig located at the Dürnrohr power station. In a second simulation the flue gas flow to the separation plant was increased. Due to the unavailability of experimental data a validation of the results from the second simulation could not be achieved.     

Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium

The electrochemical reduction of carbon dioxide on a lead electrode was studied in aqueous medium. Preliminary investigations carried out by cyclic voltammetry were used to determine the optimized conditions of electrolysis. They revealed that the CO₂ reduction process was enhanced at a pH value of 8.6 for the cathodic solution i.e. when the predominant form of CO₂ was hydrogenocarbonate ion. Long-term electrolysis was carried out using both potentiometry and amperometry methods in a filter-press cell in which the two compartments were separated by a cation-exchange membrane (Nafion^® 423). Formate was detected and quantified by chromatography as the exclusive organic compound produced with a high Faradaic yield (from 65% to 90%). This study also revealed that the operating temperature played a key role in the hydrogenation reaction of carbon dioxide into formate in aqueous medium.     

Form coke reaction processes in carbon dioxide

Uncertainty in metallurgical coke supplies has prompted development of form coke from low quality coals and fines. Reaction rates have been measured and mechanisms identified that control carbonaceous briquette reaction rate in CO₂. Three briquette formulations were prepared, characterized and coked in an inert atmosphere at high temperature. A given weight of each formulation was then reacted in a packed bed with CO₂ at 1373 K for 0.5–2 h. Partially reacted briquettes contained a solid core with some internal reaction surrounded by a loosely adhering layer of carbon-containing ash. The reaction rate of briquettes with CO₂ was affected by diffusion of CO₂ through the bulk gas and the ash-carbon layer to the core surface, as well as CO₂–carbon reaction. Key variables governing briquette reaction rate included CO₂ mole fraction and briquette void fraction.     

Electrochemical conversion of carbon dioxide to methane in aqueous NaHCO3 solution at less than 273 K

The electrochemical reduction of CO₂ on a Cu electrode was investigated in aqueous NaHCO₃ solution, at low temperature. A divided H-type cell was employed, the catholyte was 0.65 mol dm⁻³ NaHCO₃ aqueous solution and the anolyte was 1.1 mol dm⁻³ KHCO₃ aqueous solution. The temperature during the electrolysis of CO₂ was decreased stepwise to 271 K. Methane and formic acid were obtained as the main products. The maximum Faradaic efficiency of methane was 46% at −2.0 V and 271 K. The efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was significantly depressed with decreasing temperature. Based on the results of this work, the proposed electrochemical method appears to be a viable means for removing CO₂ from the atmosphere and converting it into more valuable chemicals. The synthesis of methane by the electrochemical method might be of practical interest for fuel production and the storage of solar energy.     

电厂烟气氨法脱碳技术研究进展

随着“后京都时代”的到来,电厂烟气氨法脱碳技术成为近年来新兴的CO₂减排方法研究热点之一。本文对国内外有关氨法脱碳的机理、主要工艺和参数等的相关研究给予了详细的总结与分析,并对存在的问题和技术未来发展等方面进行了阐述。现有试验及系统模拟结果表明,氨法脱碳技术可实现90%以上的CO₂脱除效率,氨水溶液具有1.0 kg CO₂/kg NH₃以上的吸收能力;其中,CO₂脱除效率、吸收能力及速率等参数主要受氨水浓度、吸收反应温度、吸收剂再生条件等因素影响。经济性研究显示,氨法联合脱除技术有望将CO₂捕获带来的电价增长控制在20%以内。     

Integrated solvent and process design using a SAFT-VR thermodynamic description: High-pressure separation of carbon dioxide and methane

The increasing importance of natural gas as an energy source poses separation challenges, due to the high pressures and high carbon dioxide concentrations of many natural gas streams. A methodology for computer-aided molecular and process design (CAMPD) applicable to such extreme conditions is presented, based on the integration of process and cost models with an advanced molecular-based equation of state, the statistical associating fluid theory for potentials of variable range (SAFT-VR). The approach is applied to carbon dioxide capture from methane using physical absorption. The search for an optimal solvent is focused on n-alkane blends. A simple flowsheet is optimised using two objectives: maximum purity and maximum net present value. The best equipment sizes, operating conditions, and average chain length of the solvent (the n-alkane) are identified, indicating n-alkane solvents offer a promising alternative. The proposed methodology can readily be extended to wider classes of solvents and to other challenging processes.     

Facilitated transport of carbon dioxide through an immobilized liquid membrane of K2CO3/KHCO3 aqueous solution

The facilitated transport of CO₂ through a hydrophilic polymeric membrane immobilized with K₂CO₃/ KHCO₃ buffer solution has been investigated. The reactions of dissolved CO₂ in electrolyzed alkaline solution must consider hydration of CO₂ with water, chemical reaction of CO₂ with OH^- and dissociation of HCO ₃ ^2- into CO ₃ ^2- . It is necessary to simplify these reactions as a simple model, which is used to analyze the transport system. From experiments in the liquid membrane with alkaline buffer solution, it is shown that the flux of CO₂ into K₂CO₃KHCO₃ aqueous solution can be enhanced by the presence of CO ₃ ^2- . A diffusion model with an overall reaction based on the film theory is proposed that predicts the experimentally observed facilitation factor with reasonable accuracy. The present model is compared with the rigorous diffusion model involving the complicated conventional chemical reactions.     

Synthesis of PCL/clay masterbatches in supercritical carbon dioxide

Pre-exfoliated nanoclays were prepared through a masterbatch process using supercritical carbon dioxide as solvent and poly(?-caprolactone) as organic matrix. In situ polymerization of ?-caprolactone in the presence of large amount of clay was conducted to obtain these easily dispersible nanoclays, collected as a dry and fine powder after reaction. Dispersion of these pre-exfoliated nanoclays in chlorinated polyethylene was also investigated. All the results confirm the specific advantages of supercritical CO₂ towards conventional solvents for filler modification.     

Separation of carbon dioxide from flue emissions using Endex principles

In an Endex reactor endothermic and exothermic reactions are directly thermally coupled and kinetically matched to achieve intrinsic thermal stability, efficient conversion, autothermal operation, and minimal heat losses. Applied to the problem of in-line carbon dioxide separation from flue gas, Endex principles hold out the promise of effecting a CO₂-capture technology of unprecedented economic viability. In this work we describe an Endex Calcium Looping reactor, in which heat released by chemisorption of carbon dioxide onto calcium oxide is used directly to drive the reverse reaction, yielding a pure stream of CO₂ for compression and geosequestration. In this initial study we model the proposed reactor as a continuous-flow dynamical system in the well-stirred limit, compute the steady states and analyse their stability properties over the operating parameter space, flag potential design and operational challenges, and suggest an optimum regime for effective operation.     

燃煤电厂烟气MDEA/PZ混合胺法碳捕集工艺模拟分析

采用混合胺吸收剂替代传统一乙醇胺（MEA）吸收剂是降低有机胺法碳捕集工艺能耗的重要方法。利用Aspen plus软件模拟了以甲基二乙醇胺(MDEA)/哌嗪(PZ)混合胺为吸收剂的燃煤电厂每年百万吨CO₂捕集工艺系统，考察了贫液负荷、MDEA/PZ混合胺浓度、MDEA/PZ比例和解吸压力等因素对解吸塔再沸器热负荷和冷凝器冷负荷的影响。通过对这些影响因素下吸收塔内液相温度分布和CO₂负荷分布变化揭示了MDEA/PZ对CO₂的吸收特性。此外，进一步分析了不同影响因素下解吸塔内气液相CO₂浓度驱动力和气液相级间温度驱动力分布特性，发现了强浓度驱动力和低温度驱动力分布更有利于降低再生能耗。研究表明，由30%MDEA和20%PZ组成的混合胺液在贫液负荷为0.08和解吸压力为2.02×10⁵Pa时，再沸器热负荷和塔顶冷凝负荷分别为2.76GJ/tCO₂和0.60GJ/tCO₂，相比传统MEA吸收剂降低了20.92%和40.0%。     

Investigation on kinetics of carbon dioxide absorption in aqueous solutions of monoethanolamine + 1, 3-diaminopropane

ABSTRACT

Environmental concerns from global warming and climate change demand carbon dioxide separation from post-combustion gases. Important parameters are involved in choosing the suitable solvent for carbon dioxide separation, including the reaction rate of carbon dioxide and the solvent. In this paper, the kinetics of carbon dioxide (CO₂) absorption in aqueous solutions of Monoethanolamine (MEA) + 1,3-Diaminopropane (DAP), a diamine containing two primary amino group, was developed. The measurements were performed in a stirred cell with a horizontal gas-liquid interface in the temperature range of 313.15–333.15 K and aqueous solutions of 10 wt% MEA + 5 wt% DAP and 12.5 wt% MEA + 2.5 wt% DAP. Experiments were conducted in an isothermal batch reactor with a horizontal gas-liquid interface under pseudo-first-order conditions, enabling the determination of the overall kinetic rate constant from the pressure drop method. Second-order reaction rate constants of CO₂ absorption in amine solutions were estimated using the calculated initial absorption rate. It was found that the rate constants in MEA+ DAP solutions were greater than in MEA solutions which means that DAP increases the reaction rate.     

The solubility of carbon dioxide and hydrogen sulfide in a 35 wt% aqueous solution of methyldiethanolamine

The solubility of hydrogen sulfide and carbon dioxide in an aqueous solution containing 35 wt% methyldiethanolamine (MDEA) (3.04 kmol/m³, 4.52 mol/kg) has been measured at 40° and 100°C at partial pressures of the acid gas up to 530 kPa. Some data for hydrogen sulfide in a 50 wt% solution of MDEA (4.38 kmol/m³, 8.39 mol/kg) were also obtained. Also, densities of CO₂-aqueous MDEA solutions were measured at 40°C.     

有机胺吸收二氧化碳的热力学和动力学研究进展

二氧化碳捕集与封存技术（CCS）是针对大气CO₂含量增高导致的全球气候变暖而提出的全球性解决方案。有机胺吸收法作为经济与技术层面最成熟的技术,是实现二氧化碳捕集的重要工艺过程。从有机胺法吸收二氧化碳的基本反应机理出发,系统评述了应用有机胺法吸收捕集CO₂的热力学与动力学性质的研究进展,介绍了不同类型胺溶剂分子结构与CO₂捕集溶解度和反应速度的关系,并对今后CO₂吸收捕集的热力学和动力学的研究方向提出了展望。     

Research on mechanism of ammonia escaping and control in the process of CO2 capture using ammonia solution

As CO₂ is the major greenhouse gas, reducing its emission has become an attentive problem in the whole world. It is very important to develop CO₂ capture technology for coal-fired power plants. Using ammonia solution to absorb CO₂ from the flue gas, which is expected to have advantages of low cost, high efficiency and high absorption load, has become an emerging, hot research area in recent years. However, this technology faces a troublesome problem of ammonia escape. This paper analyzes the mechanism of escaping ammonia; it is also shown the main existing methods to control the escape of ammonia. By comparison, it is concluded that controlling the source of ammonia is feasible. It is also shown that adding some organic additives can inhibit the escape of ammonia and enhance the CO₂ removal to some extent at the same time.