Analysis of CO2 sorption/desorption kinetic behaviors and reaction mechanisms on Li4SiO4

The CO₂ sorption/desorption kinetic behaviors on Li₄SiO₄ were analyzed. The theoretical compositions of the sorption/desorption reactions were calculated using FactSage. The sorption/desorption process on Li₄SiO₄ was investigated by comparing the shrinking core, double exponential, and Avrami–Erofeev models. The Avrami–Erofeev model fits the kinetic thermogravimetric experimental data well and, together with the double‐shell mechanism, clearly explains the sorption/desorption mechanism. The sorption process is limited by the rate of the formation and growth of the crystals with double‐shell structure consisting of Li₂CO₃ and Li₂SiO₃. The whole desorption process is found to be controlled by the rate of the formation and growth of the Li₄SiO₄ crystals. Furthermore, the influence of steam on the CO₂ sorption process was analyzed. It has been observed that the presence of steam enhance the mobility of Li⁺ and, therefore, the rate of diffusion control stage. © 2012 American Institute of Chemical Engineers AIChE J, 59: 901–911, 2013     

新型Li_4SiO_4高温吸收CO_2的动力学研究

高温固体CO2吸收剂硅酸锂材料以其较高的吸收容量、优良的循环吸收稳定性成为研究热点。文中以廉价的、具有丰富孔结构的硅藻土和碳酸锂为原料,采用高温固相法于600℃下合成了可在高温直接吸收CO2的硅酸锂材料。XRD结果分析表明所制备的材料由Li4SiO4和少量的LiAlSi2O6相组成,用同步热重分析仪(TG-DSC)研究了在等温条件下硅酸锂材料吸收CO2的性能。用双指数模型拟合了硅酸锂材料吸收CO2的过程。结果表明:吸收CO2的温度不同,硅酸锂材料吸收CO2反应的控制步也不相同。表面反应速率常数与扩散速率常数的相对大小在很大程度上影响了硅酸锂材料吸收CO2的性能。     

High-temperature CO2 adsorption over Li4SiO4 sorbents derived from different lithium sources

Li₄SiO₄ is a promising sorbent for high temperature CO₂ capture. It could be synthesized from three different Li sources (LiNO₃, LiOH, and Li₂CO₃) by using the solid state reaction method. The effects of Li sources on the structure and CO₂ adsorption/desorption properties of Li₄SiO₄ sorbents were analyzed in this work. The results showed that Li₄SiO₄ sorbents could be synthesized at a lower temperature by using LiNO₃ and LiOH as the starting materials, which could reduce the sintering during the synthesis process and increase the surface area of synthesized Li₄SiO₄. During the CO₂ adsorption/desorption cycles, Li₄SiO₄ sorbents derived from LiNO₃ and LiOH presented higher initial CO₂ adsorption capacities than those from Li₂CO₃. After 15 cycles, the adsorption efficiency of Li₄SiO₄ derived from LiNO₃ showed no or slight decrease, while that from LiOH rapidly decreased to 20% of the initial value. This was because Li₄SiO₄ derived from LiNO₃ had high surface area and porosity before CO₂ adsorption/desorption cycles, and its surface area even increased after cycles. However, the surface area of Li₄SiO₄ derived from LiOH decreased greatly due to serious sintering. For Li₄SiO₄ derived from Li₂CO₃, its morphology and surface area were almost unchanged before and after CO₂ adsorption/desorption cycles.     

CO2 Capture Performance of Calcium‐Based Sorbents in the Presence of SO2 under Pressurized Carbonation

In order to understand the effect of SO₂ on the CO₂ capture performance under pressurized carbonation conditions, tests by orthogonal design were carried out in a calcination/pressurized carbonation reactor system. The effects of variables such as carbonation temperature, carbonation pressure, SO₂ concentration, CO₂ concentration, and the number of cycles on carbonation and sulfation were investigated. A range method was employed for analysis. Phase structure and scanning electron microscopy images were measured as supplement for a reaction study. Temperature increase enhanced the SO₂ capture, leading to a rapid decay in CO₂ uptake. The carbonation pressure had a stronger effect on the CO₂ uptake than the temperature. SO₂ uptake increased rapidly with increasing pressure while CO₂ uptake decreased.     

Synthesis,kinetic study,and reaction mechanism of Li4SiO4 with CO2 in a slurry bubble column reactor

Abstract

This study was performed to investigate the synthesis, kinetic and reaction mechanism of Li₄SiO₄ with CO₂ in a slurry bubble column reactor. The Li₄SiO₄ powder sample was prepared via a solid-state reaction. The sample was characterized via X-ray diffraction (XRD) analysis and verified as a single phase. The median diameter of the sample was measured using the laser diffraction and scattering method as about 20?μm. The synthesized sample was suspended in binary molten carbonate of Li₂CO₃–K₂CO₃ having a molar ratio of 38:62. The experimental results show that Li₄SiO₄ in the slurry bubble column absorbed approximately a stoichiometric amount of CO₂. The kinetic study shows that the CO₂ reaction behavior on the Li₄SiO₄ surface was fitted to a double exponential model and the limiting step of the reaction was lithium diffusion. The mass transfer coefficient of CO₂ and rate constant of reaction with Li₄SiO₄ were studied to understand the overall absorption mechanism in the reactor. The resistance for the direct reaction of CO₂ on the Li₄SiO₄ was much smaller than the resistance for the mass transfer of CO₂ to the Li₄SiO₄. We can conclude that the direct contact of CO₂ with Li₄SiO₄ was the main path for the reaction.     

Effect of K2CO3 doping on CO2 sorption performance of silicate lithium-based sorbent prepared from citric acid treated sediment

In this paper, a low-cost and environmental-friendly leaching agent citric acid (C₆H₈O₇) was used to treat the sediment of Dianchi Lake (SDL) to synthesize lithium silicate (Li₄SiO₄) based CO₂ sorbent. The results were compared with that treated with strong acid. Moreover, the effects of preparation conditions, sorption conditions and desorption conditions on the CO₂ sorption performance of prepared Li₄SiO₄ were systematically studied. Under optimal conditions, the Li₄SiO₄ sorbent was successfully synthesized and its CO₂ sorption capacity reached 31.37% (mass), which is much higher than that synthesized from SDL treated with strong acid. It is speculated that the presence of some elements after C₆H₈O₇ treatment may promote the sorption of synthetic Li₄SiO₄ to CO₂. In addition, after doping with K₂CO₃, the CO₂ uptake increases from the original 12.02% and 22.12% to 23.96% and 32.41% (mass) under the 20% and 50% CO₂ partial pressure, respectively. More importantly, after doping K₂CO₃, the synthesized Li₄SiO₄ has a high cyclic stability under the low CO₂ partial pressure.     

CO2 Capture Behavior of Shell during Calcination/Carbonation Cycles

The cyclic carbonation performances of shells as CO₂ sorbents were investigated during multiple calcination/carbonation cycles. The carbonation kinetics of the shell and limestone are similar since they both exhibit a fast kinetically controlled reaction regime and a diffusion controlled reaction regime, but their carbonation rates differ between these two regions. Shell achieves the maximum carbonation conversion for carbonation at 680–700 °C. The mactra veneriformis shell and mussel shell exhibit higher carbonation conversions than limestone after several cycles at the same reaction conditions. The carbonation conversion of scallop shell is slightly higher than that of limestone after a series of cycles. The calcined shell appears more porous than calcined limestone, and possesses more pores > 230 nm, which allow large CO₂ diffusion‐carbonation reaction rates and higher conversion due to the increased surface area of the shell. The pores of the shell that are greater than 230 nm do not sinter significantly. The shell has more sodium ions than limestone, which probably leads to an improvement in the cyclic carbonation performance during the multiple calcination/carbonation cycles.     

硅酸锂吸收二氧化碳性能研究

通过高温固相反应法,合成出可在高温400～750℃之间直接吸收CO2的硅酸锂材料,借助热重分析仪研究了K元素的掺杂及CO2的浓度对硅酸锂材料性能的影响.试验结果表明,通过适当K元素的掺杂,能够提高硅酸锂材料吸收CO2的性能,当K元素的掺量x=0.02时,合成的硅酸锂材料在CO2气氛下于700℃保温20 min后,吸收量可达39％,吸收容量有明显提高.此外,气氛中CO2的浓度对硅酸锂材料吸收CO2的性能有较大影响.     

Stabilized Performance of Al‐Decorated and Al/Mg Co‐Decorated Spray‐Dried CaO‐Based CO2 Sorbents

The sharp loss‐in‐capacity in CO₂ capture as a result of sintering is a major drawback for CaO‐based sorbents used in the calcium looping process. The decoration of inert supports effectively stabilizes the cyclic CO₂ capture performance of CaO‐based sorbents via sintering mitigation. A range of Al‐decorated and Al/Mg co‐decorated CaO‐based sorbents were synthesized via an easily scaled‐up spray‐drying route. The decoration of Al‐based and Al/Mg‐based supports efficiently enhanced the cyclic CO₂ capture capability of CaO‐based sorbents under severe testing conditions. The CO₂ capture capacity losses of Al‐decorated and Al/Mg co‐decorated CaO‐based sorbents were alleviated, representing more stable CO₂ capture performance. The stabilized CO₂ capture performance is mainly attributed to the formation of Ca₁₂Al₁₄O₃₃, MgAl₂O₄, and MgO that act as the skeleton structures to mitigate the sintering of CaCO₃ during carbonation/calcination cycles.     

Na2CO3基吸附剂颗粒制备及其脱碳性能

采用挤压-滚圆法制备Na₂CO₃基CO₂吸附剂微球颗粒,在自行设计的CO₂吸收系统中对制备的样品进行脱碳性能测试。结合相关表征测试,探明不同载体、不同负载量的Na₂CO₃基吸附剂的微观结构、脱碳性能以及机械性能的变化规律和内在原因。研究表明：不同载体的Na₂CO₃基吸附剂颗粒脱碳性能存在明显差异,其中氧化铝负载的吸附剂（Na₂CO₃/Al₂O₃）的脱碳性能最好,可达1.14mmol/g。铝酸钙水泥负载的吸附剂（Na₂CO₃/CA）机械性能较好,但其脱碳性能最差。结合吸附剂脱碳和机械性能的综合考量,Na₂CO₃/Al₂O₃是最为合适的CO₂吸附剂,并进一步研究不同Na₂CO₃负载量的影响。研究发现随着Na₂CO₃负载量的变化,吸附剂的微观结构、脱碳性能以及机械性能都存在明显的差异。虽然60%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒的机械性能和脱碳效果较好,但其成球度较差,影响其实际应用。质量分数40%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒具有良好的脱碳性能、机械性能以及成球度,CO₂脱除量为1.36mmol/g。总体而言,利用挤压-滚圆法制备的Na₂CO₃基吸附剂颗粒具有良好的流动特性、脱碳性能和机械性能,适用于电厂烟气中的CO₂脱除。     

蒸汽活化水泥支撑钙基吸收剂活性及强度特性

拟通过蒸汽活化实现多次循环后机械成型、水泥支撑钙基吸收剂的活性再生,在鼓泡床上研究了活化前后活性,在颗粒碰撞装置上研究活化前后强度及过热处理的影响,并分析了微观结构。结果表明,失活水泥支撑颗粒活化后活性提升幅度大,950℃煅烧下活化后钙转化率由0.113升至0.419,石灰石仅由0.089增至0.278。碰撞实验显示活化后成型颗粒强度下降明显。石灰石活化后出现大量裂缝,可增加活性和削弱强度;而成型颗粒活化后未出现裂缝,但其孔隙提升更佳且表面松散,活性提升显著,强度下降也明显。对活化后颗粒进行过热处理明显改善了强度,由于其可消除晶格内空穴及缺陷。对失活水泥支撑颗粒蒸汽活化并过热处理可同时提升活性并改善强度。     

CO2捕集的研究现状及钙基吸收剂的应用

温室气体CO2是当今世界环境恶化的主要原因之一,近年来针对CO2的捕集技术也相继被研究.磷石膏是湿法冶炼磷酸的副产物,具有产量大、微辐射性等特点,严重危害自然环境和人类健康.本文阐述二氧化碳捕集与封存(CCS)以及燃烧后捕集的三大方法的具体技术原理与特点,着重分析利用钙基吸收剂捕集CO2的技术特点和优势,提出CO2捕集技术的探索方向并指出利用磷石膏分解渣作钙基吸收剂矿化捕集CO2的思路.当前对CO2捕集的研究多停留在吸收剂捕集方面,单纯吸收剂虽吸收效果较好,但其成本较高.磷石膏分解渣作钙基吸收剂不仅有着良好的捕集效果,且解决了成本问题,实现了"以废制废"的思路.     

负载型钾基CO2吸收剂的结构表征和碳酸化反应特性

CO2减排已成为21世纪人类面临的焦点问题.而在我国燃煤电厂作为CO2排放量最大、排放最集中的化石燃料燃烧场所,对其进行CO2减排技术的研究和开发势在必行.     

Mathematical modeling of a moving bed reactor for post‐combustion CO2 capture

A mathematical model for a moving bed reactor with embedded heat exchanger has been developed for application to solid sorbent‐based capture of carbon dioxide from flue gas emitted by coal‐fired power plants. The reactor model is one‐dimensional, non‐isothermal, and pressure‐driven. The two‐phase (gas and solids) model includes rigorous kinetics and heat and mass transfer between the two phases. Flow characteristics of the gas and solids in the moving bed are obtained by analogy with correlations for fixed and fluidized bed systems. From the steady‐state perspective, this work presents the impact of key design variables that can be used for optimization. From the dynamic perspective, the article shows transient profiles of key outputs that should be taken into account while designing an effective control system. In addition, the article also presents performance of a model predictive controller for the moving bed regenerator under process constraints. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3899–3914, 2016     

Coupled experimental phase diagram study and thermodynamic optimization of the Li2O–MgO–SiO2 system

A coupled key phase diagram study and critical evaluation and optimization of all available experimental data of the Li₂O–MgO–SiO₂ system was performed to obtain a set of Gibbs energy functions to reproduce all the reliable phase equilibria and thermodynamic data. Differential scanning calorimetry measurements and equilibration/quenching experiments were performed in the Li₂SiO₃–MgO and Li₄SiO₄–Mg₂SiO₄ sections, respectively, using sealed Pt capsules to prevent the volatile loss of Li. According to the present experimental results, Li₂MgSiO₄ is the only compound present in the Li₄SiO₄–Mg₂SiO₄ isopleth, which shows a peritectic melting at 1465 ± 6°C (1738 ± 6 K). The Modified Quasichemical Model, which considers short‐range ordering in the melt, was employed to describe the thermodynamic properties of the liquid phase. The Li₄SiO₄–Li₂MgSiO₄ and Mg₂SiO₄‐rich solid solutions were modeled using the Compound Energy Formalism.     

Analysis of equilibrium CO2 solubility and thermodynamic models for aqueous 1-(2-hydoxyethyl)-piperidine solution

1-(2-Hydoxyethyl)-piperidine (1-(2HE)-PP) is a new tertiary amine with desirable properties and can be potentially used to formulate superior absorbents for CO₂ capture. The equilibrium CO₂ solubility of 1-(2HE)-PP solution is measured over temperatures from 298 to 333 K, CO₂ partial pressures from 8.1 to 101.3 kPa and initial amine concentrations from 1 to 5 M. Two thermodynamic models, namely semiempirical model and activity coefficient model are developed for the system. The activity coefficient model shows better estimation solubility with an absolute average relative deviation (AARD) of 7.6%. In the comparison between the two models, a comprehensive analysis is presented. Some suggestions are provided for the similar model development. In addition, the speciation plot of CO₂ loaded 1-(2HE)-PP solution is predicted based on the activity coefficient model. The predictive pH values agree well with experimental data with AARD of 1.0%. Finally, the potential of 1-(2-HE)PP to be an alternative amine in CO₂ capture is evaluated.     

钙基碳载体造粒的捕集CO特性及力学性能

采用挤出滚圆法对钙基碳载体Ca（OH）₂进行造粒。在双固定床反应器上研究了黏结剂、支撑体和造孔剂对造粒后钙基碳载体循环捕集CO₂性能的影响,并提出采用多孔Al₂O₃球粉作为新型支撑体。结果表明,选择聚乙烯吡咯烷酮为颗粒黏结剂时最佳添加量为2%。高铝水泥和多孔Al₂O₃球粉均可作为支撑体造粒。多孔Al₂O₃球粉作为支撑体造粒后碳载体的循环捕集CO₂性能更高,其10次循环后CO₂吸收量为0.23g/g,是添加高铝水泥造粒碳载体的1.35倍。微晶纤维素作为造孔剂显著提高了造粒碳载体的循环捕集CO₂性能。多孔Al₂O₃球粉作为支撑体造粒后碳载体的抗压强度略高于高铝水泥作为支撑体。多孔Al₂O₃球粉造粒钙基碳载体拥有大量30~100nm孔隙,其比孔容高于高铝水泥造粒碳载体,这有利于CO₂捕集。     

A kinetic model of nano‐CaO reactions with CO2 in a sorption complex catalyst

This article describes the reactive kinetics of nano‐CaO with CO₂ in a sorption complex catalyst. Based on an observation of nano‐CaO reaction with CO₂ has a fast surface reaction regime and followed by a slow diffusion‐controlled regime, a criterion has been proposed to divide the fast surface reaction regime and the slow diffusion‐controlled reaction regime. The kinetics of the fast surface reaction was studied, and a new ion reaction mechanism was proposed. A surface reaction‐controlled kinetic model with a Boltzmann equation, X = X_u?X_u/[1+exp((t?t₀)k/X_u)], was developed. Experiments using nano‐CaO to react with CO₂ in a fast surface reaction regime within a sorption complex catalyst were performed using thermogravimetric analysis at 773–873 K under a N₂ atmosphere with 0.010–0.020 MPa CO₂. The activation energy of the kinetic model for carbonation is 30.2 kJ/mol, and the average relative deviation of the sorption ratio is less than 9.8%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

CFD Modeling of a Carbonation Reactor with a K‐Based Dry Sorbent for CO2 Capture

A 2D CFD simulation of the carbonation reactor is carried out to evaluate the performance of potassium‐based dry sorbent during the CO₂ capture process. A multiscale drag coefficient model is incorporated into the two‐fluid model to take the effects of clusters into account. The influence of several parameters on CO₂ removal is investigated. The results indicate that increasing the reactor height and reducing the gas velocity can lengthen the residence time of particles and enhance the CO₂ removal. The operating pressure has a significant influence on the performance of solid sorbents. A higher pressure will decrease the CO₂ removal efficiency.