真空变压吸附捕集烟道气中二氧化碳的模拟、实验及分析

采用工业硅胶作为吸附剂,利用两塔变压吸附装置进行了烟道气变压吸附碳捕集实验。利用gPROMS软件建立两塔变压吸附模型对实验过程进行模拟,对比了实验和模拟的结果,验证了模型的准确性。通过两塔变压吸附可将15%的CO₂富集到74%,收率为91.52%。在模型基础上考察了变压吸附碳捕集过程中进料量、吸附时间、顺放压力与二氧化碳收率、纯度和能耗的关系,定性分析了吸附塔压力和进料量对压缩机能耗的影响。结果表明:增大进料量、延长吸附时间、降低顺放压力,可以有效提高产品气中CO₂浓度,但同时也导致收率的下降,前两者还会造成单位能耗的增加;吸附压力越高,进料流量越大,压缩机能耗越大。     

Amine-immobilized HY zeolite for CO2 capture from hot flue gas

Solid amine-based adsorbents were widely studied as an alternative to liquid amine for post-combustion CO₂ capture (PCC). However, most of the amine adsorbents suffer from low thermal stability and poor cyclic regenerability at the temperature of hot flue gases. Here we present an amine loaded proton type Y zeolite (HY) where the amines namely monoethanolamine (MEA) and ethylenediamine (ED) are chemical immobilized via ionic bond to the zeolite framework to overcome the amine degradation problem. The MEA and ED of 5%, 10% and 20% (mass) concentration – immobilized zeolites were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, and N₂ -196 ℃ adsorption to confirm the structure integrity, amine functionalization, and surface area, respectively. The determination of the amine loading was given by C, H, N elemental analysis showing that ED has successfully grafted almost twice as many amino groups as MEA within the same solvent concentration. CO₂ adsorption capacity and thermal stability of these samples were measured using thermogravimetric analyser. The adsorption performance was tested at the adsorption temperature of 30, 60 and 90 ℃, respectively using pure CO₂ while the desorption was carried out with pure N₂ purge at the same temperature and then followed by elevated temperature at 150 ℃. It was found that all the amine@HY have a substantial high selectivity of CO₂ over N₂. The sample 20% ED@HY has the highest CO₂ adsorption capacity of 1.76 mmol·g^-1 at 90 ℃ higher than the capacity on parent NaY zeolite (1.45 mmol·g^-1 only). The amine@HY samples presented superior performance in cyclic thermal stability in the condition of the adsorption temperature of 90 ℃ and the desorption temperature of 150 ℃. These findings will foster the design of better adsorbents for CO₂ capture from flue gas in post-combustion power plants.     

CO2 capture from dry flue gas by vacuum swing adsorption: A pilot plant study

The capture and concentration of CO₂ from a dry flue gas by vacuum swing adsorption (VSA) has been experimentally demonstrated in a pilot plant. The pilot plant has the provision for using two coupled columns that are each packed with approximately 41 kg of Zeochem zeolite 13X. Breakthrough experiments were first carried out by perturbing a N₂ saturated bed with 15% CO₂ and 85% N₂ feed, which is representative of a dry flue gas from coal‐fired power plants. The breakthrough results showed long plateaus in temperature profiles confirming a near adiabatic behavior. In the process study, a basic four‐step vacuum swing adsorption (VSA) cycle comprising the following steps: pressurization with feed, adsorption, forward blowdown, and reverse evacuation was investigated first. In the absence of any coupling among the steps, a single bed was used. With this cycle configuration, CO₂ was concentrated to 95.9 ± 1% with a recovery of 86.4 ± 5.6%. To improve the process performance, a four‐step cycle with light product pressurization (LPP) using two beds was investigated. This cycle was able to achieve 94.8 ± 1% purity and 89.7 ± 5.6% recovery. The Department of Energy requirements are 95% purity and 90% recovery. The proposed underlying physics of performance improvement of the four‐step cycle with LPP has also been experimentally validated. The pilot plant results were then used for detailed validation of a one‐dimensional, nonisothermal, and nonisobaric model. Both transient profiles of various measured variables and cyclic steady state performance results were compared with the model predictions, and they were in good agreement. The energy consumptions in the pilot plant experiments were 339–583 ± 36.7 kWh tonne^?1 CO₂ captured and they were significantly different from the theoretical power consumptions obtained from isentropic compression calculations. The productivities were 0.87–1.4 ± 0.07 tonne CO₂ m^?3 adsorbent day^?1. The results from our pilot plant were also compared with available results from other pilot plant studies on CO₂ capture from flue gas. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1830–1842, 2014     

真空变温吸附捕集干烟道气中CO2的模拟研究

为减缓气候变化,减少CO₂的排放,对真空变温吸附(TVSA)从干烟道气中捕集CO₂进行了系统的研究。以沸石13X为吸附剂,设计了实验室规模的4塔连续进料的TVSA工艺,并建立数学模型进行数值模拟。模拟结果表明,通过四塔TVSA可获得纯度为97.54%,回收率为96.79%的CO₂产品气,其产率为1.7 mol· ( \mathrm{k} \mathrm{g} \text{?} \mathrm{a} \mathrm{d} \mathrm{s} ) ^-1·h^-1,能耗为3.14 \mathrm{M} \mathrm{J} · ( \mathrm{k} \mathrm{g} \text{?} \mathrm{C} {\mathrm{O}}_{\mathrm{2}} {)}_{}^{-\mathrm{1}} 。此外,考察了进料量、循环回流步骤时间、真空度对产品气纯度、回收率、吸附剂产率和工艺能耗的影响,并且分析了塔内压力与温度变化,详细探讨了塔内气固相浓度随轴向的分布。良好的工艺效果表明,TVSA有潜力成为一种能够生产高纯度高回收率的CO₂产品气,并具有良好经济效益的捕碳工艺。     

带循环的二阶变压吸附碳捕集工艺模拟、实验及分析

针对日益严重的温室效应及传统CO₂捕集和储存技术的不足,设计带循环的二阶四塔变压吸附装置捕集电厂烟道气中的二氧化碳,采用炭分子筛作为第一阶二塔处理装置吸附剂,采用13X作为第二阶二塔处理装置的吸附剂。建立上述工艺的数学模型,通过实验验证数学模型和模拟结果的准确性。模拟结果表明,本工艺可以将烟道气中的CO₂（15%）富集为纯度95%的产品气,收率为93.92%,工艺处理量为4.576 mol CO₂·h^-1·kg^-1,能耗为0.847 MJ·（kg CO₂）^-1,通过对比,本工艺具有处理量大、回收率高、纯度高的优点。在此基础上,根据数学模型分析二阶床层在一个周期内的压力变化、温度分布、固相和气相组成分布、能耗组成、生产能力。     

Purification of coal mine methane on carbon molecular sieve by vacuum pressure swing adsorption

The vacuum pressure swing adsorption (VPSA) method, as an alternative way to separate the CH₄/N₂ mixture, was adopted to purify methane from coal mine methane. The performance of the VPSA process was investigated experimentally and theoretically with a reactivated carbon molecule sieve as the adsorbent. The computer calculations were compared to the experimental data. The concentrated methane with 79% purity could be collected directly during the high-pressure adsorption step with 93% recovery and 0.0720 mL·g^–1·min^–1 productivity, when the composition of raw gas was 10/90 vol% CH₄/N₂, which is of great significance for the utility of low quality energy gas.     

Numerical analysis of CO2 concentration and recovery from flue gas by a novel vacuum swing adsorption cycle

The objective of this work is to study the feasibility of carbon dioxide concentration and recovery from flue gases using a novel VSA cycle without rinse step with the aid of mathematical modeling. A theoretical model based on conservation equations (following the one proposed by Da Silva and Rodrigues (2001)) is used for an initial evaluation of the process performance. Activated carbon is the adsorbent considered, simulating adsorption equilibrium and kinetics with the equations proposed by Kikkinides, Yang, and Cho (1993). According to the simulated results, it is possible to recover carbon dioxide with high purity (>93%) from a mixture with 13% carbon dioxide at 40 °C, with higher recovery (>90%) and a lower power consumption (<0.12 kWh/kgCO₂) than other processes with rinse step reaching the same purity. Although these results are theoretical, they show the potential advantages of this process for CO₂ capture.     

真空变压吸附分离氮气甲烷流程灵敏度分析与优化

首先采用实验室自制椰壳活性炭为吸附剂,进行了氮气/甲烷(65%/35%)原料气的真空变压吸附工艺(VPSA)分离实验。通过对比实验和gPROMS 动态模拟软件的分离效果,对变压吸附数学模型进行了验证,证明了所采用数学模型的准确性。在此基础上,对影响产品气甲烷纯度、回收率的关键决策变量进行了灵敏度分析。分析结果表明:产品气纯度主要由原料气流量和置换气流量来进行调控,产品气回收率则需要关键变量共同的作用才能实现最大化。依据灵敏度分析结果,对两塔分离氮气甲烷混合气的变压吸附工艺进行了动态优化。在最优的工况下,可以将进料组成为35%的甲烷富集到75%,回收率达到97.08%;从而达到对于废混合气的高效回收利用。     

Application of high‐pressure swing adsorption process for improvement of CO2 recovery system from flue gas

Although the super cold separator applied to the system for CO₂ recovery from flue gas can produce pure CO₂ liquid, the CO₂ recovery efficiency is low. Therefore, the addition of a PSA plant was considered for the secondary CO₂ recovery from the noncon‐densing gas to improve the efficiency. The PSA plant was operated for adsorption at the same pressure as that of the super cold separator and for desorption at the atmospheric pressure. From both the simulation and the experimental data, it was confirmed that CO₂ could be concentrated from 50% in the noncondensing gas to 70% in the recovery gas by the PSA plant and the CO₂ recovery efficiency of the plant was about 90%.     

膜分离捕集燃煤电厂烟气CO2过程优化设计

全球CO₂的排放量不断升高,导致气候问题频发。“双碳”目标下,如何高效、低成本地捕集燃煤电厂烟气CO₂已经成为迫在眉睫的问题。传统的化学吸收法由于能耗高、成本高、溶剂易挥发等问题严重制约了其发展,而膜法碳捕集因为其操作简单、能耗低、环境污染小等优势被认为是最有前景的捕集方式。本文以PI中空纤维膜为分离膜,建立和求解了气体分离膜模型。并以燃煤电厂烟气CO₂为捕集目标,利用多岛遗传算法求解了膜分离捕集CO₂工艺的不同配置,并优化了分离过程中的关键参数(膜面积、操作压力)。结果显示：在二级膜分离工艺中,二级一段膜分离工艺的第一级膜和第二级膜操作压力分别为5.8 bar和7.1 bar,第一级膜和第二级膜的面积分别为448000 m²和180000 m²时,单位捕集成本为27.36 USD/t CO₂。与二级二段膜分离以及其他几种传统的CO₂捕集方法(MEA法、相变吸收法)相比,二级一段膜分离捕集CO₂的捕集成本和能耗均最小。本研究将为CO₂捕集实现低能耗和低成本化提供依据。     

New process development and process evaluation for capturing CO2 in flue gas from power plants using ionic liquid [emim][Tf2N]

Using the ionic liquid [emim][Tf_2N] as a physical solvent, it was found by Aspen Plus simulation that it was possible to attempt to capture CO_2 from the flue gas discharged from the coal-fired unit of the power plant.Using the combination of model calculation and experimental determination, the density, isostatic heat capacity,viscosity, vapor pressure, thermal conductivity, surface tension and solubility of [emim][Tf_2N] were obtained.Based on the NRTL model, the Henry coefficient and NRTL binary interaction parameters of CO_2 dissolved in[emim][Tf_2N] were obtained by correlating [emim][Tf_2N] with the gas–liquid equilibrium data of CO_2. Firstly,the calculated relevant data is imported into Aspen Plus, and the whole process model of the ionic liquid absorption process is established. Then the absorption process is optimized according to the temperature distribution in the absorption tower to obtain a new absorption process. Finally, the density, constant pressure heat capacity,surface tension, thermal conductivity, and viscosity of [emim][Tf_2N] were changed to investigate the effect of ionic liquid properties on process energy consumption, solvent circulation and heat exchanger design. The results showed that based on the composition of the inlet gas stream to the absorbers, CO_2 with a capture rate of 90% and a mass purity higher than 99.5% was captured. These results indicate that the [emim][Tf_2N] could be used as a physical solvent for CO_2 capture from coal-fired units. In addition, the results will provide a theoretical basis for the design of new ionic liquids for CO_2 capture.     

真空变压吸附空分制氧等温与非等温过程模拟比较

应用动态柱穿透法测定的空气中氮-氧吸附平衡数据模拟两床真空变压吸附(VSA)空分制氧中等温与非等温过程;在VSA过程模拟中探讨了吸附压力、进料流量和冲洗比等过程操作条件以及吸附过程中温度的变化对产品气氧的纯度、收率和产率的影响,为VSA空分制氧过程提供一定的设计依据。     

镁矿砂回转窑窑尾烟气SDS干法脱硫工艺的设计应用

针对镁矿砂回转窑窑尾烟气污染环境的情况,阐述了碳酸氢钠干粉喷射(SDS)脱硫技术原理、实际应用与优缺点,并在实际项目中探究了镁矿砂回转窑烟气二氧化硫的去除效果。结果表明,在实际运行中采用SDS干法脱硫工艺处理后,镁矿砂回转窑烟气能够达到超低排放要求,ρ(SO2)≤35mg/m^3。项目投运后所产生的脱硫副产物主要成分为Na2SO3,可将其回收利用作为水泥添加剂辅料。该技术已成功推广应用到其他回转窑、焦炉和水泥窑烟气脱硫项目中,并取得了较好的应用效果。     

Preparation of carbon molecular sieves from carbon micro and nanofibers for sequestration of CO2

In this study, a hierarchal web of carbon micro and nanofibers was used as a precursor for the synthesis of a carbon molecular sieve (CMS). CMSs were prepared by thermal treatment of carbon fibers using a microwave heating device. The heating power and treatment time were optimized for the maximum performance of the prepared CMS for the separation of CO₂ at low concentrations from the gaseous mixture of CO₂ and air under dynamic (flow) conditions. Based on the experimental data, microwave power input of 240 W and treatment time of 15 min were found to be suitable for the maximum uptake of CO₂ by CMS. Adsorption breakthrough curves were obtained at different gas flow rates and CO₂ concentrations. CMSs prepared from the hierarchal web of carbon micro and nanofibers were found to be superior to those prepared from ACF. The CO₂ uptake was determined to be approximately 0.88 mg/g and 10 mg/g at concentrations of 500 ppm and 5000 ppm, respectively, in air.     

Design and operation of pilot plant for CO2 capture from IGCC flue gases by combined cryogenic and hydrate method

This project is a trial conducted under contract with CO₂CRC, Australia of a new CO₂ capture technology that can be applied to integrated gasification combined cycle power plants and other industrial gasification facilities. The technology is based on combination of two low temperature processes, namely cryogenic condensation and the formation of hydrates, to remove CO₂ from the gas stream. The first stage of this technology is condensation at −55 °C where CO₂ concentration is expected to be reduced by up to 75 mol%. Remaining CO₂ is captured in the form of solid hydrate at about 1 °C reducing CO₂ concentration down to 7 mol% using hydrate promoters. This integrated cryogenic condensation and CO₂ hydrate capture technology hold promise for greater reduction of CO₂ emissions at lower cost and energy demand. Overall, the process produced gas with a hydrogen content better than 90 mol%. The concentrated CO₂ stream was produced with 95-97 mol% purity in liquid form at high pressure and is available for re-use or sequestration. The enhancement of carbon dioxide hydrate formation and separation in the presence of new hydrate promoter is also discussed. A laboratory scale flow system for the continuous production of condensed CO₂ and carbon dioxide hydrates is also described and operational details are identified.