Behaviour of absorption/stripping columns for the CO2-MEA system; Modelling and experiments

A model is presented for the steady-state simulation of a CO₂ recovery pilot plant with aqueous monoethanolamine (MEA) solutions. CO₂ absorption is performed in a column packed with 2.54 cm ceramic Pall rings. CO₂ recovery is achieved in a 20 sieve tray steam stripping column. The packed column absorption model was fitted to the experimental data using the specific interfacial area of the irrigated packing as an adjustable parameter. The equivalent average bubble diameter was used as the adjusting parameter in the sieve tray stripping column. Modelling of both towers reproduces within 3% average error concentrations measured in a pilot plant. Measured temperatures were also well correlated.     

Comparison of solvent performance for CO2 capture from coal-derived flue gas: A pilot scale study

The performance of a proprietary solvent (CAER-B2), an amine-carbonate blend, for the absorption of CO₂ from coal-derived flue gas is evaluated and compared with state-of-the-art 30 wt% monoethanolamine (MEA) under similar experimental conditions in a 0.1 MWth pilot plant. The evaluation was done by comparing the carbon capture efficiency, the overall mass transfer rates, and the energy of regeneration of the solvents. For similar carbon loadings of the solvents in the scrubber, comparable mass transfer rates were obtained. The rich loading obtained for the blend was 0.50 mol CO₂/mol amine compared to 0.44 mol CO₂/mol amine for MEA. The energy of regeneration for the blend was about 10% lower than that of 30 wt% MEA. At optimum conditions, the blend shows promise in reducing the energy penalty associated with using industry standard, MEA, as a solvent for CO₂ capture.     

FAU zeolite membranes for dewatering of amine-based post-combustion CO2 capture solutions

In amine-based CO₂ capture processes, aqueous amine solvent is circulated between absorber (CO₂ absorption) and stripping (solvent regeneration) columns. To reduce solvent regeneration energy demand, a selective membrane can dewater and enrich the CO₂ concentration in solution prior to the stripper, lowering steam requirements for solution heating. In this work, a facile synthesis strategy was developed to prepare faujasite (FAU) zeolite membranes built upon polydopamine (PDA) modified α-Al₂O₃ substrates. PDA facilitated the attachment of zeolite phases onto the substrate surface to form a 3 μm membrane layer. Membrane permeation flux of 4.45 kg m⁻² h⁻¹ and 95% rejection rate calculated by either CO₂ loading or total alkalinity was achieved in dewatering of CO₂ loaded 30 wt% monoethanolamine (MEA) solution. The effects of temperature on membrane dewatering performance and stability were investigated. This study highlights the potential for process integration of membrane technology in amine-based post-combustion CO₂ capture operations.     

CO2 Absorption into Aqueous Solutions of a Polyamine (PZEA), a Sterically Hindered Amine (AMP), and their Blends

Among numerous techniques existing for reducing CO₂ emissions, CO₂ capture by absorption in aqueous alkanolamine solutions was specifically studied in this work. For the choice of the adequate amine solution, two major criteria must be taken into account: absorption performances (higher with primary and secondary amines) and energy costs for solvent regeneration (more interesting with tertiary and sterically hindered amines). The different types of amines can also be mixed in order to combine the specific advantages of each type of amines, an activation phenomenon being observed. Aqueous solutions of (piperazinyl‐1)‐2‐ethylamine (PZEA, a polyamine known as absorption activator) and 1‐amino‐2‐propanol (AMP, a sterically hindered amine), pure or mixed with other amines, are experimentally compared with respect to CO₂ removal performances by means of absorption test runs achieved in a special gas‐liquid contactor at 25 °C. The positive impact of addition of PZEA to monoethanolamine (MEA), N‐methyldiethanolamine (MDEA), and AMP solutions was clearly highlighted. The absorption performances have also been satisfactorily simulated with coherent physicochemical data.     

CO_2捕集的吸收溶解度计算和过程模拟

为了降低CO2吸收法捕集技术的能耗和成本,以目前常用的单乙醇胺(MEA)溶液吸收CO2为例,采用电解质非随机双流体热力学模型(E-NRTL),对溶液中的CO2气体溶解度进行计算,计算过程包含了化学反应平衡和汽液平衡,计算结果和文献数据相吻合。在此基础上,建立了CO2吸收过程模拟程序和包括解吸能耗、气体压缩能耗以及液体输送能耗的过程总体能耗的计算方法,继而通过过程模拟分析了吸收塔和解吸塔压力、溶液浓度和流量等因素对吸收捕集过程的总体能耗的影响,获取了最优的工艺条件,为以后新CO2吸收捕集过程提供能耗分析方法基础。     

Investigation mechanism of DEA as an activator on aqueous MEA solution for postcombustion CO2 capture

In this work, Diethanolamine (DEA) was considered as an activator to enhance the CO₂ capture performance of Monoethanolamine (MEA). The addition of DEA into MEA system was expected to improve disadvantages of MEA on regeneration heat, degradation, and corrosivity. To understand the reaction mechanism of blended MEA‐DEA solvent and CO₂, ¹³C nuclear magnetic resonance (NMR) technique was used to study the ions (MEACOO^‐, DEACOO^–, MEA, DEA, MEAH⁺, DEAH⁺, , ) speciation in the blended MEA‐DEA‐CO₂‐H₂O systems with CO₂ loading range from 0 to 0.7 mol CO₂/mol amine at the temperature of 301 K. The different ratios of MEA and DEA (MEA: DEA = 2.0:0, 1.5:0.5, 1.0:1.0, and 0:2.0) were studied to comprehensively investigate the role of DEA in the system of MEA‐DEA‐CO₂‐H₂O. The results revealed that DEA performs the coordinative role at the low CO₂ loading and the competitive role at high CO₂ loading. Additionally, the mechanism was also proposed to interpret the reaction process of the blended solvent with CO₂. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2515–2525, 2018     

Effect of addition of weak acids on CO<Subscript>2</Subscript> desorption from rich amine solvents

Experiments were conducted to study the effect of addition of four weak acids (adipic, suberic, phthalic and sebacic acids) on the regeneration of three types of CO₂-loaded rich solvents (Monoethanolamine (MEA), Diethanolamine (DEA) and Methyldiethanolamine (MDEA)). It was found that CO₂ could be released faster and in a larger quantity when the amount of acid added to the solvent was increased while other desorption conditions were maintained unchanged. Adipic acid appeared to be more effective than phthalic, suberic and sebacic acids in enhancing solvent regeneration rate. Among the three amines investigated, MEA had the highest CO₂ desorption rate, while DEA saved the most energy. The effect of adipic acid residue in the MEA solvent on CO₂ absorption was also investigated. The residue acid reduced the absorption capacity of the MEA solvent significantly when the solvent concentration was low and slightly when the concentration was high.     

Carbon dioxide absorption using a phase transitional alkanolamine–alcohol mixture

Some alkanolamine–alcohol mixtures separate into a CO₂ rich phase and a CO₂ lean phase after the absorption of CO₂, which makes possible a new approach to CO₂ capture. In this study, CO₂ absorbent solutions with various concentrations of monoethanolamine (MEA) and diethanolamine (DEA) were prepared by mixing them with alcohol. The CO₂ absorption capacities of the alkanolamine–alcohol mixtures were investigated by using a semi-batch reactor at 313 K. The species distributions of the absorbents were identified in order to determine the CO₂ absorption mechanism of these solutions. Although the CO₂ absorption capacities of the phase transitional absorbents are lower than that of aqueous solutions, we conclude from our experimental results that the phase transitional solutions have the economic advantages, and in particular lower regeneration energies, because only the CO₂-rich phase needs to be transported to the stripper.     

CO2 Capture Using Monoethanolamine in a Bubble‐Column Scrubber

A continuous bubble‐column scrubber, capturing CO₂ gas by monoethanolamine (MEA) solution in a pH‐stat operation, is used to search for optimum process parameters by means of the Taguchi method. The process variables are the pH of the solution, gas flow rate, concentration of CO₂ gas, and temperature. From the measured outlet CO₂ gas concentrations, the absorption rate and overall mass transfer coefficient can be determined with the support of a steady‐state material balance equation as well as a two‐film model. According to the signal‐to‐noise ratio, the significance sequence influencing the parameters and optimum conditions can be determined. CO₂ concentration and pH value proved to be decisive parameters, while temperature and gas flow rate were minor. Five sets of optimum conditions were obtained and could be further verified by empirical equations.     

CO<Subscript>2</Subscript> capture using aqueous solutions of K<Subscript>2</Subscript>CO<Subscript>3</Subscript>+2-methylpiperazine and monoethanolamine: Specific heat capacity and heat of absorption

The specific heat capacity, heat of CCO₂ absorption, and CCO₂ absorption capacity of aqueous solutions of potassium carbonate (K₂CO₃)+2-methylpiperazine (2-MPZ) and monoethanolamine (MEA) were measured over various temperatures. An aqueous solution of K₂CO₃+2-MPZ is a promising absorbent for CCO₂ capture because it has high CCO₂ absorption capacity with improved absorption rate and degradation stability. Aqueous solution of MEA was used as a reference absorbent for comprison of the thermodynamic characteristics. Specific heat capacity was measured using a differential scanning calorimeter (DSC), and heat of CCO₂ absorption and CCO₂ absorption capacity were measured using a differential reaction calorimeter (DRC). The CCO₂-loaded solutions had lower specific heat capacities than those of fresh solutions. Aqueous solutions of K₂CO₃+2-MPZ had lower specific heat capacity than those of MEA over the temperature ranges of 303-353 K. Under the typical operating conditions for the process (CCO₂ loading=0.23mol-CCO₂·mol^?1-solute in fresh solution, T=313 K), the heat of absorption (?ΔHabs) of aqueous solutions of K₂CO₃+2-MPZ and MEA were approximately 49 and 75 kJ·mol-CO₂, respectively. The thermodynamic data from this study can be used to design a process for CCO₂ capture.     

CO2 absorption into a phase change absorbent: Water-lean potassium prolinate/ethanol solution

Phase change solvents are attractive energy-efficient absorbents for carbon dioxide (CO₂) capture due to CO₂-rich phase formation. Potassium prolinate + water + ethanol (ProK/W/Eth) solution has shown good capture characteristics as a promising one in our previous work. In this work, absorption rate of CO₂, solubility of N₂O, and heat of absorption for ProK/W/Eth solution were investigated using a stirred cell reactor and a CPA201 reaction calorimeter and these results were also compared with the aqueous ProK and 30 mass% MEA solutions. Using ethanol as a solvent can substantially increase the CO₂ physical solubility and the absorption rate of CO₂ in ProK/W/Eth solutions is far higher than that in aqueous 30 mass% MEA solutions especially at a low CO₂ loading range. Solid precipitation, obtained from the liquid-to-solid phase change absorption, was analyzed by ¹³C NMR and DSC-TGA. The enthalpy change for ProK/W/Eth solutions at various CO₂ loading was also discussed.     

Chemical Absorption of Carbon Dioxide into Aqueous PEO Solution of Monoethanolamine

Abstract

Carbon dioxide was absorbed into aqueous polyethylene oxide (PEO) solution containing monoethanolamine (MEA) in a flat‐stirred vessel to investigate the effect of non‐Newtonian rheological behavior of PEO on the rate of chemical absorption of CO₂, where the reaction between CO₂ and MEA was assumed to be a first‐order reaction with respect to the molar concentration of CO₂ and MEA, respectively. The liquid‐side mass transfer coefficient (k_L), which was obtained from the dimensionless empirical equation containing the properties of viscoelasticity of the non‐Newtonian liquid, was used to estimate the enhancement factor due to chemical reaction. PEO with elastic property of non‐Newtonian liquid made the rate of chemical absorption of CO₂ accelerate compared with Newtonian liquid based on the same viscosity of the solution.     

Experimental study on the solvent regeneration of a CO2‐loaded MEA solution using single and hybrid solid acid catalysts

The performance of a hybrid solid acid catalyst consisting of a physical mixture of γ‐Al₂O₃ and H‐ZSM‐5 in terms of the rate and heat duty for solvent regeneration (i.e., CO₂ stripping) of a CO₂‐rich MEA solution was compared with the individual performance of γ‐Al₂O₃, H‐ZSM‐5, and H‐Y solid acid catalysts using MEA (2–7 mol/L), with initial CO₂ loading of 0.5 mol CO₂/mol MEA at 378 K. It was observed that any catalyst significantly decreased the energy required for CO₂ regeneration. The performance of the catalysts investigated ranked as follows: γ‐Al₂O₃/H‐ZSM‐5 = 2/1 > γ‐Al₂O₃ > H‐ZSM‐5 > H‐Y if the process is in the lean CO₂ loading region whereas it was H‐ZSM‐5 > γ‐Al₂O₃/H‐ZSM‐5 = 2/1 > γ‐Al₂O₃ > H‐Y if the process is in the rich CO₂ loading region. These results highlight the joint dependence on Brønsted/Lewis acidity and mesopore surface area of heat duty for solvent regeneration. © 2015 American Institute of Chemical Engineers AIChE J, 62: 753–765, 2016     

Reduction of amine mist emissions from a pilot-scale CO2 capture process using charged colloidal gas aphrons

In the CO₂ capture process from coal-derived flue gas where amine solvents are used, the flue gas can entrain small liquid droplets into the gas stream leading to emission of the amine solvent. The entrained drops, or mist, will lead to high solvent losses and cause decreased CO₂ capture performance. In order to reduce the emissions of the fine amine droplets from CO₂ absorber, a novel method using charged colloidal gas aphron (CGA) generated by an anionic surfactant was developed. The CGA absorption process for MEA emission reduction was optimized by investigating the surfactant concentration, stirring speed of the CGA generator, and capture temperature. The results show a significant reduction of MEA emissions of over 50% in the flue gas stream exiting the absorber column of a pilot scale CO₂ capture unit.     

Dynamic modelling and analysis of post-combustion CO2 chemical absorption process for coal-fired power plants

Post-combustion capture by chemical absorption using MEA solvent remains the only commercial technology for large scale CO₂ capture for coal-fired power plants. This paper presents a study of the dynamic responses of a post-combustion CO₂ capture plant by modelling and simulation. Such a plant consists mainly of the absorber (where CO₂ is chemically absorbed) and the regenerator (where the chemical solvent is regenerated). Model development and validation are described followed by dynamic analysis of the absorber and regenerator columns linked together with recycle. The gPROMS (Process Systems Enterprise Ltd.) advanced process modelling environment has been used to implement the proposed work. The study gives insights into the operation of the absorber-regenerator combination with possible disturbances arising from integrated operation with a power generation plant. It is shown that the performance of the absorber is more sensitive to the molar L/G ratio than the actual flow rates of the liquid solvent and flue gas. In addition, the importance of appropriate water balance in the absorber column is shown. A step change of the reboiler duty indicates a slow response. A case involving the combination of two fundamental CO₂ capture technologies (the partial oxyfuel mode in the furnace and the post-combustion solvent scrubbing) is studied. The flue gas composition was altered to mimic that observed with the combination. There was an initial sharp decrease in CO₂ absorption level which may not be observed in steady-state simulations.     

SO42−/ZrO2 supported on γ‐Al2O3 as a catalyst for CO2 desorption from CO2‐loaded monoethanolamine solutions

In this work, the composite catalysts, SO₄²/ZrO₂/γ‐Al₂O₃ (SZA), with different ZrO₂ and γ‐Al₂O₃ mass ratios were prepared and used for the first time for the carbon dioxide (CO₂)‐loaded monoethanolamine (MEA) solvent regeneration process to reduce the heat duty. The regeneration characteristics with five catalysts (three SZA catalysts and two parent catalysts) of a 5 M MEA solution with an initial CO₂ loading of 0.5 mol CO₂/mol amine at 98°C were investigated in terms of CO₂ desorption performance and compared with those of a blank test. All the catalysts were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, N₂ adsorption–desorption experiment, ammonia temperature programmed desorption, and pyridine‐adsorption infrared spectroscopy. The results indicate that the SZA catalysts exhibited superior catalytic activity to the parent catalysts. A possible catalytic mechanism for the CO₂ desorption process over SZA catalyst was proposed. The results reveal that SZA1/1, which possesses the highest joint value of Brφnsted acid sites (BASs) and mesopore surface area (MSA), presented the highest catalytic performance, decreasing the heat duty by 36.9% as compared to the catalyst‐free run. The SZA1/1 catalyst shows the best catalytic performance as compared with the reported catalyst for this purpose. Moreover, the SZA catalyst has advantages of low cost, good cyclic stability, easy regeneration and has no effect on the CO₂ absorption performance of MEA. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3988–4001, 2018     

Gas–liquid mass‐transfer properties in CO2 absorption system with ionic liquids

The deficiency of mass‐transfer properties in ionic liquids (ILs) has become a bottleneck in developing the novel IL‐based CO₂ capture processes. In this study, the liquid‐side mass‐transfer coefficients (k_L) were measured systematically in a stirred cell reactor by the decreasing pressure method at temperatures ranging from 303 to 323 K and over a wide range of IL concentrations from 0 to 100 wt %. Based on the data of k_L, the kinetics of chemical absorption of CO₂ with mixed solvents containing 30 wt % monoethanolamine (MEA) and 0–70 wt % ILs were investigated. The k_L in IL systems is influenced not only by the viscosity but also the molecular structures of ILs. The enhancement factors and the reaction activation energy were quantified. Considering both the mass‐transfer rates and the stability of IL in CO₂ absorption system, the new IL‐based system MEA + [bmim][NO₃] + H₂O is recommended. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2929–2939, 2014     

Analysis of the heat of reaction and regeneration in alkanolamine-CO<Subscript>2</Subscript> system

The estimation of regeneration heat of absorbent is important because it is a key factor that has an effect on the process efficiency. In this study, thermal stability and regeneration heat of aqueous amine solutions such as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), N-methyldiethanolamine (MDEA), and 1,8-diamino-pmenthane (KIER-C3) were investigated by using TGA-DSC analysis. The thermal characteristics of the fresh and CO₂ rich amine solutions were estimated. The CO₂ rich amine solutions were obtained by VLE experiments at T=40 °C. The regeneration heat of aqueous MEA solution was 76.991–66.707 kJ/mol-CO₂, which is similar to heat of absorption. The reproducibility of the results was obtained. The regeneration heat of aqueous KIER-C3 20 wt% solution (1.68 M) was lower than that of aqueous MEA 30 wt% solution (4.91 M). Therefore, the KIER-C3 can be used as an effective absorbent for acid gas removal.     

Simulations of Membrane Gas Separation: Chemical Solvent Absorption Hybrid Plants for Pre- and Post-Combustion Carbon Capture

Solvent absorption and membrane gas separation are two carbon capture technologies that show great potential for reducing emissions from stationary sources such as power plants. Here, plants combining chemical solvent absorption and membrane gas separation are considered for post-combustion capture as well as pre-combustion capture. In all ASPEN HYSYS simulations the membrane stage initially concentrates CO₂ into either the permeate or the retentate stream, which is then passed to a monoethanolamine (MEA) based solvent absorption process. In particular, post-combustion capture scenarios examined a membrane that is selective for CO₂ against N₂, while for the pre-combustion scenario a H₂-selective membrane was studied. It was found the energy demand of the combined hybrid plant was always more than that of a stand alone MEA solvent process. This was mainly due to the need to generate a pressure driving force upstream of the membrane in the post-combustion scenario or to recompress downstream gas streams in the pre-combustion scenarios. For both scenarios concentrating the CO₂ in the feed to the solvent system reduced the absorber column height and diameter, which could represent a CAPEX saving for the hybrid plant, dependent upon the membrane price. The use of a hydrogen selective membrane downstream of an oxygen fired gasifier was identified as the most prospective scenario, as it led to significant reductions in absorber size, for a relatively small membrane area and energy penalty.     

Design and study of a novel ammonia-based CO2 capture process with bipolar membrane electrodialysis

Aqueous ammonia is a promising absorbent in the field of post combustion CO₂ capture. However, the high volatilization of NH₃ results in a high energy requirement, as well as solid precipitation during the CO₂ regeneration process. A novel process was designed to reduce energy consumption and solve the problem. The bipolar membrane electrodialysis (EDBM) unit and CO₂ regeneration reactor were taken as the regeneration part. In the novel process, the bubble in the EDBM unit would be eliminated, and the regeneration of CO₂ and aqueous ammonia would be operated separately, which significantly reduced energy consumption and avoided the risk of precipitation during regeneration. According to the simulation and calculation results, the CO₂ regeneration energy consumption of the novel process using H₂SO₄ for CO₂ regeneration is 39.0% lower than that of the conventional ammonia-based process, which shows good energy saving potential. Moreover, the novel process will be more competitive as membrane technology develops.