氨基修饰微孔/介孔复合材料AM-5A-MCM-41对CO2吸附分离的分子模拟

构建了氨基修饰微孔/介孔复合材料AM-5A-MCM-41的全原子模型,采用巨正则Monte Carlo（GCMC）方法研究了它的CO₂吸附分离性能,采用加权混合规则来描述氨基和CO₂分子的弱化学作用。模拟结果表明,CO₂分子优先吸附在复合材料介孔表面的氨基附近,CO₂纯气体的吸附量和吸附热有了显著提高,而N₂的吸附量和吸附热则基本不受影响。对于CO₂和N₂的混合气分离,由于复合材料对CO₂的弱化学吸附作用,显著提高了CO₂吸附量和吸附选择性,在573 K和100 kPa时CO₂/N₂的选择性达到了87.0。通过分子模拟研究可以从微观角度了解CO₂在氨基修饰的微孔/介孔复合材料中的吸附分离的细节和机理,为实验设计和合成高效CO₂吸附剂提供指导。     

Fabrication of nickel oxide functionalized zeolite USY composite as a promising adsorbent for CO2 capture

Adsorption process is considered to be the most promising alternative for the CO₂ capture to the traditional energy-intensive amine absorption process, and the development of feasible and efficient CO₂ adsorbents is still a challenge. In this work, the NiO@USY (ultrastable Y) composites with different NiO loadings were prepared for the CO₂ adsorption using Ni(NO₃)₂ as the precursor. The composites were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, nitrogen adsorption–desorption test, scanning electron microscopy analysis, and thermogravimetric analysis, and were evaluated for the CO₂ adsorption capacity, CO₂/N₂ adsorption selectivity and CO₂ cycle adsorption capacity. The characterization results show that after the activation at 423 K, the Ni(NO₃)₂ species were well dispersed into the surface of zeolite USY, and after the further activation at 823 K, Ni(NO₃)₂ could be converted into highly dispersed NiO. The adsorption results show that the presence of the active component NiO plays an important role in improving the CO₂ adsorption performance, and the NiO@USY composite with a NiO loading of 1.5 mmol·g^-1 USY support displays a high adsorption capacity and adsorption selectivity for CO₂, and shows a good cycle stability. In addition, the Clausius–Clapeyron equation was used to evaluate the isosteric heat of adsorption of CO₂ on the NiO(1.5)@USY composite, and the heat of adsorption was 17.39–38.34 kJ·mol^-1.     

Fabrication of azobenzene-functionalized porous polymers for selective CO2 capture

Many solid adsorbents have been prepared for the CO₂ capture. In particular, the photoresponsive adsorbents have attracted extensive interests because of their tunable pore structure and variable responsive behaviors provoked by the external light. However, it is challenging to fabricate the photoresponsive adsorbents featured the big CO₂ capacity and high CO₂ selectivity. Herein, copolymerized between 4-phenylazobenzoyl chloride, 2,4,6-trichloro-1,3,5-triazine and melamine, a series of azobenzene-functionalized porous polymers (PTM-AZOs) are successfully synthesized. The PTM-AZOs are verified in possession of proper pore structures, large surface area and photoconductive properties through a series of characterization. The PTM-AZO-2 with the trans-isomerization exhibits the best CO₂ adsorption amount of 2.7 mmol·g^-1 (273 K and 0.1 MPa), while the CO₂/N₂ selectivity can reach 2459 and 607 on the trans- and cis-isomerization, respectively. The regulatable pore structures controlled by the photoresponsive azobenzene groups affect the CO₂ capture performance of the PTM-AZOs.     

乙醇胺(MEA)法燃煤电厂CO2捕集系统尾气二次污染分析

在某燃煤电厂用乙醇胺(MEA)作吸收剂进行了CO₂燃烧后捕集中试,并对系统的排放物进行了分析。吸收塔尾气和再生气用GASMET烟气监测系统进行在线监测,可得到二者组分及含量。结合电厂烟气、连续监测系统(CEMS)数据及实验室溶液分析,根据烟气数据对MEA的挥发及降解情况作了研究,比较了系统前后烟气组分的变化,讨论其尾气对环境是否造成二次污染。试验结果表明:MEA在吸收塔中主要发生氧化降解,在再生塔中主要发生热降解,且溶剂损耗主要来自氧化降解和挥发;降解的主要产物为NH₃和乙醛,二者在气体中含量变化情况与溶液中MEA浓度变化基本一致;预洗塔能除去原烟气中部分酸性气体。故CO₂捕集系统可以进一步减少电厂净烟气中的原有污染物,但也会产生新的污染组分。新生成的污染物含量很少,符合国家标准,不会造成二次污染。     

容量法测量5 A分子筛静态吸附CH4、CO和CO2的研究

采用容量法分别测量CH₄、CO和CO₂在5A分子筛上的等温吸附曲线,探究吸附温度和吸附压力对CH₄、CO和CO₂吸附量的影响。实验结果表明,吸附量随着吸附压力的上升逐渐增大。设定吸附温度在30 ℃、50 ℃和70 ℃时,5A分子筛在30 ℃时对CH₄吸附量最大,为13.60 cm³·g^-1;对CO和CO₂吸附量均在50 ℃时呈现最大值,分别为17.68 cm³·g^-1 和94.38 cm³·g^-1。而吸附温度70 ℃时,对3种气体的吸附量均减小。     

一种具有高CO吸附容量和高CO/N2及CO/CO2分离选择性的CuCl@β吸附剂

研制了一种新型的CuCl@β分子筛吸附剂材料,它不仅对CO有着高吸附容量,而且对CO/N₂和CO/CO₂的二元混合气有着高吸附选择性。利用自发单层分散的原理制备了一系列的CuCl@β分子筛材料,分别应用氮气吸附以及XRD进行表征。CO在CuCl@β分子筛上吸附等温线和动态透过曲线分别通过静态吸附和固定床实验获得。依据IAST理论模型计算了CuCl@β分子筛对CO/N₂二元混合物和CO/CO₂二元混合物的吸附选择性。研究结果表明:(1)氯化亚铜的负载增强了一氧化碳在CuCl@β分子筛上的吸附容量,其最佳负载量为0.4 g·g^-1。(2)CuCl@β分子筛吸附剂在增强CO的吸附量的同时,还降低了对二氧化碳和氮气的吸附。由于Cu⁺-CO π位络合键的存在,提高了CuCl@β分子筛对二元混合物CO/N₂和CO/CO₂的吸附选择性。(3)在低压下(0～10 kPa)下0.4CuCl@β分子筛对CO/N₂和CO/CO₂的吸附选择性分别高达1600～5200和120～370,远大于原始的β分子筛。CuCl@β分子筛对CO有着超高吸附容量以及吸附选择性,将会是一种很有潜力的CO分离提纯材料。     

The CO2 absorption and desorption performance of the triethylenetetramine + N,N-diethylethanolamine + H2O system

Post-combustion CO₂ capture (PCC) process faces significant challenge of high regeneration energy consumption. Biphasic absorbent is a promising alternative candidate which could significantly reduce the regeneration energy consumption because only the CO₂-concentrated phase should be regenerated. In this work, aqueous solutions of triethylenetetramine (TETA) and N,N-diethylethanolamine (DEEA) are found to be efficient biphasic absorbents of CO₂. The effects of the solvent composition, total amine concentration, and temperature on the absorption behavior, as well as the effect of temperature on the desorption behavior of TETA-DEEA-H₂O system were investigated. An aqueous solution of 1 mol·L^-1 TETA and 4 mol·L^-1 DEEA spontaneously separates into two liquid phases after a certain amount of CO₂ is absorbed and it shows high CO₂ absorption/desorption performance. About 99.4% of the absorbed CO₂ is found in the lower phase, which corresponds to a CO₂ absorption capacity of 3.44 mol·kg^-1. The appropriate absorption and desorption temperatures are found to be 30℃ and 90℃, respectively. The thermal analysis indicates that the heat of absorption of the 1 mol·L^-1 TETA and 4 mol·L^-1 DEEA solution is -84.38 kJ·(mol CO₂)^-1 which is 6.92 kJ·(mol CO₂)^-1 less than that of aqueous MEA. The reaction heat, sensible heat, and the vaporization heat of the TETA-DEEA-H₂O system are lower than that of the aqueous MEA, while its CO₂ capacity is higher. Thus the TETA-DEEA-H₂O system is potentially a better absorbent for the post-combustion CO₂ capture process.     

Supported ionic liquid sorbents for CO2 capture from simulated flue-gas

Supported ionic liquid (IL) sorbents for CO₂ capture were prepared by impregnating tetramethylammonium glycinate ([N₁₁₁₁] [Gly]) into four types of porous materials in this study. The CO₂ adsorption behavior was investigated in a thermogravimetric analyzer (TGA). Among them, poly(methyl methacrylate) (PMMA)-[N₁₁₁₁] [Gly] exhibits the best CO₂ adsorption properties in terms of adsorption capacity and rate. The CO₂ adsorption capacity reaches up to 2.14 mmol·g^-1 sorbent at 35℃. The fast CO₂ adsorption rate of PMMA-[N₁₁₁₁] [Gly] allows 60 min of adsorption equilibrium time at 35℃ and much shorter time of 4 min is achieved at 75℃. Further, Avrami's fractional-order kinetic model was used and fitted well with the experiment data, which shows good consistency between experimental results and theoretical model. In addition, PMMA-[N₁₁₁₁] [Gly] remained excellent durability in the continuous adsorption-desorption cycling test. Therefore, this stable PMMA-[N₁₁₁₁] [Gly] sorbent has great potential to be used for fast CO₂ adsorption from flue-gas.     

CO/N2/CO2在MOF-74(Ni)上吸附相平衡和选择性

主要研究了MOF-74(Ni)材料对CO/N₂/CO₂的吸附分离性能。应用水热法合成制备MOF-74(Ni),分别采用全自动表面积吸附仪、P-XRD、扫描电子显微镜对材料的孔隙结构和晶体形貌进行了表征,应用静态吸附法测定了CO、N₂和CO₂在MOF-74(Ni)上的吸附等温线,应用DSLF方程模拟了3种气体MOF-74(Ni)上的吸附等温线,依据IAST理论模型计算了MOF-74(Ni)对CO/N₂二元混合物和CO/CO₂二元混合物的吸附选择性。研究结果表明:在0.1 MPa和常温条件下,MOF-74(Ni)材料对CO吸附容量高达6.15 mmol·g^-1,而相同条件下N₂的吸附量只有0.86 mmol·g^-1。MOF-74(Ni)在低压下(0～40 kPa)对CO的吸附量明显高于其对CO₂的吸附量。应用IAST模型估算MOF-74(Ni)对二元混合物吸附选择性的结果表明:MOF-74(Ni)对CO/N₂混合物的吸附选择性在1000以上;MOF-74(Ni)对CO/CO₂的吸附选择性在4～9范围,在所研究的二元气体混合物吸附体系中,MOF-74(Ni)都能优先吸附CO。     

氨改性的介孔二氧化硅的直接合成和CO2吸附

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the SN+-I mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pres-sure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol•g1 and 0.03 mmol•g1, respectively, indicating high separation coefficient of CO2/N2.     

基于沸石ZSM-5的CH4/N2/CO2二元体系吸附平衡

采用Rubotherm磁悬浮天平测量CH₄、N₂和CO₂在沸石ZSM-5上的单组分吸附平衡等温线,温度273～353 K,压力0～500 kPa。采用Sips模型、Toth模型和MSL模型对单组分吸附平衡实验数据进行拟合,拟合结果良好,非线性回归得到相应的模型参数。测量双组分CO₂/N₂、CO₂/CH₄和CH₄/N₂在沸石ZSM-5上的竞争吸附平衡等温线,实验温度为293 K,实验压力为0～500 kPa。采用基于Sips模型的理想吸附溶液理论和双组分MSL模型预测双组分气体在沸石ZSM-5上的竞争吸附平衡等温线,并与实验结果进行比较,预测结果良好。比较CO₂/N₂、CO₂/CH₄以及CH₄/N₂体系在沸石ZSM-5上的竞争吸附选择性系数,探究沸石ZSM-5吸附分离烟道气（CO₂/N₂体系）、垃圾填埋气（CO₂/CH₄体系）或煤层气（CH₄/N₂体系）的可行性,为将来进行工艺设计提供基础数据。     

密闭空间低浓度CO2固态胺吸附剂长寿命评价

在密闭空间实际工况下,通过两组平行对照试验,考察了长时间吸脱附循环对固态胺材料CO₂吸附性能的影响,对材料进行长寿命试验,并验证一年内固态胺材料性能的稳定性。结果表明,两组试验分别经过2128轮和2267轮吸脱附循环后,固态胺材料仍表现出良好的吸脱附稳定性。在长寿命试验条件下,两组吸附剂的CO₂的吸附量维持在约28 mg·g^-1,有机胺含量未见流失,活性胺含量比初始材料有所提高并不再降低,材料机械强度未受到影响。结果证明,高分子树脂基固态胺材料不仅能在室温条件下高效吸附CO₂,且能在温和条件下实现CO₂的解吸,在减少能耗的同时还有利于材料使用寿命的延长,适宜作为太空密闭空间中去除低浓度CO₂的吸附材料,为航天员的生命保障提供技术支撑。     

脱硫石膏改性固体胺复合材料的制备及脱碳性能

将榴莲壳碳化制备生物炭（BC）,与硅钙渣混合作复合载体,在其表面浸渍负载五乙烯六胺（PEHA）,并加入含水分的脱硫石膏（FGDG）,得到胺功能化的含水CO₂固体吸附剂,与不含脱硫石膏的吸附剂相比吸附活性明显改善。通过FT-IR、TGA、SEM及N₂吸脱附等手段对吸附剂进行了表征,并在固定床反应器中考察了吸附剂脱硫石膏含量、吸附温度和CO₂浓度对吸附性能的影响。结果表明,脱硫石膏中水的存在改变了氨基与CO₂的相互作用机理。当脱硫石膏含量为30%、吸附温度为85℃时,CO₂最大吸附量为2.33 mmol/g。经12次循环再生后吸附量仅下降了4.2%,表现出良好的吸附稳定性。Clausius-Clapeyron方程计算的等量吸附热介于物理与化学吸附热之间,说明吸附过程中物理与化学作用同时进行。用多个动力学模型对实验数据进行拟合,pseudo-first-order与pseudo-second-order模型均不能准确拟合实验数据,而Avrami模型可较好地拟合整个吸附过程,进一步验证BC/SCS-PEHA-30% FGDG的CO₂吸附过程并非单纯的物理或化学吸附,而是两者同时发生。     

乙醇胺捕集燃煤烟气二氧化碳工艺模拟

有机胺法是最有效的燃煤烟气二氧化碳（CO₂）捕集技术之一。使用Aspen plus模拟乙醇胺（MEA）捕获烟气CO₂的过程,先进行单独的吸收塔与再生塔模拟,在单独系统模型收敛的基础上,再进行吸收-解吸的综合模拟。在入塔烟气流量为8.22 m³/min、CO₂物质的量分数为0.18、MEA流量为2 311.3 kg/h、MEA物质的量分数为0.12条件下,MEA捕集燃煤烟气中CO₂的模拟结果: CO₂脱除率为69.3%,净化气中CO₂物质的量分数为5.33×10^-2,再生塔顶再生气中CO₂物质的量分数为0.956,基本达到了设计要求。此为更深入地开展胺法吸收CO₂的研究提供了依据。     

有机胺功能化介孔固体吸附剂吸附分离CO2性能研究

针对当前固体胺CO₂吸附剂存在吸附容量小、循环稳定性差等问题,采用高比表面积、易嫁接胺的介孔SBA-15作为载体,研究分子筛模板剂脱除方法和有机胺改性方法对制备的固体吸附剂吸附性能的影响,并采用N₂物理吸附、X射线衍射、红外光谱、热失重分析等表征技术并对样品进行表征。实验结果表明,通过嫁接和浸渍能够合成出不同有机胺负载量的胺功能化吸附剂,其中混合胺嫁接法改性的APTES-SBA（U）-T60吸附剂其吸附容量最大,在75℃下的纯CO₂气氛中吸附量达到192.05 mg/g,优于溶剂萃取和煅烧法去除模板剂。此外,混合胺嫁接法制备的样品在多次的吸/脱附操作下,CO₂吸附稳定性良好,表明混合胺修饰的吸附剂具有很好的稳定性和再生性。     

吸附法碳捕集固体胺吸附剂成型技术研究进展

吸附法碳捕集技术是实现工业过程或大气中CO₂分离与脱除的重要途径之一,高性能吸附剂的开发是该技术的关键。固体胺吸附剂由于其优异的CO₂吸附量、选择性以及较低的再生能耗,近年来受到了广泛的关注,但用于工业的成型吸附剂仍面临机械强度低、稳定性差和胺流失严重等关键难题,难以在工业中大范围的推广应用。本文分析了固体胺成型吸附剂制备面临的主要难题,重点总结了近年来国内外吸附剂成型技术的研发进展,并对固体胺工业吸附剂的发展方向进行了展望。未来固体胺吸附法碳捕集技术的研发重点在于立足吸附反应机理和工业烟气的特性,创新成型固体胺吸附剂制备技术,提升吸附剂的CO₂吸附量、胺效率、机械与循环稳定性,研发低能耗的配套吸附工艺和核心装置。     

Design and experiment of high-productivity two-stage vacuum pressure swing adsorption process for carbon capturing from dry flue gas

A two-stage vacuum pressure swing adsorption (VPSA) process that coupled kinetically controlled and equilibrium controlled separation process with reflux has been investigated for capturing carbon dioxide from dry flue gas (85% N₂/15% CO₂). In the first enriching stage, carbon molecular sieve (CMS), which shows kinetic selectivity for CO₂/N₂, is adopted as the adsorbent to remove most N₂ in feed gas, thereby upgrading CO₂ and significantly reducing the amount for further refinement. The second stage loads zeolite 13X as adsorbent to purify the CO₂-rich flow from the first stage for meeting the requirements of National Energy Technology Laboratory. Series of experiments have been conducted for adsorption isotherms measuring and lab-scale experimental validation as well as analysis. The effect of feed composition on the separation performance of the PSA system was studied experimentally and theoretically here. The optimal results achieved 95.1% purity and 92.9% recovery with a high CO₂ productivity (1.89 mol CO₂·h^-1·kg^-1) and an appropriate energy consumption of 1.07 MJ·(kg CO₂)^-1. Further analysis has been carried out by simulation for explicating the temperature, pressure, and concentration distribution at cyclic steady state.     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

Optimization of the gas separation performance of polyurethane–zeolite 3A and ZSM-5 mixed matrix membranes using response surface methodology

In the present work, the response surface method software was used with five measurement levels with three factors.These were applied for the optimization of operating parameters that affected gas separation performance of polyurethane–zeolite 3A, ZSM-5 mixed matrix membranes.The basis of the experiments was a rotatable central composite design(CCD).The three independent variables studied were: zeolite content(0–24 wt%), operating temperature(25–45 ℃) and operating pressure(0.2–0.1 MPa).The effects of these three variables on the selectivity and permeability membranes were studied by the analysis of variance(ANOVA).Optimal conditions for the enhancement of gas separation performances of polyurethane–3A zeolite were found to be 18 wt%, 30 ℃ and 0.8 MPa respectively.Under these conditions, the permeabilities of carbon dioxide, methane, oxygen and nitrogen gases were measured at 138.4, 22.9, 15.7 and 6.4 Barrer respectively while the CO_2/CH_4, CO_2/N_2 and O_2/N_2 selectivities were 5.8, 22.5 and 2.5, respectively.Also, the optimal conditions for improvement of the gas separation performance of polyurethane–ZSM 5 were found to be 15.64 wt%, 30 ℃ and 4 bar.The permeabilities of these four gases(i.e.carbon dioxide, methane, oxygen and nitrogen) were 164.7, 21.2, 21.5 and 8.1 Barrer while the CO_2/CH_4, CO_2/N_2 and O_2/N_2 selectivities were 7.8, 20.6 and 2.7 respectively.     

胺基CO2固体吸附剂脱碳特性及SO2的影响

燃煤电厂烟气中存在的微量SO₂对胺基CO₂固体吸附剂的碳酸化反应及循环特性有不利影响。利用固定床反应器,针对采用溶胶凝胶法制备的胺基CO₂固体吸附剂的碳酸化特性及其在含SO₂气氛下的失效规律进行了实验研究,并结合红外光谱、有机元素分析、BET等测试手段,研究其失效机理。结果表明,所制备的胺基CO₂固体吸附剂在反应温度50℃时具有较好的碳酸化反应特性和循环特性。当反应气氛中存在SO₂时,由于生成了不可再生的亚硫酸/硫酸盐类物质而导致胺基活性位损失,孔隙结构发生变化,影响了吸附剂的脱碳性能,但适当提高反应温度可提高吸附剂的碳酸化反应竞争性。